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Designing Porphyrinic Covalent Organic Frameworks for the Photodynamic Inactivation of Bacteria

  • Jan Hynek
    Jan Hynek
    Institute of Inorganic Chemistry, Czech Academy of Sciences, Husinec-Řež 1001, 250 68 Řež, Czech Republic
    Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 43 Praha 2, Czech Republic
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  • , 
  • Jaroslav Zelenka
    Jaroslav Zelenka
    Department of Biochemistry and Microbiology, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha 6, Czech Republic
    More by Jaroslav Zelenka
  • , 
  • Jiří Rathouský
    Jiří Rathouský
    J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Praha 8, Czech Republic
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  • , 
  • Pavel Kubát
    Pavel Kubát
    J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Praha 8, Czech Republic
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    Orcidhttp://orcid.org/0000-0002-7861-9212
  • , 
  • Tomáš Ruml
    Tomáš Ruml
    Department of Biochemistry and Microbiology, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha 6, Czech Republic
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  • , 
  • Jan Demel
    Jan Demel
    Institute of Inorganic Chemistry, Czech Academy of Sciences, Husinec-Řež 1001, 250 68 Řež, Czech Republic
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    Orcidhttp://orcid.org/0000-0001-7796-6338
  • , and 
  • Kamil Lang*
    Kamil Lang
    Institute of Inorganic Chemistry, Czech Academy of Sciences, Husinec-Řež 1001, 250 68 Řež, Czech Republic
    *E-mail: [email protected]
    More by Kamil Lang
    Orcidhttp://orcid.org/0000-0002-4151-8805
Cite this: ACS Appl. Mater. Interfaces 2018, 10, 10, 8527–8535
Publication Date (Web):February 22, 2018
https://doi.org/10.1021/acsami.7b19835
Copyright © 2018 American Chemical Society
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Abstract

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Microbial colonization of biomedical devices is a recognized complication contributing to healthcare-associated infections. One of the possible approaches to prevent surfaces from the biofilm formation is antimicrobial photodynamic inactivation based on the cytotoxic effect of singlet oxygen, O2(1Δg), a short-lived, highly oxidative species, produced by energy transfer between excited photosensitizers and molecular oxygen. We synthesized porphyrin-based covalent organic frameworks (COFs) by Schiff-base chemistry. These novel COFs have a three-dimensional, diamond-like structure. The detailed analysis of their photophysical and photochemical properties shows that the COFs effectively produce O2(1Δg) under visible light irradiation, and especially three-dimensional structures have strong antibacterial effects toward Pseudomonas aeruginosa and Enterococcus faecalis biofilms. The COFs exhibit high photostability and broad spectral efficiency. Hence, the porphyrinic COFs are suitable candidates for the design of antibacterial coating for indoor applications.

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1. Introduction

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Increasing resistance of bacteria to antibiotics makes curing many diseases difficult. (1) In addition, bacteria can form cohesive networks, called biofilms, held together by a hydrated extracellular polymeric substance, consisting of proteins, lipids, polysaccharides, and nucleic acids. This form of bacterial growth is prevalent in nature and allows metabolic symbiosis between different bacterial strains or differently supplied bacteria from one strain. The close proximity of bacterial cells and the presence of extracellular DNA in the biofilm matrix enable transfer of genetic elements encoding virulence and resistance factors. The biofilms of virulent and multiresistant bacteria can be several orders of magnitude more resistant to antibiotics and disinfectants than separated bacteria; this represents a serious problem, especially in hospitals with local accumulation of immunocompromised persons susceptible to infections. One of the bacteria, which effectively forms resistant biofilms causing severe problems in the food industry and medicine, is Pseudomonas aeruginosa. (2)
To mitigate biofilm formation, numerous antibacterial agents and antiseptic techniques have been proposed. (3) A promising method for fighting microorganisms is antimicrobial photodynamic inactivation (PDI). (4) It relies on the formation of reactive oxygen species (ROS), including singlet oxygen, O2(1Δg), a short-lived, highly oxidative agent with bactericidal (5) and virucidal (6) properties generated in situ via energy transfer from an excited molecule of a photosensitizer to an oxygen molecule. Typical examples of photosensitizers are porphyrins and phthalocyanines. (7) However, these molecules tend to aggregate which results in losses of the photosensitizing activity. A possible solution to overcome these obstacles is the synthesis of porphyrin-based solid photosensitizers with a forced and well-defined arrangement of porphyrin molecules. To name several of these solids, layered metal hydroxides, (8) metal–organic frameworks, (9−11) conjugated microporous polymers, (12) or covalent organic frameworks (13) have been already described, including their photoactivity with respect to the production of O2(1Δg).
Covalent organic frameworks (COFs) are a class of porous crystalline materials composed of organic building blocks connected by reversibly formed covalent bonds, such as boroxine, (14) boronyl ester, (15) triazine, (16) or imine (17) linkage. Since 2005, when the first COFs were published by Yaghi et al., (18) various two-dimensional (2D) frameworks have been synthesized. (19) In contrast, only a limited number of three-dimensional (3D) frameworks has been reported so far. (20,21) Although COFs have been first explored for gas adsorption and storage applications, the incorporation of functional building blocks has opened up new potential applications. Especially, porphyrins are promising building blocks due to their planar geometry and rigidity coupled with inherent functionalities such as photosensitizing and redox-active properties. These properties enabled to use porphyrinic COFs in catalytic, (22−25) electrocatalytic, (26) sensing, (27) photochemical, (13,28) energy harvesting, (29) and storage (30) applications.
We present the syntheses and characterization of porphyrinic COFs where the porphyrin blocks are linked together by the Schiff-base reaction. The sp3 hybridized carbon atom in tetraphenyl methane connected with the planar porphyrin linker leads to the diamond-like framework. The results show that the COF topology, i.e., 2D (COF-366) (31) vs 3D structures, affects the productivity of O2(1Δg) and the resulting antibacterial properties. Especially, the 3D COF materials exhibit excellent antibacterial effects under visible light and are supposed to be well-suited for the fabrication of antibacterial polystyrene coatings due to high photostability, broad spectral efficiency, and good dispersibility in polystyrene.

2. Experimental Section

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2.1. Materials

Tetrakis(4-aminophenyl)methane (Manchester Organics, UK), Pd(PPh3)4, Pd(acac)2, MgSO4, terephthalaldehyde, polystyrene (average MW ∼192000 g mol–1), (aminomethyl)polystyrene (200–400 mesh, extent of labeling: 4.0 mmol g–1 loading, 2% cross-linked), 5,10,15,20-tetraphenylporphyrin (TPP), acetonitrile (Chromasolv), and 9,10-diphenylanthracene (all Sigma-Aldrich), 5,10,15,20-tetrakis(4-aminophenyl)porphyrin, 4-formylbenzeneboronic acid (both Frontier-Scientific, USA), 5,15-dibromo-10,20-diphenylporphyrin (DPPBr, PorphyChem, France), CH2Cl2 (Lachner, Czech Republic), NaCl, NaHCO3, and K2CO3 (all Lachema, Czech Republic), tetrahydrofuran (THF), 1,4-dioxane (both Penta, Czech Republic), and Hoechst 33342 (ThermoFisher Scientific) were used as purchased. For Suzuki coupling reactions, 1,4-dioxane (water-free, VWR Chemicals) was dried using an SP-1 solvent purification system (LC Technology Solutions).

2.2. Instrumental Methods

1H and 13C NMR spectroscopy was performed on a Varian Mercury 400Plus Instrument or a JEOL 600 MHz NMR spectrometer. 13C cross-polarization NMR spectra were recorded using a JEOL 600 MHz NMR spectrometer at 10 kHz MAS rate. Powder X-ray diffraction patterns were recorded on a PANalytical X’Pert PRO diffractometer in the Bragg–Brentano geometry equipped with a conventional X-ray tube (Co Kα, 40 kV, 30 mA) and a multichannel detector X’Celarator with an antiscatter shield. Thermal analyses were carried out using a Setaram SETSYS Evolution-16-MS instrument coupled with a mass spectrometer. Fourier transform infrared spectra (FTIR) were collected on a Nicolet NEXUS 670-FT spectrometer in KBr pellets (2000–400 cm–1) or using a Praying Mantis (Harrick) diffuse reflection accessory (4000–2000 cm–1). CHN elemental analysis was performed using a standard combustion technique. Textural properties were determined by the analysis of nitrogen sorption isotherms obtained at ca. 77 K with a Micromeritics ASAP 2010 apparatus. Prior to sorption experiments, the samples were outgassed at 80 °C for at least 24 h. The sorption isotherms were analyzed by several techniques, including the BET method, Broekhoff–de Boer (BdB) t-plots, and NLDFT methods for various pore shapes and interaction potentials (as provided by the Micromeritics software), in order to achieve consistent pore sizes and surface areas.
The UV/vis absorption spectra of COF dispersions in acetonitrile were recorded on a PerkinElmer Lambda 35 equipped with a Labsphere RSA-PE-20 integration sphere. The luminescence properties of COFs and O2(1Δg) luminescence spectra were monitored on a Fluorolog 3 spectrometer using a cooled TBX-05-C photon detection module (Horiba Jobin Yvon) and a Hamamatsu H10330-45 photomultiplier, respectively. The fluorescence lifetime measurements were performed using a laser diode excitation at 405 nm (NanoLED-405LH, pulse width 750 ps, repetition rate 1 MHz). The fluorescence was recorded at 660 and 720 nm using a cooled TBX-05-C photon detection module in a time-correlated single-photon counting regime. The decay curves were fitted with exponential functions using the iterative reconvolution procedure of the DAS6 software (v. 6.8, Horiba Jobin Yvon).
Transient absorption measurements were performed on a laser kinetic spectrometer LKS 20 (Applied Photophysics, U.K.) equipped with a Lambda Physik FL 3002 dye laser (425 nm, pulse width 28 ns), a 150 W Xe lamp, and a R928 photomultiplier (Hamamatsu). The triplet state kinetics was monitored either by transient absorption at 460 nm (3D-TPP, 2D-TPP) or phosphorescence at 710 nm (3D-PdTPP). The bimolecular rate constants kO2 for the quenching of the triplet states by molecular oxygen were evaluated using the Stern–Volmer equation, 1/τT = 1/τT0 + kO2 [O2], and oxygen solubility in air-saturated acetonitrile (2.42 mM), (32) where τT and τT0 are the triplet state lifetimes at given oxygen concentration [O2] and under oxygen-free conditions, respectively. The fractions of the porphyrin triplet states quenched by molecular oxygen in air-saturated dispersions were calculated as fTair = 1– τTair/τT0. The kinetics of O2(1Δg) luminescence was recorded at 1270 nm at the right angle to 425 nm laser pulses (FL3002 dye laser, pulse width ∼28 ns) using a homemade Ge detector. The signal from the detector was collected in a 600 MHz oscilloscope (Agilent Infiniium), and the signal-to-noise ratio was improved by the averaging of 500 individual traces. The quantum yields of singlet oxygen formation (ΦΔ) in acetonitrile were estimated by the comparative method using TPP (ΦΔ = 0.60) (33) as a standard.

2.3. Syntheses of Precursors and COFs

The porphyrin building blocks were synthesized as shown in Scheme 1 (see the Supporting Information for details). The aldehyde derivative of 5,10,15,20-tetraphenyl porphyrin 1 was obtained by the Suzuki–Miyaura cross-coupling reaction and the following metalation of 1 with Pd(acac)2 in toluene yielded 2 (Supporting Information (SI) Figures S1–S4).

Scheme 1

Scheme 1. Syntheses of Precursors and COFs Including Abbreviations Used in the Text
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2.3.1. Preparation of 3D-TPP

Compound 1 (50 mg, 75 μmol) was dissolved in 2.7 mL of 1,4-dioxane and 14.2 mg of tetrakis(4-aminophenyl)methane (37 μmol) was dissolved in 0.8 mL of 1,4-dioxane. Then both solutions were mixed together in a glass ampule and 0.2 mL of 3 M acetic acid was added. The ampule was treated by three freeze–pump–thaw cycles, evacuated, sealed up, and heated up to 120 °C for 72 h. After cooling down, the ampule was opened and the resulting precipitate was collected by filtration. The product was properly washed by 1,4-dioxane and THF, followed by 24 h Soxhlet extraction with THF. Yield: 48 mg, 78%. Elemental Analysis Calcd: C, 85.38%; H, 4.41%; N, 10.21%. Found: C, 81.35%; H, 4.43%; N, 9.24%.

2.3.2. Preparation of 3D-PdTPP

Compound 2 (58 mg, 75 μmol) was dissolved in 2.7 mL of 1,4-dioxane, and 14.2 mg of tetrakis(4-aminophenyl)methane (37 μmol) was dissolved in 0.8 mL of 1,4-dioxane. Both solutions were inserted into a glass ampule, and 0.2 mL of 3 M acetic acid was added. The ampule was treated by three freeze–pump–thaw cycles, evacuated, sealed up, and heated up to 120 °C for 72 h. After cooling down, the ampule was opened and the resulting precipitate was collected by filtration. The product was properly washed by 1,4-dioxane and THF, followed by 24 h Soxhlet extraction with THF. Yield: 47 mg, 67%. Elemental Analysis Calcd: C, 75.77%; H, 3.70%; N, 9.06%. Found: C, 70.99%; H, 3.91%; N, 8.19%.

2.3.3. Preparation of 2D-TPP (COF-366)

The material was prepared according to the procedure reported by Yaghi et al. (31) 5,10,15,20-Tetrakis(4-aminophenyl)porphyrin (54 mg, 80 μmol) was dissolved in 2 mL of ethanol, and 22.4 mg of terephthalaldehyde (167 μmol) was dissolved in 2 mL of mesitylene. Both solutions were inserted into a glass ampule, and 0.4 mL of 6 M acetic acid was added. The ampule was treated with three freeze–pump–thaw cycles, evacuated, sealed up, and heated up to 120 °C for 72 h. After cooling down, the ampule was opened and the resulting precipitate was collected by filtration. The product was properly washed by 1,4-dioxane and THF, followed by 24 h Soxhlet extraction with THF. Yield: 42 mg, 58%. Elemental Analysis Calcd: C, 82.74%; H, 4.40%; N, 12.86%. Found: C, 76.84%; H, 4.80%; N, 12.85%.

2.4. Photosensitization Activity

The photosensitizing ability of COFs was assessed using the reaction of photoproduced O2(1Δg) with 9,10-diphenyl anthracene leading to the corresponding endoperoxide. The course of the reaction was followed by a decreasing absorption of 9,10-diphenyl anthracene between 230–410 nm using UV/vis spectroscopy. In each experiment, 1.0 mg of COF was dispersed in 20 mL of 10–4 M 9,10-diphenyl anthracene in acetonitrile and placed in a quartz cuvette. After sonication for 10 s, the dispersion was stirred with a magnetic bar and continuously irradiated by a 300 W Xe lamp (ozone free, Newport) equipped with a water filter and a long-pass filter (435 nm, Newport) for 3 h. The aliquots were taken at regular time intervals, centrifuged (10000 rpm, 10 min, Hettich Rotina 35 centrifuge), filtered through a 0.2 μm PTFE Millipore filter, and inserted into a 10 × 10 mm quartz cell to measure the corresponding UV/vis spectrum. The irradiation experiments were performed in air.

2.5. Preparation of Antibacterial Coatings

The antibacterial coatings were prepared on 12 × 12 mm glass plates. One mg mL–1 of polystyrene was dissolved in saturated THF solution of (aminomethyl)polystyrene (∼0.15 mg mL–1), and 60 μL of this solution was drop-casted on the plate. Then, fine powder of COFs was homogeneously scattered on the surface of the wet coating (∼0.35 mg cm–2). The coatings for blank experiments were prepared by the same procedure; however, no COF was added. The solvent was evaporated to dryness in air, and the plates were thoroughly washed with water and air-dried. The coatings were tested for their stability as follows: the coatings were immersed in water and continually irradiated by 460 nm light in the same setup as used for antibacterial tests. The aliquots taken in regular intervals up to 24 h were analyzed for the presence of dissolved porphyrins by UV/vis spectroscopy.

2.6. Bacterial Inactivation Testing

Two bacterial strains, Gram-negative Pseudomonas aeruginosa and Gram-positive Enterococcus faecalis were from the microbial collection of the University of Chemistry and Technology, Prague. The bacteria cultures were maintained in Luria–Bertani (LB) agar and cultured in the LB medium, pH 7.
For viability experiments, the 24 h bacterial cultures were inoculated into Petri dishes with the fresh LB medium to a final density of 1 McFarland. Then the coated plates were immersed into the media with the functional side downward. The dishes were either stored in the dark (blank experiments) or irradiated either with a 150 W halogen lamp (Conrad electronics) equipped with a water filter (50 mW cm–2) or with 12 × 10 W LED light source (Cameo) at 460 (20 mW cm–2) or 525 (7 mW cm–2) nm for the indicated time period (24 h, 48 h). Next, the plates were removed from the dishes, washed three times with phosphate-buffered saline, and the formation of bacterial biofilms was inspected with a bright field inverted microscope with 400× magnification. The biofilms were then fixed with 100% ice-cold methanol for 15 min and stained with the Hoechst stain according to the manufacturer protocol. (34) The stained glasses were put with the functional side downward onto the dishes with a microscopic cover glass bottom (MatTek) and inspected using a confocal microscope (Olympus/Andor xD, 400× magnitude). The Hoechst staining was measured using 405 nm laser excitation. Images were analyzed using the ImageJ software, and the biofilm density was measured as the total stained surface of the image. The data sets were analyzed with the SigmaStat software (Systat). The Student t test was performed after testing for the normal distribution. The results with p < 0.01 were considered significant due to multiple comparisons.

3. Results and Discussion

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3.1. Synthesis and Structural Characterization

We have already demonstrated that porphyrin-containing conjugated microporous polymers are efficient photosensitizers of O2(1Δg). (12) The utilization of this functionality and to impose adhesion of bacteria on the coating surfaces, we designed COFs bound together by the Schiff-base reaction. In this design, the terminal −NH2 groups provide stronger adhesion with bacterial cell walls. (35) 2D-TPP, also known as COF-366, was prepared using a procedure based on the Schiff-base formation. (31) Three-dimensional COFs were synthesized analogously to the method developed by Yaghi et al., who prepared a C═N bonded COF with the diamond-like structure from tetrakis(4-aminophenyl)methane and terephthaldehyde (Scheme 1). (20) Instead of terephthaldehyde, we used porphyrinic linker molecules 1 and 2 with the ability to produce O2(1Δg). At the final step, the resulting solids were purified by the Soxhlet extraction with THF to remove unreacted components. The COF materials were fully characterized by 13C MAS NMR, FTIR, powder X-ray diffraction, and thermal and elemental analyses (details in the Supporting Information). The textural properties were assessed by the analysis of N2 adsorption isotherms.
Powder X-ray diffraction pattern (SI Figure S5) of 2D-TPP shows characteristic diffractions at 4.0° and 9.1°, corresponding to a basal spacing of 25.2 Å, which is in agreement with the reported values for COF-366. (31) In contrast, both 3D-TPP and 3D-PdTPP do not have any characteristic diffractions, confirming their rather disordered nature. 13C CP-MAS NMR spectra display broad signals in the range between 110 and 138 ppm (SI Figure S6). The peaks at 158 ppm indicate the presence of imine linkages of the building blocks. In the case of 2D-TPP, the peak of terminal aldehyde groups at 190 ppm can be also recognized. Three-dimensional COFs show intensive peaks of aromatic carbon atoms of the tetraphenyl methane building blocks at 142 ppm and small peaks of quaternary carbon atoms of tetraphenyl methane at 65 ppm.
FTIR spectra (SI Figure S7) exhibit the C═N stretching vibration at 1620 cm–1, which is in accordance with the formed imine bond in prepared COFs. The stretching aromatic C–H vibrations are located in the region between 3024 and 3055 cm–1, and a sharp pyrrole ring vibration is at 794–798 cm–1. The peaks at 1700 cm–1 belong to residual aldehyde groups, and the peaks at 3380 and 3470 cm–1 are attributed to stretching N–H vibrations of residual NH2 groups. A characteristic signal of the pyrrole N–H stretching at 3315 cm–1 disappears in the case of 3D-PdTPP because of the exchange of hydrogen atoms for coordinated palladium atom. The combination of FTIR and 13C CP-MAS NMR data confirm the proposed structure of 3D COFs. The thermal analyses reveal thermal stability of porphyrinic COFs up to 300 °C in air (SI Figure S8). The combustion process is accompanied by the evolution of CO2, H2O, and NOx.
The porosity of COFs was determined by the analysis of the nitrogen sorption isotherms at ca. 77 K (Table 1). The sorption isotherms of all COFs feature very broad hysteresis loops with the desorption branch running in parallel to the adsorption one, joining it at the closure point at the relative pressure as low as ca. 0.01 (SI Figure S9). As nitrogen desorption at such low relative pressures is a very slow process, it requires as much as 10 h to achieve the equilibrium. It is apparently due to an elastic nature of the polymer network leading to structural expansion caused by the breakthrough of nitrogen molecules during adsorption and their retention or blocking during desorption.
Table 1. Texture Parameters of Investigated COFsa
COFtextureSBET (m2 g–1)Vmicrob (cm3 g–1)Smicrob (m2 g–1)Vmesob (cm3 g–1)Smesob (m2 g–1)Dmax (nm)Sext (m2 g–1)
3D-TPPmicro-meso bimodal830.02430.08351.2, 95
3D-PdTPPmesoporous50000.12507–8very small
2D-TPPmicroporous4750.2047500∼2very small
a

SBET stands for the BET surface area; V is the pore volume of micropores or mesopores determined by the Broekhoff–de Boer t-plot method; Dmax is the pore width determined by the NLDFT method, corresponding to the maximum/maxima of the pore size distribution; Sext is the external surface area.

b

Determined by the Broekhoff–de Boer t-plot method.

As 3D-TPP contains both micropores and mesopores, the range of validity of the Brunauer–Emmett–Teller (BET) equation is limited to relative pressures between 0.05 and 0.12. The total surface area is significantly lower than that for other COF materials, (31) probably due to interpenetration of the diamond-like structure. The complexation of palladium in 3D-PdTPP led to a disappearance of micropores and to a decrease in the BET surface area when compared with 3D-TPP. The pore size distribution of mesopores is wide without any characteristic width, which indicates that these mesopores are rather related to structural defects than to organized mesoporosity. The 2D-TPP material contains wider micropores about 2 nm in size, which is in an agreement with the structure where the distance between the carbon centers of the opposite phenyl rings is approximately 2 nm. As the pore width is at the border between micropore and mesopore range, the BET model was applicable providing a surface area of 475 m2 g–1 and a pore volume of 0.20 cm3 g–1. These values are lower than those reported for COF-366 (735 m2 g–1 and 0.32 cm3 g–1). (31)

3.2. Spectral and Photochemical Properties

The spectral features of COFs and the triplet state dynamics are fundamental properties for assessment of materials designed to produce O2(1Δg). The UV/vis absorption spectra of the COF dispersions in acetonitrile display the characteristic Soret and Q bands of the porphyrin units (Figure 1). In comparison with the sharp Soret bands of monomeric TPP at 413 nm, the porphyrin units constituting the polymer backbone are broadened and red-shifted, indicating interactions between the porphyrin units in these materials. Similarly, the Q bands exhibit a red-shift.

Figure 1

Figure 1. Normalized absorption spectra of 2D-TPP (a), 3D-TPP (b), and 3D-PdTPP (c) dispersed in acetonitrile compared with the spectrum of TPP in acetonitrile (d).

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The Q(0,0) and Q(0,1) fluorescence bands are broadened and slightly red-shifted when compared to the corresponding bands of TPP (SI Figure S10). Also, fluorescence lifetimes are shortened, and in contrast to TPP with a lifetime 9.20 ns, the fluorescence decay curves are biphasic with two components: 1.94 (9%) and 11.9 (91%) ns for 3D-TPP and ≤0.4 (10%) and 9.02 (90%) ns for 2D-TPP. Because Pd-porphyrin moieties are phosphorescent, the triplet states of 3D-PdTPP can be probed by luminescence spectroscopy (Table 2). In the absence of oxygen, the fluorescence band at 609 nm is accompanied by the phosphorescence bands at 699 and approximately 765 nm (Figure 2). The phosphorescence lifetime, corresponding to the lifetime of the triplet states, is 200 μs in an oxygen-free environment.
Table 2. Photophysical Properties of COF Dispersions in Acetonitrilea
 triplet statesO2(1Δg)
 τT0 (μs)kO2 (M–1 s–1)fTairΦΔτΔ/μs
3D-TPP4901.4 × 109>0.9990.5875
3D-PdTPP2001.3 × 1090.9980.5678
2D-TPP4601.9 × 109>0.9990.6777
TPP681.6 × 1090.9970.60b75
a

τT0 stands for the lifetime of the porphyrin triplet states in argon-saturated acetonitrile; kO2 is the bimolecular rate constant of the triplet state quenching by oxygen; fTair = 1 – τT/τT0, i.e., it is the fraction of the triplet states quenched by oxygen in air-saturated acetonitrile; ΦΔ is the quantum yield of singlet oxygen formation; τΔ is the lifetime of O2(1Δg).

b

Literature value. (33)

Figure 2

Figure 2. Phosphorescence emission spectra of 3D-PdTPP dispersions in acetonitrile saturated by air (a) and in the absence of oxygen (b). The excitation wavelength was 410 nm. Inset: Corresponding luminescence band of O2(1Δg) upon 520 nm excitation.

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The formation of the triplet states of 2D-TPP and 3D-TPP was monitored by transient absorption spectroscopy at 460 nm (SI Figure S11). Interestingly, the lifetimes of the triplet states (τT0) for metal-free COFs are several times longer than that of molecular TPP, indicating the reduction of nonradiative relaxation processes due to the limited contact of the incorporated porphyrin units with the solvent (Table 2). The results document that the TPP and PdTPP units, constituting the COF backbone, produce the long-lived triplet states after excitation by visible light. Transient absorption spectra of these triplet states have a broad maximum around 460 nm, resembling the spectrum of molecular TPP in solution (SI Figure S11D).
The triplet states of COFs are considerably quenched by molecular oxygen as documented by disappearance of phosphorescence bands of 3D-PdTPP (Figure 2), high rate constants kO2, and high fractions of the porphyrin triplet states trapped by oxygen fTair (SI Figure S11, Table 2). These results initiated the investigation of the production of O2(1Δg) by measuring its characteristic luminescence in the near-infrared region. As anticipated, all three COFs exhibit a luminescence band of O2(1Δg) at approximately 1270 nm (Figure 2, inset), confirming the formation of O2(1Δg) in acetonitrile dispersions upon excitation at the Soret or Q bands of the embedded porphyrin units. The temporal profiles of O2(1Δg) luminescence allowed the evaluation of O2(1Δg) lifetimes, τΔ, after fitting to a single-exponential function with the exclusion of the initial part, governed by the O2(1Δg) formation kinetics (Table 2, SI Figure S12). The obtained O2(1Δg) lifetimes correspond with the reported O2(1Δg) lifetime in acetonitrile, (36) indicating a minimal, if any, self-quenching effect of COFs toward O2(1Δg). Comparison of O2(1Δg) luminescence amplitudes of the COF dispersions with that of TPP solution allowed estimation of the ΦΔ values, even though the increased light scattering level of COF dispersions causes some uncertainty (Table 2). The analysis indicates that COF materials remain good photosensitizers and their production of O2(1Δg) is fully comparable with that of individual TPP molecules in organic solvents. The measured photosensitizing activity of COFs is surprising because high local concentrations of individual porphyrin molecules, e.g., in aggregates, leads to considerable diminishing of the O2(1Δg) production due to fast competitive relaxations of the excited states. Evidently, the arranged porphyrin units in COFs appear to minimally affect their photosensitizing activity, indicating that COFs may produce high local concentrations of O2(1Δg) needed for inactivation of bacteria.

3.3. Photosenzitizing Properties

The ability of O2(1Δg), produced by COFs, to oxidize external targets was evaluated by the photooxidation reaction of 9,10-diphenylanthracene to the corresponding endoperoxide. As shown in Figure 3, 3D-PdTPP is the most efficient photooxidative material. The efficiency evidently originates from the composition of COFs rather than from the textural properties because 3D-PdTPP and 3D-TPP with surface areas of tens m2 g–1 photooxidize the substrate more effectively than two-dimensional 2D-TPP with a surface area of 475 m2 g–1. To prove the photostability of COFs, 3D-PdTPP was separated from the solvent, washed, and reused twice. After 3 h of irradiation, the conversion of 9,10-diphenylanthracene was 79, 85, and 87% in the first, second, and third run, respectively (Figure S13). Thus, the O2(1Δg) productivity was preserved within the experimental error, documenting the photochemical stability of 3D-PdTPP similarly to the stability reported previously for covalently bound porphyrin networks connected via C–C bonds. (12)

Figure 3

Figure 3. Reaction of photosensitized O2(1Δg) produced by COF dispersions with 9,10-diphenylanthracene in acetonitrile. Blank experiments performed in the absence of COFs excluded any photoreaction of 9,10-diphenylanthracene itself.

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The presented results prove the formation of O2(1Δg), its oxidative potential, and material photostability therefore unambiguously indicate that investigated porphyrin-based COFs can be considered as promising O2(1Δg) photosensitizers.

3.4. Photodynamic Inactivation of Bacteria

We employed two conditional pathogens with a well-known ability to form biofilms for testing the antibacterial efficacy of the coatings made of COFs. Pseudomonas aeruginosa is G– aerobic rod bacterium ubiquitously present in nature. The growth of P. aeruginosa biofilms on hospital equipment, including catheters and ventilators, could seriously endanger patients with burns, immunocompromised patients, or newborns. (37)Enterococcus faecalis is G+ round facultative anaerobic bacterium often forming chains. It is a natural component of human colonic microflora and a dangerous conditional pathogen due to its unusually high natural resistance to antibiotics and environmental stresses. (38) It is a source of nosocomial infections of urinary and bile tract.
Both bacterial strains formed single-cell-thick stable biofilms after 24 h and multicell-thick biofilms after 48 h of incubation at room temperature. The growth of bacteria on the COF coatings occurred mostly in the gaps between COF domains, thus seemingly decreasing the relative density of bacteria even in the dark, compared to the blank coatings without COFs (Figure 4A,B and SI Figure S14). This effect is pronounced in case of P. aeruginosa with bigger cells and forming less dense biofilms. In contrast to the biofilm growth in the dark, the formation of biofilms was completely inhibited under irradiation with either a 460 nm LED light source (Figure 4A,B) or halogen lamp (SI Figure S15). On the basis of the above-described photophysical properties of COFs, these effects can be attributed to their O2(1Δg) photosensitizing activity. The antibacterial function induced by 525 nm light toward P. aeruginosa was limited to the 3D-TPP and 3D-PdTPP coatings (Figure 4A), probably due to lower intensity of 525 nm light (7 mW cm–2) compared to 460 nm light (20 mW cm–2).

Figure 4

Figure 4. Antimicrobial function of the COF coatings. The surfaces were incubated 24 h in the dark (black) and under 460 (20 mW cm–2, blue) or 525 nm irradiation (7 mW cm–2, green) with P. aeruginosa (A) and E. faecalis (B). A similar experiment was performed after 48 h incubation under 460 nm light (C). To test the direct killing of cells in the biofilms, the biofilms of P. aeruginosa and E. faecalis were established by 24 h incubation in the dark, followed by 4 h irradiation with 460 nm light (D). The blank experiments were performed with the polymer coating without COFs. In all cases, the amount of the biofilm is quantified as percentage of the surface covered with bacteria (y axis). The experiments were analyzed by the Student t test, and the results with p < 0.01 (labeled as *) are considered as significant.

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The photostability of the COF coatings was assessed by measuring the antibacterial effects after 48 h of continuous irradiation with 460 nm light (Figure 4C). Clearly, all the coatings remain antibacterial, however, only the 3D-TPP coatings maintained the same magnitude of the antibacterial effect, indicating their superior long-lasting activity. In addition, we excluded the release of porphyrins from the material during the bacterial photoinactivation experiments. It implies that the imino bonds within the COFs structure are stable when exposed to aqueous environment and irradiation, therefore, the antibacterial effect is caused by the photosensitizing activity of COFs and not by their partial dissolution.
All three COFs are also effective in destroying already existing biofilms and killing biofilm cells. As documented in Figure 4D, the biofilms formed during 24 h incubation in the dark were completely destroyed after 4 h irradiation with 460 nm light. Because the experiments investigating inhibition of the biofilm formation were performed at relatively high total energies, the efficacy of the most effective COF, 3D-TPP, was evaluated using considerably lower light intensity of 1 mW cm–2 (SI Figure S16), i.e., 20 times lower intensity than that used in the experiment described in Figure 4A. Also in this case, the formation of the P. aeruginosa biofilm was fully inhibited, whereas no effect was observed on destruction of the already established biofilm.
We found strong photoantibacterial effects of COFs, especially of 3D-TPP, which exhibited high photostability, broad spectral efficiency, and good dispersibility in the polystyrene coating. Importantly, the effect of COFs deposited on the surface was only local as we never observed any change in the cell density of the bacterial suspension in the dish with immersed glass plates nor any inhibitory effect on the formation of the biofilm on the other side of the plate. The presence of basic amino groups in all materials, as indicated by FTIR, appears to be advantageous for the PDI application because in this way the surface of the photosensitizers can interact strongly with the bacteria. (39)

Conclusions

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In conclusion, we successfully synthesized and characterized porphyrinic COFs bound together by the Schiff-base reaction with the 2D and 3D topology. The COFs produce O2(1Δg) in yields fully comparable with those of TPP molecules in organic solvents, suggesting that the photosensitizing activities of the COFs are not affected by high local concentrations of individual porphyrin units in the structure. On the basis of this finding, the COFs are materials producing high localized O2(1Δg) fluxes, needed for inactivation of bacteria on surfaces. This propensity is advantageous when compared with the behavior of molecular porphyrin sensitizers. In such cases, the production of O2(1Δg) is strongly reduced by the formation of aggregates, especially at higher porphyrin concentrations, in which nonradiative relaxation channels are fast and predominate over the formation of the excited states responsible for the generation of O2(1Δg). The design of the antibacterial coatings made of COFs is promising because COFs are photostable and have high quantum yields of O2(1Δg), allowing their effective application for a long period.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b19835.

  • Syntheses of precursors, solid state characterizations, fluorescence, transient spectroscopy, singlet oxygen, biocidal effects (PDF)

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Author Information

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  • Corresponding Author
  • Authors
    • Jan Hynek - Institute of Inorganic Chemistry, Czech Academy of Sciences, Husinec-Řež 1001, 250 68 Řež, Czech Republic;  Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 43 Praha 2, Czech Republic
    • Jaroslav Zelenka - Department of Biochemistry and Microbiology, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha 6, Czech Republic
    • Jiří Rathouský - J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Praha 8, Czech Republic
    • Pavel Kubát - J. Heyrovský Institute of Physical Chemistry, Czech Academy of Sciences, Dolejškova 3, 182 23 Praha 8, Czech Republic;  Orcidhttp://orcid.org/0000-0002-7861-9212
    • Tomáš Ruml - Department of Biochemistry and Microbiology, University of Chemistry and Technology Prague, Technická 5, 166 28 Praha 6, Czech Republic
    • Jan Demel - Institute of Inorganic Chemistry, Czech Academy of Sciences, Husinec-Řež 1001, 250 68 Řež, Czech Republic;  Orcidhttp://orcid.org/0000-0001-7796-6338
  • Notes
    The authors declare no competing financial interest.

Acknowledgments

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This work was supported by the Czech Science Foundation (no. 16-15020S), the Operative program Prague—Competitiveness (OPPC CZ.2.16/3.1.00/21537, OPPC CZ.2.16/3.1.00/24503), and the National Program of Sustainability (NPU I LO1601). J.H. gratefully acknowledges the Charles University Grant Agency (no. 252216) for financial support.

References

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    Lin, G.; Ding, H.; Chen, R.; Peng, Z.; Wang, B.; Wang, C. 3D Porphyrin-based covalent organic frameworks. J. Am. Chem. Soc. 2017, 139, 8705– 8709,  DOI: 10.1021/jacs.7b04141
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    13
    3D Porphyrin-Based Covalent Organic Frameworks
    Lin, Guiqing; Ding, Huimin; Chen, Rufan; Peng, Zhengkang; Wang, Baoshan; Wang, Cheng
    Journal of the American Chemical Society (2017), 139 (25), 8705-8709CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The design and synthesis of three-dimensional covalent org. frameworks (3D COFs) bearing photoelec. units were considered as a big challenge. Herein, for the first time, we reported the targeted synthesis of two 3D porphyrin-based COFs (3D-Por-COF and 3D-CuPor-COF), starting from tetrahedral (3D-Td) and square (2D-C4) building blocks connected through [4 + 4] imine condensation reactions. On the basis of structural characterizations, 3D-Por-COF and 3D-CuPor-COF are microporous materials with high surface areas, and are proposed to adopt a 2-fold interpenetrated pts topol. with Pmc21 space group. Interestingly, both 3D COFs are photosensitive and can be used as heterogeneous catalyst for generating singlet oxygen under photoirradn. However, 3D-Por-COF shows enhanced photocatalytic activity compared with 3D-CuPor-COF, indicating the properties of 3D porphyrin-based COFs can be tuned by metalation of porphyrin rings. The results reported here will greatly inspire us to design and synthesize 3D COFs bearing other metalloporphyrins for interesting applications (e.g., catalysis) in the future.
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  14. 14
    Brucks, S. D.; Bunck, D. N.; Dichtel, W. R. Functionalization of 3D covalent organic frameworks using monofunctional boronic acids. Polymer 2014, 55, 330– 334,  DOI: 10.1016/j.polymer.2013.07.030
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    14
    Functionalization of 3D covalent organic frameworks using monofunctional boronic acids
    Brucks, Spencer D.; Bunck, David N.; Dichtel, William R.
    Polymer (2014), 55 (1), 330-334CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
    Co-crystg. a monomer capable of forming a three-dimensional covalent org. framework (3D COF) with a truncated analog represents a robust strategy to functionalize the pores of these cryst. polymer networks. Here we elaborate this approach by demonstrating that monofunctional arylboronic acids serve as effective truncation/functionalization agents for COF-102, a boroxine-linked 3D network derived from the dehydration of a tetrahedral tetrakis(boronic acid) monomer. The COF-102 network forms under typical solvothermal conditions, even in the presence of a large excess of 4-tolylboronic acid, which is incorporated into the polymer's boroxine linkages up to a max. loading level of ca. 33 mol%. This finding indicates the max. truncation level for the COF-102 network and suggests that framework crystn. is irreversible. At high feed ratios of the monofunctional boronic acid, the isolated COF-102-tolyl powders are initially contaminated by significant amts. of tris(4-tolyl)boroxine, which is removed through a soln.-based activation process to provide COF-102-tolyl samples with high functionalization d., long-range order, and permanent porosity. We also demonstrate the generality of this truncation study by evaluating several other readily available arylboronic acids, each of which are incorporated into the COF similarly. Together these findings demonstrate the simplicity and generality of this truncation/functionalization approach, as well as its fundamental limits.
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  15. 15
    Zhang, J.; Wang, L.; Li, N.; Liu, J.; Zhang, W.; Zhang, Z.; Zhou, N.; Zhu, X. A novel azobenzene covalent organic framework. CrystEngComm 2014, 16, 6547– 6551,  DOI: 10.1039/C4CE00369A
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    15
    A novel azobenzene covalent organic framework
    Zhang, Jian; Wang, Laibing; Li, Na; Liu, Jiangfei; Zhang, Wei; Zhang, Zhengbiao; Zhou, Nianchen; Zhu, Xiulin
    CrystEngComm (2014), 16 (29), 6547-6551CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
    A novel azobenzene (Azo) monomer was synthesized and employed to produce Azo-contg. covalent org. frameworks (Azo-COF) through the borate ester formation reaction. The trans-to-cis photoisomerization of Azo units in Azo-COF occurred under irradn. with 365 nm UV light. The photoisomerization of Azo units could decrease the crystallinity of Azo-COF but could not change the pore size of Azo-COF.
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  16. 16
    Liu, X.; Li, H.; Zhang, Y.; Xu, B.; A, S.; Xia, H.; Mu, Y. Enhanced carbon dioxide uptake by metalloporphyrin-based microporous covalent triazine framework. Polym. Chem. 2013, 4, 2445– 2448,  DOI: 10.1039/c3py00083d
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    16
    Enhanced carbon dioxide uptake by metalloporphyrin-based microporous covalent triazine framework
    Liu, Xiaoming; Li, He; Zhang, Yuwei; Xu, Bo; A, Sigen; Xia, Hong; Mu, Ying
    Polymer Chemistry (2013), 4 (8), 2445-2448CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    A class of metal functional microporous covalent triazine frameworks was prepd. using a metalloporphyrin as a single building block, which is insol. in common org. solvents and water, and can remain stable up to 500 °C under nitrogen atm. According to the nitrogen physisorption isotherms, the highest Brunauer-Emmett-Teller sp. surface area up to 1510 m2 g-1 was obtained for the new polymer framework with a pore vol. of 2.674 cm3 g-1. The polymer framework displays excellent carbon dioxide uptake capacity (up to 13.9 wt%) at 273 K and 1 bar, which is influenced significantly by the porosity of the frameworks and functional activated sites in the skeletons.
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  17. 17
    Neti, V. S. P. K.; Wu, X.; Deng, S.; Echegoyen, L. Selective CO2 capture in an imine linked porphyrin porous polymer. Polym. Chem. 2013, 4, 4566– 4569,  DOI: 10.1039/c3py00798g
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    17
    Selective CO2 capture in an imine linked porphyrin porous polymer
    Neti, Venkata S. Pavan K.; Wu, Xiaofei; Deng, Shuguang; Echegoyen, Luis
    Polymer Chemistry (2013), 4 (17), 4566-4569CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
    A new microporous imine-linked porous porphyrin polymer, CuPor-BPDC, has been solvothermally synthesized. The CuPor-BPDC showed high CO2 capture (5.5 wt% at 273 K/1 bar) and very good selectivity for CO2/CH4 adsorption (5.6) at 1.0 bar and 273 K, and exhibited a BET surface area of 442 m2 g-1 with high thermal stability (up to 400 °C), thus showing good potential for CO2 capture.
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  18. 18
    Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; Matzger, A. J.; Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks. Science 2005, 310, 1166– 1170,  DOI: 10.1126/science.1120411
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    18
    Porous, Crystalline, Covalent Organic Frameworks
    Cote, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.; O'Keeffe, Michael; Matzger, Adam J.; Yaghi, Omar M.
    Science (Washington, DC, United States) (2005), 310 (5751), 1166-1170CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    Covalent org. frameworks (COFs) have been designed and successfully synthesized by condensation reactions of Ph diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly cryst. products (C3H2BO)6•(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P63/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temps. up to 500° to 600°C), permanent porosity, and high surface areas (711 and 1590 square meters per g, resp.).
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  19. 19
    Segura, J. L.; Mancheño, M. J.; Zamora, F. Covalent organic frameworks based on Schiff-base chemistry: Synthesis, properties and potential applications. Chem. Soc. Rev. 2016, 45, 5635– 5671,  DOI: 10.1039/C5CS00878F
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    Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications
    Segura, Jose L.; Mancheno, Maria J.; Zamora, Felix
    Chemical Society Reviews (2016), 45 (20), 5635-5671CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
    A review. A summary of current state-of-the-art on the design principles and synthetic strategies toward covalent org.-frameworks based on Schiff-base chem., collects and rationalizes their physicochem. properties, as well as aims to provide perspectives of potential applications which are at the forefront of research in materials science.
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  20. 20
    Uribe-Romo, F. J.; Hunt, J. R.; Furukawa, H.; Klöck, C.; O’Keeffe, M.; Yaghi, O. M. A crystalline imine-linked 3-D porous covalent organic framework. J. Am. Chem. Soc. 2009, 131, 4570– 4571,  DOI: 10.1021/ja8096256
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    20
    A Crystalline Imine-Linked 3-D Porous Covalent Organic Framework
    Uribe-Romo, Fernando J.; Hunt, Joseph R.; Furukawa, Hiroyasu; Kloeck, Cornelius; O'Keeffe, Michael; Yaghi, Omar M.
    Journal of the American Chemical Society (2009), 131 (13), 4570-4571CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    A new cryst. porous three-dimensional covalent org. framework, termed COF-300, was synthesized and structurally characterized. Tetrahedral tetra-(4-anilyl)-methane and linear terephthaldehyde building blocks were condensed to form imine linkages in a material whose x-ray crystal structure shows five independent diamond frameworks. Despite the interpenetration, the structure has pores of 7.2 Å diam. Thus, COF-300 shows thermal stability up to 490 °C and permanent porosity with a surface area of 1360 m2 g-1.
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  21. 21
    Fang, Q.; Wang, J.; Gu, S.; Kaspar, R. B.; Zhuang, Z.; Zheng, J.; Guo, H.; Qiu, S.; Yan, Y. 3D porous crystalline polyimide covalent organic frameworks for drug delivery. J. Am. Chem. Soc. 2015, 137, 8352– 8355,  DOI: 10.1021/jacs.5b04147
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    21
    3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery
    Fang, Qianrong; Wang, Junhua; Gu, Shuang; Kaspar, Robert B.; Zhuang, Zhongbin; Zheng, Jie; Guo, Hongxia; Qiu, Shilun; Yan, Yushan
    Journal of the American Chemical Society (2015), 137 (26), 8352-8355CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Three-dimensional porous cryst. polyimide covalent org. frameworks (termed PI-COFs) have been synthesized. These PI-COFs feature non- or interpenetrated structures that can be obtained by choosing tetrahedral building units of different sizes. Both PI-COFs show high thermal stability (>450 °C) and surface area (up to 2403 m2 g-1). They also show high loading and good release control for drug delivery applications.
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  22. 22
    Shinde, D. B.; Kandambeth, S.; Pachfule, P.; Kumar, R. R.; Banerjee, R. Bifunctional covalent organic frameworks with two dimensional organocatalytic micropores. Chem. Commun. 2015, 51, 310– 313,  DOI: 10.1039/C4CC07104B
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    Bifunctional covalent organic frameworks with two dimensional organocatalytic micropores
    Shinde, Digambar Balaji; Kandambeth, Sharath; Pachfule, Pradip; Kumar, Raya Rahul; Banerjee, Rahul
    Chemical Communications (Cambridge, United Kingdom) (2015), 51 (2), 310-313CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
    We report the successful incorporation of bifunctional (acid/base) catalytic sites in the cryst. organocatalytic porous COF - 2,3-dihydroxyterephthaldehyde linked to 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine (2,3-DhaTph). Due to the presence of acidic (catechol) and basic (porphyrin) sites, 2,3-DhaTph shows significant selectivity, reusability, and excellent ability to perform the cascade reaction. Example reactions included reacting acetals, e.g., 4-MeC6H4CH(OMe)2, with malononitrile to give the corresponding benzylidenemalononitrile, e.g., 4-MeC6H4CH:C(CN)2. The cascade reaction proceeds via two sequential steps: acid-catalyzed deacetalization and base-catalyzed Knoevenagel condensation.
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  23. 23
    Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E. M.; Zhao, Y.; Paris, A. R.; Kim, D.; Yang, P.; Yaghi, O. M.; Chang, C. J. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 2015, 349, 1208– 1213,  DOI: 10.1126/science.aac8343
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    23
    Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
    Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao; Kornienko, Nikolay; Nichols, Eva M.; Zhao, Yingbo; Paris, Aubrey R.; Kim, Dohyung; Yang, Peidong; Yaghi, Omar M.; Chang, Christopher J.
    Science (Washington, DC, United States) (2015), 349 (6253), 1208-1213CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
    Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here modular optimization is reported of covalent org. frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by org. struts through imine bonds, to prep. a catalytic material for aq. electrochem. redn. of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover nos. (up to 290,000, with initial turnover frequency of 9400 h-1) at pH 7 with an overpotential of -0.55 V, equiv. to a 26-fold improvement in activity compared with the mol. cobalt complex, with no degrdn. over 24 h. X-ray absorption data reveal the effect of the COF environment on the electronic structure of the catalytic cobalt centers.
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  24. 24
    Hou, Y.; Zhang, X.; Sun, J.; Lin, S.; Qi, D.; Hong, R.; Li, D.; Xiao, X.; Jiang, J. Good Suzuki-coupling reaction performance of Pd immobilized at the metal-free porphyrin-based covalent organic framework. Microporous Mesoporous Mater. 2015, 214, 108– 114,  DOI: 10.1016/j.micromeso.2015.05.002
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    24
    Good Suzuki-coupling reaction performance of Pd immobilized at the metal-free porphyrin-based covalent organic framework
    Hou, Yuxia; Zhang, Xiaomei; Sun, Junshan; Lin, Sha; Qi, Dongdong; Hong, Runrun; Li, Dianqing; Xiao, Xin; Jiang, Jianzhuang
    Microporous and Mesoporous Materials (2015), 214 (), 108-114CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
    A metal-free 5,10,15,20-tetra(p-amino-phenyl)porphyrin (H2TAPP) with addnl. nitrogen atoms at the tetrapyrrole periphery was employed to construct a nitrogen-rich covalent org. framework (COF, H2P-Bph-COF) with the help of 4,4'-biphenyldialdehyde under solvothermal condition. The abundant and periodically distributed nitrogen (N) atoms in H2P-Bph-COF stabilize and uniformly disperse the palladium (Pd) ions inside the COF structure, resulting in a remarkable catalytic activity towards the Suzuki-coupling reaction between bromoarenes (i.e. aryl bromides) and arylboronic acids under mild condition with high yield of 97.1-98.5%. The present result appears to extend the catalysis application of porphyrin-based COFs from radical or carbene participated oxidn. reactions into the Suzuki-coupling reaction. The synthesis of the target compd. (catalyst) was achieved by a complexation reaction of palladium acetate with a preformed poly(imine)-Schiff-base polymer [i.e., [1,1'-biphenyl]-4,4'-dicarboxaldehyde polymer with 4,4',4'',4'''-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis[benzenamine]]. Starting materials included (phenyl)boronic acid, 1-bromo-4-nitrobenzene, 4-bromobenzoic acid Me ester, 4-bromobenzenemethanol, 4-bromobenzonitrile, 4-bromophenol, 4-bromobenzenamine. The title compds. thus formed included 1,1'-biphenyl derivs. (i.e., biaryls) such as [1,1'-Biphenyl]-4-carboxaldehyde, [1,1'-biphenyl]-4-carboxylic acid Me ester, [1,1'-biphenyl]-4-carboxylic acid, Me ester, [1,1'-Biphenyl]-4-methanol, [1,1'-biphenyl]-4-ol, [1,1'-biphenyl]-4-carbonitrile, [1,1'-biphenyl]-4-amine.
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    Singh, M. K.; Bandyopadhyay, D. Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity. J. Chem. Sci. 2016, 128, 1– 8,  DOI: 10.1007/s12039-015-0994-8
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    25
    Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity
    Singh, Manoj Kumar; Bandyopadhyay, Debkumar
    Journal of Chemical Sciences (Berlin, Germany) (2016), 128 (1), 1-8CODEN: JCSBB5; ISSN:0974-3626. (Springer GmbH)
    Two nanoporous perylene bis-imide linked metalloporphyrin framework catalysts have been synthesized via condensation of 5,10,15,20-tetrakis-(4'-aminophenyl) iron(III) porphyrin chloride or 5,10, 15,20-tetrakis-(4'-aminophenyl) manganese(III) porphyrin chloride with perylene-3,4,9,10-tetracarboxylic dianhydride. Both the materials were cryst. in nature and were characterized by electron microscopy techniques, solid-state 1H- 13C CP/MS NMR, powder X-ray diffraction (PXRD), and magnetic susceptibility measurements. The nitrogen gas physisorption study has indicated that both materials are porous in nature and have BET surface area with 653 m2/g and 974 m2/g with uniform pore size of 2.8 nm. These materials were found to act as very good heterogeneous catalysts for selective oxidn. of alkanes and alkenes with tert-Bu hydroperoxide and were not degraded even after multiple uses up to 10 cycles.
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    Ren, S.-B.; Wang, J.; Xia, X.-H. Highly efficient oxygen reduction electrocatalyst derived from a new three-dimensional polyporphyrin. ACS Appl. Mater. Interfaces 2016, 8, 25875– 25880,  DOI: 10.1021/acsami.6b05560
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    Highly Efficient Oxygen Reduction Electrocatalyst Derived from a New Three-Dimensional PolyPorphyrin
    Ren, Shi-Bin; Wang, Jiong; Xia, Xing-Hua
    ACS Applied Materials & Interfaces (2016), 8 (39), 25875-25880CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    Metal-encapsulated nitrogen-doping porous carbonaceous materials (NDPCs) prepd. from metalloporphyrin-based covalent org. frameworks (MP-COFs) have become very promising candidates for highly effective oxygen redn. electrocatalysts. To enhance the ORR performance and durability of these NDPCs in novel energy conversion and storage devices, we develop a new type of metal-encapsulated NDPCs (HBY-COF-900) composed of FeN4 active sites by introduction of metalloporphyrin into porous COFs. Comparable to the benchmark 20% Pt/C, HBY-COF-900 in acidic solns. exhibits higher oxygen redn. electrocatalytic activity, long-term durability, and good CO tolerance. These properties can be attributed to a synergistic effect of FeN4 active sites, high graphitization, and porous structure. This work opens an avenue for the development of metal-encapsulated NDPCs from three-dimensional polyporphyrin prepd. by one-step polymn.
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    Zhang, C.; Zhang, S.; Yan, Y.; Xia, F.; Huang, A.; Xian, Y. Highly fluorescent polyimide covalent organic nanosheets as sensing probes for the detection of 2,4,6-trinitrophenol. ACS Appl. Mater. Interfaces 2017, 9, 13415– 13421,  DOI: 10.1021/acsami.6b16423
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    27
    Highly Fluorescent Polyimide Covalent Organic Nanosheets as Sensing Probes for the Detection of 2,4,6-Trinitrophenol
    Zhang, Cuiling; Zhang, Shiming; Yan, Yinghan; Xia, Fei; Huang, Anni; Xian, Yuezhong
    ACS Applied Materials & Interfaces (2017), 9 (15), 13415-13421CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    A new fluorescent polyimide covalent org. framework (PI-COF) was successfully synthesized through solvothermal route using tetrakis(4-aminophenyl) porphyrin and perylenetetracarboxylic dianhydride, which possesses porous cryst. and excellent thermal stability (>500°). Also, few-layered PI covalent org. nanosheets (PI-CONs) can be easily obtained from the fluorescent PI-COF through a facile liq. phase exfoliation approach, which were confirmed by at. force microscopy and TEM anal. It is interesting that the fluorescent intensity of PI-CONs is obviously enhanced relative to that of PI-COF. The PI-CONs were successfully used as an efficient fluorescent probe for the highly sensitive and selective detection of 2,4,6-trinitrophenol (TNP). The mechanism might be attributed to the combination of electron transfer and inner filter effect based on DFT calcns. and spectral overlap data. The system exhibits a good linear response toward TNP at 0.5-10 μM with a detection limit of 0.25 μM.
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    Chen, X.; Addicoat, M.; Jin, E.; Zhai, L.; Xu, H.; Huang, N.; Guo, Z.; Liu, L.; Irle, S.; Jiang, D. Locking covalent organic frameworks with hydrogen bonds: General and remarkable effects on crystalline structure, physical properties, and photochemical activity. J. Am. Chem. Soc. 2015, 137, 3241– 3247,  DOI: 10.1021/ja509602c
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    Locking Covalent Organic Frameworks with Hydrogen Bonds: General and Remarkable Effects on Crystalline Structure, Physical Properties, and Photochemical Activity
    Chen, Xiong; Addicoat, Matthew; Jin, Enquan; Zhai, Lipeng; Xu, Hong; Huang, Ning; Guo, Zhaoqi; Liu, Lili; Irle, Stephan; Jiang, Donglin
    Journal of the American Chemical Society (2015), 137 (9), 3241-3247CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Two-dimensional covalent org. frameworks (2-dimensional COFs) locked with intralayer hydrogen-bonding (H-bonding) interactions were synthesized. The H-bonding interaction sites were located on the edge units of the imine-linked tetragonal porphyrin COFs, and the contents of the H-bonding sites in the COFs were synthetically tuned using a three-component condensation system. The intralayer H-bonding interactions suppress the torsion of the edge units and lock the tetragonal sheets in a planar conformation. This planarization enhances the interlayer interactions and triggers extended π-cloud delocalization over the 2-dimensional sheets. Upon AA stacking, the resulting COFs with layered 2-dimensional sheets amplify these effects and strongly affect the phys. properties of the material, including improving their crystallinity, enhancing their porosity, increasing their light-harvesting capability, reducing their band gap, and enhancing their photocatalytic activity toward the generation of singlet oxygen. These remarkable effects on the structure and properties of the material were obsd. for both freebase and metalloporphyin COFs. These results imply that exploration of supramol. ensembles would open a new approach to the structural and functional design of COFs.
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    A new azodioxy-linked porphyrin-based semiconductive covalent organic framework with I2 doping-enhanced photoconductivity
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    CrystEngComm (2016), 18 (23), 4259-4263CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
    A room-temp. soln. phase reaction was developed to synthesize a covalent org. framework (COF) for the first time. The synthesized azodioxy-linked porphyrin-based COF (POR-COF) possesses a 2D chess board-like structure in the ab-plane and a 1D channel with an open-window size of around 1.9 nm along the c-axis in the modeled crystal structure. The elec. cond. of POR-COF increases by more than 3 orders of magnitude through I2 doping. The photocond. of the I2-doped COF material was also studied firstly. POR-COF shows interesting doping-enhanced photo-current generation.
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    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (19), 7416-7421CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Covalent org. frameworks (COFs) represent an emerging class of porous cryst. materials and have recently shown interesting applications in energy storage. Herein, we report the construction of a cycle-stable sulfur electrode by embedding sulfur into a 2D COF. The designed porphyrin-based COF (Por-COF), featuring a relatively large pore vol. and narrow pore size distribution, has been employed as a host material for sulfur storage in Li-S batteries. With a 55% sulfur loading in the composite, the thus-prepd. cathode delivers a capacity of 633 mA h g-1 after 200 cycles at 0.5C charge/discharge rates. Therefore, embedding sulfur in the nanopores of the Por-COF significantly improves the performance of the sulfur cathode. Considering the flexible design of COFs, we believe that it is possible to synthesize a 2D COF host with a suitable pore environment to produce more stable Li-S batteries, which may help in exploration of the structure-property relationship between the host material and cell performance.
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    The effect of solvent on the lifetime of singlet oxygen, O2(a(1)Δg), particularly the pronounced H/D solvent isotope effect, has drawn the attention of chemists for almost 50 years. The currently accepted model for this phenomenon is built on a foundation in which the electronic excitation energy of O2(a(1)Δg) is transferred to vibrational modes in a solvent molecule, with oxygen returning to its ground electronic state, O2(X(3)Σg(-)). This model of electronic-to-vibrational (e-to-v) energy transfer specifically focusses on the solvent as a "sink" for the excitation energy of O2(a(1)Δg). On the basis of temperature-dependent changes in the solvent-mediated O2(a(1)Δg) lifetime, we demonstrate that this energy-sink-based model has limitations and needs to be re-formulated. We now show that the effect of solvent on the O2(a(1)Δg) lifetime is more reasonably interpreted by considering an activation barrier that reflects the extent to which a solvent molecule perturbs the forbidden O2(a(1)Δg) → O2(X(3)Σg(-)) transition. For a given solvent molecule, this barrier reflects contributions from (a) the oxygen-solvent charge transfer state that mediates nonradiative coupling between the O2(a(1)Δg) and O2(X(3)Σg(-)) states, and (b) vibrations of specific bonds in the solvent molecule. The latter establishes connectivity to the desirable features of the energy-sink-based model. Moreover, temperature-dependent H/D solvent isotope effects imply that tunneling through this barrier plays a role in the mechanism for O2(a(1)Δg) deactivation, even at room temperature. Although we focus on a long-standing problem involving O2(a(1)Δg), our results and interpretation touch fundamental issues of interest to chemists at large.
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    Pseudomonas aeruginosa Biofilms in Disease
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    Microbial Ecology (2014), 68 (1), 1-12CODEN: MCBEBU; ISSN:0095-3628. (Springer)
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    Optimizing future treatment of enterococcal infections: attacking the biofilm?
    Paganelli, Fernanda L.; Willems, Rob J.; Leavis, Helen L.
    Trends in Microbiology (2012), 20 (1), 40-49CODEN: TRMIEA; ISSN:0966-842X. (Elsevier Ltd.)
    A review. Enterococcus faecalis and Enterococcus faecium are among the leading causative agents of nosocomial infections and are infamous for their resistance to many antibiotics. They cause difficult-to-treat infections, often originating from biofilm-mediated infections assocd. with implanted medical devices or endocarditis. Biofilms protect bacteria against antibiotics and phagocytosis, and phys. removal of devices or infected tissue is often needed but is frequently not possible. Currently there are no clin. available compds. that disassemble biofilms. In this review we discuss all known structural and regulatory genes involved in enterococcal biofilm formation, the compds. directed against biofilm formation that were studied, and potentially useful targets for future drugs to treat enterococcal biofilm-assocd. infections.
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    Yin, R.; Hamblin, M. R. Antimicrobial photosensitizers: Drug discovery under the spotlight. Curr. Med. Chem. 2015, 22, 2159– 2185,  DOI: 10.2174/0929867322666150319120134
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    Antimicrobial Photosensitizers: Drug Discovery Under the Spotlight
    Yin, Rui; Hamblin, Michael R.
    Current Medicinal Chemistry (2015), 22 (18), 2159-2185CODEN: CMCHE7; ISSN:0929-8673. (Bentham Science Publishers Ltd.)
    A review. Although photodynamic therapy (PDT) was discovered over a hundred years ago by its ability to destroy microorganisms, it has been developed mainly as a cancer therapy. In recent years, due to the inexorable rise in multi-antibiotic resistant strains of pathogens, PDT is being considered as a versatile antimicrobial approach to which microbial cells will not be able to develop resistance. The goal of this review is to survey the different classes of chem. compds. that have been tested as antimicrobial photosensitizers. Some of these compds. have been known for many years, while others have been rationally designed based on recently discovered structural principles. Tetrapyrrole-based compds. (some of which are approved as cancer therapies) that efficiently generate singlet oxygen are more efficient and broad-spectrum when they bear cationic charges, As the macrocycle structure moves from porphyrins to chlorins to phthalocyanines to bacteriochlorins the long wavelength absorption moves to the near-IR where tissue penetration is better. Four main types of natural products have been tested: curcumin, riboflavin, hypericin and psoralens. Phenothiazinium dyes, such as methylene blue and toluidine blue, have been tested, and some are clin. approved. A variety of non-phenothiazinium dyes with xanthene, triarylmethane and indocyanine structures have also been tested. New ring structures based on BODIPY, squaraine and fullerene cages can also mediate antimicrobial PDT. Finally the process of photocatalysis using titanium dioxide can also have medical uses. Designing new antimicrobial photosensitizers is likely to keep chemists engaged for a long time to come.
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  • Abstract

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    Scheme 1

    Scheme 1. Syntheses of Precursors and COFs Including Abbreviations Used in the Text
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    Figure 1

    Figure 1. Normalized absorption spectra of 2D-TPP (a), 3D-TPP (b), and 3D-PdTPP (c) dispersed in acetonitrile compared with the spectrum of TPP in acetonitrile (d).

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    Figure 2

    Figure 2. Phosphorescence emission spectra of 3D-PdTPP dispersions in acetonitrile saturated by air (a) and in the absence of oxygen (b). The excitation wavelength was 410 nm. Inset: Corresponding luminescence band of O2(1Δg) upon 520 nm excitation.

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    Figure 3

    Figure 3. Reaction of photosensitized O2(1Δg) produced by COF dispersions with 9,10-diphenylanthracene in acetonitrile. Blank experiments performed in the absence of COFs excluded any photoreaction of 9,10-diphenylanthracene itself.

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    Figure 4

    Figure 4. Antimicrobial function of the COF coatings. The surfaces were incubated 24 h in the dark (black) and under 460 (20 mW cm–2, blue) or 525 nm irradiation (7 mW cm–2, green) with P. aeruginosa (A) and E. faecalis (B). A similar experiment was performed after 48 h incubation under 460 nm light (C). To test the direct killing of cells in the biofilms, the biofilms of P. aeruginosa and E. faecalis were established by 24 h incubation in the dark, followed by 4 h irradiation with 460 nm light (D). The blank experiments were performed with the polymer coating without COFs. In all cases, the amount of the biofilm is quantified as percentage of the surface covered with bacteria (y axis). The experiments were analyzed by the Student t test, and the results with p < 0.01 (labeled as *) are considered as significant.

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      Neoh, Koon Gee; Li, Min; Kang, En-Tang; Chiong, Edmund; Tambyah, Paul Anantharajah
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2017), 5 (11), 2045-2067CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      Indwelling medical devices such as catheters are a ubiquitous and indispensable component in modern medical practice for improving therapeutic outcomes for patients. Yet at the same time, they can be a cause of healthcare-assocd. infections contributing to patient morbidity and mortality, and healthcare costs. Other surface-related complications can also arise from interactions of the catheter with biol. components in the in vivo environment. This review summarizes the progress made in the development of antimicrobial surfaces, and the application of surface modification strategies to three important classes of catheters: urinary catheters, intravascular catheters and peritoneal dialysis catheters. The review also provides a perspective on the challenges in translating favorable developments from in vitro studies into similar clin. outcomes.
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    4. 4
      Hamblin, M. R. Antimicrobial photodynamic inactivation: A bright new technique to kill resistant microbes. Curr. Opin. Microbiol. 2016, 33, 67– 73,  DOI: 10.1016/j.mib.2016.06.008
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      Antimicrobial photodynamic inactivation: a bright new technique to kill resistant microbes
      Hamblin, Michael R.
      Current Opinion in Microbiology (2016), 33 (), 67-73CODEN: COMIF7; ISSN:1369-5274. (Elsevier Ltd.)
      A review. Photodynamic therapy (PDT) uses photosensitizers (non-toxic dyes) that are activated by absorption of visible light to form reactive oxygen species (including singlet oxygen) that can oxidize biomols. and destroy cells. Antimicrobial photodynamic inactivation (aPDI) can treat localized infections. aPDI neither causes any resistance to develop in microbes, nor is affected by existing drug resistance status. We discuss some recent developments in aPDI. New photosensitizers including polycationic conjugates, stable synthetic bacteriochlorins and functionalized fullerenes are described. The microbial killing by aPDI can be synergistically potentiated (several logs) by harmless inorg. salts via photochem. Genetically engineered bioluminescent microbial cells allow PDT to treat infections in animal models. Photoantimicrobials have a promising future in the face of the unrelenting increase in antibiotic resistance.
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    5. 5
      Malik, Z.; Hanania, J.; Nitzan, Y. New trends in photobiology bactericidal effects of photoactivated porphyrins — An alternative approach to antimicrobial drugs. J. Photochem. Photobiol., B 1990, 5, 281– 293,  DOI: 10.1016/1011-1344(90)85044-W
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      Bactericidal effects of photoactivated porphyrins - an alternative approach to antimicrobial drugs
      Malik, Zvi; Hanania, Judith; Nitzan, Yeshayau
      Journal of Photochemistry and Photobiology, B: Biology (1990), 5 (3-4), 281-93CODEN: JPPBEG; ISSN:1011-1344.
      A review with 52 refs. Photoactivated porphyrins display a potent cytotoxic activity towards a variety of gram-pos. bacteria, mycoplasma and yeasts, but not gram-neg. cells. The prerequisite for photosensitization of a microbial cell is the binding of porphyrin to the cytoplasmic membrane in a pH-dependent manner. On illumination, the membrane bound, and possibly, cytoplasmic porphyrin mols. generate singlet O and radicals which sensitize biomols. and lead to cell death. The immediate inhibition of cell growth on photodynamic treatment is accompanied by alterations in cell wall and membrane synthesis, leading to the formation of large mesosomes adjacent to the unaccomplished septa. Hemin bound to microbial cells exerts cytotoxic activity by peroxidative and oxidative reactions independent of light. Future research in the field may enhance the possibility of using porphyrin photosensitization for treatment of microbial infections. Such clin. use will be unrelated to the antibiotic resistance of the pathogen. Resistance of gram-neg. bacteria to porphyrin photosensitization is the main impediment to its use as a broad spectrum antibacterial method.
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    6. 6
      Lhotáková, Y.; Plíštil, L.; Morávková, A.; Kubát, P.; Lang, K.; Forstová, J.; Mosinger, J. Virucidal nanofiber textiles based on photosensitized production of singlet oxygen. PLoS One 2012, 7, e49226,  DOI: 10.1371/journal.pone.0049226
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      Virucidal nanofiber textiles based on photosensitized production of singlet oxygen
      Lhotakova, Yveta; Plistil, Lukas; Moravkova, Alena; Kubat, Pavel; Lang, Kamil; Forstova, Jitka; Mosinger, Jiri
      PLoS One (2012), 7 (11), e49226CODEN: POLNCL; ISSN:1932-6203. (Public Library of Science)
      Novel biomaterials based on hydrophilic polycaprolactone and polyurethane (Tecophilic) nanofibers with an encapsulated 5,10,15,20-tetraphenylporphyrin photosensitizer were prepd. by electrospinning. The doped nanofiber textiles efficiently photo-generate O2(1Δg), which oxidize external chem. and biol. substrates/targets. Strong photo-virucidal effects toward non-enveloped polyomaviruses and enveloped baculoviruses were obsd. on the surface of these textiles. The photo-virucidal effect was confirmed by a decrease in virus infectivity. In contrast, no virucidal effect was detected in the absence of light and/or the encapsulated photosensitizer.
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    7. 7
      Lang, K.; Mosinger, J.; Wagnerová, D. M. Photophysical properties of porphyrinoid sensitizers non-covalently bound to host molecules; models for photodynamic therapy. Coord. Chem. Rev. 2004, 248, 321– 350,  DOI: 10.1016/j.ccr.2004.02.004
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      Photophysical properties of porphyrinoid sensitizers non-covalently bound to host molecules; models for photodynamic therapy
      Lang, K.; Mosinger, J.; Wagnerova, D. M.
      Coordination Chemistry Reviews (2004), 248 (3-4), 321-350CODEN: CCHRAM; ISSN:0010-8545. (Elsevier Science B.V.)
      A review. The binding of photosensitizers to host mols. is discussed from the perspective of how the confinement in a mol. assembly influences the sensitizer's photophys. properties. In connection with photodynamic therapy (PDT) of cancer during which the administered sensitizer necessarily interacts with the biol. material the problem becomes of utmost importance. This review surveys changes of photophys. behavior of porphyrins, metalloporphyrins and other porphyrinoid sensitizers induced by their interaction with biopolymers (proteins, nucleic acids), liposomes or synthetic sensitizer carriers (cyclodextrins, calixarenes). The structure, charge, and physicochem. properties of the sensitizer predetermine the type of interaction with the surrounding microenvironment and are manifested by changes in absorption, fluorescence, kinetics of deactivation of the excited states, and generation of singlet oxygen. As follows from the collected data, binding of the sensitizer does not restrict formation of the excited states but influences the kinetics. Various consequences of binding on the form and photophys. parameters of the sensitizers are discussed and general features of the mutual interaction are outlined.
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    8. 8
      Demel, J.; Lang, K. Layered hydroxide–porphyrin hybrid materials: synthesis, structure, and properties. Eur. J. Inorg. Chem. 2012, 2012, 5154– 5164,  DOI: 10.1002/ejic.201200400
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      Layered Hydroxide-Porphyrin Hybrid Materials: Synthesis, Structure, and Properties
      Demel, Jan; Lang, Kamil
      European Journal of Inorganic Chemistry (2012), 2012 (32), 5154-5164CODEN: EJICFO; ISSN:1434-1948. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Layered hydroxide-porphyrin hybrids are attracting attention on account of their possible photophys., photochem., catalytic, and sensing applications. In comparison to free porphyrin and phthalocyanine mols., the hybrids possess several potential advantages such as improved thermal and chem. stability, redn. of aggregation, tuning by layered hydroxide compn., and arrangement in transparent films. This review illustrates recent advances in the design, synthesis, and understanding of the structural alignment of bulky porphyrin-like mols. in the interlayer space. Special emphasis is placed on the utilization of their spectral and photophys. properties for the possible fabrication of light-triggered materials for bactericidal purposes. We describe examples from our lab. and others, review their catalytic and sensing properties, and highlight the potential directions for further developments.
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    9. 9
      Demel, J.; Kubát, P.; Millange, F.; Marrot, J.; Císařová, I.; Lang, K. Lanthanide-porphyrin hybrids: From layered structures to metal–organic frameworks with photophysical properties. Inorg. Chem. 2013, 52, 2779– 2786,  DOI: 10.1021/ic400182u
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      9
      Lanthanide-Porphyrin Hybrids: from Layered Structures to Metal-Organic Frameworks with Photophysical Properties
      Demel, Jan; Kubat, Pavel; Millange, Franck; Marrot, Jerome; Cisarova, Ivana; Lang, Kamil
      Inorganic Chemistry (2013), 52 (5), 2779-2786CODEN: INOCAJ; ISSN:0020-1669. (American Chemical Society)
      Rare-earth layered hydroxides with intercalated tetrasulfonated porphyrins and corresponding to the chem. formula Ln2(OH)4.7(Por)0.33·2H2O (Ln = Eu3+, Tb3+; Por = 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) and PdTPPS) were prepd. to study their photophys. properties. A slight variation of the synthetic procedure led to the metal-org. framework (MOF) assembled from a distorted octahedral oxometalate cluster [Eu6(μ6-O)(μ3-OH)8(H2O)14]8+. These secondary building units (SBUs) are linked together by six distorted porphyrin units. During activation, the original SBU loses not only H2O mols. from the coordination sphere but also the central μ6-O atom. The loss of the central atom results in the distortion of the octahedral [Eu6(μ6-O)(μ3-OH)8(H2O)14]8+ SBU into a trigonal antiprismatic [Eu6(μ3-OH)8(H2O)2]10+ SBU with two μ3-OH groups nearly in plane with the Eu atoms and the redn. of pores to ∼2 × 3 Å. As a result, the MOF has no accessible porosity. This transformation was thoroughly characterized by single-crystal x-ray crystallog. anal. of both phases. Solid-state photophys. studies suggest that the MOF material is fluorescent; however, in contrast to the prepd. layered hydroxides, the as-prepd. MOF is an effective sensitizer of singlet oxygen, O2(1Δg), with a relatively long lifetime of 23 ± 1 μs. The transition is also accompanied by variation in photophys. properties of the coordinated TPPS. The alteration of the fluorescence properties and of the O2(1Δg) lifetime presents an opportunity for prepn. of MOFs with O2-sensing ability or with oxidn. potential toward org. mols. by O2(1Δg).
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    10. 10
      Bůžek, D.; Zelenka, J.; Ulbrich, P.; Ruml, T.; Křı́žová, I.; Lang, J.; Kubát, P.; Demel, J.; Kirakci, K.; Lang, K. Nanoscaled porphyrinic metal-organic frameworks: Photosensitizer delivery systems for photodynamic therapy. J. Mater. Chem. B 2017, 5, 1815– 1821,  DOI: 10.1039/C6TB03230C
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      10
      Nanoscaled porphyrinic metal-organic frameworks: photosensitizer delivery systems for photodynamic therapy
      Buzek, Daniel; Zelenka, Jaroslav; Ulbrich, Pavel; Ruml, Tomas; Krizova, Ivana; Lang, Jan; Kubat, Pavel; Demel, Jan; Kirakci, Kaplan; Lang, Kamil
      Journal of Materials Chemistry B: Materials for Biology and Medicine (2017), 5 (9), 1815-1821CODEN: JMCBDV; ISSN:2050-7518. (Royal Society of Chemistry)
      The photocytotoxic activity of porphyrin-contg. materials including metal-org. frameworks (MOFs) has attracted ever increasing interest. We have developed a simple synthesis of hexagonal PCN-222/MOF-545 nanoparticles, which are powerful in inducing reactive oxygen species-mediated apoptosis of cancer cells upon visible light irradn. The extent of the cytotoxic effect well correlates with the nanoparticle size and structural instability. High phototoxicity of the presented nanoparticles and their deactivation within several hours open up the door to possible applications in cancer therapy.
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    11. 11
      Hynek, J.; Ondrušová, S.; Bůžek, D.; Kovář, P.; Rathouský, J.; Demel, J. Postsynthetic modification of a zirconium metal-organic framework at the inorganic secondary building unit with diphenylphosphinic acid for increased photosensitizing properties and stability. Chem. Commun. 2017, 53, 8557– 8560,  DOI: 10.1039/C7CC05068B
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      11
      Postsynthetic modification of a zirconium metal-organic framework at the inorganic secondary building unit with diphenylphosphinic acid for increased photosensitizing properties and stability
      Hynek, J.; Ondrusova, S.; Buzek, D.; Kovar, P.; Rathousky, J.; Demel, J.
      Chemical Communications (Cambridge, United Kingdom) (2017), 53 (61), 8557-8560CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      A zirconium metal-org. framework (MOF) PCN-<222≥ was postsynthetically modified with diphenylphosphinic acid, resulting in an increased stability when activated from water and 4 times higher photosensitizing properties for singlet oxygen prodn. The phosphinic acid did not compromise the crystallinity of the MOF but made strong bonds with the zirconia secondary building units.
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    12. 12
      Hynek, J.; Rathouský, J.; Demel, J.; Lang, K. Design of porphyrin-based conjugated microporous polymers with enhanced singlet oxygen productivity. RSC Adv. 2016, 6, 44279– 44287,  DOI: 10.1039/C6RA04066G
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      12
      Design of porphyrin-based conjugated microporous polymers with enhanced singlet oxygen productivity
      Hynek, Jan; Rathousky, Jiri; Demel, Jan; Lang, Kamil
      RSC Advances (2016), 6 (50), 44279-44287CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      Novel non-toxic materials with antimicrobial surfaces are needed for medicinal applications. Potential alternatives for bacterial inactivation include materials that produce singlet oxygen, O2(1Δg), a short-lived, highly oxidative, and cytotoxic species. We synthesized a promising group of materials, porphyrin-based conjugated microporous polymers (CMPs), which effectively generate O2(1Δg) under visible light irradn. CMPs were rationally designed and synthesized to maximize O2(1Δg) prodn. A strategy based on three-dimensional frameworks allowed the immediate environment of the porphyrin units to be tuned and their structure-property relationships to be elucidated. We investigated the photophys. and photochem. properties of the frameworks and compared them with the properties of porphyrin-based CMPs and metal-org. frameworks. In general, the O2(1Δg) prodn. activity of the CMPs correlated with neither the surface area nor with the pore vol. The novel CMPs displayed high O2(1Δg) prodn., were stable in org. solvents, and did not undergo measurable photobleaching.
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    13. 13
      Lin, G.; Ding, H.; Chen, R.; Peng, Z.; Wang, B.; Wang, C. 3D Porphyrin-based covalent organic frameworks. J. Am. Chem. Soc. 2017, 139, 8705– 8709,  DOI: 10.1021/jacs.7b04141
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      3D Porphyrin-Based Covalent Organic Frameworks
      Lin, Guiqing; Ding, Huimin; Chen, Rufan; Peng, Zhengkang; Wang, Baoshan; Wang, Cheng
      Journal of the American Chemical Society (2017), 139 (25), 8705-8709CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The design and synthesis of three-dimensional covalent org. frameworks (3D COFs) bearing photoelec. units were considered as a big challenge. Herein, for the first time, we reported the targeted synthesis of two 3D porphyrin-based COFs (3D-Por-COF and 3D-CuPor-COF), starting from tetrahedral (3D-Td) and square (2D-C4) building blocks connected through [4 + 4] imine condensation reactions. On the basis of structural characterizations, 3D-Por-COF and 3D-CuPor-COF are microporous materials with high surface areas, and are proposed to adopt a 2-fold interpenetrated pts topol. with Pmc21 space group. Interestingly, both 3D COFs are photosensitive and can be used as heterogeneous catalyst for generating singlet oxygen under photoirradn. However, 3D-Por-COF shows enhanced photocatalytic activity compared with 3D-CuPor-COF, indicating the properties of 3D porphyrin-based COFs can be tuned by metalation of porphyrin rings. The results reported here will greatly inspire us to design and synthesize 3D COFs bearing other metalloporphyrins for interesting applications (e.g., catalysis) in the future.
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      Brucks, S. D.; Bunck, D. N.; Dichtel, W. R. Functionalization of 3D covalent organic frameworks using monofunctional boronic acids. Polymer 2014, 55, 330– 334,  DOI: 10.1016/j.polymer.2013.07.030
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      Functionalization of 3D covalent organic frameworks using monofunctional boronic acids
      Brucks, Spencer D.; Bunck, David N.; Dichtel, William R.
      Polymer (2014), 55 (1), 330-334CODEN: POLMAG; ISSN:0032-3861. (Elsevier Ltd.)
      Co-crystg. a monomer capable of forming a three-dimensional covalent org. framework (3D COF) with a truncated analog represents a robust strategy to functionalize the pores of these cryst. polymer networks. Here we elaborate this approach by demonstrating that monofunctional arylboronic acids serve as effective truncation/functionalization agents for COF-102, a boroxine-linked 3D network derived from the dehydration of a tetrahedral tetrakis(boronic acid) monomer. The COF-102 network forms under typical solvothermal conditions, even in the presence of a large excess of 4-tolylboronic acid, which is incorporated into the polymer's boroxine linkages up to a max. loading level of ca. 33 mol%. This finding indicates the max. truncation level for the COF-102 network and suggests that framework crystn. is irreversible. At high feed ratios of the monofunctional boronic acid, the isolated COF-102-tolyl powders are initially contaminated by significant amts. of tris(4-tolyl)boroxine, which is removed through a soln.-based activation process to provide COF-102-tolyl samples with high functionalization d., long-range order, and permanent porosity. We also demonstrate the generality of this truncation study by evaluating several other readily available arylboronic acids, each of which are incorporated into the COF similarly. Together these findings demonstrate the simplicity and generality of this truncation/functionalization approach, as well as its fundamental limits.
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    15. 15
      Zhang, J.; Wang, L.; Li, N.; Liu, J.; Zhang, W.; Zhang, Z.; Zhou, N.; Zhu, X. A novel azobenzene covalent organic framework. CrystEngComm 2014, 16, 6547– 6551,  DOI: 10.1039/C4CE00369A
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      A novel azobenzene covalent organic framework
      Zhang, Jian; Wang, Laibing; Li, Na; Liu, Jiangfei; Zhang, Wei; Zhang, Zhengbiao; Zhou, Nianchen; Zhu, Xiulin
      CrystEngComm (2014), 16 (29), 6547-6551CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      A novel azobenzene (Azo) monomer was synthesized and employed to produce Azo-contg. covalent org. frameworks (Azo-COF) through the borate ester formation reaction. The trans-to-cis photoisomerization of Azo units in Azo-COF occurred under irradn. with 365 nm UV light. The photoisomerization of Azo units could decrease the crystallinity of Azo-COF but could not change the pore size of Azo-COF.
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      Liu, X.; Li, H.; Zhang, Y.; Xu, B.; A, S.; Xia, H.; Mu, Y. Enhanced carbon dioxide uptake by metalloporphyrin-based microporous covalent triazine framework. Polym. Chem. 2013, 4, 2445– 2448,  DOI: 10.1039/c3py00083d
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      Enhanced carbon dioxide uptake by metalloporphyrin-based microporous covalent triazine framework
      Liu, Xiaoming; Li, He; Zhang, Yuwei; Xu, Bo; A, Sigen; Xia, Hong; Mu, Ying
      Polymer Chemistry (2013), 4 (8), 2445-2448CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      A class of metal functional microporous covalent triazine frameworks was prepd. using a metalloporphyrin as a single building block, which is insol. in common org. solvents and water, and can remain stable up to 500 °C under nitrogen atm. According to the nitrogen physisorption isotherms, the highest Brunauer-Emmett-Teller sp. surface area up to 1510 m2 g-1 was obtained for the new polymer framework with a pore vol. of 2.674 cm3 g-1. The polymer framework displays excellent carbon dioxide uptake capacity (up to 13.9 wt%) at 273 K and 1 bar, which is influenced significantly by the porosity of the frameworks and functional activated sites in the skeletons.
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      Neti, V. S. P. K.; Wu, X.; Deng, S.; Echegoyen, L. Selective CO2 capture in an imine linked porphyrin porous polymer. Polym. Chem. 2013, 4, 4566– 4569,  DOI: 10.1039/c3py00798g
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      Selective CO2 capture in an imine linked porphyrin porous polymer
      Neti, Venkata S. Pavan K.; Wu, Xiaofei; Deng, Shuguang; Echegoyen, Luis
      Polymer Chemistry (2013), 4 (17), 4566-4569CODEN: PCOHC2; ISSN:1759-9962. (Royal Society of Chemistry)
      A new microporous imine-linked porous porphyrin polymer, CuPor-BPDC, has been solvothermally synthesized. The CuPor-BPDC showed high CO2 capture (5.5 wt% at 273 K/1 bar) and very good selectivity for CO2/CH4 adsorption (5.6) at 1.0 bar and 273 K, and exhibited a BET surface area of 442 m2 g-1 with high thermal stability (up to 400 °C), thus showing good potential for CO2 capture.
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    18. 18
      Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O’Keeffe, M.; Matzger, A. J.; Yaghi, O. M. Porous, Crystalline, Covalent Organic Frameworks. Science 2005, 310, 1166– 1170,  DOI: 10.1126/science.1120411
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      Porous, Crystalline, Covalent Organic Frameworks
      Cote, Adrien P.; Benin, Annabelle I.; Ockwig, Nathan W.; O'Keeffe, Michael; Matzger, Adam J.; Yaghi, Omar M.
      Science (Washington, DC, United States) (2005), 310 (5751), 1166-1170CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      Covalent org. frameworks (COFs) have been designed and successfully synthesized by condensation reactions of Ph diboronic acid {C6H4[B(OH)2]2} and hexahydroxytriphenylene [C18H6(OH)6]. Powder x-ray diffraction studies of the highly cryst. products (C3H2BO)6•(C9H12)1 (COF-1) and C9H4BO2 (COF-5) revealed expanded porous graphitic layers that are either staggered (COF-1, P63/mmc) or eclipsed (COF-5, P6/mmm). Their crystal structures are entirely held by strong bonds between B, C, and O atoms to form rigid porous architectures with pore sizes ranging from 7 to 27 angstroms. COF-1 and COF-5 exhibit high thermal stability (to temps. up to 500° to 600°C), permanent porosity, and high surface areas (711 and 1590 square meters per g, resp.).
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      Segura, J. L.; Mancheño, M. J.; Zamora, F. Covalent organic frameworks based on Schiff-base chemistry: Synthesis, properties and potential applications. Chem. Soc. Rev. 2016, 45, 5635– 5671,  DOI: 10.1039/C5CS00878F
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      Covalent organic frameworks based on Schiff-base chemistry: synthesis, properties and potential applications
      Segura, Jose L.; Mancheno, Maria J.; Zamora, Felix
      Chemical Society Reviews (2016), 45 (20), 5635-5671CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. A summary of current state-of-the-art on the design principles and synthetic strategies toward covalent org.-frameworks based on Schiff-base chem., collects and rationalizes their physicochem. properties, as well as aims to provide perspectives of potential applications which are at the forefront of research in materials science.
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      Uribe-Romo, F. J.; Hunt, J. R.; Furukawa, H.; Klöck, C.; O’Keeffe, M.; Yaghi, O. M. A crystalline imine-linked 3-D porous covalent organic framework. J. Am. Chem. Soc. 2009, 131, 4570– 4571,  DOI: 10.1021/ja8096256
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      20
      A Crystalline Imine-Linked 3-D Porous Covalent Organic Framework
      Uribe-Romo, Fernando J.; Hunt, Joseph R.; Furukawa, Hiroyasu; Kloeck, Cornelius; O'Keeffe, Michael; Yaghi, Omar M.
      Journal of the American Chemical Society (2009), 131 (13), 4570-4571CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      A new cryst. porous three-dimensional covalent org. framework, termed COF-300, was synthesized and structurally characterized. Tetrahedral tetra-(4-anilyl)-methane and linear terephthaldehyde building blocks were condensed to form imine linkages in a material whose x-ray crystal structure shows five independent diamond frameworks. Despite the interpenetration, the structure has pores of 7.2 Å diam. Thus, COF-300 shows thermal stability up to 490 °C and permanent porosity with a surface area of 1360 m2 g-1.
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    21. 21
      Fang, Q.; Wang, J.; Gu, S.; Kaspar, R. B.; Zhuang, Z.; Zheng, J.; Guo, H.; Qiu, S.; Yan, Y. 3D porous crystalline polyimide covalent organic frameworks for drug delivery. J. Am. Chem. Soc. 2015, 137, 8352– 8355,  DOI: 10.1021/jacs.5b04147
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      21
      3D Porous Crystalline Polyimide Covalent Organic Frameworks for Drug Delivery
      Fang, Qianrong; Wang, Junhua; Gu, Shuang; Kaspar, Robert B.; Zhuang, Zhongbin; Zheng, Jie; Guo, Hongxia; Qiu, Shilun; Yan, Yushan
      Journal of the American Chemical Society (2015), 137 (26), 8352-8355CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Three-dimensional porous cryst. polyimide covalent org. frameworks (termed PI-COFs) have been synthesized. These PI-COFs feature non- or interpenetrated structures that can be obtained by choosing tetrahedral building units of different sizes. Both PI-COFs show high thermal stability (>450 °C) and surface area (up to 2403 m2 g-1). They also show high loading and good release control for drug delivery applications.
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    22. 22
      Shinde, D. B.; Kandambeth, S.; Pachfule, P.; Kumar, R. R.; Banerjee, R. Bifunctional covalent organic frameworks with two dimensional organocatalytic micropores. Chem. Commun. 2015, 51, 310– 313,  DOI: 10.1039/C4CC07104B
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      22
      Bifunctional covalent organic frameworks with two dimensional organocatalytic micropores
      Shinde, Digambar Balaji; Kandambeth, Sharath; Pachfule, Pradip; Kumar, Raya Rahul; Banerjee, Rahul
      Chemical Communications (Cambridge, United Kingdom) (2015), 51 (2), 310-313CODEN: CHCOFS; ISSN:1359-7345. (Royal Society of Chemistry)
      We report the successful incorporation of bifunctional (acid/base) catalytic sites in the cryst. organocatalytic porous COF - 2,3-dihydroxyterephthaldehyde linked to 5,10,15,20-tetrakis(4-aminophenyl)-21H,23H-porphine (2,3-DhaTph). Due to the presence of acidic (catechol) and basic (porphyrin) sites, 2,3-DhaTph shows significant selectivity, reusability, and excellent ability to perform the cascade reaction. Example reactions included reacting acetals, e.g., 4-MeC6H4CH(OMe)2, with malononitrile to give the corresponding benzylidenemalononitrile, e.g., 4-MeC6H4CH:C(CN)2. The cascade reaction proceeds via two sequential steps: acid-catalyzed deacetalization and base-catalyzed Knoevenagel condensation.
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    23. 23
      Lin, S.; Diercks, C. S.; Zhang, Y.-B.; Kornienko, N.; Nichols, E. M.; Zhao, Y.; Paris, A. R.; Kim, D.; Yang, P.; Yaghi, O. M.; Chang, C. J. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. Science 2015, 349, 1208– 1213,  DOI: 10.1126/science.aac8343
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      23
      Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
      Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao; Kornienko, Nikolay; Nichols, Eva M.; Zhao, Yingbo; Paris, Aubrey R.; Kim, Dohyung; Yang, Peidong; Yaghi, Omar M.; Chang, Christopher J.
      Science (Washington, DC, United States) (2015), 349 (6253), 1208-1213CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here modular optimization is reported of covalent org. frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by org. struts through imine bonds, to prep. a catalytic material for aq. electrochem. redn. of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover nos. (up to 290,000, with initial turnover frequency of 9400 h-1) at pH 7 with an overpotential of -0.55 V, equiv. to a 26-fold improvement in activity compared with the mol. cobalt complex, with no degrdn. over 24 h. X-ray absorption data reveal the effect of the COF environment on the electronic structure of the catalytic cobalt centers.
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    24. 24
      Hou, Y.; Zhang, X.; Sun, J.; Lin, S.; Qi, D.; Hong, R.; Li, D.; Xiao, X.; Jiang, J. Good Suzuki-coupling reaction performance of Pd immobilized at the metal-free porphyrin-based covalent organic framework. Microporous Mesoporous Mater. 2015, 214, 108– 114,  DOI: 10.1016/j.micromeso.2015.05.002
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      24
      Good Suzuki-coupling reaction performance of Pd immobilized at the metal-free porphyrin-based covalent organic framework
      Hou, Yuxia; Zhang, Xiaomei; Sun, Junshan; Lin, Sha; Qi, Dongdong; Hong, Runrun; Li, Dianqing; Xiao, Xin; Jiang, Jianzhuang
      Microporous and Mesoporous Materials (2015), 214 (), 108-114CODEN: MIMMFJ; ISSN:1387-1811. (Elsevier Inc.)
      A metal-free 5,10,15,20-tetra(p-amino-phenyl)porphyrin (H2TAPP) with addnl. nitrogen atoms at the tetrapyrrole periphery was employed to construct a nitrogen-rich covalent org. framework (COF, H2P-Bph-COF) with the help of 4,4'-biphenyldialdehyde under solvothermal condition. The abundant and periodically distributed nitrogen (N) atoms in H2P-Bph-COF stabilize and uniformly disperse the palladium (Pd) ions inside the COF structure, resulting in a remarkable catalytic activity towards the Suzuki-coupling reaction between bromoarenes (i.e. aryl bromides) and arylboronic acids under mild condition with high yield of 97.1-98.5%. The present result appears to extend the catalysis application of porphyrin-based COFs from radical or carbene participated oxidn. reactions into the Suzuki-coupling reaction. The synthesis of the target compd. (catalyst) was achieved by a complexation reaction of palladium acetate with a preformed poly(imine)-Schiff-base polymer [i.e., [1,1'-biphenyl]-4,4'-dicarboxaldehyde polymer with 4,4',4'',4'''-(21H,23H-porphine-5,10,15,20-tetrayl)tetrakis[benzenamine]]. Starting materials included (phenyl)boronic acid, 1-bromo-4-nitrobenzene, 4-bromobenzoic acid Me ester, 4-bromobenzenemethanol, 4-bromobenzonitrile, 4-bromophenol, 4-bromobenzenamine. The title compds. thus formed included 1,1'-biphenyl derivs. (i.e., biaryls) such as [1,1'-Biphenyl]-4-carboxaldehyde, [1,1'-biphenyl]-4-carboxylic acid Me ester, [1,1'-biphenyl]-4-carboxylic acid, Me ester, [1,1'-Biphenyl]-4-methanol, [1,1'-biphenyl]-4-ol, [1,1'-biphenyl]-4-carbonitrile, [1,1'-biphenyl]-4-amine.
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    25. 25
      Singh, M. K.; Bandyopadhyay, D. Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity. J. Chem. Sci. 2016, 128, 1– 8,  DOI: 10.1007/s12039-015-0994-8
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      25
      Design and synthesis of nanoporous perylene bis-imide linked metalloporphyrin frameworks and their catalytic activity
      Singh, Manoj Kumar; Bandyopadhyay, Debkumar
      Journal of Chemical Sciences (Berlin, Germany) (2016), 128 (1), 1-8CODEN: JCSBB5; ISSN:0974-3626. (Springer GmbH)
      Two nanoporous perylene bis-imide linked metalloporphyrin framework catalysts have been synthesized via condensation of 5,10,15,20-tetrakis-(4'-aminophenyl) iron(III) porphyrin chloride or 5,10, 15,20-tetrakis-(4'-aminophenyl) manganese(III) porphyrin chloride with perylene-3,4,9,10-tetracarboxylic dianhydride. Both the materials were cryst. in nature and were characterized by electron microscopy techniques, solid-state 1H- 13C CP/MS NMR, powder X-ray diffraction (PXRD), and magnetic susceptibility measurements. The nitrogen gas physisorption study has indicated that both materials are porous in nature and have BET surface area with 653 m2/g and 974 m2/g with uniform pore size of 2.8 nm. These materials were found to act as very good heterogeneous catalysts for selective oxidn. of alkanes and alkenes with tert-Bu hydroperoxide and were not degraded even after multiple uses up to 10 cycles.
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    26. 26
      Ren, S.-B.; Wang, J.; Xia, X.-H. Highly efficient oxygen reduction electrocatalyst derived from a new three-dimensional polyporphyrin. ACS Appl. Mater. Interfaces 2016, 8, 25875– 25880,  DOI: 10.1021/acsami.6b05560
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      26
      Highly Efficient Oxygen Reduction Electrocatalyst Derived from a New Three-Dimensional PolyPorphyrin
      Ren, Shi-Bin; Wang, Jiong; Xia, Xing-Hua
      ACS Applied Materials & Interfaces (2016), 8 (39), 25875-25880CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      Metal-encapsulated nitrogen-doping porous carbonaceous materials (NDPCs) prepd. from metalloporphyrin-based covalent org. frameworks (MP-COFs) have become very promising candidates for highly effective oxygen redn. electrocatalysts. To enhance the ORR performance and durability of these NDPCs in novel energy conversion and storage devices, we develop a new type of metal-encapsulated NDPCs (HBY-COF-900) composed of FeN4 active sites by introduction of metalloporphyrin into porous COFs. Comparable to the benchmark 20% Pt/C, HBY-COF-900 in acidic solns. exhibits higher oxygen redn. electrocatalytic activity, long-term durability, and good CO tolerance. These properties can be attributed to a synergistic effect of FeN4 active sites, high graphitization, and porous structure. This work opens an avenue for the development of metal-encapsulated NDPCs from three-dimensional polyporphyrin prepd. by one-step polymn.
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    27. 27
      Zhang, C.; Zhang, S.; Yan, Y.; Xia, F.; Huang, A.; Xian, Y. Highly fluorescent polyimide covalent organic nanosheets as sensing probes for the detection of 2,4,6-trinitrophenol. ACS Appl. Mater. Interfaces 2017, 9, 13415– 13421,  DOI: 10.1021/acsami.6b16423
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      27
      Highly Fluorescent Polyimide Covalent Organic Nanosheets as Sensing Probes for the Detection of 2,4,6-Trinitrophenol
      Zhang, Cuiling; Zhang, Shiming; Yan, Yinghan; Xia, Fei; Huang, Anni; Xian, Yuezhong
      ACS Applied Materials & Interfaces (2017), 9 (15), 13415-13421CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      A new fluorescent polyimide covalent org. framework (PI-COF) was successfully synthesized through solvothermal route using tetrakis(4-aminophenyl) porphyrin and perylenetetracarboxylic dianhydride, which possesses porous cryst. and excellent thermal stability (>500°). Also, few-layered PI covalent org. nanosheets (PI-CONs) can be easily obtained from the fluorescent PI-COF through a facile liq. phase exfoliation approach, which were confirmed by at. force microscopy and TEM anal. It is interesting that the fluorescent intensity of PI-CONs is obviously enhanced relative to that of PI-COF. The PI-CONs were successfully used as an efficient fluorescent probe for the highly sensitive and selective detection of 2,4,6-trinitrophenol (TNP). The mechanism might be attributed to the combination of electron transfer and inner filter effect based on DFT calcns. and spectral overlap data. The system exhibits a good linear response toward TNP at 0.5-10 μM with a detection limit of 0.25 μM.
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    28. 28
      Chen, X.; Addicoat, M.; Jin, E.; Zhai, L.; Xu, H.; Huang, N.; Guo, Z.; Liu, L.; Irle, S.; Jiang, D. Locking covalent organic frameworks with hydrogen bonds: General and remarkable effects on crystalline structure, physical properties, and photochemical activity. J. Am. Chem. Soc. 2015, 137, 3241– 3247,  DOI: 10.1021/ja509602c
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      Locking Covalent Organic Frameworks with Hydrogen Bonds: General and Remarkable Effects on Crystalline Structure, Physical Properties, and Photochemical Activity
      Chen, Xiong; Addicoat, Matthew; Jin, Enquan; Zhai, Lipeng; Xu, Hong; Huang, Ning; Guo, Zhaoqi; Liu, Lili; Irle, Stephan; Jiang, Donglin
      Journal of the American Chemical Society (2015), 137 (9), 3241-3247CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Two-dimensional covalent org. frameworks (2-dimensional COFs) locked with intralayer hydrogen-bonding (H-bonding) interactions were synthesized. The H-bonding interaction sites were located on the edge units of the imine-linked tetragonal porphyrin COFs, and the contents of the H-bonding sites in the COFs were synthetically tuned using a three-component condensation system. The intralayer H-bonding interactions suppress the torsion of the edge units and lock the tetragonal sheets in a planar conformation. This planarization enhances the interlayer interactions and triggers extended π-cloud delocalization over the 2-dimensional sheets. Upon AA stacking, the resulting COFs with layered 2-dimensional sheets amplify these effects and strongly affect the phys. properties of the material, including improving their crystallinity, enhancing their porosity, increasing their light-harvesting capability, reducing their band gap, and enhancing their photocatalytic activity toward the generation of singlet oxygen. These remarkable effects on the structure and properties of the material were obsd. for both freebase and metalloporphyin COFs. These results imply that exploration of supramol. ensembles would open a new approach to the structural and functional design of COFs.
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    29. 29
      Nath, B.; Li, W.-H.; Huang, J.-H.; Wang, G.-E.; Fu, Z.-h.; Yao, M.-S.; Xu, G. A new azodioxy-linked porphyrin-based semiconductive covalent organic framework with I2 doping-enhanced photoconductivity. CrystEngComm 2016, 18, 4259– 4263,  DOI: 10.1039/C6CE00168H
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      29
      A new azodioxy-linked porphyrin-based semiconductive covalent organic framework with I2 doping-enhanced photoconductivity
      Nath, Bhaskar; Li, Wen-Hua; Huang, Jia-Hong; Wang, Guan-E.; Fu, Zhi-hua; Yao, Ming-Shui; Xu, Gang
      CrystEngComm (2016), 18 (23), 4259-4263CODEN: CRECF4; ISSN:1466-8033. (Royal Society of Chemistry)
      A room-temp. soln. phase reaction was developed to synthesize a covalent org. framework (COF) for the first time. The synthesized azodioxy-linked porphyrin-based COF (POR-COF) possesses a 2D chess board-like structure in the ab-plane and a 1D channel with an open-window size of around 1.9 nm along the c-axis in the modeled crystal structure. The elec. cond. of POR-COF increases by more than 3 orders of magnitude through I2 doping. The photocond. of the I2-doped COF material was also studied firstly. POR-COF shows interesting doping-enhanced photo-current generation.
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    30. 30
      Liao, H.; Wang, H.; Ding, H.; Meng, X.; Xu, H.; Wang, B.; Ai, X.; Wang, C. A 2D porous porphyrin-based covalent organic framework for sulfur storage in lithium-sulfur batteries. J. Mater. Chem. A 2016, 4, 7416– 7421,  DOI: 10.1039/C6TA00483K
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      30
      A 2D porous porphyrin-based covalent organic framework for sulfur storage in lithium-sulfur batteries
      Liao, Huaping; Wang, Hongmin; Ding, Huimin; Meng, Xiangshi; Xu, Hai; Wang, Baoshan; Ai, Xinping; Wang, Cheng
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (19), 7416-7421CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Covalent org. frameworks (COFs) represent an emerging class of porous cryst. materials and have recently shown interesting applications in energy storage. Herein, we report the construction of a cycle-stable sulfur electrode by embedding sulfur into a 2D COF. The designed porphyrin-based COF (Por-COF), featuring a relatively large pore vol. and narrow pore size distribution, has been employed as a host material for sulfur storage in Li-S batteries. With a 55% sulfur loading in the composite, the thus-prepd. cathode delivers a capacity of 633 mA h g-1 after 200 cycles at 0.5C charge/discharge rates. Therefore, embedding sulfur in the nanopores of the Por-COF significantly improves the performance of the sulfur cathode. Considering the flexible design of COFs, we believe that it is possible to synthesize a 2D COF host with a suitable pore environment to produce more stable Li-S batteries, which may help in exploration of the structure-property relationship between the host material and cell performance.
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    31. 31
      Wan, S.; Gándara, F.; Asano, A.; Furukawa, H.; Saeki, A.; Dey, S. K.; Liao, L.; Ambrogio, M. W.; Botros, Y. Y.; Duan, X.; Seki, S.; Stoddart, J. F.; Yaghi, O. M. Covalent organic frameworks with high charge carrier mobility. Chem. Mater. 2011, 23, 4094– 4097,  DOI: 10.1021/cm201140r
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      Covalent Organic Frameworks with High Charge Carrier Mobility
      Wan, Shun; Gandara, Felipe; Asano, Atsushi; Furukawa, Hiroyasu; Saeki, Akinori; Dey, Sanjeev K.; Liao, Lei; Ambrogio, Michael W.; Botros, Youssry Y.; Duan, Xiang-Feng; Seki, Shu; Stoddart, J. Fraser; Yaghi, Omar M.
      Chemistry of Materials (2011), 23 (18), 4094-4097CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      Two covalent org. frameworks (COFs) with structures based on covalently linked porphyrin units were synthesized. These cryst. compds. afford sheets in which the porphyrin units are stacked laterally to give an efficient conducting interface. The two porphyrin COFs (COF-366 and COF-66, resp.) were detd. to be hole conducting with mobilities as high as 8.1 and 3.0 cm2 V-1 s-1. Therefore, these multifunctional conducting COFs combine thermal stability, elec. cond., high charge mobility, and pore accessibility, which represent an important discovery in the push to design viable plastic electronics and optoelectronic systems.
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      Franco, C.; Olmsted, J. Photochemical determination of the solubility of oxygen in various media. Talanta 1990, 37, 905– 909,  DOI: 10.1016/0039-9140(90)80251-A
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      Photochemical determination of the solubility of oxygen in various media
      Franco, Chris; Olmsted, John, III
      Talanta (1990), 37 (9), 905-9CODEN: TLNTA2; ISSN:0039-9140.
      A photochem. method for detg. the oxygen concn. in air-satd. nonaq. solvents was developed. Solns. contg. a sensitizer (Rose Bengal or Methylene Blue) and 1,3-diphenylisobenzofuran (DPIBF) as an oxygen acceptor are irradiated at 546 or 633 nm and the absorbance at 404 nm is monitored. The dissolved oxygen content is found from the change in absorbance and the known 1:1 stoichiometry of addn. of singlet oxygen to DPIBF. The solubilities found, accurate to ±6%, for oxygen in air-equilibrated solvents, are (mM): acetone, 2.37; acetonitrile, 2.42; DMSO, 0.33; ethanol, 1.94; N-methylformamide, 1.31. Measurements on mixed acetone-N-methylformamide solvents showed that the soly. of oxygen does not vary with solvent compn. in a predictable manner.
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      Schmidt, R.; Afshari, E. Effect of solvent on the phosphorescence rate constant of singlet molecular oxygen (1Δg). J. Phys. Chem. 1990, 94, 4377– 4378,  DOI: 10.1021/j100373a096
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      Paul, J. H. Use of Hoechst dyes 33258 and 33342 for enumeration of attached and planktonic bacteria. Appl. Environ. Microbiol. 1982, 43, 939– 944
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      Mamone, L.; Ferreyra, D. D.; Gándara, L.; Di Venosa, G.; Vallecorsa, P.; Sáenz, D.; Calvo, G.; Batlle, A.; Buzzola, F.; Durantini, E. N.; Casas, A. Photodynamic inactivation of planktonic and biofilm growing bacteria mediated by a meso-substituted porphyrin bearing four basic amino groups. J. Photochem. Photobiol., B 2016, 161, 222– 229,  DOI: 10.1016/j.jphotobiol.2016.05.026
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      Photodynamic inactivation of planktonic and biofilm growing bacteria mediated by a meso-substituted porphyrin bearing four basic amino groups
      Mamone, L.; Ferreyra, D. D.; Gandara, L.; Di Venosa, G.; Vallecorsa, P.; Saenz, D.; Calvo, Gustavo; Batlle, A.; Buzzola, F.; Durantini, E. N.; Casas, A.
      Journal of Photochemistry and Photobiology, B: Biology (2016), 161 (), 222-229CODEN: JPPBEG; ISSN:1011-1344. (Elsevier B.V.)
      Biofilm-assocd. diseases account for 80% of all infections in humans. Due to the emergence of antibiotic resistances, alternative therapies such as Photodynamic Inactivation (PDI) of microorganisms have emerged. Porphyrins with intrinsic pos. charges have been proposed as successful photosensitizers (PSs) against microorganisms. We have recently designed the new synthetic porphyrin 5,10,15,20-tetrakis[4-(3-N,N-dimethylammoniumpropoxy)phenyl]porphyrin (TAPP) contg. four basic amine groups in the periphery of the tetrapyrrolic macrocycle, which can acquire pos. charges at physiol. pH, thus favoring the interaction with biomembranes. Illumination of planktonic cultures of Staphylococcus aureus at 180 J/cm2 in the presence of 2.5μM TAPP induced complete bacteria eradication.For the TAPP-PDI treatment of S. aureus biofilms, higher light fluences and PS concns. were needed. Employing 20μM TAPP and 180 J/cm2, around 3-log CFU redn. were obtained. In order to det. the efficacy of TAPP-PDI on Gram-neg. bacteria, we performed planktonic and biofilm assays employing Pseudomonas aeruginosa. Much higher TAPP doses as compared to S. aureus were needed to achieve planktonic bacteria photosensitization (3-log CFU redn. at 20μM TAPP and 180 J/cm2). On the other hand, high concns. of TAPP were nontoxic to P. aeruginosa growing on biofilms, and employing 30μM TAPP and 180 J/cm2 we obtained 3-log CFU redn. The main conclusion of the present work is that TAPP is a promising and efficient PS capable of promoting photodynamic killing of both Gram-neg. and -pos. in planktonic bacteria, though more effectively in the latter. In addn., TAPP-PDI induces similar photoinactivation rates in both bacteria types growing on biofilms, with lower dark toxicity in the Gram-neg. one.
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      Bregnhøj, M.; Westberg, M.; Jensen, F.; Ogilby, P. R. Solvent-dependent singlet oxygen lifetimes: Temperature effects implicate tunneling and charge-transfer interactions. Phys. Chem. Chem. Phys. 2016, 18, 22946– 22961,  DOI: 10.1039/C6CP01635A
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      Solvent-dependent singlet oxygen lifetimes: temperature effects implicate tunneling and charge-transfer interactions
      Bregnhoj Mikkel; Westberg Michael; Jensen Frank; Ogilby Peter R
      Physical chemistry chemical physics : PCCP (2016), 18 (33), 22946-61 ISSN:.
      The effect of solvent on the lifetime of singlet oxygen, O2(a(1)Δg), particularly the pronounced H/D solvent isotope effect, has drawn the attention of chemists for almost 50 years. The currently accepted model for this phenomenon is built on a foundation in which the electronic excitation energy of O2(a(1)Δg) is transferred to vibrational modes in a solvent molecule, with oxygen returning to its ground electronic state, O2(X(3)Σg(-)). This model of electronic-to-vibrational (e-to-v) energy transfer specifically focusses on the solvent as a "sink" for the excitation energy of O2(a(1)Δg). On the basis of temperature-dependent changes in the solvent-mediated O2(a(1)Δg) lifetime, we demonstrate that this energy-sink-based model has limitations and needs to be re-formulated. We now show that the effect of solvent on the O2(a(1)Δg) lifetime is more reasonably interpreted by considering an activation barrier that reflects the extent to which a solvent molecule perturbs the forbidden O2(a(1)Δg) → O2(X(3)Σg(-)) transition. For a given solvent molecule, this barrier reflects contributions from (a) the oxygen-solvent charge transfer state that mediates nonradiative coupling between the O2(a(1)Δg) and O2(X(3)Σg(-)) states, and (b) vibrations of specific bonds in the solvent molecule. The latter establishes connectivity to the desirable features of the energy-sink-based model. Moreover, temperature-dependent H/D solvent isotope effects imply that tunneling through this barrier plays a role in the mechanism for O2(a(1)Δg) deactivation, even at room temperature. Although we focus on a long-standing problem involving O2(a(1)Δg), our results and interpretation touch fundamental issues of interest to chemists at large.
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      Mulcahy, L. R.; Isabella, V. M.; Lewis, K. Pseudomonas aeruginosa biofilms in disease. Microb. Ecol. 2014, 68, 1– 12,  DOI: 10.1007/s00248-013-0297-x
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      Pseudomonas aeruginosa Biofilms in Disease
      Mulcahy, Lawrence R.; Isabella, Vincent M.; Lewis, Kim
      Microbial Ecology (2014), 68 (1), 1-12CODEN: MCBEBU; ISSN:0095-3628. (Springer)
      A review. Pseudomonas aeruginosa is a ubiquitous organism that is the focus of intense research because of its prominent role in disease. Due to its relatively large genome and flexible metabolic capabilities, this organism exploits numerous environmental niches. It is an opportunistic pathogen that sets upon the human host when the normal immune defenses are disabled. Its deadliness is most apparent in cystic fibrosis patients, but it also is a major problem in burn wounds, chronic wounds, chronic obstructive pulmonary disorder, surface growth on implanted biomaterials, and within hospital surface and water supplies, where it poses a host of threats to vulnerable patients (Peleg and Hooper, N Engl J Med 362:1804-1813, 2010; Breathnach et al., J Hosp Infect 82:19-24, 2012). Once established in the patient, P. aeruginosa can be esp. difficult to treat. The genome encodes a host of resistance genes, including multidrug efflux pumps (Poole, J Mol Microbiol Biotechnol 3:255-264, 2001) and enzymes conferring resistance to beta-lactam and aminoglycoside antibotics (Vahdani et al., Annal Burns Fire Disast 25:78-81, 2012), making therapy against this gram-neg. pathogen particularly challenging due to the lack of novel antimicrobial therapeutics (Lewis, Nature 485: 439-440, 2012). This challenge is compounded by the ability of P. aeruginosa to grow in a biofilm, which may enhance its ability to cause infections by protecting bacteria from host defenses and chemotherapy. Here, we review recent studies of P. aeruginosa biofilms with a focus on how this unique mode of growth contributes to its ability to cause recalcitrant infections.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVagsb3E&md5=902853cd62a89a689667d7462c70100e
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      Paganelli, F. L.; Willems, R. J.; Leavis, H. L. Optimizing future treatment of enterococcal infections: Attacking the biofilm?. Trends Microbiol. 2012, 20, 40– 49,  DOI: 10.1016/j.tim.2011.11.001
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      Optimizing future treatment of enterococcal infections: attacking the biofilm?
      Paganelli, Fernanda L.; Willems, Rob J.; Leavis, Helen L.
      Trends in Microbiology (2012), 20 (1), 40-49CODEN: TRMIEA; ISSN:0966-842X. (Elsevier Ltd.)
      A review. Enterococcus faecalis and Enterococcus faecium are among the leading causative agents of nosocomial infections and are infamous for their resistance to many antibiotics. They cause difficult-to-treat infections, often originating from biofilm-mediated infections assocd. with implanted medical devices or endocarditis. Biofilms protect bacteria against antibiotics and phagocytosis, and phys. removal of devices or infected tissue is often needed but is frequently not possible. Currently there are no clin. available compds. that disassemble biofilms. In this review we discuss all known structural and regulatory genes involved in enterococcal biofilm formation, the compds. directed against biofilm formation that were studied, and potentially useful targets for future drugs to treat enterococcal biofilm-assocd. infections.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XltVWqtQ%253D%253D&md5=ca245a8517ccedcbfb9e947d9dc69cca
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      Yin, R.; Hamblin, M. R. Antimicrobial photosensitizers: Drug discovery under the spotlight. Curr. Med. Chem. 2015, 22, 2159– 2185,  DOI: 10.2174/0929867322666150319120134
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      Antimicrobial Photosensitizers: Drug Discovery Under the Spotlight
      Yin, Rui; Hamblin, Michael R.
      Current Medicinal Chemistry (2015), 22 (18), 2159-2185CODEN: CMCHE7; ISSN:0929-8673. (Bentham Science Publishers Ltd.)
      A review. Although photodynamic therapy (PDT) was discovered over a hundred years ago by its ability to destroy microorganisms, it has been developed mainly as a cancer therapy. In recent years, due to the inexorable rise in multi-antibiotic resistant strains of pathogens, PDT is being considered as a versatile antimicrobial approach to which microbial cells will not be able to develop resistance. The goal of this review is to survey the different classes of chem. compds. that have been tested as antimicrobial photosensitizers. Some of these compds. have been known for many years, while others have been rationally designed based on recently discovered structural principles. Tetrapyrrole-based compds. (some of which are approved as cancer therapies) that efficiently generate singlet oxygen are more efficient and broad-spectrum when they bear cationic charges, As the macrocycle structure moves from porphyrins to chlorins to phthalocyanines to bacteriochlorins the long wavelength absorption moves to the near-IR where tissue penetration is better. Four main types of natural products have been tested: curcumin, riboflavin, hypericin and psoralens. Phenothiazinium dyes, such as methylene blue and toluidine blue, have been tested, and some are clin. approved. A variety of non-phenothiazinium dyes with xanthene, triarylmethane and indocyanine structures have also been tested. New ring structures based on BODIPY, squaraine and fullerene cages can also mediate antimicrobial PDT. Finally the process of photocatalysis using titanium dioxide can also have medical uses. Designing new antimicrobial photosensitizers is likely to keep chemists engaged for a long time to come.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtFWmurnO&md5=4054d0fc0dcc11d647b55784b0ec1753

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