Porphyrin Polymer Research Articles

Copper‐infused zinc porphyrin supramolecular polymersomes for triple synergistic combat against wound bacterial biofilm infections

AbstractBacterial biofilm infections (BBI) on wound surfaces and implants pose a significant clinical challenge due to the impermeable nature of biofilms and obstacles in tissue repair. Traditional photothermal therapy (PTT) or chemodynamic therapy (CDT), whether used alone or in combination, often causes damage to surrounding normal tissues from high operating temperatures or elevated levels of reactive oxygen species, leading to unsatisfactory anti‐biofilm effects. This study introduces a novel copper ions loaded zinc porphyrin polymer vesicle (Cu‐PPS) that employs a triple synergistic approach involving PTT, CDT, and bacterial cuproptosis‐like death (BCD). Cu‐PPS exhibits exceptional photothermal efficiency of 51.06%, promoting the release of copper ions under photothermal stimulation, enhancing CDT and BCD effectiveness, and facilitating mature biofilm clearance and tissue repair. This approach achieves a bactericidal rate exceeding 99% and an anti‐biofilm rate of 93.32% in vitro and also excellent efficacy in treating BBI in vivo. This study presents an innovative therapeutic strategy for combating biofilm infections, addressing the challenges encountered in the clinical management of BBI.

Interfacial Synthesis of Two‐Dimensional Porphyrin Polymer Films with Large Optical Nonlinearity

Two‐dimensional polymers (2DPs) and their layer‐stacked 2D covalent organic frameworks have recently emerged as nonlinear optical (NLO) materials for potential applications in optics. However, the chemistry for designing third‐order NLO 2DP films with large nonlinear absorption coefficient (β) has remained a mystery. Herein, three highly crystalline porphyrin‐integrated 2D polyimines (named as 2DPI‐Zn‐Azo, 2DPI‐2H‐Azo, and 2DPI‐Zn), which are homogeneous films showing large lateral areas over cm2, uniform transparency, and thickness of tens of nanometers are reported. Particularly, the 2DPI‐Zn‐Azo film comprising zinc porphyrin and –NN– displays a large saturable absorption under 532 nm and the highest β (−1.88 × 105 cm GW−1) among the three 2D polyimines, that is also 2–5 orders of magnitude higher than the state‐of‐art performance of photoactive small molecules, porphyrin‐integrated 2DPs, and inorganic 2D materials. Control experiments in combination with theoretical calculation discover that the embedding of metal centers and –NN– results in highly delocalized π‐electrons and narrow bandgap in 2DPI‐Zn‐Azo, which enables fast transfer of the photogenerated electrons after the light‐excited charge separation, thus boosting the NLO performance. This work opens up a new path for the construction of highly efficient third‐order NLO film materials, and pushes the development of 2DPs for optics and optoelectronics.

Engineering Single‐Atom Catalysts on Conjugated Porphyrin Polymer Photocatalysts via E‐Waste for Sustainable Photocatalysis

AbstractThis study presents a surface engineering strategy utilizing electronic waste (e‐waste) to incorporate single‐atom catalysts on conjugated polymers. Employing a conjugated porphyrin polymeric photocatalyst, gold single‐atom‐site catalysts are successfully introduced using the acidic metal leachates from e‐waste, where metal speciation and composition are regulated during the metal loading processes. The resulting photocatalyst with gold single atoms demonstrates a remarkable hydrogen peroxide (H2O2) selectivity of up to 97.56%, yielding a pure H2O2 solution at 73.3 µm h−1 under white LED illumination. The produced H2O2 is activated to •OH radicals on the same polymer with mixed gold and iron atoms, enabling a photo‐Fenton reaction and the complete degradation of toxic microcystin‐LR within 10 min under visible light. This study highlights the universal applicability of the metal mining strategy in various photoreactions. It is believed that this discovery pioneers sustainable photocatalysis, allowing the tuning of reactivity and selectivity on photocatalytic surfaces using metal waste.

Nanozyme-catalyzed oxygen self-supplying mitochondria-targeting nanoplatform for precise photodynamic therapy

Local hypoxia in tumors poses significant challenges to the effectiveness of oxygen-dependent photodynamic therapy (PDT). Herein, a versatile mitochondrial targeting and pH-responsive nanozyme platform (noted as Mito CPs-p) is developed for solving local hypoxia in tumors and enhancing the PDT efficiency. Mito CPs-p, which consists of carbon-dot-supported atomically dispersed platinum (CPs) with further surface modifications of triphenylphosphine (PPh3) and pH-responsive porphyrin polymers. The PDT of Mito CPs-p was activated in acidic tumor microenvironment and exposed platinum for catalyzing endogenous H2O2 decomposition to produce O2 at tumor sites, due to the hydrophobic-hydrophilic transition of pH-responsive porphyrin-containing polymers in Mito CPs-p from hydrophobic to hydrophilic, which can markedly enhance PDT efficiency. Besides, the rational integration of mitochondria-targeting will improve the bioavailability of reactive oxygen species and further strengthen the PDT efficiency. In vitro results indicated that Mito CPs-p has exhibited excellent mitochondrial targeting capability and the ROS yield of Mito CPs-p was dramatically amplified. In vivo data further revealed that the Mito CPs-p displayed superb therapeutic efficacy. Hence, the Mito CPs-p provides new insights for efficient PDT in hypoxia solid tumors.

Exploring the effect of porphyrin chemical structure on the performance of polymer-based Pressure-Sensitive Paints

Pressure sensitive paints (PSPs) are a powerful optical oxygen sensor technique for measuring the surface pressure distribution upon an aircraft model in wind tunnel testing. Traditional PSPs have relied heavily on platinum(II)-5,10,15,20-tetrakis-(2,3,4,5,6-pentafluorphenyl)-porphyrin due to its reasonable quantum yield of emission, high pressure sensitivity, resistance to photo oxidation, and commercial availability. This work investigates the effect of luminophore chemical structure on PSP performance by altering the degree, substitution pattern, and nature of halogen atom on the phenyl groups of ten different Pt(II) tetraphenyl porphyrins. From this initial screening it was found that platinum(II)-5,10,15,20-tetrakis-(3,5-bis(trifluoromethyl)phenyl)-porphyrin polymer PSPs had a substantially lower temperature sensitivity and a slightly higher pressure sensitivity. Using this new luminophore a Fluoro/Isopropyl/Butyl (FIB) polymer based PSP formulation was optimised whereby it was found that 3.2% w/v of FIB polymer and 800 μM concentration of platinum(II)-5,10,15,20-tetrakis-(3,5-bis(trifluoromethyl)phenyl)-porphyrin gave a low temperature sensitivity at 100 kPa for a single component polymer based PSP of 0.22%/K and a relatively high pressure sensitivity at 293 K of 0.846, exceeding current commercial PSP performance.

Composite porphyrin-based conjugated microporous polymer/graphene oxide capable of photo-triggered combinational antibacterial therapy and wound healing

Developing antibiotic-free treatment strategies to cope with the crisis on drug-resistant bacteria, are urgently needed. Antibiotics-independent physical approaches, especially the non-invasive phototherapies, worked through the assistance of photosensitizer (PS), have geared intensive attention and interests. Here, composite porphyrin-based conjugated microporous polymer/graphene oxide, denoted as GO-TAPP, combining the advantages of each component perfectly, was developed as broad-spectrum antibacterial agent. GO-TAPP, prepared via the self-oxidation coupling of tetraethynyl porphyrin on the surface of graphene oxide, could exert synergistic photothermal (PTT, ascribed to the graphene) and photodynamic (PDT, derived from the Porphyrin polymer) antimicrobial effectiveness. Both the in vivo and in vitro experiments have confirmed GO-TAPP are extremely potent against the Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) pathogens, which presents a remarkably enhanced sterilizing effect in comparison with its counterparts (the bare GO, and TAPP). Meanwhile, the synergistic effect of GO-TAPP could significantly accelerate the healing of open wound infected by bacterial. Altogether, this work proposed a new approach for the rational preparation of highly biocompatible graphene-based composite materials as antibiotic-free agents with synergistic antibacterial effect to combat bacterial infections.

Thiophene-based porphyrin polymers for Mercury (II) efficient removal in aqueous solution

Development of novel sulf-functionalized porous organic polymers (POPs) for Mercury (II) (Hg2+) removal is of great significant, but the adsorbents always suffered by the low adsorption capacity, stability, and efficiency for the reason that the common construction of functionalized POPs from the functionalized monomers or post-functionalization of the POPs always sacrifice the porosity. In this paper, porphyrin-based POPs with different heteroatoms were constructed through the aldehyde monomer (benzene, 2,5-thiophenedicarboxaldehyde and thieno[3,2-b]thiophene-2,5-dicarboxaldehyde) and pyrrole according to the Adler-Longo method. In this way, nitrogen (N) in pyrrole and sulfur (S) in thiophene structures were embed into the backbone structure of the polymers. The functional structures not only act as the linking building block into the stable cross-linking structure, but also offer abundant uncovered functional sites for Hg2+ adsorption, resulting the porphyrin-based POPs high Hg2+ capacity (1049 mg/g), removal efficiency (more than 99.9%), good reusability and selectivity for its highest heteroatoms contents. The adsorption mechanism confirmed the cooperative coordination of N in porphyrin and S in thiophene with Hg2+. This work confirmed the functional groups play more important role in heavy metal adsorption, and the embedded functional sites into backbone also promotes the stability and the adsorption performance.

Structure and Properties of Synthetic Porphyrins and Porphyrin–Polymer Systems

Structure and Properties of Synthetic Porphyrins and Porphyrin–Polymer Systems

SYNTHESIS, PROPERTIES, AND APPLICATIONS OF SUPRAMOLECULAR LIQUID CRYSTAL MATERIALS AND ACRYLAMIDE PORPHYRIN POLYMERS

A review of the work in the field of design, study of properties, and application of liquid crystal materials and acrylamide porphyrin polymers, performed at the Department of Chemistry and Technology of High-molecular Compounds, in the laboratory of Supramolecular and liquid crystal systems and in the laboratory of Polymer materials of the Research Institute of Macroheterocyclic compounds of the Ivanovo State University of Chemical Technology over the past 10 years, is presented. Synthetic methods were developed, mesogenic compounds and mixed liquid crystal compositions based on classical and supramolecular mesogens doped with additives containing polar, amphiprotic and chiral groups were obtained and studied. The mechanisms of chiral transport in the mesophase were studied. The results on the use of liquid crystals as light and heat stabilizers of polymeric materials are presented. Stationary phases for gas-liquid chromatography based on supramolecular mesogens, macroheterocyclic compounds with high structural selectivity with respect to various isomers were developed. Methods have been developed for the synthesis of water-soluble porphyrin polymers and porphyrin-containing hydrogels based on acrylamide and synthetic porphyrin monomers, realizable both under thermal heating and under microwave radiation. It is shown that a change in the ratio and nature of the components, as well as the polymerization conditions in the synthesis of porphyrin polymers provides targeted control of the properties of the resulting compounds. The molecular-mass and spectral characteristics of the obtained polymers, their surface morphology and sorption properties of porphyrin-containing acrylamide hydrogels are investigated. For citation: Burmistrov V.A., Aleksandriiskii V.V., Novikov I.V., Pechnikova N.L., Shilov I.V., Lyubimtsev A.V., Ageeva T.A., Koifman O.I. Synthesis, properties, and applications of supramolecular liquid crystal materials and acrylamide porphyrin polymers. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 31-51. DOI: 10.6060/ivkkt.20236607. 6832j.

Identification of Supramolecular Structures of Porphyrin Polymer on Single-Walled Carbon Nanotube Surface Using Microscopic Imaging Techniques

Although the supramolecular structure of porphyrin polymers on flat surfaces (i.e., mica and HOPG) has been extensively studied, the self-assembly arrays of porphyrin polymers on the SWNT (as curved nanocarbon surfaces) have yet to be fully identified and/or investigated, especially using microscopic imaging techniques, i.e., scanning tunneling microscopy (STM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). This study reports the identification of the supramolecular structure of poly-[5,15-bis-(3,5-isopentoxyphenyl)-10,20-bis ethynylporphyrinato]-zinc (II) on the SWNT surface using mainly AFM and HR-TEM microscopic imaging techniques. After synthesizing around >900 mer of porphyrin polymer (via Glaser-Hay coupling); the as-prepared porphyrin polymer is then non-covalently adsorbed on SWNT surface. Afterward, the resultant porphyrin/SWNT nanocomposite is then anchored with gold nanoparticles (AuNPs), which are used as a marker, via coordination bonding to produce a porphyrin polymer/AuNPs/SWNT hybrid. The polymer, AuNPs, nanocomposite, and/or nanohybrid are characterized using 1H-NMR, mass spectrometry, UV-visible spectroscopy, AFM, as well as HR-TEM measuring techniques. The self-assembly arrays of porphyrin polymers moieties (marked with AuNPs) prefer to form a coplanar well-ordered, regular, repeated array (rather than wrapping) between neighboring molecules along the polymer chain on the tube surface. This will help with further understanding, designing, and fabricating novel supramolecular architectonics of porphyrin/SWNT-based devices.

Synthesis and Design of Hybrid Metalloporphyrin Polymers Based on Palladium (II) and Copper (II) Cations and Axial Complexes of Pyridyl-Substituted Sn(IV)Porphyrins with Octopamine.

Supramolecular metalloporphyrin polymers formed by binding tetrapyrrolic macrocycle peripheral nitrogen atoms to Pd(II) cations and Sn(IV)porphyrins extra-ligands reaction centers to Cu(II) cations were obtained and identified. The structure and the formation mechanism of obtained hydrophobic Sn(IV)-porphyrin oligomers and polymers in solution were established, and their resistance to UV radiation and changes in solution temperature was studied. It was shown that the investigated polyporphyrin nanostructures are porous materials with predominance cylindrical mesopores. Density functional theory (DFT) was used to geometrically optimize the experimentally obtained supramolecular porphyrin polymers. The sizes of unit cells in porphyrin tubular structures were determined and coincided with the experimental data. The results obtained can be used to create highly porous materials for separation, storage, transportation, and controlled release of substrates of different nature, including highly volatile, explosive, and toxic gases.

Efficient removal of Hg0 in flue gas using a novel Sn-based porphyrin polymer

A Sn-based porphyrin polymer (TAPP(Sn)-FAC) synthesized in a mild condition was introduced for the Hg0 removal in flue gas. The properties characterization of materials revealed the two-dimensional sheet structure, an amorphous structure and high stability of TAPP(Sn)-FAC, and Sn was successfully incorporated into TAPP-FAC in the form of SnN. The removal performance of Hg0 under different conditions was investigated using a lab-scale fixed-bed reactor. TAPP(Sn)-FAC presented an excellent Hg0 removal efficiency from 100 °C to 250 °C, which can reach 8 mg/g of Hg0 capture capacity at 100 °C for 300 min. Besides, TAPP(Sn)-FAC had a strong sulfur and water resistance, and the presence of NO and O2 had a facilitating effect for Hg0 removal. Moreover, the existence of Sn can enhance the Hg0 adsorption and oxidation capacity of TAPP(Sn)-FAC by promoting the electron transfer process. Furthermore, TAPP(Sn)-FAC presented an excellent chemical stability, which was a promising material in the Hg0 removal in flue gas.

Synthesis of porphyrin and resorcinarene-based porous organic polymers for the superfast adsorption of bisphenol A and cationic herbicides

Porphyrin and resorcinarene-based POPs were synthesized via a post-modification strategy with a superfast removal rate towards bisphenol A and cationic herbicides.

Coalescing solar-to-chemical and carbon circular economy: mediated by metal-free porphyrin and triazine-based porous organic polymer under natural sunlight

The integration of organic transformation with photocatalytic CO2 reduction represents a strategic synergy that enhances the efficient utilization of e−/h+, thereby driving the advancement in the realm of sustainable photocatalysis.

Conjugated porphyrin polymer films with nickel single sites for the electrocatalytic oxygen evolution reaction.

Directly fused nickel(ii) porphyrins are successfully investigated as heterogeneous single-site catalysts for the oxygen evolution reaction (OER). Conjugated polymer thin films from Ni(ii) 5,15-(di-4-methoxycarbonylphenyl)porphyrin (pNiDCOOMePP) and Ni(ii) 5,15-diphenylporphyrin (pNiDPP) showed an OER onset overpotential of 270 mV, and current densities of 1.6 mA cm-2 and 1.2 mA cm-2 at 1.6 V vs. RHE, respectively, representing almost a hundred times higher activity than those of monomeric thin films. The fused porphyrin thin films are more kinetically and thermodynamically active than their non-polymerized counterparts mainly due to the formation of conjugated structures enabling a dinuclear radical oxo-coupling (ROC) mechanism at low overpotential. More importantly, we have deciphered the role of the porphyrin substituent in the conformation and performance of porphyrin conjugated polymers as (1) to control the extension of the conjugated system during the oCVD reaction, allowing the retention of the valence band deep enough to provide a high thermodynamic water oxidation potential, (2) to provide a flexible molecular geometry to facilitate O2 formation from the interaction between the Ni-O sites and to weaken the π-bond of the *Ni-O sites for enhanced radical character, and (3) to optimize the water interaction with the central metal cation of the porphyrin for superior electrocatalytic properties. These findings open the scope for molecular engineering and further integration of directly fused porphyrin-based conjugated polymers as efficient heterogeneous catalysts.

Photogenerated charge separation at BiVO4 photoanodes enhanced by a Ag-modified porphyrin polymer skeleton.

Bismuth vanadate (BiVO4) has been considered a promising photoactive material in photoelectrochemical (PEC) water-splitting systems. However, the performance of BiVO4-based photoanodes is currently unsatisfactory, indicating the need for new architectural designs to improve their efficiency. In this paper, a porphyrin-phosphazene polymer (THPP-HCCP) was synthesized with a sizeable conjugated structure, and Ag particles were deposited on its surface as an organic-inorganic composite interface improvement layer. The deposition of the composite polymer film on BiVO4 resulted in a significant increase in photocurrent density, reaching up to 2.2 mA cm-2 (1.23 V vs. RHE), almost three times higher than pristine BiVO4, which benefits from the synergistic effect of Ag nanoparticles and porphyrin-phosphazene. Furthermore, photophysical and intensity-modulated photocurrent analysis demonstrated that the Ag-THPP-HCCP heterostructures could broaden the light-absorbing range and facilitate hole transfer to the semiconductor surface, resulting in an improved water oxidation process. The dynamic charge transport behavior of Ag-THPP-HCCP/BiVO4 was investigated using scanning photoelectrochemical microscopy, which showed that the rate constant (Keff) exhibits an almost 4-fold increase compared to pristine BiVO4, indicating a significant improvement in the transport of photogenerated holes. This experiment presents a novel strategy for designing high-efficiency polymer-based photoanodes.

Supramolecular chiral sensing by supramolecular helical polymers.

A tetrakis(porphyrin) with branched side chains self-assembled to form supramolecular helical polymers both in solution and in the solid state. The helicity of the supramolecular polymers was determined by the chirality of solvent molecules, which permitted the polymer chains to be used in chiral sensing.

A trifunctional N-doped activated carbon–ceria shell, derived from covalent porphyrin polymers for promoting Pt activity in fuel cell cathode performance

Covalent porous porphyrin-derived N-doped hollow carbon-containing ceria as an excellent support for Pt dispersion, improving durability and activity in proton-exchange membrane fuel cell applications.

Heterometallic Porphyrin Conjugated Polymer Thin Films—A Gas‐Phase Approach for the Engineering of New Fused Porphyrin Systems

AbstractFor the first time, the simultaneous synthesis and deposition of heterometallic porphyrin conjugated polymer thin films from a simple and scalable gas‐phase approach are reported. The oxidative chemical vapor deposition (oCVD) reaction of 5,15‐(diaryl) porphyrins chelated with different metal cations (M = Co(II), Ni(II), Zn(II), Cu(II), Pd(II)) readily yields the formation of new hetero‐metalated fused porphyrin tapes, such as evidenced by in‐depth high‐resolution mass spectrometry studies. The impact of the coreactants on the regioselectivity of the intermolecular dehydrogenative coupling reaction and the formation of double or triple bonds between the porphyrin units is demonstrated. The oCVD reaction of multiple porphyrins brings the possibility to easily engineer the chemical features and the electronic and optoelectronic properties of these highly conjugated porphyrin polymers. Particularly, it is demonstrated that porphyrin conjugated polymers having different chelated metal cations can achieve higher electrical conductivities and promote narrower bandgaps. The gas‐phase approach presented herein overcomes the main limitations of the conventional solution‐based approaches and opens the path to the engineering of a novel class donor–acceptor heterometallic polymers with high interest in several fields including multimetallic electrocatalysis, photocatalysis, sensing, and nonlinear optics applications.

Porphyrin Polymers Bearing N,N'-Ethylene Crosslinkers as Photosensitizers against Bacteria.

The appearance of microbes resistant to antibiotics requires the development of alternative therapies for the treatment of infectious diseases. In this work two polymers, PTPPF16-EDA and PZnTPPF16-EDA, were synthesized by the nucleophilic aromatic substitution of 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin and its Zn(II) complex with ethylenediamine, respectively. In these structures, the tetrapyrrolic macrocycles were N,N'-ethylene crosslinked, which gives them greater mobility. The absorption spectra of the polymers showed a bathochromic shift of the Soret band of ~10 nm with respect to the monomers. This effect was also found in the red fluorescence emission peaks. Furthermore, both polymeric materials produced singlet molecular oxygen with high quantum yields. In addition, they were capable of generating superoxide anion radicals. Photodynamic inactivation sensitized by these polymers was tested in Staphylococcus aureus and Escherichia coli bacteria. A decrease in cell viability greater than 7 log (99.9999%) was observed in S. aureus incubated with 0.5 μM photosensitizer upon 30 min of irradiation. Under these conditions, a low inactivation of E. coli (0.5 log) was found. However, when the cells were treated with KI, the elimination of the Gram-negative bacteria was achieved. Therefore, these polymeric structures are interesting antimicrobial photosensitizing materials for the inactivation of pathogens.