Meso-substituted cationic 3-and 4-N-Pyridylporphyrins and their Zn(II)derivatives for antibacterial photodynamic therapy

Photodynamic inactivation of microorganisms known as antibacterial photodynamic therapy(APDT)is one of the most promising and innovative approaches for the destruction of pathogenic microorganisms.Among the photosensitizers(PSs),compounds based on cationic porphyrins/metalloporphyrins are most successfully used to inactivate microorganisms.Series of meso-substituted cationic pyridylporphyrins and metalloporphyrins with various peripheral groups in the third and fourth positions of the pyrrole ring have been synthesized in Armenia.The aim of this work was to determine and test the most e®ective cationic porphyrins and metalloporphyrins with high photoactivity against Gram negative and Gram positive microorganisms.It was shown that the synthesized cationic pyridylporphyrins/metalloporphyrins exhibit a high degree of phototoxicity towards both types of bacteria,including the methicillinresistant S.aureus strain.Zinc complexes of porphyrins are more phototoxic than metal-free porphyrin analogs.The e®ectiveness of these Zn–metalloporphyrins on bacteria is consistent with the level of singlet oxygen generation.It was found that the high antibacterial activity of the studied cationic porphyrins/metalloporphyrins depends on four factors:the presence in the porphyrin macrocycle of a positive charge(+4),a central metal atom(Zn2þÞand hydrophobic peripheral functional groups as well as high values of quantum yields of singlet oxygen.The results indicate that meso-substituted cationic pyridylporphyrins/metalloporphyrins cannd wider application in photoinactivation of bacteria than anionic or neutral PSs usually used in APDT.

Occurrence and distribution of metals and porphyrins in Nigerian coal minerals

The metal contents of Nigerian coal minerals were analyzed using an atomic absorption spectrophotometer. Calcium, Na, and Fe occurred as the major elements with concentrations ranging from 9 782 μg/g for Ca to 432 μg/g for Na whereas K, Mg, Mn, Ni, Cr, Zn, Pb, and Cu, which occurred at trace levels ranged from 673.73 μg/g for Mg to 2.97 μg/g for Mn. The results of the quantitative analysis of porphyrins extracted from the coal minerals showed that Onyeama coal has the highest amount of porphyrins (ca～0.96 μg/g) while Okpara has the lowest (ca～0.30 μg/g). The porphyrins were qualitatively characterized by a combination of thin layer chromatography (TLC), infrared, and ultraviolet-visible spectrophotometers. The results of the mid infrared analysis (MIR) showed the presence of absorption bands at 3 440 cm～1～3 450 cm-1 and 1 640 cm-1～1 680 cm-1 , which are owing to the stretching vibrations of N ─ H and C─ C of aromatics, with C─ H out of plane (oop) bending vibrations at wavenumbers less than 900 cm-1, all of which are characteristic absorptions of porphyrin free base. The ultraviolet-visible data showed prominent peaks at ～400 nm(Soret band) and at wavelength ranges of 535 nm～550 nm(β-band) and 565 nm～ 600 nm (α-band) for the coal porphyrins analyzed. The geochemical significance of the metals and porphyrins in coal minerals are discussed.

Enhanced electrocatalytic activity of iron amino porphyrins using a flow cell for reduction of CO_(2) to CO

The flexibility of molecular catalysts is highly coveted for the electrochemical reduction of carbon dioxide(CO_(2)) to carbon monoxide(CO) in both homogeneous and heterogeneous systems.While the electrocatalytic activity of molecular catalysts has been widely studied in H-cells;their less studied capabilities in more efficient flow cell reactors have the potential to rival that of heterogeneous catalysts.In this work,a comparative study of amino functionalized iron-tetraphenylporphyrins(amino-Fe-TPPs) immobilized onto carbonaceous materials in both H-cells and flow cells was conducted to selectively reduce CO_(2) to CO.In a flow cell set up operating in alkaline media,the resulting hybrid catalyst exhibits 87% faradaic efficiency(FE) with extraordinary current density(j) of 119 mA/cm^(2) and turnover frequency(TOF) of 14 s^(-1) at-1.0 V vs.RHE.This remarkable catalytic activity was achieved through thoughtful combination of molecular and flow cell design that provides an effective strategy for future immobilized heterogeneous approaches toward CO_(2) reduction reactions(CO_(2) RRs).

Synthesis of Substituted u-Oxo-bis[tetra-phenyl porphyrinatoiron] Compounds from Free Base Porphyrins by a One-pot Method

A novel method for synthesis of substituted u-oxo-bis[tetraphenyl porphyrinatoiron] compotmds （[TRPPFe]20） based on the reaction among free base porphyrins （TRPPH2）, FeSO4·7H2O and H2O in one pot was proposed and investigated. Four kinds of [TRPPFe]2O were synthesized by this novel synthetic method, and their structures were characterized by elemental analysis, infrared spectra and UV-vis spectroscopy. The reaction conditions, including the effect of different iron salts on the formation of [TRPPFe]2O, the reaction time between FeSO4-7H2O and TRPPH2, the molar ratio of FeSO4-7H2O/TRPPH2 as well as the volume ratio of H2O/DMF, were investigated. The [TRPPFe]2O yield of 93% 98% could be obtained under the following optimal conditions： the reaction time of FeSOn-7H2O with TRPPH2 was about 10 h, the molar ratio of FeSOn-7H2O/TRPPH2 about 5 ： 1, and the volume ratio of H2O/DMF exceeded 2 ： 1. Further research indicated that only TRPPFeCI were formed once FeSOn-7H2O was replaced by FeCl2-4H2O, the reason of which might be that halogen ions in iron salts interfered the formation of [TRPPFe]2O, suggesting that halogen ions should be avoided in this novel synthetic method.

Liquid-phase epoxidation of propylene with molecular oxygen by chloride manganese meso-tetraphenylporphyrins

Propylene molecule owns two active sites,the direct epoxidation of propylene by dioxygen is still a challenge due to the limitation of selectivity.In this work,the direct liquid-phase propylene aerobic epoxidation protocol by chloride manganese meso-tetraphenylporphyrin(MnTPPCl)was developed.The conversion of propylene was 12.7%,and the selectivity towards PO(propylene oxide)reached up to 80.5%.The formation of PO was attributed to the mechanism via high-valent Mn species,which was confirmed by means of in situ UV–vis spectrum.

Electrochemical Behavior of Novel Bis(Aliphatic Amine) Ruthenium(Ⅱ)and Osmium (Ⅱ) Porphyrins

Bis (aliphatic amine ) ruthenium (Ⅱ) and osmium (Ⅱ) porphyrins, M (Por )-(H2NR)2 andM(Por) (HNR'2)2, [M = Ru and Os; Por=meso-tetrakis (p-tolyl)porphyrinato (TTP), meso-tetrakis (4-chlorophenyl )porphyrinato (4-Cl-TPP ), meso-tetrakis (3, 5-dichlorophenyl) porphyrinato (3, 5-Cl-TPP ) andmeso-tetraphenyl porphyrinato(TPP); R=methyl, ethyl, iso-propyl and t-butyl; R'=methyl and ethyl]were synthesized by us. The electrochemical behavior of these complexes in 1,2-dichloroethane with TBABF4as supporting electrolyte, has been studied by cyclic voltammetry and controlled potential electrolysis. Bis(aliphatic amine)ruthenium (Ⅱ)porphyrins under go reversible one-electron oxidation and one-electron reduction processes in 1,2-dichloroethane solution. The osmium(Ⅱ) analogues is shown two oxidation couplesⅢ and Ⅴ, an additional small wave Ⅳ. The redox potentials of these complexes are markedly dependent onthe nature of the substituent bound to the phenyl group of the porphyrin ring. It is obvious that redox potentials increases the electron-withdrawing power of the substituents increases. The couple I was found at-0. 34, -0. 23 and -0. 15 V vs CP2 Fe+/o (Cp2Fe = ferrocene) for Ru (TPP ) (H2NBu-t)2, Ru (4-Cl-TPP)(H2NBu-t)2 and Ru (3, 5-Cl-TPP) (H2NBu-t)2 respectively.

AXIAL LIGATION AND ESR STUDIES OF 2－BENZENIMI DAZOLETHIOL －LINKED IRON（III） PORPHYRINS

The axial ligation properties of 2-benzenimidazolethiol-linked iron(III)porphyrins are presented along with their ESR studies

SYNTHESIS， SURFACE POTENTIAL AND NONLINEAR OPTICAL PROPERTIES OF NEW AMPHIPHILIC PORPHYRINS

A new kind of amphiphilic porphyrin containing only one carboxyl on the β point of porphyrin ring was synthesized. The surface potential and SHG (Second Harmonic Generation) efficiency of monolayer were measured and the relationship between the surface potential,SHG and the structure of molecule was discussed.

Possible therapeutic targets and promising drugs based on unsymmetrical hetaryl-substituted porphyrins to combat SARS-CoV-2

Coronavirus disease 2019 is a serious disease that causes acute respiratory syndrome and negatively affects the central nervous system.Severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)crosses the blood-brain barrier due to the spike(S) protein on the surface of the viral particles.Thus,it is important to develop compounds that not only have an inhibitory effect but are also capable of completely deactivating the S protein function.This study describes the purposeful modification of porphyrins and proposes compounds,asymmetrically hetaryl-substituted porphyrins with benzothiazole,benzoxazole,and N-methylbenzimidazole residues,to deactivate the S protein functions.Molecular docking of SARS-CoV-2 proteins with hetaryl-substituted porphyrins showed that the viral S protein,nucleocapsid(N) protein,and non-structural protein 13(nsp13) exhibited the highest binding affinity.Hetaryl-substituted porphyrins form strong complexes(13-14 kcal/mol) with the receptor-binding domain of the S protein,while the distance from the porphyrins to the receptor-binding motif(RBM)does not exceed 20 ?;therefore,RBM can be oxidized by ^(1)O_(2),which is generated by porphyrin.Hetarylsubstituted porphyrins interact with the N protein in the serine/arginine-rich region,and a number of vulnerable amino acid residues are located in the photooxidation zone.This damage complicates the packaging of viral RNA into new virions.High-energy binding of hetaryl-substituted porphyrins with the N-and C-terminal domains of nsp13 was observed.This binding blocks the action of nsp13 as an enzyme of exoribonuclease and methyltransferase,thereby preventing RNA replication and processing.A procedure for the synthesis of hetaryl-substituted porphyrins was developed,new compounds were obtained,their structures were identified,and their photocatalytic properties were studied.

Distortions and Deformations of Metaled Meso-Substituted and Unsubstituted Porphyrins and Derivatives in Crystal Structures

Experimental crystallographic structural parameters of a range of metaled meso-substituted and unsubstituted porphyrins were reviewed to show how far the meso-substitution by any functional group and the insertion of metal in the porphyrins core macrocycle may affect the geometry. The analysis of twists and angles has shown two kinds of distortions: external [T(Cβ-Cα-Cmeso-Xn) and T(Cβ-Cα-Cmeso-Cα)] and internal [T(Nm-Cα-Cmeso-Xn) and T(Nn-Cα-Cmeso-Cα)] with averages of [+6°and –6°] and [–5°and +5°], respectively. In the meso-substituted case, the external and internal twists Cβ-Cα-Cmeso-X and N-Cα-Cmeso-X, respectively are oppositely orientated. Similar effect is observed in meso-unsubstituted of Cβ-Cα- Cmeso-H and N-Cα-Cmeso-H. However, the external distortions are more significant than internal. Considering the same order, the limit of distortions is [97°and 132°(–48°)] for external and [91°(–89°) and 52°] for internal. In the two cases, the substituents have opposite directions of distortions. The meso-substituted porphyrins have a high limit of twisting than usubstituted one, depending of the weight of substituents. The average of the bond angular deformations is 168°, almost planar. However, the limit of angular deformation is 94°.

Application of an Optical Biosensor to Study the Interaction between Porphyrins and Wheat Germ Agglutinin

An optical biosensor with a stirred cuvette has been used to monitor the interaction of immobilized wheat germ agglutinin （WGA） with two water-soluble cationic porphyrins, The association constants （Ka） of the free base porphyrin and its Zn（Ⅱ） complex form were 2. 66 and 27.31 × 10^5 l,/mol at 20 ℃ respectively. The interactions of the free base porphyrin were further investigated at temperatures between 15 ℃ and 37 ℃, The thermodynamics parameters, changes in free energy, enthalpy and entropy, were -31.23, 22.92, 54.15 ld/mol respectively. The heat capacity change was -355.53 J · mol^-1·K^-1 The binding was driven by entropic contribution, and showed strong enthalpy-entropy compensation. It was governed primarily by hydrophobic forces.

Synthesis of Mn(Ⅲ) Complexes of New "Tailed" Porphyrins and Their Application as Carriers for PVC Membrane SCN-Anion-Selective Electrode

Three new 'tailed' porphyrins and their corresponding Mn(Ⅲ) metalloporphyrins were synthesized and characterized. The potentiometric response characteristics of the PVC membrane electrode based on the Mn(Ⅲ) complexes of the three new 'tailed' porphyrins toward SCN- have been studied.

Synthesis of β-Cyclodextrin Bonded Metal Porphyrins

6-Deoxy- 6-iodo-β-cyclodextrin (1) reacted with 5-(p-aminophenyl)-10, 15,20-triphenyl porphyrin(2), 5-(p-aminophenyl)-10,15,20-triphenyl nickel(Ⅱ) porphyrin [NiⅡTPPNH2P](3),5-(p-aminophenyl)-10,15,20-triphenyl manganese(Ⅲ) porphyrin [MnⅢTPPNH2P] (4) and 5-(p-aminophenyl)-10,l5,20-triphenyl carbonyl ruthenium porphyrin [RuⅡ (CO)TPPNH2P] (5) to generate the compounds 6-9, respectively. Those new compound 5-9 have been identified by 1H NMR, IR, MS and UV-visible spectra and elemental analysis.

Synthesis of Novel Tailed Porphyrins with Covalently Linked Saccharide

The reaction of 5-(p-hydroxyphenyl)-10, 15, 20- (p-methoxy phenyl) porphyrin with Br(CH2)4 Br produced monobromo substituted porphyrin 1. The tailed porphyrins 2–4 were synthesized by the reactions of 1 with small molecular offering biological activities such as D-glucose, D-glucuronic acid. These new compounds were confirmed by1H NMR, IR, UV-vis and element analyses.

Influence of the metal sites of M-N-C(M=Co, Fe, Mn) catalysts derived from metalloporphyrins in ethylbenzene oxidation

Transition metal catalysts M-N-C（M = Co,Fe,Mn） were synthesized by a template-free method by heating meso-tetraphenyl porphyrins（i.e.CoTPP,FeTPPCl,MnTPPCl） precursors.The catalysts were characterized by N2 adsorption-desorption,thermogravimetry,high-resolution transmission electron microscopy,and Raman and X-ray photoelectron spectroscopy.The selective oxidation of ethylbenzene with molecular oxygen under a solvent-free condition was carried out to explore the catalytic performance of the M-N-Cs,which exhibited different catalytic performance.That was ascribed to the difference in M（Co,Fe,Mn） and different graphitization degree forming during the heating process,in which M（Co,Fe,Mn） might have different catalytic activity on the formation of the M-N-C catalyst.All the M-N-C composites had remarkable recyclability in the selective oxidation of ethylbenzene.

The Application of Novel Electrochemical Approach to Antioxidant Activity Assay of Metal Porphyrins with Bulky 3,5-Diisobornyl-4-hydroxyphenyl Moieties

The complexes of biogenic metals (Zn2+,Cu2+,Co2+,Mn3+,Fe3+) based on meso-tetra(3,5-diisobor- nyl-4-hydroxyphenyl)porphyrin 1 were synthesized. The electrochemical behavior of these com-pounds was studied using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. The antioxidant activity of complexes was estimated by means of the electrochemical assay based on the hydrogen atom transfer reaction to the stable radical 2,2’-diphenyl-1-picrylhydrazyl (DPPH). The RDE method was applied for this process monitoring. It was shown that the efficiency of the metal complexes (Cu2+,Co2+,Mn2+,Ni2+,Fe3+) is practically the same order as that of free base porphyrin 1. However the Zn2+ complex demonstrates significantly higher antioxidant activity, and the stoichiometry of the reaction was determined as σ = 4. The results demonstrate that porphyrin macrocycle can directly affect the antioxidant properties of 2,6-diisobornylphenol.

Band Gap Opening of Graphene by Noncovalent π-π Interaction with Porphyrins

Graphene has been recognized as a promising 2D material with many new properties. However, pristine graphene is gapless which hinders its direct application towards graphene-based semiconducting devices. Recently, various ways have been proposed to overcome this problem. In this study, we report a robust method to open a gap in graphene via noncovalent functionalization with porphyrin molecules. Two type of porphyrins, namely, iron protoporphyrin (FePP) and zinc protoporphryin (ZnPP) were independently physisorbed on graphene grown on nickel by chemical vapour deposition (CVD) resulting in a bandgap opening in graphene. Using a statistical analysis of scanning tunneling spectroscopy (STS) measurements, we demonstrated that the magnitude of the band gap depends on the type of deposited porphyrin molecule.The π-π stacking of FePP on graphene yielded a considerably larger band gap value (0.45 eV) than physisorbed ZnPP (0.23 eV). We proposed that the origin of different band gap value is governed due to the metallic character of the respective porphyrin.

Cobalt porphyrins supported on carbon nanotubes as model catalysts of metal-N_(4)/C sites for oxygen electrocatalysis

Transition-metal based M-N_4/C catalysts are appealing for electrocatalytic oxygen reduction reaction(ORR) and oxygen evolution reaction(OER). Employing model catalysts, which have well-defined molecular structures and coordination environments, to investigate electrocatalytic performance of M-N_4/C sites for ORR and OER is of fundamental significance. Herein, we reported the use of Co tetra(phenyl)porphyrin 1 and Co tetra(pentafluorophenyl)porphyrin 2 as models to probe the role of Co-N_4/C sites for oxygen electrocatalysis. We showed that Co porphyrin 1 is more efficient than its structural analogue 2 for oxygen electrocatalysis in alkaline aqueous solutions, indicating that the electronrich Co-N_4/C site is more favored when noncovalently adsorbed on carbon supports. This work inspires rational design of reaction-oriented catalysts for sustainable energy storage and conversion technologies.

Study on the synthesis and antimicrobial activity of novel cationic porphyrins

A novel series of quaternary ammonium cationic derivatives based on tetrapyridyl-porphyrin was synthesized. All the compounds were evaluated for their in vitro antibacterial activities against S. aureus, E. coli and P. aeruginosa, and antifungal activities against C. albicans, where microorganisms were exposed and unexposed to the irradiation. The results revealed that some of these compounds, especially, 3a and 4a displayed satisfactory antibacterial activity against Gram-positive bacteria S. aureus and moderate antifungal activity against C. albicans. Unfortunately, Gram-negative bacteria P aeruginasa was resistant to all compounds. The antimicrobial activity was found to be sensitive to the functional groups attached on the aromatic ring and the complex metal in the porphyrin ring, and decreased with the increase of electron-withdrawing capability of the functional groups. These preliminary results suggested that the remarkable antibacterial efficiency against S. aureus makes these substances promising antimicrobial agents.