Indium Porphyrins Research Articles

Photodynamic antimicrobial activity of indium(III) porphyrin complexes against foodborne pathogens

Photodynamic antimicrobial activity of indium(III) porphyrin complexes against foodborne pathogens

The Photodynamic Antibacterial Activity Properties of a Series of Indium(III) Porphyrins and their Gold and Silver Nanoparticle Conjugates

AbstractIn(III) tetraarylporphyrin complexes with 4‐thiomethylphenyl (1‐InPor), thien‐3‐yl (2‐InPor), thien‐2‐yl (3‐InPor) and 5‐bromothien‐2‐yl (4‐InPor) meso‐aryl rings have been synthesized and characterized. The complexes have been conjugated to gold and silver nanoparticles (AuNPs and AgNPs). The photodynamic antimicrobial chemotherapy (PACT) activities of 1–4‐InPor and their AuNP and AgNP conjugates have been investigated against both planktonic bacteria and biofilms of Gram‐(+) S. aureus and Gram‐(−) E. coli. 2.5 μg.mL−1 solutions of 1–4‐InPor exhibited favorable PACT activities against planktonic S. aureus with high Log10 reduction values in the 4.28–7.69 range upon 75 min photoirradiation with a Thorlabs M625L3 LED (240 mW.cm−2) mounted onto the illumination chamber of a Modulight 7710 medical laser system to provide a dose at the well‐plate of 86 mJ.cm−2.min−1. In contrast, low values in the 1.4–1.9 range were obtained against E. coli with 10 μg.mL−1 solutions. 1–4‐InPor exhibited relatively low PACT activity against the biofilm cells of S. aureus and E. coli. Conjugation of 1–4‐InPor to AgNPs and AuNPs significantly enhanced the PACT activities. This is demonstrated by the complete eradication of planktonic S. aureus at shorter irradiation times with high Log10 values>7.69 and moderate Log10 values>2 against planktonic E. coli for the meso‐thienylporphyrin conjugates.

Microemulsion-Assisted Self-Assembly of Indium Porphyrin Photosensitizers with Enhanced Photodynamic Therapy.

Designing and constructing supramolecular photosensitizer nanosystems with highly efficient photodynamic therapy (PDT) is vital in the nanomedical field. Despite recent advances in forming well-defined superstructures, the relationship between molecular arrangement in nanostructures and photodynamic properties has rarely been involved, which is crucial for developing stable photosensitizers for highly efficient PDT. In this work, through a microemulsion-assisted self-assembly approach, indium porphyrin (InTPP) was used to fabricate a series of morphology-controlled self-assemblies, including nanorods, nanospheres, nanoplates, and nanoparticles. They possessed structure-dependent 1O2 generation efficiency. Compared with the other three nanostructures, InTPP nanorods featuring strong π-π stacking, J-aggregation, and high crystallinity proved to be much more efficient at singlet oxygen (1O2) production. Also, theoretical modeling and photophysical experiments verified that the intermolecular π-π stacking in the nanorods could cause a decreased singlet-triplet energy gap (ΔEST) compared with the monomer. This played a key role in enhancing intersystem crossing and facilitating 1O2 generation. Both in vitro and in vivo experiments demonstrated that the InTPP nanorods could trigger cell apoptosis and tumor ablation upon laser irradiation (635 nm, 0.1 W/cm2) and exhibited negligible dark toxicity and high phototoxicity. Thus, the supramolecular self-assembly strategy provides an avenue for designing high-performance photosensitizer nanosystems for photodynamic therapy and beyond.

Synthesis, Chemical Structure, and Ground- and Excited-State Spectral Characteristics of (Porphyrinato)(chloro)indium(III) and Its Complexes with C60 and Pyridyl-Substituted Fullero[60]pyrrolidine

New complexes of [5,10,15,20-tetra-(4-methoxyphenyl)porphinato](chloro)indium(III) ((Cl)InTPP(p-OCH3)4) with unsubstituted C60 and 1-methyl-2-(pyridin-4'-yl)-3,4- fullero[60]pyrrolidine (PyC60) were synthesized in toluene. The stability constants of 1 : 1 complexes (dyads) were determined using UV-vis and fluorescence spectroscopy. The dyads were characterized by IR and 1H NMR spectroscopy data. It was established that fluorescence of (Cl)InTPP(p-OCH3)4 is quenched upon gradual addition of fullerenes. The numerical values of the Stern–Volmer quenching constants (KSV) were determined. The most important charge transfer characteristics of dyads (the lifetime of charge-separated states and charge separation and recombination constants), needed for further consideration of dyads based on indium(III) porphyrins as photoinduced electron transfer systems, were determined using femtosecond laser spectroscopy.

Photodynamic activity of novel cationic porphyrins conjugated to graphene quantum dots against Staphylococcus aureus

Novel 5-(pyridyl)-10-15-20-tris(4-bromophenyl) porphyrin (complex 1), indium metal derivative (complex 2), and quaternized derivative (complex 3) were synthesized and conjugated to graphene quantum dots (GQDs). The conjugation of the porphyrins to GQDs was through [Formula: see text]-[Formula: see text] stacking. Herein, the [Formula: see text]-[Formula: see text] stacking approach was used to avoid covalent conjugation which might compromise the intrinsic chemical and physical properties. The photodynamic activities of the proposed nanomaterials were assessed towards Staphylococcus aureus cell obliteration. The photophysical properties of the prepared complexes were also studied prior to the application. Moreover, a decrease in fluorescence lifetimes was observed upon metalation of complex 1. As anticipated, singlet oxygen quantum yield ([Formula: see text] increased notably upon heavy metal (indium) insertion and upon composite formation. Antimicrobial photodynamic therapy comparative studies were done on quaternized and unquaternized indium porphyrins conjugated to GQDs. Complex 3-GQDs exhibited the highest antibacterial activities compared to other complexes, and this was attributed to the high [Formula: see text] which plays an imperative role in photodynamic therapy applications.

Amphiphilic axially modified cationic indium-porphyrins linked to hydrophilic magnetic nanoparticles for photodynamic antimicrobial chemotherapy against gram-negative strain; Escherichia coli

In this study, we report on the synthesis, characterization, and application of indium porphyrins linked to silver core-shell magnetic nanoparticles for in vitro photodynamic antimicrobial chemotherapy (PACT) against gram-negative strain, E. coli. This work compares the photophysicochemical and PACT activities of InCl 5-p-carboxyphenyl-10-15-20-(tris-4-methylpyridinium)-triiodide porphyrin (1), InCl 5-p-carboxyphenyl-10-15-20-(tris-4-hexylpyridinium)-triiodide porphyrin (2), In (para-aminophenyl) 5,10,15,20-tetrakis(4-methylpyridinium)-tetraiodide porphyrin (3), and In (para-aminophenyl) 5,10,15,20-tetrakis(4-hexylpyridinium)-tetraiodide porphyrin (4). The comparisons were based on the structure and number of charges. Hydrophilic and hydrophobic characters of the amphiphilic porphyrins were studied by comparing the effect of the different alkyl halides (iodomethane and iodohexane) quaternizing agents. The porphyrin complexes were further linked to magnetic nanoparticles to facilitate antimicrobial synergy and recovery of the complexes after use. High Log reduction values ranging from 7.19 to 9.58 were obtained for the quaternized complexes.

Synthesis and characterisations of non-covalently bound aniline–indium(III) porphyrins

The aniline–indium(III) porphyrin chromophoric systems in which aniline is bonded non-covalently with porphyrin macrocycles were obtained by the treatment of each of the indium(III) porphyrins, i.e. tetra-p-methoxyphenyl indium(III) porphyrin and tetra-p-chlorophenyl indium(III) porphyrin with neutral aniline in CHCl3/CH3OH mixtures. The prepared aniline–indium(III) porphyrin chromophoric systems were successfully characterised by using FT-IR spectroscopy, 1H NMR spectroscopy and ESI-mass spectrometry. The 1H NMR and UV–Visible absorption spectroscopic studies of aniline–indium(III) porphyrin systems were further recorded as a function of pure aniline concentration in proper solvents. The results of these spectroscopic studies indicate the existence of interchromophoric interactions between aniline and indium(III) porphyrins which increase with the increase in pure aniline concentrations. Powder X-ray diffraction (PXRD) measurement data reflects change in crystalline phases of parent complexes upon incorporation of aniline molecules. Thermogravimetric analysis (TGA) indicates that aniline-incorporated indium(III) porphyrins are less thermally stable than their parent complexes.

Enhancement of photodynamic antimicrobialtherapy through the use of cationic indium porphyrin conjugated to Ag/CuFe2O4 nanoparticles.

Photodynamic antimicrobial chemotherapy (PACT) is being actively researched as a possible alternative for antimicrobial agents. This study focuses on the application of neutral indium 5-p-carboxyphenyl-10-15-20-(tri-4-pyridyl)porphyrin and cationic indium 5-p-carboxyphenyl-10-15-20-(tris-4-methylpyridyl)-porphyrin triiodide conjugated to 6-mercapo-1-hexanol functionalized Ag/CuFe2O4 magnetic nanoparticles for photo-inactivation of S. aureus bacteria. Comparative studies were done on quaternized and unquaternized indium porphyrin complexes conjugated to Ag/CuFe2O4, where log reduction of 9.27 was obtained for quaternized conjugate and 0.83 for unquaternized conjugate.

Single hydroxo-bridged group 13 metalloporphyrin dimers: Solution studies and solid-state structures

The syntheses of indium, gallium and aluminum porphyrin dimers with a single hydroxo-bridge, [Formula: see text][M(Porph)]2(OH)[Formula: see text], are described. Emphasis is given to indium and gallium derivatives. The X-ray structures for [Formula: see text] [Ga(OEP)]2(OH)[Formula: see text] ClO4 and [Formula: see text] [In(OEP)]2(OH)[Formula: see text] ClO4 (two forms) are presented. The dimeric molecules can be synthesized by the acid-treatment of the corresponding hydroxo-ligated monomeric complexes [M(OEP)(OH)] and [M(TPP)(OH)]. The nature of the starting material (the hydroxo-ligated monomer) was first suggested by IR spectroscopy and further proved by proton-deuterium exchange followed by 1H NMR spectroscopy. The structure of a monomeric indium hydroxide complex, [In(OEP)(OH)], is also presented. The synthesis of the dimer for all metals can be monitored by UV-vis spectroscopy, which clearly demonstrates that a blue-shift of the Soret band accompanies formation of the dimer from the monomer. A strong [Formula: see text]–[Formula: see text]interaction between the two porphyrin rings of these [Formula: see text]-hydroxo-bridged dimers is confirmed both by solution state studies (1H NMR and UV-vis spectroscopy) and the X-ray structures of [Formula: see text] [M(OEP)]2(OH)[Formula: see text] ClO4 (M = In, Ga). In addition, exposure of methylene chloride solutions of these bridged complexes to white light afforded the corresponding chloro derivatives, [M(Porph)Cl]. The stereochemistry of a range of [Formula: see text]-hydroxo dimers is discussed and DFT simulations at the HSEH1PBE/SDD level of theory provide suitable structural models and further electronic structure insights on selected [Ga(Porph)(OH)] and [Formula: see text] [Ga(Porph)]2(OH)[Formula: see text][Formula: see text] derivatives.

Synthesis and spectroscopic properties of axial phenoxide and para amino phenoxide incorporated indium (III) porphyrins

Tetrakis-4-methoxyphenyl indium(III) porphyrins containing phenolic and para amino phenolic moieties in the apical sites have been successfully prepared and characterized spectroscopically. The phases and structure evolutions of prepared porphyrins were deduced from powder X-ray diffraction (PXRD). The axial coordination of phenolic moieties induces slight shift of the 1H NMR signals of indium porphyrin macrocycles. The measurements of UV–Visible absorptions of porphyrins in CH2Cl2 and CH3COOC2H5 reflects that axially ligated metal chelates at neutral pH display hyperchromicity of absorption bands compared to unligated metal porphyrin. The most striking feature was the structural stability of indium porphyrins under basic (pH = 10) as well as acidic media (pH = 4). On the other hand, the metal free ligand 5, 10, 15, 20-Tetrakis-(4-methoxyphenyl) porphyrin, H2TMP (I) undergoes J type aggregation in acidic media (pH = 4). The robustness of indium porphyrins especially in acidic media are in strong contrary to other sitting atop (SAT) or out of plane (OOP) complexes which are usually demetallized under acidic pH. All the prepared macro rings exhibit negative solvatochromism reflected by the blue shift of absorption bands in CH3COOC2H5 (more polar) than in CH2Cl2 (less polar). The photoluminescence emissions in indium(III) species are significantly quenched relative to metal free ligand (I) due to internal heavy atom effect and distortion of ligand plane. The quenching of fluorescence bands are more pronounced in axially ligated metal porphyrins. The lesser excited state lifetimes of indium(III) porphyrins relative to free base analog (I) may be ascribed to spin orbit coupling induced by indium(III) ion in the respective metal chelates.

Crystallographic elucidations of indium(III) porphyrin conformations, morphology and aggregation behaviour: Comparative optical study of free base porphyrins and their indium(III) derivatives at varying pH

The supramolecular structural architectures of 5, 10, 15, 20-Tetrakis-(4-methoxyphenylporphyrinato) indium (III) chloride (I) and 5, 10, 15, 20-Tetrakis-(4-methylphenylporphyrinato) indium (III) chloride (II) have been determined from their three dimensional X-ray diffraction data. Complex I crystallizes in the orthorhombic space group, Pbca with a = 23.0083 (4) Å, b = 15.2447 (3) Å, c = 23.3737 (4) Å, α = β = γ = 90°, V = 8198.5 (3) Å3 and Z = 8, whereas complex II crystallizes in the triclinic space group, P-1 with a = 12.0737 (5) Å, b = 12.1000 (5) Å, c = 14.1682 (6) Å, α = 88.560 (3)°, β = 78.730 (3)°, γ = 78.280 (3)° V = 1987.40 (14) Å3 and Z = 2. The geometries around In+3 ions in both the complexes are square pyramidal giving dome shaped architectures to the metalloporphyrins. In their respective crystal lattices, the monomeric units of complex I and II are packed in J-type (head-to-tail) supramolecular aggregation. These monomers are linked into their three dimensional supramolecular networks by various non covalent forces. Further the packing of monomers of each complex in their respective unit cells leaves significant void volumes (porosities). The optical absorption spectra of complex I and II and their free base analogues i.e. 5, 10, 15, 20-Tetrakis-(4-methoxyphenyl) porphyrin, H2TMP and 5, 10, 15, 20-Tetrakis-(4-methylphenyl) porphyrin, H2TTP have also been investigated in CH2Cl2 at different ionic strengths of the media. The investigations revealed that both the free bases exist as simple monomers, j-aggregates and dianionic monomers at neutral (pH = 7), acidic (pH = 4 and lower) and basic (pH = 10) media conditions. Also at high ionic strength of the media, the free bases undergo charge transfer electronic transitions. The two In3+ porphyrin exists as simple monomers at pH = 7. However at pH = 5 and lower, the In3+ ions in complex II is remarkably easily replaced by the protons of the acid to generate the corresponding protonated free base monomers which simultaneously aggregate in J-type stacking mode. In contrast to complex II that exhibits low stability in acidic media, the complex I remain intact in such media reflecting extremely high stability of the complex. The insertion of In3+ ions into the porphyrinic cores of free bases causes bathochromic shift followed by increase in the intensities of absorption bands. The appearance of two set of doublets for ortho phenyl protons in the 1H NMR spectra of each complex is attributed to the magnetic inequivalence of their ortho phenyl protons caused by the pulling of In+3 ions above the mean porphyrin planes.

Thermodynamics of the equilibrium of the reaction between (5,10,15,20-tetra(2-methoxyphenyl)porphinato)chloroindium(III) and pyridine

The results from thermodynamic and quantum-chemical studies of the reversible reaction between (5,10,15,20-tetra(2-methoxyphenyl)porphinato)chloroindium(III) and pyridine are reported. The main physicochemical parameters of properties of its supramolecular products are obtained and analyzed. The addition of pyridine molecules to metalloporphyrin proceeds in one step to attain an equilibrium state with the formation of supramolecules with a stoichiometry of 2: 1; spectral characteristics and parameters of the stability of the latter are identified. The possibility of using substituted indium(III)porphyrin for further research in the field of hybrid solar cells is discussed.

Assembly of an indium–porphyrin framework JLU-Liu7: a mesoporous metal–organic framework with high gas adsorption and separation of light hydrocarbons

A novel mesoporous indium–porphyrin framework JLU-Liu7 with frl net has been successfully synthesized. It exhibits high performance for gas adsorption and light hydrocarbon separation.

A robust indium-porphyrin framework for CO2 capture and chemical transformation.

An indium based metal-porphyrinic framework, denoted NUPF-3, was prepared based on a new amido-decorated porphyrin ligand. NUPF-3 possesses a rarely seen 4-fold interpenetrated pts framework with segmented pores and dense metalloporphyrin central sites. The structure can retain its crystallinity in commonly used solvents, as well as acidic/alkaline solutions with pH ranging from 1 to 12 for 48 h, exhibiting high chemical stability. Meanwhile, thermal analysis reveals that NUPF-3 possesses relatively high thermal stability. Owing to the presence of amido groups, structural interpenetration and a charged framework, NUPF-3 exhibits relatively high CO2 uptake. Moreover, NUPF-3 could be used as a good heterogeneous catalyst for cycloaddition of CO2 and epoxides, under relatively mild conditions, with good recyclability.

Five‐Coordinate Indium(III) Porphyrins with Hydroxy and Carboxy BODIPY as Axial Ligands: Synthesis, Characterization and Photophysical Studies

AbstractA new series of dyads (TPP)In–O–BDP and (TPP)In–OOC–BDP comprising an indium tetraphenylporphyrin (TPP)In–Cl axially substituted with different boron dipyrrin (bodipy) chromophores are reported. Both compounds were synthesized by the reaction between (TPP)In–Cl and corresponding bodipy units in the presence of a NaH base. Two reference compounds (TPP)In–O–Ph and (TPP)In–OOC–Ph have also been synthesized in order to compare their photophysical and electrochemical properties with the final dyads. The photophysical properties of the compounds were investigated by UV/Vis and fluorescence spectroscopy studies at room temperature as well as at 77 K. Fluorescence spectra suggest weak excited state interactions between the bodipy chromophore and the indium–porphyrin unit. The electrochemical as well as the 1H NMR and 13C NMR spectroscopic data also support the formation of the dyads (TPP)In–O–BDP and (TPP)In–OOC–BDP. Furthermore, DFT and TDDFT calculations were carried out to obtain insight into the electronic properties of the dyads.

Facile control of the charge density and photocatalytic activity of an anionic indium porphyrin framework via in situ metalation.

An anionic indium porphyrin framework (UNLPF-10) consisting of rare Williams β-tetrakaidecahedral cages was constructed using an octatopic ligand linked with 4-connected [In(COO)4](-) SBUs. Remarkably, the extent of indium metalation of porphyrin macrocycles in UNLPF-10 can be facilely tuned in situ depending on the M/L ratio during synthesis, resulting in a controllable framework charge density and photocatalytic activity toward the selective oxygenation of sulfides.

Synthesis and Spectroscopic Characterization of Some New Axially Ligated Indium(III) Macrocyclic Complexes and Their Biological Activities.

The synthesis and spectroscopic characterization of new axially ligated indium(III) porphyrin complexes were reported. Chloroindium(III) porphyrin (TPPIn-Cl) was obtained in good yield by treating the corresponding free base with indium trichloride. The action of the different phenols on chloroderivatives (TPPIn-Cl) led to the corresponding phenolato complexes (TPPIn-X). These derivatives were characterized on the basis of mass spectrometry, 1H-NMR, IR, and UV-visible data. The separation and isolation of these derivatives have been achieved through chromatography. The spectral properties of free base porphyrin and its corresponding metallated and axially ligated indium(III) porphyrin compounds were compared with each other. A detailed analysis of UV-Vis, 1H-NMR, and IR suggested the transformation from free base porphyrin to indium(III) porphyrin. Besides, 13C-NMR and fluorescence spectra were also reported and interpreted. The stability of these derivatives has also been studied through thermogravimetry. The complexes were also screened for anticancerous activities. Among all the complexes, 4-MePhO-InTPP shows highest anticancerous activity. The title complexe, TPPIn-X (where X = different phenolates), represents a five-coordinate indium(III) porphyrin complex in a square-pyramidal geometry with the phenolate anion as the axial ligand.

Syntheses and photodynamic properties of glucopyranoside-conjugated indium(III) porphyrins as a bifunctional agent

The glucopyranoside-conjugated porphyrins, H 2 TPP {p- O -( CH 2)2- O - OAcGlc } (1), [ InTPP {p- O -( CH 2)2- O - OAcGlc }] NO 3 (2), H 2 TPP {p- O -( CH 2)2- O - Glc } (3), [ InTPP {p- O -( CH 2)2- O - Glc ]- NO 3 (4) and ZnTPP {p- O -( CH 2)2- O - OAcGlc } (5) were synthesized, and characterized by 1 H NMR, 13 C NMR, ESI-MS, UV-vis spectroscopies and elemental analyses. In the 1 H NMR spectrum of 2, two sets of signals were observed for H -atoms of the phenyl group of porphyrin, indicating that 2 has the axial chirality due to a NO 3 ion coordinating to the indium atom. Abilities of the singlet oxygen production of these porphyrins, investigated by using 1,3-diphenylisobenzofuran (DPBF) as a quencher, were higher than those of the free-based and zinc porphyrins, reflecting the heavy atom effect. The photodynamic properties of these porphyrin derivatives were investigated against COLO 679. All of the glucopyranoside-conjugated porphyrins exhibited the high photocytotoxicity compared with Laserphyrin®. Above all, 4 exhibited the highest photocytotoxicity, coinciding with the high abilities of this complex for the singlet oxygen production and the cell permeability.

Chloride-selective membrane electrodes and optodes based on an indium(III) porphyrin for the determination of chloride in a sequential injection analysis system

Two quasi-independent methods for potentiometric and optical determination of chloride were simultaneously implemented in a flow system, providing real-time assessment of the quality of results. A potentiometric and an optical polymeric membrane doped with the same indium(III) octaethyl-porphyrin were used as sensor ionophore. The working mechanism and the analytical characteristics of these porphyrin-based sensors with respect to dynamic range, selectivity, repeatability and lifetime are discussed. These sensors, utilised as detectors in a flow system, were applied for the analysis of chloride in pharmaceutical solutions. The quality of the results obtained was evaluated by comparison with those provided by the reference method and no significant statistical differences at the 95% confidence level were observed. The simultaneous attainment of two measurements permitted the standardisation of results in real time and the detection of failures in the procedure.

Elimination of dimer formation in InIIIporphyrin-based anion-selective membranes by covalent attachment of the ionophore.

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.