Hydrophobic Porphyrin Research Articles

Porphyrin encapsulated in organic polymers: Electropolymerization and preliminary investigations on electrocatalytic activity

AbstractIn the present work, the incorporation of hydrophobic porphyrins in organic polymers through electrochemically induced polymerization of monomers on conventional electrodes and the preliminary investigations on the electrocatalytic activity of these modified electrodes are explained. Electropolymerized porphyrins show better activity than organic polymers of N‐isopropylacrylamide, triethylene glycol methyl ether methacrylate, and glycerol 1,3‐diglycerolate diacrylate for nitrite oxidation due to the presence of cobalt metal ion. Among the porphyrins investigated, electropolymerized cobalt tetra‐2‐thienylporphyrin requires the least overpotential, due to ease of polymerization and better coating on glassy carbon electrode compared with that of cobalt tetraphenylporphyrin and cobalt tetra‐3‐thienylporphyrin. On encapsulating these porphyrins in organic polymers, improved current and lower overpotential are noticed.

A Porphyrinic Metal-Organic Framework with Cooperative Adsorption Domains for PFAS Removal from Water.

The removal of toxic poly- and perfluoroalkyl substances (PFAS) as persistent pollutants from wastewater is imperative but challenging for water remediation. Many adsorbents including activated carbon, biochar, and clay minerals have been investigated for PFAS removal, but most of these materials are faced with high cost or/and low efficiency. The use of metal-organic frameworks (MOFs) as sorbents is attractive for efficient removal of PFAS due to their tailor-made structures and high surface areas. Herein, we synthesized, characterized a water stable Zr-based porphyrinic MOF (PCN-224) with cooperative adsorption domains, and demonstrated its excellent capture performance toward perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorobutane sulfonate (PFBS). PCN-224 has maximum uptake capacities of 963, 517, and 395 mg g-1 for PFOS, PFHxS, and PFBS, respectively, which are much higher than that of granular activated carbon. Moreover, coexistent anions (Cl-, SO4 2-) and humic acid have negligible effects on PFOS adsorption. The excellent adsorption performance of PCN-224 toward PFOS is due to the orthogonal cationic channel pores with a diameter of 1.9 nm, the hydrophobic porphyrin units, and the Zr6 clusters with acidic sites. PCN-224 can be readily regenerated and reused. This work highlights the potential of MOFs with multiple adsorption domains for water remediation.

Hydrophobic Porphyrin Titanium-Based MOFs for Visible-Light-Driven CO2 Reduction to Formate.

Three hydrophobic porphyrin titanium-based metal-organic frameworks (MOFs) (HPA/DGIST-1, DPA/DGIST-1, and OPA/DGIST-1) were synthesized through a postsynthetic coordination reaction by using alkylphosphonic acid of different lengths (HPA, hexylphosphonic acid; DPA, dodecylphosphonic acid; OPA, octadecylphosphonic acid). Compared with the hydrophilic DGIST-1, modified DGIST-1 exhibits excellent hydrophobicity and presents good stability in humid atmospheres. Due to the introduction of porphyrin ligands, HPA/DGIST-1, DPA/DGIST-1, and OPA/DGIST-1 showed good visible-light absorption (380-700 nm) and sensitive photogenerated charge responses. When acted as catalysts, these hydrophobic Ti-MOFs can selectively reduce CO2 to HCOO- under visible-light irradiation with average reaction rates of 150.9, 178.5, and 228.3 μmol·h-1·g-1, where these values are 1.3-2.0 times higher than the system mediated by the initial porphyrin Ti-MOF catalyst. 13C NMR spectroscopy demonstrates that the catalytic product HCOO- anion originates from the reactant CO2. The photocatalytic experiments, electron paramagnetic resonance, and photoluminescence spectra tests showed that porphyrin ligands and Ti-O units can act as catalytic activity centers to realize the conversion of CO2 to HCOO-. This work demonstrated that the combination of porphyrin titanium-based MOF and alkyl hydrophobic groups is an effective way to enhance the stability of titanium-based MOFs and maintain their high photocatalytic performance.

Molecular designs with PEG groups for water-solubilization of sparsely substituted porphyrins

Two relatively short polyethylene glycol (PEG) groups suffice to impart aqueous solubility to an otherwise hydrophobic porphyrin.

Chirality induction to porphyrin derivatives co-confined at the air-water interface with silica nano-helices: towards enantioselective thin solid film surfaces.

A supramolecular approach based on self-assembled structures allows the formation of large structured co-assemblies based on chiral and achiral compounds with original physicochemical features. In this contribution, an achiral and hydrophobic porphyrin was co-assembled at the air-water interface with mesoscopic silica nano-helices dispersed in the water subphase of a Langmuir trough without covalent bond formation. This procedure allowed transferring the porphyrin/nano-helix co-assemblies on a solid support within a thin hybrid layer. The interaction between the two species was characterized using spectroscopic techniques and atomic force microscopy. As evidenced by the circular dichroism measurements performed directly on solid films, tunable chirality was induced to the porphyrin aggregates according to the chirality of the silica nano-helices. When the co-assemblies were transferred on surface plasmon resonance (SPR) slides and exposed to aqueous solutions of histidine enantiomers, selective chiral discrimination was observed which was determined by the matching/mismatching between the chirality of the analyte and the helicity of the nano-helical structure.

Drastic differences between the release kinetics of two highly related porphyrins in liposomal membranes: mTHPP and pTHPP

HypothesisThe release of hydrophobic compounds from liposomal membranes occurs by partitioning and is thus determined by the physicochemical properties (e.g. logP and water solubility) of the drug. We postulate that even minor structural differences, e.g. the position of the phenolic OH-group of the hydrophobic porphyrins mTHPP and pTHPP (meta vs. para substitution), distinctly affect their partitioning and release behavior from liposomes. ExperimentsThe release and redistribution of mTHPP and pTHPP from lecithin or POPC/POPG liposomes to different acceptor particles (DSPE-mPEG micelles and liposomes) was studied by asymmetrical flow field-flow fractionation to separate donor and acceptor particles. Reversed phase HPLC was applied to detect differences in partitioning. Molecular dynamics (MD) simulations were carried out to obtain molecular insight in the different behavior of the two compounds inside a lipid bilayer. FindingsDespite the minor differences in chemical structure, mTHPP is more hydrophobic and redistributes much slower to both acceptor phases than pTHPP. MD simulations indicate that compared to pTHPP, mTHPP makes stronger hydrogen bonds with the lipid head groups, is oriented more parallel to the lipid tails and is embedded slightly deeper in the membrane.

The Influence of Irrigating Solutions on the Penetration of Epoxy AH Plus Sealer in Dentinal Tubules—In Vitro Confocal Microscopy Study

Background: The proper sealing of the root canal seems to be critical to obtain a stable result of endodontic therapy. The sealer’s penetration into dentinal tubules during root canal treatment is probably a crucial factor to provide better clinical results. The aim of this study was to compare the effect of three irrigation protocols on the penetration of the epoxy sealer into dentinal tubules and two dyes used to stain the sealer. Methods: Ninety single-canaled human teeth with straight roots were used. The root canals were instrumented with Reciproc instruments up to the size 40/04 ISO. The teeth were divided into three groups (n = 30). The root canals of each group were rinsed accordingly: the control group 1: 5.25% sodium hypochlorite (NaOCl); the experimental group 2: smear layer removal (two times alternatively: 40% citric acid and 5.25% NaOCl) and NaOCl; the experimental group 3: smear layer removal (same as in group 2) and isopropyl alcohol. In each group the roots were further divided into 2 subgroups (n = 15). The root canals were obturated using warm vertical compaction technique of gutta-percha with AH Plus sealer marked with hydrophilic fluorescein (subgroup F) or hydrophobic porphyrin (subgroup P). After 72 h, one-millimeter-thick cross-sections were cut in two, five and eight millimeters distance from the apex. The depth of the penetration of the sealer into the dentinal tubules (resin tags) was measured with the use of a confocal laser microscope. Results: In of all the root parts, the longest resin tags were observed in group 2, whereas the shortest ones were found in group 1 (in the porphyrin subgroups all differences were statistically significant). Within the fluorescein subgroups, the differences between all groups were statistically significant in the middle section of the roots. In the apical and the coronal sections, significant differences were observed between group 1 and the other two groups. Conclusions: The isopropyl alcohol at the end of the irrigating protocol did not affect the higher sealer penetration of the sealer into the dentinal tubules compared with sodium hypochlorite. With the limitation of this study, the hydrophobic porphyrin may be considered as the favorable dye choice to stain endodontic sealers in further studies with confocal laser scanning microscopy, but the methods and reagents used should still be in the research phase.

Control of the Biodegradability of Piezoelectric Peptide Nanotubes Integrated with Hydrophobic Porphyrin.

Diphenylalanine (FF) is a piezoelectric material that is widely known for its high piezoelectric constant, self-assembly characteristics, and ease of manufacture. Because of its biocompatible nature, it is useful for implantable applications. However, its use in real applications is challenging because it degrades too easily in the body due to its solubility in water (0.76 g/mL). Upon incorporation of hydrophobic and biocompatible porphyrins into the FF, the degradability of the piezoelectric FF and their piezoelectric nanogenerators (PENGs) is controlled. Porphyrin-incorporated FFs are also formed as piezoelectric nanostructures well aligned on the substrate through self-assembly, and their piezoelectric properties are comparable to those of FF. The FF-based PENG degrades in only 5 min, whereas the FF-porphyrin-based PENG produces a stable output for >15 min in phosphate-buffered saline. This strategy for realizing biodegradable functional materials and devices with tunable degradation rates in the body can be applied to many implantable electronics.

Effect of Water-Micellar Solvents on the Spectral and Luminescence Parameters of Hydrophobic Porphyrins

Effect of Water-Micellar Solvents on the Spectral and Luminescence Parameters of Hydrophobic Porphyrins

Encapsulation of Hydrophobic Porphyrins into Biocompatible Nanoparticles: An Easy Way to Benefit of Their Two-Photon Phototherapeutic Effect without Hydrophilic Functionalization.

Simple SummaryEfficient photosensitizers for photodyanmic therapy (PDT) need to be soluble in physiologic media. This requirement often complicates significantly the chemical access to such compounds, resulting in lower availability and higher production costs for the best representatives. Given that their screening and selection is often initially conducted in organic media from series of hydrophobic model compounds, the possibility to use directly such hydrophobic photosensitizers in real PDT studies was highly desirable to speed up their definitive identification but also to alleviate their cost. In this respect, PMLABe polymeric nanoparticles (NPs) were presently probed as nanocarriers to water-solubilize hydophobic star-shaped porphyrin-based which turned out to be promising oxygen photosensitizers for theranostic approaches. We show here that PDT conducted using such NPs loaded with these compounds is as efficient than when functional hydrosoluble analogues of these photosensitiers are tested alone and that tracking of the photosensitizer by fluorescence imaging is even easier.Star-shaped hydrophobic porphyrins, acting as powerful fluorescent two-photon photosensitizers for oxygen in organic solvents, can easily be loaded into PMLABe polymeric nanoparticles at various concentrations. In this contribution, the performance of these porphyrin-containing nanoparticles in terms of photodynamic therapy (PDT) is compared to those of the corresponding water-soluble porphyrin analogues when irradiated in MCF-7 cancer cells. While quite promising results are obtained for performing PDT with these nanoparticles, validating this approach as a mean for using more easily accessible and less expensive photosensitizers, from a synthetic perspective, we also show that their luminescence can still be used for bioimaging purposes in spite of their confinement in the nanoparticles, validating also the use of these nano-objects for theranostic purposes.

Modern Methods for the Sustainable Synthesis of Metalloporphyrins

Metalloporphyrins are involved in many and diverse applications that require the preparation of these compounds in an efficient manner, which nowadays, also involves taking into consideration sustainability issues. In this context, we use ball milling mechanochemistry and sonochemistry for the rational development of synthetic strategies for the sustainable preparation of metalloporphyrins. Zinc, copper, cobalt and palladium complexes of hydrophobic porphyrins were obtained in high yields and under mechanical action with a moderate excess of the metal salt, without any solvent or additive. Sonochemistry prove to be a good alternative for the preparation of metal complexes of water-soluble porphyrins in good yields and short reaction times. Both strategies have good sustainability scores, close to the ideal values, which is useful in comparing and helping to choose the more adequate method.

Norfloxacin and gentamicin degradation catalyzed by manganese porphyrins under mild conditions: the importance of toxicity assessment.

The current work assessed the degradation degree and the degradation products derived from norfloxacin (NOR) and gentamicin (GEN) using iodosylbenzene and iodobenzene diacetate, in the presence of manganese porphyrin as catalysts. Better results for NOR degradation (> 80%) were obtained when more hydrophobic porphyrins were employed. β-brominated manganese porphyrins showed a lower GEN degradation (~ 25%) than the non-brominated ones (~ 35%), probably due to their steric hindrance. In any case, complete mineralization was achieved neither for NOR nor for GEN, and the assignment of the generated products, complemented by the study of their toxicity, was an important step performed. From the obtained results, no correlation was found between the number of identified products and the reported toxicity value (rSpearman,NOR = 0.006; p value = 0.986 and rSpearman,GEN = - 0,198; p value = 0.583), which reinforces the idea of synergism and antagonistic phenomena. The higher degradation degree could have led to products of lower steric hindrance and easier penetration into the A. fischeri cells, which subsequently led to an increase in toxicity for these experiments. In most cases, the products presented higher toxicity than the original compound, which raises a concern about their occurrence in environmental matrices.

A Robust Oxygen-Carrying Hemoglobin-Based Natural Sonosensitizer for Sonodynamic Cancer Therapy.

The development of novel sonosensitizers with outstanding reactive oxygen (ROS) generation capacity and great biocompatibility poses a significant challenge for the clinical practice of sonodynamic therapy (SDT). In this work, hemoglobin (Hb) with natural metalloporphyrin was first shown to possess great potential as a sonosensitizer. Compared with traditional organic sonosensitizers, Hb had satisfactory sono-sensitizing efficiency because four the porphyrin molecules were separated by four polypeptide chains. This effectively avoided the problem of low ROS quantum yield caused by the stacking of hydrophobic porphyrins. Meanwhile, Hb is an efficient and safe oxygen carrier that may release O2 at hypoxic tumors site, which improved tumor oxygenation and subsequently enhanced SDT efficacy. Therefore, Hb was integrated with zeolitic imidazolate framework 8 (ZIF-8) to form a nanoplatform that demonstrated a potent suppression effect on deep-seated tumors under ultrasound irradiation.

PH-controlled solubilization of photosensitizer tetraphenylporphyrin

pH-controlled solubilization technique for hydrophobic porphyrin photosensitizers, which tetrapyrrole platform is a pH-dependent anion-molecular receptor, using anionic amphiphilic nanoparticles is proposed. Water-soluble forms of tetraphenylporphyrin were made as the complexes with sodium dodecyl sulfate micelles H2P(Ph)4/(NaDS)64 and with nanoparticles of biocompatible polysulfonate Nafion DE 1020 H2P(Ph)4/NNP. Diprotonation of these complexes leads to the fluorescence enhancement in the “therapeutic window” spectral region, and the integral intensity exceeds the value for the PDT drug Fotoditazin®. A unique feature of the excited complex H2P(Ph)4/NNP is the shift of its protonation equilibrium to the physiological pH value of healthy tissues. This pH value is the starting point of pH-induced H2P(Ph)4/NNP fluorescence increasing. In the pH range, corresponds to the acidic tumors microenvironment, integral fluorescence of H4P2+(Ph)4/NNP increases to 250%, which is quarter of the maximum fluorescence value. These results demonstrate the possibility and the concept of pH-dependent “off-on” photosensitizers for photodynamic theranostics based on H2P(Ph)4 derivatives, with low fluorescence and phototoxicity in normal tissues and high fluorescence and phototoxicity inside the tumor microenvironment.

Effect of Chitosan on the Activity of Water-Soluble and Hydrophobic Porphyrin Photosensitizers Solubilized by Amphiphilic Polymers.

In this work, we studied the photocatalytic activity of photosensitizers (PSs) of various natures solubilized with polyvinylpyrrolidone (PVP) and ternary block copolymer ethylene and propylene oxide Pluronic F127 (F127) in a model reaction of tryptophan photo-oxidation in water in the presence of chitosan (CT). Water-soluble compounds (dimegin and trisodium salt of chlorin e6 (Ce6)) and hydrophobic porphyrins (tetraphenylporphyrin (TPP) and its fluorine derivative (TPPF20)) were used as PSs. It was shown that the use of chitosan (Mw ~100 kDa) makes it possible to obtain a system whose activity is comparable to that of the photosensitizer-amphiphilic polymer systems. Thus, the previously observed drop in the photosensitizing activity of PS in the presence of a polysaccharide and amphiphilic polymers (AP) was absent in this case. At the same time, chitosan had practically no inhibitory effect on hydrophobic porphyrins solubilized by Pluronic F127.

A versatile method for surface functionalization and hydrophobization of gold nanoparticles

A convenient, one-step, approach for surface modification with hydrophobic thiol or its dye-derivative of hydrophilic citrate-capped Au nanoparticles (Cit–AuNPs) is demonstrated. This method depended on the solubility of both Cit–AuNP and thiol or its derivative in the reaction solvent. We investigated a variety of solvents for Cit–AuNPs with 15–75 nm sizes and a capping molecule, octadecanethiol (ODT) or a disulfide derivative of hydrophobic porphyrin (PC10S)2. As to ODT, surface immobilization of Cit–AuNPs with ODT was successful in 2-propanol, while N,N-dimethylformamide was best in the case of (PC10S)2. In both cases, surface modified AuNPs were redispersible even after storing under dried powder conditions. Two-dimensional monoparticle films of surface-modified AuNPs by the Langmuir–Blodgett method with ethylene glycol as subphase could be formed and exhibit surface-enhanced Raman scattering. Spectra from the porphyrin skeleton were certainly observed, with the maximum photoluminescence enhancement of 15-fold, around 50-nm size. As to AuNP with 17-nm diameter, mixed monolayer assemblies of (PC10S)2 and octanethiol with different concentration ratios were fabricated and spectroscopic enhancement effects due to localized surface plasmon resonance were investigated.

Demetalation of Surface Porphyrins at the Solid-Liquid Interface.

Understanding the factors that control the demetalation of surface porphyrins at the solid-liquid interface is important as the molecular properties of porphyrins are largely determined by their metal centers. In this work, we used X-ray photoelectron spectroscopy (XPS) to follow the demetalation of Zn and Cd tetraphenylporphyrin molecules (ZnTPP and CdTPP) adsorbed as three-monolayer-thin multilayer films on Au(111), by exposing the molecular layers to acidic aqueous solutions. We found that porphyrin molecules at the solid-liquid interface are less prone to lose their metal center than molecules in solution. We propose that this behavior is due to either the incoming protons provided by the solution or the outgoing metal ion having to pass through the hydrophobic porphyrin multilayers where they cannot be solvated. Our results are relevant for the design of molecular devices based on porphyrin molecules adsorbed on solid surfaces.

Solvent Extraction of Zinc(II) and Manganese(II) with 5,10,15,20-Tetraphenyl -21H,23H-Porphine (TPP) through The Metal Exchange Reaction of LEAD(II)-TPP (Dept.M)

An investigation was carried out on the extraction of aqueous Zn(II) and Mn(π) with a hydrophobic porphyrin (5,10,15,20-tetraphenyl-21H,23H porphine, TPP) through a metal exchange reaction of Pb(π)-TPP. The distribution ratios (D) of these metals were found to be independent of the Pb(π) concentration in the aqueous phase. Pb(π) in the aqueous phase acted as a catalyst which promoted the metal-TPP complexation.

The Self-Aggregation of Porphyrins with Multiple Chiral Centers in Organic/Aqueous Media: The Case of Sugar- and Steroid-Porphyrin Conjugates.

An overview of the solvent-driven aggregation of a series of chiral porphyrin derivatives studied by optical methods (UV/Vis, fluorescence, CD and RLS spectroscopies) is herein reported. The investigated porphyrins are characterized by the presence in the meso-positions of glycol-, steroidal- and glucosteroidal moieties, conferring amphiphilicity and solubility in aqueous media to the primarily hydrophobic porphyrin platform. Aggregation of the macrocycles is driven by a change in bulk solvent composition, forming architectures with supramolecular chirality, steered by the stereogenic centers on the porphyrin peripheral positions. The aggregation behavior and chiroptical properties of the final aggregated species strongly depend on the number and stereogenicity of the ancillary groups that dictate the mutual spatial arrangement of the porphyrin chromophores and their further organization in larger structures, usually detectable by different microscopies, such as AFM and SEM. Kinetic studies are fundamental to understand the aggregation mechanism, which is frequently found to be dependent on the substrate concentration. Additionally, Molecular Mechanics calculations can give insights into the intimate nature of the driving forces governing the self-assembly process. The critical use of these combined methods can shed light on the overall self-assembly process of chirally-functionalized macrocycles, with important implications on the development of chiral porphyrin-based materials.

A Discrete Platinum(II) Amphiphile: Construction, Characterization, and Controllable Self-Assembly in Different Solvents.

"Coordination-driven self-assembly" offers us an efficient method to fabricate 3D metallacages and 2D metallacycles with controllable shape and size via simple building blocks. Herein, a new discrete platinum(II) amphiphile (AOM), which contains hydrophilic tris(ethylene oxide) chains and a hydrophobic porphyrin unit, was constructed successfully by using "coordination-driven self-assembly". From various characterization methods, such as UV-vis spectroscopy, dynamic light scattering, transmission electron microscopy, scanning electron microscopy, and small-angle X-ray scattering, we found that AOM can self-assemble into vesicles, curved vesicles with open ends, and at last stable bilayer nanotubes in aqueous solution at room temperature and flexible cross-linked structures at about 60 °C. In contrast, AOM formed rigid bilayer nanosheets of micrometers in width and millimeters in length in n-hexane. We hope this investigation will pave the way for the fabrication of controllable soft materials.