Porphyrin Chloride Research Articles

5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin Zinc and Chloro-aluminum Phthalocyanine Disulfonate in Photodynamic Therapy of Colorectal Adenocarcinoma In Vitro.

Colorectal cancer (CRC) is one of the most widespread malignancies. One of the alternative therapeutic methods appears to be photodynamic therapy (PDT). This study investigated the efficiency of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin zinc (ZnTPPS4) and chloro-aluminum phthalocyanine disulfonate (ClAlPcS2) with two commercial photosensitive compounds 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin (TMPyP) and tetramethylthionine chloride (methylene blue, MB) in PDT for CRC in vitro. In addition to the study of the photodynamic effect on the viability of the colorectal carcinoma cell line HT29, cellular uptake, ROS production, and DNA damage were investigated. All photosensitizers showed good accumulation within HT29 cells, high efficiency in killing the cells, and a concentration-dependent increase in the production of ROS. PDT using ZnTPPS4 and ClAlPcS2 may be effective in the treatment of CRC, achieving a similar photocytotoxic effect at much lower concentrations compared to MB.

Effects of MnTBAP on Porcine Semen Cryopreservation and Capacitation.

Antioxidants protect cellular function and structure by neutralizing the oxidative stress caused by increased reactive oxygen species (ROS) during sperm freezing. Studies on cryopreservation using various antioxidants have demonstrated encouraging results. Many studies have used antioxidants to increase the efficiency of sperm freezing and to improve the success rate of artificial insemination and pregnancy. Manganese (III) tetrakis (4-benzoic acid) porphyrin chloride (MnTBAP) is a newly synthesized antioxidant with positive effects on sperm morphology and capacitation in humans, rams, and stallions. In this study, porcine semen was treated with 0, 50, 100, and 150 μM of MnTBAP based on a Tris-egg-yolk extender and frozen to determine whether MnTBAP can assist the status of sperm during cryopreservation. First, motility was assessed using the computer-assisted sperm analysis (CASA) system, with the 100 μM treatment group showing the highest motile rate (66.8%) compared with that of the other groups (control, 51.1%; 50 μM and 150 μM, 59.6%); therefore, the remaining analyses were conducted comparing the two groups (control vs. 100 μM group; p < 0.01). Second, fluorescence staining was applied to examine the control and 100 μM groups using fluorescence microscopy. The viability (41.7% vs. 62.4%) and the acrosome integrity (77.9% vs. 86.4%) differed significantly (p < 0.05). In addition, the mitochondrial membrane potential (MMP) was 46.5% vs. 51.9%; the fragmentation rate, estimated using the Sperm-sus-Halomax kit, was 63.4% vs. 57.4%; and the detected caspase activity was 30.1% vs. 22.9%. These tended to be higher in the treated group but did not differ significantly. Third, measurements using FACSLyric revealed that the 100 μM treatment group exhibited a state of elevated normal lipid arrangement within the plasma membrane and diminished levels of apoptosis and ROS (p < 0.01). We assessed the expression of genes relevant to antioxidant effectiveness using real-time RT-qPCR. Our findings indicated significant alterations in the expression levels of various mRNA species, with the exception of NOX5 (p < 0.05). Finally, the straws were dissolved and used to treat matured denuded oocytes to investigate the effect on fertilization and embryo development in vitro. The cleavage rate was (77.6% vs. 84.1%), and the blastocyst rate was 9.7% vs. 11.4% (p < 0.05). In conclusion, these results suggest that MnTBAP positively affected sperm freeze-thawing, improving the fertilization capacity, and leading to increased embryo development.

A Self-Assembled MOF-Escherichia Coli Hybrid System for Light-Driven Fuels and Valuable Chemicals Synthesis.

The development of semi-artificial photosynthetic systems, which integrate metal-organic frameworks (MOFs) with industrial microbial cell factories for light-driven synthesis of fuels and valuable chemicals, represents a highly promising avenue for both research advancements and practical applications. In this study, an MOF (PCN-222) utilizing racemic-(4-carboxyphenyl) porphyrin and zirconium chloride (ZrCl4) as primary constituents is synthesized. Employing a self-assembly process, a hybrid system is constructed, integrating engineered Escherichia coli (E. coli) to investigate light-driven hydrogen and lysine production. These results demonstrate that the light-irradiated biohybrid system efficiently produce H2 with a quantum efficiency of 0.75% under full spectrum illumination, the elevated intracellular reducing power NADPH is also observed. By optimizing the conditions, the biohybrid system achieves a maximum lysine production of 18.25mg L-1, surpassing that of pure bacteria by 332%. Further investigations into interfacial electron transfer mechanisms reveals that PCN-222 efficiently captures light and facilitates the transfer of photo-generated electrons into E. coli cells. It is proposed that the interfacial energy transfer process is mediated by riboflavin, with facilitation by secreted small organic acids acting as hole scavengers for PCN-222. This study establishes a crucial foundation for future research into the light-driven biomanufacturing using E. coli-based hybrid systems.

Adjunctive treatments for pneumococcal meningitis: a systematic review of experimental animal models.

New treatments are needed to improve the prognosis of pneumococcal meningitis. We performed a systematic review on adjunctive treatments in animal models of pneumococcal meningitis in order to identify treatments with the most potential to progress to clinical trials. Studies testing therapy adjunctive to antibiotics in animal models of pneumococcal meningitis were included. A literature search was performed using Medline, Embase and Scopus for studies published from 1990 up to 17 February 2023. Two investigators screened studies for inclusion and independently extracted data. Treatment effect was assessed on the clinical parameters disease severity, hearing loss and cognitive impairment and the biological parameters inflammation, brain injury and bacterial load. Adjunctive treatments were evaluated by their effect on these outcomes and the quality, number and size of studies that investigated the treatments. Risk of bias was assessed with the SYRCLE risk of bias tool. A total of 58 of 2462 identified studies were included, which used 2703 experimental animals. Disease modelling was performed in rats (29 studies), rabbits (13 studies), mice (12 studies), gerbils (3 studies) or both rats and mice (1 study). Meningitis was induced by injection of Streptococcus pneumoniae into the subarachnoid space. Randomization of experimental groups was performed in 37 of 58 studies (64%) and 12 studies (12%) were investigator-blinded. Overall, 54 treatment regimens using 46 adjunctive drugs were evaluated: most commonly dexamethasone (16 studies), daptomycin (5 studies), complement component 5 (C5; 3 studies) antibody and Mn(III)tetrakis(4-benzoicacid)porphyrin chloride (MnTBAP; 3 studies). The most frequently evaluated outcome parameters were inflammation [32 studies (55%)] and brain injury [32 studies (55%)], followed by disease severity [30 studies (52%)], hearing loss [24 studies (41%)], bacterial load [18 studies (31%)] and cognitive impairment [9 studies (16%)]. Adjunctive therapy that improved clinical outcomes in multiple studies was dexamethasone (6 studies), C5 antibodies (3 studies) and daptomycin (3 studies). HMGB1 inhibitors, matrix metalloproteinase inhibitors, neurotrophins, antioxidants and paquinimod also improved clinical parameters but only in single or small studies. Evaluating the treatment effect of adjunctive therapy was complicated by study heterogeneity regarding the animal models used and outcomes reported. In conclusion, 24 of 54 treatment regimens (44%) tested improved clinically relevant outcomes in experimental pneumococcal meningitis but few were tested in multiple well-designed studies. The most promising new adjunctive treatments are with C5 antibodies or daptomycin, suggesting that these drugs could be tested in clinical trials.

Influence of graphene on the electronic and magnetic properties of an iron(III) porphyrin chloride complex.

Although iron-based single atom catalysts are regarded as a promising alternative to precious metal catalysts, their precise electronic structures during catalysis still pose challenges for computational descriptions. A particularly urgent issue to be addressed is the influence of the environment on the electronic structure, and how to describe this accurately using computational methods. Here, we study an iron porphyrin chloride complex adsorbed on a graphene sheet using density functional theory calculations to probe how much the electronic structure is influenced by the presence of a graphene layer. Our results indicate that weak interactions due to van der Waals forces dominate between the porphyrin complex and graphene, and only a small amount of charge is transferred between the two entities. Furthermore, the interplay of the ligand field environment, strong p-d hybridization, and correlation effects within the complex are strongly involved in determining the spin state of the iron ion. By bridging molecular chemistry and solid state physics, this study provides first steps towards a joint analysis of the properties of iron-based catalysts from first principles.

A multifunctional metal-organic framework nanosystem disrupts redox homeostasis for synergistic therapy

Synergistic therapies of photodynamic therapy (PDT) and chemodynamic therapy (CDT) via metal-organic frameworks (MOF) for cancer treatment have recently attracted a lot of attentions because of the limitations of insufficient reactive oxygen species (ROS) in single-modality approaches. However, few studies explored on the use of increased ROS synergized with chemotherapy (CT) to address the issue of inadequate anti-tumor efficacy in single-modality regimens. Here, the desired cascade nanoplatforms (noted as MOF(Cu)@Dox-PL NPs) were fabricated by a solvothermal method using tetrakis (4-carboxyphenyl) porphyrin (TCPP) and zirconyl(di)chloride octahydrate (ZrOCl2·8H2O) as raw material, followed by Cu2+ introduced into the porphyrin ring and doxorubicin (DOX) loaded into the nanoframework. In addition, the nanoparticles (NPs) were electrostatically and hydrophobically coated with phospholipid (PL) to improve the biocompatibility of the nanosystems. Singlet oxygen (1O2) was created by the MOF(Cu)@Dox-PL NPs to disturb intracellular redox equilibrium. The acidic microenvironment in cancer cells may cause the prior release of DOX, which encourages the production of hydrogen peroxide (H2O2). And the doped Cu2+ could deplete overexpressed reduced glutathione (GSH) to produce hydroxyl radicals (·OH) by catalyzing H2O2, further causing redox dyshomeostasis. In vivo experiments revealed that MOF(Cu)@Dox-PL nanosystem possessed good biosafety and a compelling therapeutic effect in 4T1 tumor-bearing mice. As a novel nanosystem, MOF(Cu)@Dox-PL NPs showed great potential in synergistic therapy based on redox dyshomeostasis for improving anti-tumor efficacy with high specificity.

Kinetics of chromium(V)-oxo and chromium(IV)-oxo porphyrins: Reactivity and mechanism for sulfoxidation reactions

In this work, chromium(IV)-oxo porphyrins [CrIV(Por)(O)] (2) (Por = porphyrin) were produced either by oxidation of [CrIII(Por)Cl] (1) with iodobenzene diacetate or visible light photolysis of porphyrin‑chromium(III) chlorates. Subsequent oxidation of 2 with silver perchlorate gave chromium(V)-oxo porphyrins [CrV(Por)(O)](ClO4) (3) in three porphyrin ligands, including 5,10,15,20-tetramesitylporphyrin(TMP, a), 5,10,15,20-tetrakis(2,6-difluorophenyl)porphyrin(TDFPP, b), and 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (TPFPP, c). Complexes 2 and 3 reacted with thioanisoles to produce the corresponding sulfoxides, and their kinetics of sulfoxidation reactions with a series of aryl methyl sulfides(thioanisoles) were studied in organic solutions. Chromium(V)-oxo porphyrins are several orders of magnitudes more reactive than chromium(IV)-oxo species, and representative second-order rate constants (kox) for the oxidation of thioansole are (0.40 ± 0.01) M−1 s−1 (3a), and (2.82 ± 0.20) × 102 M−1 s−1 (3b), and (2.20 ± 0.01) × 103 M−1 s−1 (3c). The order of reactivity for 2 and 3 follows TPFPP > TDFPP > TMP, in agreement with the electrophilic nature of metal-oxo complexes. Hammett analyses indicate significant charge transfer in the transition states for oxidation of para-substituted thioanisoles by [CrV(Por)(O)]+. The ρ+ constants are −1.69 for 3a, −2.63 for 3b, and − 2.89 for 3c, respectively, mirror values found previously for related metal-oxo species. A mechanism involving the electrophilic attack of the CrV-oxo at sulfides to form a sulfur cation intermediate in the rate-determining step is suggested. Competition studies with chromium(III) porphyrin chloride and PhI(OAc)2 gave relative rate constants for oxidations of competing thioanisoles that closely match ratios of absolute rate constants from chromium(V)-oxo species, which are true oxidants under catalytic conditions.

Cobalt(III)- and rhodium(III)-porphyrin complexes for the effective degradation of fentanyl: Biological inactivation and mechanistic insights

Cobalt(III) and rhodium(III) complexes containing the water-soluble porphyrin ligand meso-tri(4-sulfonatophenyl)mono(4-carboxyphenyl)porphine (C1S3TPP), [Rh(C1S3TPP)]Nax•nH2O (1) and [Co(C1S3TPP)]Nax•nH2O (2) were prepared from the direct reaction of free porphyrin and metal chloride salts in refluxing MeOH/DMF or EtOH/H2O. Compounds 1 and 2 were characterized using UV–vis and 1H NMR spectroscopies, and high-resolution mass spectrometry. Cell culture based assays of opioid receptor activation showed that while the rhodium complex reduced fentanyl opioid activity 113-fold to an IC50 value of 1.7 μM, the cobalt complex reduced fentanyl activity by 160-fold to an IC50 value of 2.4 μM. An oxidative mechanism for fentanyl breakdown is proposed.

Evidence of carbon-supported porphyrins pyrolyzed for the oxygen reduction reaction keeping integrity

Fe(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (FeTPP) and Co(III) 5,10,15,20-(tetraphenyl)porphyrin chloride (CoTPP) were adsorbed on carbon Vulcan and studied as electrocatalysts for the oxygen reduction reaction (ORR) before and after pyrolysis. The pyrolysis process was also simulated through ab initio molecular dynamic simulations and the minimum energy path for the O2 dissociation after the interaction with the metal center of the FeTPP and CoTPP were calculated. After the pyrolysis the FeTPP showed the best performances reducing O2 completely to H2O with increased limiting current and lower overpotential. Tafel slops for the various catalysts did not change after the pyrolytic process suggesting that the mechanism for the ORR is not affected by the heat treatment. TEM images, X-ray diffraction, XPS spectroscopy, 57Fe Mössbauer, and DFT simulations, suggest that there is no breakdown of the macrocyclic complex at elevated temperatures, and that the macro cyclic geometry is preserved. Small variations in the Metal-O2 (M-O2) binding energies and the M–N bond length were observed which is attributed to the dispersive interaction between the macrocycles and the irregular surface of the Vulcan substrate induced by the heat treatment and causing better interaction with the O2 molecule. The theoretical strategy herein applied well simulate and explain the nature of the M–N–C active sites and the performances towards the ORR.

Synthesis and in vitro analysis of novel gallium tetrakis(4-methoxyphenyl)porphyrin and its long-acting nanoparticle as a potent antimycobacterial agent

Bacterial heme uptake pathways offer a novel target for antimicrobial drug discovery. Recently, gallium (Ga) porphyrin complexes were found to be effective against mycobacterial heme uptake pathways. The goal of the current study is to build on this foundation and develop a new Ga(III) porphyrin and its nanoparticles, formulated by a single emulsion-evaporation technique to inhibit the growth of Mycobacterium avium complex (MAC) with enhanced properties. Gallium 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin chloride (GaMeOTP) was synthesized from 5,10,15,20-tetrakis(4-methoxyphenyl)porphyrin and GaCl3. GaMeOTP showed enhanced antimicrobial activity against MAC104 and some clinical M. avium isolates. The synthesized Ga(III) porphyrin antimicrobial activity resulted in the overproduction of reactive oxygen species. Our study also demonstrated that F127 nanoparticles encapsulating GaMeOTP exhibited a smaller size than GaTP nanoparticles and a better duration of activity in MAC-infected macrophages compared to the free GaMeOTP. The nanoparticles were trafficked to endosomal compartments within MAC-infected macrophages, likely contributing to the antimicrobial activity of the drug.

Multienzyme-like Reactivity Cooperatively Impairs Glutathione Peroxidase 4 and Ferroptosis Suppressor Protein 1 Pathways in Triple-Negative Breast Cancer for Sensitized Ferroptosis Therapy.

Ferroptosis is a recently discovered route of regulated cell death that offers the opportunities for the treatment of chemotherapy-resistant tumor indications, but its efficacy can be affected by the glutathione peroxidase 4 (GPX4) and ferroptosis suppressor protein 1 (FSP1) antioxidant mechanisms, posing significant challenges for its clinical translation. In this study, we report a Cu-tetra(4-carboxyphenyl)porphyrin chloride(Fe(III)) (Cu-TCPP(Fe)) metal organic framework (MOF)-based nanosystem for the efficient incorporation of Au nanoparticles (NPs) and RSL3, which can demonstrate enzyme-like activities to universally suppress the antiferroptotic pathways in tumor cells for amplifying ferroptotic damage. Herein, Cu-TCPP(Fe) MOF nanosheets were integrated with Au NPs via in situ nucleation and loaded with RSL3 via π-π stacking, which were eventually modified with polyethylene glycol (PEG) and iRGD for tumor-targeted drug delivery. Specifically, the Au NPs can demonstrate glucose oxidase-like activities for efficient glucose depletion, thus disrupting the pentose phosphate pathway to impede reduced glutathione (GSH) biosynthesis and prevent the recycling of coenzyme Q10 (CoQ10) to CoQ10H2, while Cu species can oxidize GSH into oxidized glutathione (GSSG). These nanocatalytic activities can lead to the simultaneous inhibition of the GPX4/GSH and FSP1/CoQ10H2 pathways and cooperate with the GPX4-deactivating function of RSL3 to cause pronounced ferroptotic damage, thereby providing a strong rationale for the application of ferroptosis therapy in the clinic.

Carbon monoxide activation of delayed rectifier potassium currents of human cardiac fibroblasts through diverse pathways.

To identify the effect and mechanism of carbon monoxide (CO) on delayed rectifier K+ currents (IK) of human cardiac fibroblasts (HCFs), we used the whole-cell mode patch-clamp technique. Application of CO delivered by carbon monoxide-releasing molecule-3 (CORM3) increased the amplitude of outward K+ currents, and diphenyl phosphine oxide-1 (a specific IK blocker) inhibited the currents. CORM3-induced augmentation was blocked by pretreatment with nitric oxide synthase blockers (L-NG-monomethyl arginine citrate and L-NG-nitro arginine methyl ester). Pretreatment with KT5823 (a protein kinas G blocker), 1H-[1,-2,-4] oxadiazolo-[4,-3-a] quinoxalin-1-on (ODQ, a soluble guanylate cyclase blocker), KT5720 (a protein kinase A blocker), and SQ22536 (an adenylate cyclase blocker) blocked the CORM3 stimulating effect on IK. In addition, pretreatment with SB239063 (a p38 mitogen-activated protein kinase [MAPK] blocker) and PD98059 (a p44/42 MAPK blocker) also blocked the CORM3’s effect on the currents. When testing the involvement of S-nitrosylation, pretreatment of N-ethylmaleimide (a thiol-alkylating reagent) blocked CO-induced IK activation and DL-dithiothreitol (a reducing agent) reversed this effect. Pretreatment with 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)-21H,23H porphyrin manganese (III) pentachloride and manganese (III) tetrakis (4-benzoic acid) porphyrin chloride (superoxide dismutase mimetics), diphenyleneiodonium chloride (an NADPH oxidase blocker), or allopurinol (a xanthine oxidase blocker) also inhibited CO-induced IK activation. These results suggest that CO enhances IK in HCFs through the nitric oxide, phosphorylation by protein kinase G, protein kinase A, and MAPK, S-nitrosylation and reduction/oxidation (redox) signaling pathways.

Visible-LED-light-driven photocatalytic synthesis of N-heterocycles mediated by a polyoxometalate-containing mesoporous zirconium metal-organic framework

A mesoporous metal-organic framework with photothermal properties, namely PCN-222, was solvothermally synthesized from meso-tetra(4-carboxyphenyl)porphyrin and zirconium chloride employing both benzoic acid (BA) and trifluoroacetic acid (TFA) as modifiers. The MOF material subsequently served as a porous support for a polyoxometalate (POM), H3PW12O40, via a facile impregnation method which rendered a novel porous POM@PCN-222 composite. The solid was characterized by FT-IR, PXRD, SEM/EDX, TGA/DSC, ICP-OES, UV–Vis DRS, cyclic voltammetry (CV), and BET surface area. The one-pot synthesis of N-heterocycles (pyridine derivatives) was investigated utilizing the hybrid material via one-pot pseudo four-component reaction between aromatic aldehydes, methyl acetoacetate and ammonium acetate promoted under visible LED light irradiation in the presence of molecular oxygen as green oxidant. Products were selectively formed in good yields in the presence of the recyclable heterogeneous solid. Remarkably, POM@PCN-222 showed a superior performance for this procedure as compared to both unfunctionalized MOF and POM. The photosensitizer and photothermal properties of the porphyrin linkers combined with Lewis acidic sites derived from PW12 and Zr6-nodes were responsible for the observed excelling performance. To understand the mechanism, control investigations, electron paramagnetic resonance (EPR) analysis and FT-IR reaction monitoring were performed. The work discloses, for the first time, a simple and environmentally friendly approach for the direct production of pyridines via one-pot thermo-photocatalytic approach using a novel POM-modified MOF in the absence of any chemical additive.

Thermal Stability Kinetics and Shelf Life Estimation of the Redox-Active Therapeutic and Mimic of Superoxide Dismutase Enzyme, Mn(III) meso-Tetrakis(N-ethylpyridinium-2-yl)porphyrin Chloride (MnTE-2-PyPCl5, BMX-010).

Mn(III) meso-tetrakis(N-ethylpyridinium-2-yl)porphyrin chloride (MnTE-2-PyPCl5, BMX-010, and AEOL10113) is among the most studied superoxide dismutase (SOD) mimics and redox-active therapeutics, being currently tested as a drug candidate in a phase II clinical trial on atopic dermatitis and itch. The thermal stability of active pharmaceutical ingredients (API) is useful for estimating the expiration date and shelf life of pharmaceutical products under various storage and handling conditions. The thermal decomposition and kinetic parameters of MnTE-2-PyPCl5 were determined by thermogravimetry (TG) under nonisothermal and isothermal conditions. The first thermal degradation pathway affecting Mn-porphyrin structural integrity and, thus, activity and bioavailability was associated with loss of ethyl chloride via N-dealkylation reaction. The thermal stability kinetics of the N-dealkylation process leading to MnTE-2-PyPCl5 decomposition was investigated by using isoconversional models and artificial neural network. The new multilayer perceptron (MLP) artificial neural network approach allowed the simultaneous study of ten solid-state kinetic models and showed that MnTE-2-PyPCl5 degradation is better explained by a combination of various mechanisms, with major contributions from the contraction models R1 and R2. The calculated activation energy values from isothermal and nonisothermal data were about 90 kJ mol–1 on average and agreed with one another. According to the R1 modelling of the isothermal decomposition data, the estimated shelf life value for 10% decomposition (t90%) of MnTE-2-PyPCl5 at 25°C was approximately 17 years, which is consistent with the high solid-state stability of the compound. These results represent the first study on the solid-state decomposition kinetics of Mn(III) 2-N-alkylpyridylporphyrins, contributing to the development of this class of redox-active therapeutics and SOD mimics and providing supporting data to protocols on purification, handling, storage, formulation, expiration date, and general use of these compounds.

Significantly boosted oxygen electrocatalysis with cooperation between cobalt and iron porphyrins.

Developing electrocatalysts for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is of great importance. Herein, Co tetrakis(pentafluorophenyl)porphyrin (Co-P) and Fe chloride tetrakis(pentafluorophenyl)porphyrin (Fe-P) were loaded on carbon nanotubes (CNTs) for combining the electrocatalytic advantages of both Co-P and Fe-P. The resultant (Co-P)0.5(Fe-P)0.5@CNT composite displayed significantly boosted activity for the selective four-electron ORR with a half-wave potential of 0.80 V versus reversible hydrogen electrode (RHE) and for the OER with a potential of 1.65 V versus RHE to obtain 10 mA cm-2 current density in 0.1 M KOH. A Zn-air battery assembled from (Co-P)0.5(Fe-P)0.5@CNT exhibited a small charge-discharge voltage gap of 0.74 V at 2 mA cm-2, a high power density of 174.5 mW cm-2 and a good rechargeable stability (>120 cycles).

Enzyme-Free Tandem Reaction Strategy for Surface-Enhanced Raman Scattering Detection of Glucose by Using the Composite of Au Nanoparticles and Porphyrin-Based Metal-Organic Framework.

In this work, an S hybrid nanosheet with multiple functions is synthesized by in situ modification of gold nanoparticles (AuNPs) onto two-dimensional (2D) metalloporphyrinic metal-organic framework (MOF) (Cu-tetra(4-carboxyphenyl)porphyrin chloride(Fe(III)), designated as AuNPs/Cu-TCPP(Fe). Cu-TCPP(Fe) nanosheets contribute peroxidase-like activity, and AuNPs have glucose oxidase (GOx) mimicking performance, which induce the cascade catalysis reactions to convert glucose into hydrogen peroxide (H2O2), and then, by using AuNP catalysis, H2O2 oxidizes the no Raman-active leucomalachite green (LMG) into the Raman-active malachite green (MG). Simultaneously, in the presence of AuNPs, sensitive and selective surface-enhanced Raman scattering (SERS) determination of glucose can be achieved. The bioenzyme-free SERS assay based on such AuNPs/Cu-TCPP(Fe) nanosheets is used for detection of glucose in saliva, showing good recovery from 96.9 to 100.8%. The work paves a new way to design a nanozyme-based SERS protocol for biomolecule analysis.

Polyacrylic acid/polyethylene glycol hybrid antifouling interface for photoelectrochemical immunosensing of MDA-MB-231 cells using BiOBr/FeTPPCl/BiOI co-sensitized composite as matrix

An ultrasensitive photoelectrochemical (PEC) antifouling immunosensor was proposed using BiOBr/FeTPPCl/BiOI as matrix and polyacrylic acid (PAA)/polyethylene glycol (PEG) as hybrid antifouling interface for MDA-MB-231 detection. An indium tin oxide (ITO) electrode was successively modified with bismuth oxybromide (BiOBr) with layered crystal structure, which was sensitized with tetraphenyl iron(Ⅲ) porphyrin chloride (FeTPPCl) to widen the absorption range of visible light, and decorated with bismuth oxyiodide (BiOI) nanosheets to improve the PEC response. The joint action of PAA and PEG could offset the adsorption of non-specific proteins on the immunosensing interface for obtaining good antifouling performance. Based on the specific interaction of sialic acid (SA) on the cytomembrane with 3-aminophenylboronic acid (APBA), and the synergistic antifouling effect of PEG and PAA, a simple PEC immunosensing method was developed for the quantitative determination of MDA-MB-231 cells. This proposed antifouling PEC immunosensor exhibited a wide linear range (1 × 102 ∼ 1 × 106 cells·mL-1) and a low detection limit (30 cells·mL-1). The development of antibody-free immunosensors may improve the application for the diagnosis of human breast cancer.

Fused Metalloporphyrin Thin Film with Tunable Porosity via Chemical Vapor Deposition.

Porous and highly conjugated multiply fused porphyrin thin films are prepared from a fast and single-step chemical vapor deposition approach. While the solution-based coupling of porphyrins is usually undertaken at room temperature, the gas phase reaction of nickel(II) 5,15-(diphenyl)porphyrin and iron(III) chloride (FeCl3) is investigated for temperatures as high as 200 °C. Helium ion and atomic force microscopy, supported by weight and thickness measurements, shows a drastic decrease of the fused porphyrin thin film’s density accompanied by the formation of a mesoporous morphology upon increase of the reaction temperature. The increase of the film’s porosity is attributed to formation of a greater amount of HCl (originated from both the oxidative coupling and chlorination reactions) and the release of gaseous FeCl3 byproducts, i.e., Cl2, at higher deposition temperatures. In addition, high resolution mass spectrometry reveals that increase of the reaction temperature promotes a higher degree of conjugation of the fused porphyrins chains, which ensures that high electronic conductivities are maintained along with high porosity. The method reported herein could enable the engineering of fused porphyrin thin films in sensing and catalytic devices.

Base-Promoted C–O Bond Cleavage of Primary Alcohols by Iridium(III) Porphyrin Chloride

Various Ir(por)-benzyls and Ir(por)-alkyls (por = porphyrinato dianion ligand) were successfully synthesized with benzyl and 1° alkyl alcohols by C–O bond cleavage with Ir(ttp)(CO)Cl (ttp = 5,10,15...

Facile synthesis of large-area ultrathin two-dimensional supramolecular nanosheets in water

Synthesizing large-area ultrathin two-dimensional (2D) nanostructures in aqueous media has received considerable increasing attention but remains a big challenge. Herein, we report a facile method for the synthesis of two unprecedented large-area ultrathin 2D supramolecular nanosheets via ionic self-assembly in water. Upon consideration of electrostatic interaction and repulsive effect, deprotonated tetrakis(4-carboxyphenyl)porphyrin (TCPP) or Fe(III) tetra(4-carboxyphenyl)porphine chloride (TCPP(Fe)) as connection vertex and protonated bis(2-dimethylaminoethyl) ether (BDMAEE) unit as bridging edge connect with each other to form few-layer 2D nanosheet with a thickness of ~ 1.8–1.9 nm, while the lateral size can close to one hundred micrometers. Moreover, the well-dispersed 2D TCPP(Fe)-BDMAEE with heme-like active center displays intrinsic peroxidase-like catalytic activity, which can be used to detect hydrogen peroxide. The present facile strategy highlights new opportunities in constructing large-area ultrathin 2D supramolecular nanomaterials and paves the avenue to expand their potential applications.