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Langmuir : the ACS Journal of Surfaces... Aug 2022Microbe-catalyzed surface modification is a promising method for the production of special targeting nanomaterials. A bacterium-selective material can be obtained by...
Microbe-catalyzed surface modification is a promising method for the production of special targeting nanomaterials. A bacterium-selective material can be obtained by investigating the microbe-catalyzed mineralization of proteins. Herein, a novel method was fabricated for the biosynthesis of FeS-decorated porphyrin-protein clusters (P-CA@BE) ()-catalyzed bio-Fe(III) reduction and bio-sulfidation of porphyrin (P), caffeic acid (CA), and protein [bovine serum albumin (BSA)] assemblies. The assembly (P-CA@BSA) was identified by spectroscopic methods. Next, the P-CA@BSA assembly was transferred into FeS-decorated porphyrin-protein clusters (P-CA@BE) catalyzed by . There are partial β-folding proteins in P-CA@BE, which selectively recognize () and show different antibacterial properties against and . Results demonstrate that the -catalyzed mineralization of the porphyrin-protein assembly is an effective method for the biosynthesis of -sensitive metal-protein clusters.
Topics: Bacterial Proteins; Escherichia coli; Ferric Compounds; Ferrous Compounds; Porphyrins; Serum Albumin, Bovine; Staphylococcus aureus
PubMed: 35980392
DOI: 10.1021/acs.langmuir.2c00964 -
Bioorganic & Medicinal Chemistry Letters Apr 2022Bacterial heme uptake pathways offer a novel target for antimicrobial drug discovery. Recently, gallium (Ga) porphyrin complexes were found to be effective against...
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 GaCl. 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.
Topics: Anti-Bacterial Agents; Anti-Infective Agents; Gallium; Heme; Mycobacterium avium Complex; Nanoparticles; Porphyrins
PubMed: 35219822
DOI: 10.1016/j.bmcl.2022.128645 -
International Journal of Molecular... Dec 2022In this study, organo-inorganic nanohybrids with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin...
In this study, organo-inorganic nanohybrids with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (, M = 2H, Zn(II) and Pd(II)) into gadolinium layered hydroxide (). The combination of powder XRD, CHNS analysis, FT-IR, EDX, and TG confirmed the layered structure of the reaction products. The basal interplanar distances in samples were 22.3-22.6 Å, corresponding to the size of an intercalated tetrapyrrole molecule. According to SEM data, hybrids consisted of individual lamellar nanoparticles 20-50 nm in thickness. The enzyme-like activity of individual constituents, and sulfoporphyrins , and , and hybrid materials, was studied by chemiluminescence analysis using the ABAP/luminol system in phosphate buffer solution. All the individual porphyrins exhibited dose-dependent antioxidant properties with respect to alkylperoxyl radicals at pH 7.4. The intercalation of free base porphyrin into the preserved the radical scavenging properties of the product. Conversely, in samples containing Zn(II) and Pd(II) complexes, the antioxidant properties of the porphyrins changed to dose-dependent prooxidant activity. Thus, an efficient approach to the design and synthesis of advanced materials with switchable enzyme-like activity was developed.
Topics: Porphyrins; Gadolinium; Spectroscopy, Fourier Transform Infrared; Hydroxides
PubMed: 36499698
DOI: 10.3390/ijms232315373 -
The Journal of Organic Chemistry Apr 2022The synthesis of porphyrin and chlorin derivatives has attracted significant attention due to their numerous applications. Herein, we report an environment friendly...
The synthesis of porphyrin and chlorin derivatives has attracted significant attention due to their numerous applications. Herein, we report an environment friendly oxidant- and catalyst-free electrooxidative cross-coupling approach for multiple coupling reactions to synthesize C-N, C-O, and C-S substituted porphyrin and chlorin derivatives. For C-N cross-coupling reactions, diaminated porphyrins were obtained as the main products, while using 4-bromo-2,6-dimethyl aniline resulted in monoaminated product. Similarly, electrochemical catalysis of porphyrins with phenol and thiophene produced -disubstituted porphyrins in moderate yields under a smaller current. Chlorins were also applicable, and 20-substituted products were efficiently produced regioselectively. To the best of our knowledge, this work represents the first example of electrooxidative C-X cross-coupling of porphyrins and chlorins.
Topics: Catalysis; Oxidants; Porphyrins
PubMed: 35302772
DOI: 10.1021/acs.joc.2c00031 -
ACS Nano Jan 2024Porphyrins and their derivatives are widely used as photosensitizers and sonosensitizers in tumor treatment. Nevertheless, their poor water solubility and low chemical...
Near-Infrared-II-Activatable Self-Assembled Manganese Porphyrin-Gold Heterostructures for Photoacoustic Imaging-Guided Sonodynamic-Augmented Photothermal/Photodynamic Therapy.
Porphyrins and their derivatives are widely used as photosensitizers and sonosensitizers in tumor treatment. Nevertheless, their poor water solubility and low chemical stability reduce their singlet oxygen (O) yield and, consequently, their photodynamic therapy (PDT) and sonodynamic therapy (SDT) efficiency. Although strategies for porphyrin molecule assembly have been developed to augment O generation, there is scope for further improving PDT and SDT efficiencies. Herein, we synthesized ordered manganese porphyrin (SM) nanoparticles with well-defined self-assembled metalloporphyrin networks that enabled efficient energy transfer for enhanced photocatalytic and sonocatalytic activity in O production. Subsequently, Au nanoparticles were grown on the SM surface by anchoring the terminal alkynyl of porphyrin to form plasmonic SMA heterostructures, which showed the excellent near-infrared-II (NIR-II) region absorption and photothermal properties, and facilitated electron-hole pair separation and transfer. With the modification of hyaluronic acid (HA), SMAH heterostructure nanocomposites exhibited good water solubility and were actively targeted to cancer cells. Under NIR-II light and ultrasound (US) irradiation, the SMAH generates hyperthermia, and a large amount of O, inducing cancer cell damage. Both and studies confirmed that the SMAH nanocomposites effectively suppressed tumor growth by decreasing GSH levels in SDT-augmented PDT/PTT. Moreover, by utilizing the strong absorption in the NIR-II window, SMAH nanocomposites can achieve NIR-II photoacoustic imaging-guided combined cancer treatment. This work provides a paradigm for enhancing the O yield of metalloporphyrins to improve the synergistic therapeutic effect of SDT/PDT/PTT.
Topics: Humans; Photochemotherapy; Manganese; Porphyrins; Gold; Photoacoustic Techniques; Metal Nanoparticles; Phototherapy; Nanoparticles; Neoplasms; Water; Cell Line, Tumor
PubMed: 38117769
DOI: 10.1021/acsnano.3c09011 -
Organic & Biomolecular Chemistry Jun 2023Porphyrin-fullerene composite systems are attracting great attention as photodynamic agents; however, water-soluble derivatives are still scarce. Herein, we prepared...
Porphyrin-fullerene composite systems are attracting great attention as photodynamic agents; however, water-soluble derivatives are still scarce. Herein, we prepared noncovalently a lipid membrane-incorporated porphyrin-fullerene composite system with relative stability in aqueous solution. As in the case of porphyrin-fullerene composite systems in nonpolar solvents, efficient formation of singlet oxygen occurred photoinduced energy transfer between porphyrin and fullerene as the predominant pathway in the photodynamic activity under the hydrophobic conditions of the lipid membranes, resulting in enhanced photodynamic activity toward Colon26 and HeLa cells compared with the individual porphyrin and fullerene components. Furthermore, the porphyrin-fullerene composite system exhibited high selectivity toward HeLa cells over normal mouse fibroblast L929 cells.
Topics: Animals; Mice; Humans; Porphyrins; Fullerenes; HeLa Cells; Energy Transfer; Lipids
PubMed: 37248815
DOI: 10.1039/d3ob00027c -
Langmuir : the ACS Journal of Surfaces... Mar 2022Porphyrin assemblies have controllable morphology, high biocompatibility, and good optical properties and were widely used in biomedical diagnosis and treatment. With...
Porphyrin assemblies have controllable morphology, high biocompatibility, and good optical properties and were widely used in biomedical diagnosis and treatment. With the development of DNA biotechnology, combining DNA with porphyrin assemblies can broaden the biological applications of porphyrins. Porphyrin assemblies can serve as nanocarriers for DNA, although the fundamental interactions between them are not well understood. In this work, zinc meso-tetra(4-pyridyl)porphyrin (ZnTPyP) assemblies were prepared in the presence of various surfactants and at different pH values, yielding a variety of aggregation forms. Among them, the hexagonal stacking form exposes more pyridine substituents, and the hydrogen bonding force between the substituents and the DNA bases allows the DNA to be quickly adsorbed on the surface of the assemblies. The effects of DNA sequence and length were systematically tested. In particular, the adsorption of duplex DNA was less efficient compared to the adsorption of single-stranded DNA. This fundamental study is useful for the further combination of DNA and porphyrin assemblies to prepare new functional hybrid nanomaterials.
Topics: Adsorption; DNA; Metalloporphyrins; Nanostructures; Oligonucleotides; Porphyrins; Zinc Compounds
PubMed: 35258306
DOI: 10.1021/acs.langmuir.2c00108 -
Biomaterials Science Feb 2023Porphyrinic covalent organic frameworks (COFs) have emerged as prospective materials in photodynamic and photothermal sterilization. However, it is still a great...
Acrylate-functionalized porphyrin-covalent organic framework for bacterial-targeted and reaction-enhanced synergistic phototherapy/chemotherapy toward sterilization and wound healing.
Porphyrinic covalent organic frameworks (COFs) have emerged as prospective materials in photodynamic and photothermal sterilization. However, it is still a great challenge to construct an efficient COF-based sterilizing agent with good photothermal and photodynamic properties and bacterial targeting ability. Herein, we report a multifunctional porphyrin-COF for bacterial-targeted and reaction-enhanced synergistic phototherapy/chemotherapy for sterilization and wound healing. The ordered crystal structure of the porphyrin-COF not only effectively avoids the self-aggregation-induced quenching of the porphyrin monomer, but also facilitates the storage and transport of singlet oxygen. The acrylate substituent in the other monomer serves as a bacterial targeting moiety and the reaction site with the sulfhydryl group of the bacterial surface protein a Michael addition reaction, thus fixing the bacteria on the surface of COF and making them lose the colonization ability. Furthermore, the bonding of COF and bacteria further amplifies the therapeutic efficiency of phototherapy. Therefore, the developed multifunctional sterilization platform not only provides a new strategy for the design of novel bactericidal materials but also broadens the biological applications of COF-based materials.
Topics: Metal-Organic Frameworks; Porphyrins; Phototherapy; Bacteria; Wound Healing
PubMed: 36648453
DOI: 10.1039/d2bm01723g -
ChemMedChem Feb 2022Porphyrin selectively shows tumour accumulation and has attracted attention as a carrier molecule for drug delivery systems (DDS). Porphyrin has two functional sites...
Porphyrin selectively shows tumour accumulation and has attracted attention as a carrier molecule for drug delivery systems (DDS). Porphyrin has two functional sites termed the meso- and β-positions. In previous work, meso-porphyrin derivatives with an alkyl group were found to exhibit greater accumulation in human breast cancer cells (MCF-7). To identify the correlation between porphyrin accumulation and functional porphyrin positions of other functional groups, the accumulation of porphyrin derivatives with a phenyl group was investigated. The β-porphyrin derivative with a phenyl group showed higher accumulation in MCF-7 cells and greater affinity for albumin than the meso-porphyrin derivative. The results of density functional theory (DFT) calculations suggest that the β-porphyrin derivative with a phenyl group had higher planarity across the total structure than the meso-porphyrin derivative. It was concluded that the greater planarity of the β-porphyrin derivative with a phenyl group might lead to superior MCF-7 cell accumulation.
Topics: Density Functional Theory; Drug Delivery Systems; Humans; MCF-7 Cells; Molecular Structure; Porphyrins
PubMed: 34859953
DOI: 10.1002/cmdc.202100636 -
Biometals : An International Journal on... Dec 2023Photodynamic therapy (PDT) is a promising technique for the treatment of various diseases. In this sense, the singlet oxygen quantum yield (Φ) is a physical-chemical...
Photodynamic therapy (PDT) is a promising technique for the treatment of various diseases. In this sense, the singlet oxygen quantum yield (Φ) is a physical-chemical property that allows to stablish the applicability of a potential photosensitizers (PS) as a drug for PDT. In the herein report, the Φ of three photosensitizers was determined: metal-free tetrahydroxyphenyl porphyrin (THPP), THPP-Zn and the THPP-V metal complexes. Their biological application was also evaluated. Therefore, the in vitro study was carried out to assess their biological activity against Escherichia coli. The metal-porphyrin complexes exhibited highest activities against the bacterial strain Escherichia coli. at the highest concentration (175 μg/mL) and show better activity than the free base ligand (salts and blank solution). Results indicated a relation between Φ and the inhibitory activity against Escherichia coli, thus, whereas higher is the Φ, higher is the inhibitory activity. The values of the Φ and the inhibitory activity follows the tendency THPP-Zn > THPP > THPP-V. Furthermore, quantum chemical calculations allowed to gain deep insight into the electronic and optical properties of THPP-Zn macrocycle, which let to verify the most probable energy transfer pathway involved in the singlet oxygen generation.
Topics: Porphyrins; Photosensitizing Agents; Photochemotherapy; Singlet Oxygen; Coordination Complexes; Escherichia coli; Zinc
PubMed: 37344742
DOI: 10.1007/s10534-023-00514-9