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As a mussel-inspired material, polydopamine (PDA), possesses many properties, such as a simple preparation process, good biocompatibility, strong adhesive property, easy functionalization, outstanding photothermal conversion efficiency, and strong quenching effect. PDA has attracted increasingly considerable attention because it provides a simple and versatile approach to functionalize material surfaces for obtaining a variety of multifunctional nanomaterials. In this review, recent significant research developments of PDA including its synthesis and polymerization mechanism, physicochemical properties, different nano/microstructures, and diverse applications are summarized and discussed. For the sections of its applications in surface modification and biomedicine, we mainly highlight the achievements in the past few years (2016-2019). The remaining challenges and future perspectives of PDA-based nanoplatforms are discussed rationally at the end. This timely and overall review should be desirable for a wide range of scientists and facilitate further development of surface coating methods and the production of PDA-based materials.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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The black-brown biopigment eumelanin screens the harmful ultraviolet (UV) radiation in the human skin. In industry, the absorption of plastics in the UV range is improved by the inclusion of additives. Our work reports an evaluation of the biopigment eumelanin as a nature-inspired additive for polymers to improve their UV-absorption. Eumelanin, being non-toxic and produced by natural sources, represents an interesting candidate for sustainable plastic additives. We fabricated eumelanin-including films of commercial linear low-density polyethylene (LLDPE), a plastic ubiquitous in packaging applications. The films were obtained by melt-compounding and compression molding. The melanin free acid treatment (MFA) was used to enhance the biopigment dispersion in the films. We observed that amounts of eumelanin as low as 0.8% wt. bring about an increase of the UV absorption up to one order of magnitude in the UVA range. We also assessed the effect of eumelanin on the film stability under prolonged UV irradiation: the biopigment proved to work both as UV-absorption enhancer but also as a photo-prooxidant, as inferred by thermogravimetric analysis (TGA) and infrared (IR) spectroscopy.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

29/9/2021 News Can You Really Do Chemisty Experiments About 3131-52-0

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A process for the preparation of 5,6-disubstituted indoles in which a 4-5-disubstituted-2,beta-nitrostyrene is subjected to a reductive cyclization in the presence of a water soluble dithionite salt.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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The single most misleading aspect of structure elucidation of naturally occurring biopolymers lies in the removal and preparation of the sample for chemical and physical composition analysis. We present a method for the application of electron spectroscopy for chemical analysis (ESCA or XPS (X-ray photoelectron spectroscopy)) to elucidate the chemical composition and organic functional group distribution within one type of biopolymer, eumelanin. Qualitative and quantitative elemental analyses were calibrated with model compounds. In addition, the relative proportions of the different carbon, oxygen, and nitrogen functionalities within these eumelanin precursor model compounds and the polymers generated from them are presented. The ESCA results showed that eumelanin has structural and compositonal components consisting of both aromatic and partially oxidized units of 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid.

A reaction mechanism is the microscopic path by which reactants are transformed into products. Each step is an elementary reaction. In my other articles, you can also check out more blogs about 3131-52-0

Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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Under biologically relevant conditions, co-oxidation of 5,6-dihydroxyindole (1) and 5,6-dihydroxyindole-2-carboxylic acid (2) affords, in addition to a complex mixture of homopolymers of the two indoles, a small but significant amount of a cross-coupling product which was isolated as the tetra-O-acetyl derivative and assigned the biindolyl structure 3.Key Words: 5,6-dihydroxyindoles; oxidative polymerisation; eumelanins; melanogenesis

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

26-Sep-2021 News Extended knowledge of 3131-52-0

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As a rule, o-semiquinones decay through disproportionation leading to equimolar amounts of catechol and o-quinone products. However, the o-semiquinone 1S generated by pulse radiolysis oxidation of the eumelanin precursor 5,6-dihydroxyindole (1) decays with second-order kinetics to generate broad visible chromophores that are incompatible with the predicted absorption of 5,6-indolequinone (1Q). Using an integrated chemical, pulse radiolytic and computational approach as well as deuterium labeling, we show herein that 1S and related 5,6-dihydroxyindole semiquinones decay mainly by a free radical coupling mechanism. This conclusion was supported by the inverse kinetic isotope effect observed with deuterated 1S, the identification of unprecedented dihydrobiindole products by one-electron oxidation of 1, the good matching of simulated absorption profiles of free radical coupling products of 1S with experimental spectra, and a detailed computational analysis of the kinetics and thermodynamics of the disproportionation equilibrium and free radical coupling of 1S versus 1-1Q coupling. These results disclose, to the best of our knowledge, the first example of free radical dimerization of o-semiquinones outcompeting the classic disproportionation-driven catechol-quinone coupling and suggest that this hitherto unrecognized process may be of broader relevance than previously believed.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

26-Sep-2021 News Discovery of 3131-52-0

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The origin of pyrrole-2,3,5-tricarboxylic acid (PTCA), the most characteristic degradation product of melanins, was investigated by use of synthetic pigments prepared from the major biosynthetic precursors, 5,6-dihydroxyindole (DHI) and 5,6-dihydroxyindole-2-carboxylic acid (DHICA).Under the reported conditions, i.e. acidic permanganate, oxidative degradation of DHI- and DHICA-melanins afforded PTCA in 0.15 and 3.0percent w/w yield, respectively.A significant improvement of PTCA yields up to 7percent was obtained using alkaline hydrogen peroxide as the oxidising agent.Under these conditions pyrrole-2,3-dicarboxylic acid (PDCA) was also obtained in significant yields.Investigations of the oxidative degradation of some model indole obligomers (1-4) provided unambiguous evidence that PTCA may originate from 2-linked DHI-units in the pigment polymer as well as from DHICA-derived units, whereas PDCA arises from DHI-units not substituted at 2-position.Monitoring of the oxidation of dimer 1 to PTCA showed the intermediate formation of DHICA.Accordingly, a mechanistic route is proposed for the degradation of 2-substituted DHI-units in melanin polymer to PTCA, which also accounts for the observed yields of formation of the pyrrole acid from the model oligomers.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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The ubiquitous type-3 copper enzyme polyphenol oxidase (PPO) has found itself the subject of profound inhibitor research due to its role in fruit and vegetable browning and mammalian pigmentation. The enzyme itself has also been applied in the fields of bioremediation, biocatalysis and biosensing. However, the nature of PPO substrate specificity has remained elusive despite years of study. Numerous theories have been proposed to account for the difference in tyrosinase and catechol oxidase activity. The ?blocker residue? theory suggests that bulky residues near the active site cover CuA, preventing monophenol coordination. The ?second shell? theory suggests that residues distant (?8 A) from the active site, guide and position substrates within the active site based on their properties e.g., hydrophobic, electrostatic. It is also hypothesized that binding specificity is related to oxidation mechanisms of the catalytic cycle, conferred by coordination of a conserved water molecule by other conserved residues. In this review, we highlight recent developments in the structural and mechanistic studies of PPOs and consolidate key concepts in our understanding toward the substrate specificity of PPOs.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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Melanin, primarily responsible in humans for hair, eye and skin pigmentation, is produced by melanocytes through a process called melanogenesis. However, the abnormal accumulation of melanin causes dermatological problems such as cafe-au-lait macules ephelides (freckles), solar lentigo (age spots) and melasma, as well as cancer and vitiligo. Hence the regulation of melanogenesis is very important for treating hyperpigmentary disorders. Numerous antimelanogenic agents that target tyrosinase activity and/or stability, melanosome maturation, transfer and trafficking, or melanogenesis-related signaling pathways have been developed. This article reviews recent advances in research and development of human tyrosinase and melanogenesis-related signaling pathway inhibitors. Attempts have been made to provide a complete description of the mechanism of action of inhibitors on various melanogenesis signaling pathways.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles

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Understanding the interaction of metal ions with melanin structures is essential to know some intricate functions of this kind of compounds in the living systems. The coordination chemistry of vanadyl oxycation, VO(II), and copper, Cu(II), in a synthetic L-dopa melanin (SM) was investigated using electron paramagnetic resonance (EPR), Fourier transform infrared (FT IR) and ultraviolet-visible (UV-Vis) spectroscopy. The EPR and FT IR spectra indicated axially coordinated VO(II) ions bound to catecholate functional groups, and a fraction of the Cu(II) ions in a square planar structure partially coordinated to carboxylate functional groups. The resolved EPR perpendicular super hyperfine splitting constant, AN?, and the Cu(II) complex EPR parallel parameters g? and A? values indicated two magnetically equivalent nitrogen atoms in a plane with the coordination sphere, CuN2O2. The ultraviolet-visible (UV-Vis) spectra of solid samples indicate supramolecular structure constitution for the synthesized VO(II)SM and Cu(II)SM complexes.

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Reference:
Indole alkaloid derivatives as building blocks of natural products from Bacillus thuringiensis and Bacillus velezensis and their antibacterial and antifungal activity study,
Preparation of Indole Containing Building Blocks for the Regiospecific Construction of Indole Appended Pyrazoles and Pyrroles