Antioxidant Polymers with Enhanced Neuroprotection Against Insulin Fibrillation

Lipoic acid (LA) and dihydrolipoic acid (DHLA) are well established antioxidants to scavenge reactive oxygen species (ROS). However, they are carboxylates with ≈4.7 pKa making them negatively charged at physiological pH (7.4) reducing their passive diffusion through cell membranes. LA is known to be capable of reducing protein fibrillation. Incorporation of LA and especially DHLA in polymer side chains are scarce. Herein, the first examples of the anti-amyloidogenic effect of LA and DHLA incorporated into the side-chain of a block copolymer with a water-soluble poly(polyethylene glycol methyl ether methacrylate) (PPEGMA) segment are presented. The resultant polymers show improved ROS scavenging activity and improved ability to reduce insulin fibrillation compared to free LA and DHLA. Furthermore, the resultant polymers are also capable of disintegrating preformed insulin firbrils. Interestingly, polymers with dihydro-lipoate moieties showed 93% free radical scavenging activity with 91% anti-fibrillating efficacies for insulin protein confirmed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay and Thioflavin T (ThT) dye binding study, respectively. Further, the antioxidant polymers increase the cell viability against fibrillar insulin aggregates that may be involved in the etiology of several diseases. Overall, this work reveals that antioxidant polymer-based therapeutic agents can serve as a powerful modulation strategy for developing novel drugs in future against amyloid-related disorders.     

Sunlight-Induced In Situ Isomerization of Both Ligands in a Mixed-Ligand Coordination Polymer: From Photosalient to Photoinert Crystals

Reaction of Zn(NO₃)₂ ⋅ 6H₂O, maleic acid (H₂mal) and trans-4-(1-naphthylvinyl)pyridine (trans-nvp) in the dark results in the formation of a one-dimensional coordination polymer (1D CP) [Zn(mal)(trans-nvp)] ( 1 ), which is photosalient in nature. The crystals of 1 pop violently under UV light and moderately in sunlight, and generate cyclobutane ligands. However, the same reaction mixture kept in visible light exhibits the rare example of in situ isomerization of both ligands: cis-trans transformation of maleate and trans-cis isomerization of the nvp ligands, and subsequent formation of another 1D CP [Zn(fum)(cis-nvp)₂(H₂O)₂] ( 2 , H₂fum=fumaric acid), which is found to be photoinert. Thus, altering the reaction condition from dark to visible light gives rise to photosalient to photoinert crystals.     

Synthesis,characterization and arsenate binding events of new mononuclear copper(II) complexes

Two new mononuclear copper (II) complexes [Cu(L)(H₂O)Cl] (1) and [Cu(L)(H₂O)(SCN)] (2) (HL = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol) have been synthesized and characterized in order to investigate their binding interaction with arsenate ions. Complexes 1 and 2 were synthesized by performing reaction of CuCl₂·2H₂O or CuCl₂·2H₂O/NH₄SCN, respectively, with HL using Et₃N as mild base in MeOH solution at room temperature, and characterized by employing a number of analytical techniques, for example, elemental analysis, molar electrical conductivity, FTIR, UV–Vis and mass spectrometry. Their structures, optimized at DFT/B3LYP/6-311G level, show that the copper atom in 1 and 2 exhibits a distorted square pyramidal geometry. In H₂O/MeOH (3:1; v/v) solution, complexes 1 and 2 were examined for their binding affinity towards arsenate ions. The UV–Vis spectroscopic results specify that the arsenate group binds with 1 and 2 in 1:1 M ratio. The UV–Vis titration data were successfully utilized to calculate the binding constants of arsenate-bound Cu(II) complexes, and the values are found to be 1.723 × 10⁴ M^?1 and 2.161 × 10⁴ M^?1, corresponding to 1/AsO₄^3? and 2/AsO₄^3? assemblies, respectively.     

Microwave-Assisted Green Synthesis of Carbon Quantum Dots Derived from Calotropis Gigantea as a Fluorescent Probe for Bioimaging

Journal of Fluorescence - An eco-friendly, cost-effective, and convenient approach for synthesizing biocompatible fluorescent carbon quantum dots (CQDs) from the leaf extract of the medicinal plant...     

Design and Synthesis of ZnII‐Coordination Polymers Anchored with NSAIDs: Metallovesicle Formation and Multi‐drug Delivery

A series of coordination polymers synthesized from a bis‐pyridyl linker, namely 4,4′‐azopyridine ( L ), selected non‐steroidal‐anti‐inflammatory drugs (NSAIDs), namely diclofenac ( Dic ), ibuprofen ( Ibu ), flurbiprofen ( Flu ), mefenamic acid ( Mefe ), and naproxen ( Nap ), and Zn(NO₃)₂ were characterized by single crystal X‐ray diffraction. One of the coordination polymers, namely CP3 derived from Flu , was able to form metallovesicles in DMSO, DMSO/H₂O and DMSO/DMEM (biological media) as revealed by TEM, AFM and DLS. Metallovesicle formation by CP3 was further supported by loading a fluorescent dye, namely calcein, as well as an anti‐cancer drug, doxorubicin hydrochloride ( DOX ), as revealed by UV‐vis and emission spectra, and fluorescence microscopy. DOX ‐loaded metallovesicles of CP3 ( DOX@CP3‐vesicle ) could be delivered in vitro to a highly aggressive human breast cancer cell line, namely MDA‐MB‐231, as revealed by MTT and cell migration assays, and also cell imaging performed under laser scanning confocal microscope (LSCM). Thus, a proof of concept for developing a multi‐drug delivery system derived from a metallovesicle for delivering an anti‐cancer drug to cancer cells is demonstrated for the first time.     

Palladium-catalysed direct arylations of NH-free pyrrole and N-tosylpyrrole with aryl bromides

The palladium-catalysed direct coupling of aryl halides with pyrroles provides a greener access to arylated pyrroles than more classical couplings such as Suzuki, Stille or Negishi reactions. However, so far, NH-free pyrrole and N-tosylpyrrole gave disappointing results for such couplings either in terms of regioselectivity of the arylation, catalyst loading or substrate scope. The reactivity of both NH-free pyrrole and N-tosylpyrrole was studied, and the tosylated pyrrole led to higher yields of coupling products due to better conversions of the aryl bromides. A range of aryl bromides undergo regioselective coupling at C2 of N-tosylpyrrole in moderate to good yields using 1 mol % [Pd(Cl(C₃H₅)]₂ as the catalyst, KOAc as the base in DMAc.     

Thermal analysis of some analogous thiols and their palladium complexes

Differential thermal analysis (DTA) and thermogravimetric analysis (TGA) have been conducted on several analogous heterocyclic thiols and their complexes with palladium in air, over the temperature range of 25-800 degrees . A rough order of thermal stability of the ligands and the complexes has been deduced.     

Immobilization of a copper-Schiff base complex in a Y-zeolite matrix: Preparation,chromogenic behavior and catalytic oxidation

A new zeolite-immobilized hybrid catalyst Cu(MeO-salen)-NaY has been prepared by encapsulating [Cu(MeO-salen)(H₂O)] (1) [where MeO-salenH₂ = N,N′-(ethylene)-bis-(3-methoxysalicylaldimine)] in a NaY zeolite matrix. The hybrid material has been characterized by UV–Vis, IR and EPR spectrometry and by X-ray powder diffraction analysis. The pristine complex [Cu(MeO-salen)(H₂O)] (1) has also been synthesized and characterized by all the spectrometric methods mentioned above as well as by single crystal X-ray diffraction analysis. A brilliant color change (green to red) has been observed when the complex [Cu(MeO-salen)(H₂O)] (1) is immobilized in the zeolitic matrix. X-ray powder diffraction analysis of Cu(MeO-salen)-NaY reveals that the structural integrity of the mother zeolite in the hybrid material remains intact upon immobilization of the complex. The coordination geometry around the Cu^II ion in [Cu(MeO-salen)(H₂O)] is found to be square pyramidal. Spectroscopic studies indicate that coordination geometry of the complex undergoes a significant distortion when it is entrapped in the zeolite cavity. While Cu(MeO-salen)-NaY shows excellent catalytic activity and product selectivity in the hydroxylation of phenol and 1-naphthol, [Cu(MeO-salen)(H₂O)] (1) remains virtually catalytically inactive in these reactions.     

Ordered dispersion of ZnO quantum dots in SiO2 matrix and its strong emission properties

ZnO nanoparticles in the form of quantum dots (QDs) have been dispersed in SiO₂ matrix using StÖber method to form ZnO QDs-SiO₂ nanocomposites. Addition of tetraethyl orthosilicate (TEOS) to an ethanolic solution of ZnO nanoparticles produces random dispersion. On the other hand, addition of ZnO nanoparticles to an already hydrolyzed ethanolic TEOS solution results in a chain-like ordered dispersion. The photoluminescence spectra of the as-grown nanocomposites show strong emission in the ultraviolet region. When annealed at higher temperature, depending on the sample type, these show strong red or white emission. Interestingly, when the excitation is removed, the orderly dispersed ZnO QDs-SiO₂ composite shows a very bright blue fluorescence visible by naked eyes for few seconds indicating their promise for display applications. The emission property has been explained in the light of structure–property relationship.     

Synchronization of chaotic modulated time delay networks in presence of noise

We study the constructive role of noises in a Lorenz system with functional delay. The effect of delay can change the dynamics of the system to a chaotic one from its steady state. Induced synchronization with white and colored (red and green) noises are observed between two identical uncoupled systems and enhancement of synchrony is also observed with unidirectional coupling. We investigate both the phenomena in a globally coupled network in the presence of white and color noises.