Synthesis and biological evaluation of some heterocyclic scaffolds based on the multifunctional N-(4-acetylphenyl)-2-chloroacetamide

The chloroacetamide derivative, 1 , was used as a versatile precursor for the synthesis of various types of N-aryl-2-(benzothiazol-2-ylthio)acetamide derivatives. The reaction of 1 with 2-mercaptobenzothiazole followed by condensation reaction of the produced sulfide with phenylhydrazine, 2-cyanoacetohydrazide, and/or thiosemicarbazide furnished the conforming condensation products, 4 , 7 , and 10 , respectively. Treatment of the phenylhydrazone product, 4 , with Vilsmeier formylation reagent (POCl₃/DMF) yielded the corresponding 4-formylpyrazole derivative, 5 . The thiosemicarbazone product, 10 , was reacted with ethyl bromoacetate to furnish the thiazolin-4-one derivative, 11 . The substitution reactions of chloroacetamide derivative, 1 , with 2-mercapto-4,6-dimethylnicotinonitrile and 6-amino-2-mercaptopyrimidin-4-ol, were explored to identify the sulfide products, 14 and 17 . Cyclization of 14 into its corresponding thieno[2,3-b]pyridine compound, 15 , was performed using sodium ethoxide. The thiosemicarbazone, 10 , and sulfide derivative, 14 , were found to be the most potent antibacterial compounds against Escherichia coli and Staphylococcus aureus, exhibiting growth inhibitory activities of 80.8% and 91.7%, respectively. Moreover, the thiosemicarbazone, 10 , displayed the most significant antioxidant activity with inhibitory activity of 82.6%, which comes close to the antioxidant activity of L-ascorbic acid.     

Synthesis of diverse novel compounds with anticipated antitumor activities starting with biphenyl chalcone

The chalcone as (E)-1-([1,1′-biphenyl]-4-yl)-3-(3,4-dimethoxyphenyl)prop-2-en-1-one ( 3 ) was reacted with various active methylene compounds via Michael addition reaction under different conditions. In one hand, chalcone 3 reacted with isatin and glycine in one pot reaction via 1,3-dipolar cycloaddition reaction. On the other hand, chalcone 3 was also reacted with different N-nucleophiles via direct addition on the carbonyl group to award cyclic and/or acyclic products. Meanwhile, the reaction of chalcone 3 with S-benzylthiuronium chloride afforded the thio-Michael addition product. Chalcone 3 and 10 novel synthesized compounds were screened against two cell lines (HepG2 and MCF-7). Among of them, thiosemicarbazone 16 , oxime 14 and pyrimidine-2(1H)-thione 19 derivatives revealed an excellent activity against both cell lines (IC₅₀ values = 6.79-12.91 μM), whereas thiosemicarbazone 16 (6.79 ± 0.5 and 7.58 ± 0.6 μM) showed the highest activity.     

Fabrication and characterization of a novel wound scaffold based on polyurethane added with Channa striatus for wound dressing applications

Abstract

Wound healing is a complex process and it involves restoration of damaged skin tissues. Several wound dressings comprising naturally made substances are constantly investigated to assist wound healing. In this research, a new wound dressing based on polyurethane (PU) supplemented with essence of Channa striatus (CS) fish oil was made by electrospinning. Morphological study depicted the reduction in fiber diameter than PU with the addition of fish oil (0.552?±?0.109?μm for 8:1 v/v% and 0.519?±?0.196?μm 7:2 v/v%) than the pristine PU (0.971?±?0.205?µm). Fourier transform infrared spectroscopy (FTIR) analysis revealed the presence of fish oil in the composite as identified through increasing peak intensity. Fish oil resulted in the hydrophilic behavior (88?±?3 (8:1 v/v) and 70?±?6 (7:2 v/v)) as revealed in the contact angle analysis. Thermal gravimetric analysis (TGA) showed the superior thermal behavior of the wound dressing patch compared to the PU. Atomic force microscopy (AFM) analysis insinuated a decrease in the surface roughness of the pristine polyurethane with the added fish oil. Coagulation assays signified the delay in the blood clotting time portraying its anti-thrombogenic behavior. Hemolytic assay revealed the less toxic nature of the developed nanocomposites with the red blood cells (RBC’s) depicting its safety with blood. Hence, polyurethane nanofibers supplemented with fish oil made them as deserving candidates for wound dressing application.     

Bipolar Electrochemiluminescence Imaging: A Way to Investigate the Passivation of Silicon Surfaces

This work depicts the original combination of electrochemiluminescence (ECL) and bipolar electrochemistry (BPE) to map in real-time the oxidation of silicon in microchannels. We fabricated model silicon-PDMS microfluidic chips, optionally containing a restriction, and monitored the evolution of the surface reactivity using ECL. BPE was used to remotely promote ECL at the silicon surface inside microfluidic channels. The effects of the fluidic design, the applied potential and the resistance of the channel (controlled by the fluidic configuration) on the silicon polarization and oxide formation were investigated. A potential difference down to 6 V was sufficient to induce ECL, which is two orders of magnitude less than in classical BPE configurations. Increasing the resistance of the channel led to an increase in the current passing through the silicon and boosted the intensity of ECL signals. Finally, the possibility of achieving electrochemical reactions at predetermined locations on the microfluidic chip was investigated using a patterning of the silicon oxide surface by etched micrometric squares. This ECL imaging approach opens exciting perspectives for the precise understanding and implementation of electrochemical functionalization on passivating materials. In addition, it may help the development and the design of fully integrated microfluidic biochips paving the way for development of original bioanalytical applications.     

Synthesis and Characterization of Polyesters Based on Diethylketone Moiety

A new class of unsaturated polyesters based on diethylketone have been prepared by interfacial polymerization of 2,4-bis（4-hydroxybenzylidene）-3-pentanone（I） and 2,4-bis（4-hydroxy-3-methoxybenzylidene）-3-pentanone（II） with 4,4’-azodibenzoyl chloride and 3,3’-azodibenzoyl chloride at ambient temperature. The model compounds were synthesized by reaction of（I） and（II） with benzoyl chloride. The new monomers, model compounds and polyesters have been characterized by different spectral analyses. The polyesters have inherent viscosity of 0.55-0.80 d L/g and moderate number average molecular weight（Mn） in the range of 6150-7400 g/mol. Most of the compounds exhibited their solubility in aprotic solvents while partial solubility in various halogenated organic solvents was observed. The temperatures of 10% weight loss were high（225-330 °C） in nitrogen, indicating that these polyesters have excellent thermal stability. Doping with iodine dramatically raised the conductivity and produced brown colored semiconductive polymers with a maximum conductivity of 2.7 × 10-6 --1cm-1. Moreover, the morphological properties of selected example of polyesters were detected by SEM.     

Amino acid catalyzed neogenesis of carbohydrates: a plausible ancient transformation

Hexose sugars play a fundamental role in vital biochemical processes and their biosynthesis is achieved through enzyme-catalyzed pathways. Herein we disclose the ability of amino acids to catalyze the asymmetric neogenesis of carbohydrates by sequential cross-aldol reactions. The amino acids mediate the asymmetric de novo synthesis of natural L- and D-hexoses and their analogues with excellent stereoselectivity in organic solvents. In some cases, the four new stereocenters are assembled with almost absolute stereocontrol. The unique feature of these results is that, when an amino acid is employed as the catalyst, a single reaction sequence can convert a protected glycol aldehyde into a hexose in one step. For example, proline and its derivatives catalyze the asymmetric neogenesis of allose with >99 % ee in one chemical manipulation. Furthermore, all amino acids tested catalyzed the asymmetric formation of natural sugars under prebiotic conditions, with alanine being the smallest catalyst. The inherent simplicity of this catalytic process suggests that a catalytic prebiotic "gluconeogenesis" may occur, in which amino acids transfer their stereochemical information to sugars. In addition, the amino acid catalyzed stereoselective sequential cross-aldol reactions were performed as a two-step procedure with different aldehydes as acceptors and nucleophiles. The employment of two different amino acids as catalysts for the iterative direct aldol reactions enabled the asymmetric synthesis of deoxysugars with >99 % ee. In addition, the direct amino acid catalyzed C(2)+C(2)+C(2) methodology is a new entry for the short, highly enantioselective de novo synthesis of carbohydrate derivatives, isotope-labeled sugars, and polyketide natural products. The one-pot asymmetric de novo syntheses of deoxy and polyketide carbohydrates involved a novel dynamic kinetic asymmetric transformation (DYKAT) mediated by an amino acid.     

On the equivalence of acidic centers in H-beta zeolites tested by Fries rearrangement of phenyl acetate

The heterogeneously catalyzed liquid phase Fries rearrangement reaction of phenyl acetate was carried out on Beta zeolites reexchanged with different amounts of metal cations. The aim of this work was to determine the influence of the amount of Brønsted acid sites as the catalytic active centers on the conversion. Sodium and potassium ions as well as divalent calcium and zinc ions were used in the reexchange procedure. The conversion shows a linear dependency on the degree of ion reexchange following the theoretically expected values. So the results prove that the bridged hydroxyl groups are indeed the dominating active centers and that their strength seems to be independent of the degree of reexchange; consequently, their acidic strength should be identical. A special emphasis was placed on the reexchange with divalent metal ions. It was shown that one divalent ion is not able to replace two protons as is supposed to be necessary for the charge balance—so a 1:1 stoichiometry is needed to assume to explain the catalytic results.     

Synthesis,characterization, fluorescence and redox features of new <Emphasis Type="Italic">vic</Emphasis>-dioxime ligand bearing pyrene and its metal complexes

A new vic-dioxime ligand, N,N′-bis(aminopyreneglyoxime) (LH₂), and its copper(II), nickel(II) and cobalt(II) metal complexes were synthesized and characterized by elemental analyses, IR, UVVIS and ¹H and ¹³C NMR spectra (for the ligand). Mononuclear complexes were synthesized by a reaction of ligand (LH₂) and salts of Co(II), Ni(II), and Cu(II) in ethanol. The complexes have the metal-ligand ratio of 1: 2 and metals are coordinated by N,N′ atoms of vicinal dioximes. The ligand acts in a polydentate fashion bending through nitrogen atoms in the presence of a base, as do most vic-dioximes. Detection of a H-bonding in the Co(II), Ni(II), and Cu(II) complexes by IR revealed the square-planar MN₄ coordination of mononuclear complexes. Fluorescent properties of the ligand and its complexes arise from pyrene units conjugated with a vic-dioxime moiety. Fluorescence emission spectra of the ligand showed a drastic decrease in its fluorescence intensity upon metal binding. The electrochemical properties of the complexes were studied by the cyclic voltammetry technique. The nickel complex displayed an irreversible oxidation process while the copper complex exhibited a quasi-reversible oxidation and reduction processes based on the copper Cu(II)/Cu(III) and Cu(II)/Cu(I) couples, respectively.     

A branch and cut algorithm for the location-routing problem with simultaneous pickup and delivery

This paper addresses a location-routing problem with simultaneous pickup and delivery (LRPSPD) which is a general case of the location-routing problem. The LRPSPD is defined as finding locations of the depots and designing vehicle routes in such a way that pickup and delivery demands of each customer must be performed with same vehicle and the overall cost is minimized. We propose an effective branch-and-cut algorithm for solving the LRPSPD. The proposed algorithm implements several valid inequalities adapted from the literature for the problem and a local search based on simulated annealing algorithm to obtain upper bounds. Computational results, for a large number of instances derived from the literature, show that some instances with up to 88 customers and 8 potential depots can be solved in a reasonable computation time.