scholarly journals THERMOSTABLE EPOXIDE COMPOSITION BASED ON AROMATIC DIAMIDODISULFOIMIDE RESIN

ASJ. ◽  
2021 ◽  
Vol 1 (51) ◽  
pp. 35-40
Author(s):  
F. Mammadaliyeva
Keyword(s):  
High Reactivity ◽  
Oxirane Ring ◽  
Aprotic Solvents ◽  
Large Excess ◽  
Triethylbenzylammonium Chloride ◽  
Brown Color

New epoxide oligomers have been obtained by the interaction of p-phenylenediaminediamidodisulfoimide with a large excess of epichlorohydrin in the presence of triethylbenzylammonium chloride. The synthesized epoxide oligomers are a viscous product of dark brown color, well soluble in aprotic solvents (DMFA, DMSO), as well as in acetone and dioxane. These cooligomers include hydroxynaphthylene and phenylenediimine structural fragments possessing solubility, meltability and high reactivity in the reactions with the oxirane ring of epoxide compounds in composition of macromolecules. The cooligomer of m-phenylenediamine with α-naphthol was used for curing of diamidodisulfoimide resin.

Role of Aluminium on the Microstructure and Corrosion Behaviour of Magnesium Prepared by Powder Metallurgy Method

2020 ◽  
Vol 17 (3) ◽  
pp. 8206-8213
Author(s):  
J. Alias
Keyword(s):  
Corrosion Resistance ◽  
Powder Metallurgy ◽  
Corrosion Behaviour ◽  
Corrosion Current ◽  
Optical Microscope ◽  
High Reactivity ◽  
Aluminium Content ◽  
Powder Metallurgy Method ◽  
X Ray Diffraction ◽  
Promising Development

Much research on magnesium (Mg) emphasises creating good corrosion resistance of magnesium, due to its high reactivity in most environments. In this study, powder metallurgy (PM) technique is used to produce Mg samples with a variation of aluminium (Al) composition. The effect of aluminium composition on the microstructure development, including the phase analysis was characterised by optical microscope (OM), scanning electron microscopy (SEM) and x-ray diffraction (XRD). The mechanical property of Mg sample was performed through Vickers microhardness. The results showed that the addition of aluminium in the synthesised Mg sample formed distribution of Al-rich phases of Mg17Al12, with 50 wt.% of aluminium content in the Mg sample exhibited larger fraction and distribution of Al-rich phases as compared to the 20 wt.% and 10 wt.% of aluminium content. The microhardness values were also increased at 20 wt.% and 50 wt.% of aluminium content, comparable to the standard microhardness value of the annealed Mg. A similar trend in corrosion resistance of the Mg immersed in 3.5 wt.% NaCl solution was observed. The corrosion behaviour was evaluated based on potentiodynamic polarisation behaviour. The corrosion current density, icorr, is observed to decrease with the increase of Al composition in the Mg sample, corresponding to the increase in corrosion resistance due to the formation of aluminium oxide layer on the Al-rich surface that acted as the corrosion barrier. Overall, the inclusion of aluminium in this study demonstrates the promising development of high corrosion resistant Mg alloys.

Bimetallic Radical Redox-Relay Catalysis for the Isomerization of Epoxides to Allylic Alcohols

2019 ◽  
Author(s):  
Ke-Yin Ye ◽  
Terry McCallum ◽  
Song Lin
Keyword(s):  
Ring Opening ◽  
High Reactivity ◽  
Hydrogen Atom Transfer ◽  
Organic Radicals ◽  
Epoxide Ring ◽  
Allylic Alcohols ◽  
Epoxide Ring Opening ◽  
Bond Forming ◽  
Co Catalysts ◽  
The Rich

Organic radicals are generally short-lived intermediates with exceptionally high reactivity. Strategically, achieving synthetically useful transformations mediated by organic radicals requires both efficient initiation and selective termination events. Here, we report a new catalytic strategy, namely bimetallic radical redox-relay, in the regio- and stereoselective rearrangement of epoxides to allylic alcohols. This approach exploits the rich redox chemistry of Ti and Co complexes and merges reductive epoxide ring opening (initiation) with hydrogen atom transfer (termination). Critically, upon effecting key bond-forming and -breaking events, Ti and Co catalysts undergo proton-transfer/electron-transfer with one another to achieve turnover, thus constituting a truly synergistic dual catalytic system.<br>

A Plug-and-Play Approach for the De Novo Generation of Dually Functionalised Bispecifics

2019 ◽  
Author(s):  
Antoine Maruani ◽  
Peter A. Szijj ◽  
Calise Bahou ◽  
João C. F. Nogueira ◽  
Stephen Caddick ◽  
...  
Keyword(s):  
De Novo ◽  
Therapeutic Index ◽  
Antibody Fragments ◽  
Bispecific Antibodies ◽  
Full Potential ◽  
Mechanisms Of Resistance ◽  
Large Excess ◽  
Chemical Methods ◽  
New Class ◽  
Novel Approach

<p>Diseases are multifactorial, with redundancies and synergies between various pathways. However, most of the antibody-based therapeutics in clinical trials and on the market interact with only one target thus limiting their efficacy. The targeting of multiple epitopes could improve the therapeutic index of treatment and counteract mechanisms of resistance. To this effect, a new class of therapeutics emerged: bispecific antibodies.</p><p>Bispecific formation using chemical methods is rare and low yielding and/or requires a large excess of one of the two proteins to avoid homodimerisation. In order for chemically prepared bispecifics to deliver their full potential, high-yielding, modular and reliable cross-linking technologies are required. Herein, we describe a novel approach not only for the rapid and high-yielding chemical generation of bispecific antibodies from native antibody fragments, but also for the site-specific dual functionalisation of the resulting bioconjugates. Based on orthogonal clickable functional groups, this strategy enables the assembly of functionalised bispecifics with controlled loading in a modular and convergent manner.</p>

Iridium-Catalyzed Silylation of C-H bonds in Unactivated Arenes: A Sterically-Encumbered Phenanthroline Ligand Accelerates Catalysis Enabling New Reactivity

2019 ◽  
Author(s):  
Caleb Karmel ◽  
Zhewei Chen ◽  
John Hartwig
Keyword(s):  
High Activity ◽  
Functional Group ◽  
Activity Analysis ◽  
High Reactivity ◽  
High Yield ◽  
Phen Ligand ◽  
Mechanistic Studies ◽  
Phenanthroline Ligand ◽  
First Time ◽  
New System

We report a new system for the silylation of aryl C-H bonds. The combination of [Ir(cod)(OMe)]<sub>2</sub> and 2,9-Me<sub>2</sub>-phenanthroline (2,9-Me<sub>2</sub>phen) catalyzes the silylation of arenes at lower temperatures and with faster rates than those reported previously, when the hydrogen byproduct is removed, and with high functional group tolerance and regioselectivity. Inhibition of reactions by the H<sub>2</sub> byproduct is shown to limit the silylation of aryl C-H bonds in the presence of the most active catalysts, thereby masking their high activity. Analysis of initial rates uncovered the high reactivity of the catalyst containing the sterically hindered 2,9-Me<sub>2</sub>phen ligand but accompanying rapid inhibition by hydrogen. With this catalyst, under a flow of nitrogen to remove hydrogen, electron-rich arenes, including those containing sensitive functional groups, undergo silylation in high yield for the first time, and arenes that underwent silylation with prior catalysts react over much shorter times with lower catalyst loadings. The synthetic value of this methodology is demonstrated by the preparation of key intermediates in the synthesis of medicinally important compounds in concise sequences comprising silylation and functionalization. Mechanistic studies demonstrate that the cleavage of the aryl C-H bond is reversible and that the higher rates observed with the 2,9-Me<sub>2</sub>phen ligand is due to a more thermodynamically favorable oxidative addition of aryl C-H bonds.

Isotopically Labeled Desthiobiotin Azide (isoDTB) Tags Enable Global Profiling of the Bacterial Cysteinome

2019 ◽  
Author(s):  
Patrick R. A. Zanon ◽  
Lisa Lewald ◽  
Stephan M. Hacker
Keyword(s):  
Binding Sites ◽  
Bacterial Resistance ◽  
Mevalonate Pathway ◽  
Rapid Development ◽  
High Reactivity ◽  
Functional Importance ◽  
Essential Proteins ◽  
Covalent Inhibitors ◽  
Druggable Targets ◽  
Covalent Ligands

Rapid development of bacterial resistance has led to an urgent need to find new druggable targets for antibiotics. In this context, residue-specific chemoproteomic approaches enable proteome-wide identification of binding sites for covalent inhibitors. Here, we describe isotopically labeled desthiobiotin azide (isoDTB) tags that are easily synthesized, shorten the chemoproteomic workflow and allow an increased coverage of cysteines in bacterial systems. We quantify 59% of all cysteines in essential proteins in <i>Staphylococcus aureus</i> and discover 88 cysteines with high reactivity, which correlates with functional importance. Furthermore, we identify 268 cysteines that are engaged by covalent ligands. We verify inhibition of HMG-CoA synthase, which will allow addressing the bacterial mevalonate pathway through a new target. Overall, a comprehensive map of the bacterial cysteinome is obtained, which will facilitate the development of antibiotics with novel modes-of-action.

A New Species of Rhacophorus Genus (Amphibia: Anura: Rhacophoridae: Rhacophorinae) from Van Ban District, Lao Cai Province, Northern Vietnam

2019 ◽  
Vol 26 (6) ◽  
pp. 325-334
Author(s):  
Ivan I. Kropachev ◽  
Nikolai L. Orlov ◽  
Hoa Thi Ninh ◽  
Tao Thien Nguyen
Keyword(s):  
New Species ◽  
Distal Part ◽  
Slender Body ◽  
Northern Vietnam ◽  
Lao Cai ◽  
Lower Ratio ◽  
A New Species ◽  
Green Triangle ◽  
Brown Color

We describe a new species of the Rhacophorus genus, which differs from all species known in Asia by the combination of characters. It strongly differs also from small and middle-sized species of Rhacophorus sensu lato: Rhacophorus calcaneus Smith, 1924, Leptomantis cyanopunctatus (Manthey et Steiof, 1998), Rhacophorus hoabinhensis Nguyen, Pham, Nguyen, Ninh et Ziegler, 2017, Rhacophorus hoanglienensis Orlov, Lathrop, Murphy et Ho, 2001, Zhangixalus jarujini (Matsui et Panha, 2006), Rhacophorus laoshan Mo, Jiang, Xie et Ohler, 2008, Rhacophorus pardalis Günther, 1858, Rhacophorus rhodopus Liu et Hu, 1960, Rhacophorus robertingeri Orlov, Poyarkov, Vassilieva, Ananjeva, Nguyen, Sang, and Geissler, 2012, Leptomantis robinsonii (Boulenger, 1903), Rhacophorus spelaeus Orlov, Gnophanxay, Phimminith, and Phomphoumy, 2010, Rhacophorus translineatus Wu, 1977, Rhacophorus turpes Smith, 1940, Rhacophorus vampyrus Rowley, Le, Thi, Stuart et Hoang, 2010, Rhacophorus viridimaculatus Ostroshabov, Orlov et Nguyen, 2013 by having brown color with two green dorsolateral stripes starting at the groin level and connecting through the distal part of eyelid with green triangle on the head, slender body and head, lower ratio HW/HL 0.86, lower HW/SVL 0.28 and lower ratio HL/SVL 0.32.

A Study on the Rearrangement of Dialkyl 1-Aryl-1-hydroxymethylphosphonates to Benzyl Phosphates

2020 ◽  
Vol 24 (4) ◽  
pp. 465-471 ◽  
Author(s):  
Zita Rádai ◽  
Réka Szabó ◽  
Áron Szigetvári ◽  
Nóra Zsuzsa Kiss ◽  
Zoltán Mucsi ◽  
...  
Keyword(s):  
Quantum Chemical ◽  
Room Temperature ◽  
Phase Transfer ◽  
One Pot ◽  
Substrate Dependence ◽  
Triethylbenzylammonium Chloride ◽  
One Step ◽  
The Pudovik Reaction ◽  
The One ◽  
Solid Liquid

The phospha-Brook rearrangement of dialkyl 1-aryl-1-hydroxymethylphosphonates (HPs) to the corresponding benzyl phosphates (BPs) has been elaborated under solid-liquid phase transfer catalytic conditions. The best procedure involved the use of triethylbenzylammonium chloride as the catalyst and Cs2CO3 as the base in acetonitrile as the solvent at room temperature. The substrate dependence of the rearrangement has been studied, and the mechanism of the transformation under discussion was explored by quantum chemical calculations. The key intermediate is an oxaphosphirane. The one-pot version starting with the Pudovik reaction has also been developed. The conditions of this tandem transformation were the same, as those for the one-step HP→BP conversion.

Solvation of ions by dipolar aprotic solvents and water. A CNDO/2 study

1985 ◽  
Vol 50 (11) ◽  
pp. 2493-2508 ◽  
Author(s):  
Petr Kyselka ◽  
Zdeněk Havlas ◽  
Ivo Sláma
Keyword(s):  
Binary Mixtures ◽  
Quantum Chemical ◽  
Chemical Method ◽  
Molecular Structures ◽  
Dimethyl Sulphoxide ◽  
Ternary Mixtures ◽  
Aprotic Solvents ◽  
Quantum Chemical Method ◽  
Solvation Of Ions ◽  
Dipolar Aprotic Solvents

Solvation of Li+, Be2+, Na+, Mg2+, and Al3+ ions has been studied in binary mixtures with dimethyl sulphoxide, dimethylformamide, acetonitrile and water, and in ternary mixtures of the organic solvents with water. The CNDO/2 quantum chemical method was used to calculate the energies of solvation, molecular structures and charge distributions for the complexes acetonitrile...ion (1:1, 2:1, 4:1), dimethyl sulphoxide...ion (1:1), dimethylformamide...ion (1:1), and acetonitrile (dimethyl sulphoxide, dimethylformamide)...ion...water (1:1:1).

Oxidation of (1-hydroxybenzyl)ferrocene and its derivatives substituted in phenyl ring with bis(triphenylsilyl) chromate

1982 ◽  
Vol 47 (12) ◽  
pp. 3375-3380 ◽  
Author(s):  
Jaroslav Holeček ◽  
Karel Handlíř ◽  
Milan Nádvorník ◽  
Milan Vlček
Keyword(s):  
Linear Dependence ◽  
Rate Constants ◽  
Oxidation Rate ◽  
Phenyl Ring ◽  
Equilibrium Constants ◽  
Aprotic Solvents ◽  
Protonation Equilibrium ◽  
Oxidation Of Alcohols ◽  
Hammett Σ Constants ◽  
Sulphuric Acid Medium

Kinetics have been studied of oxidation of (1-hydroxybenzyl)ferrocenes substituted in phenyl ring with bis(triphenylsilyl) chromate in benzene solutions as well as protonation of these alcohols in sulphuric acid medium. Logarithms of the oxidation rate constants (kobs, 20-40 °C) and those of the protonation equilibrium constants (KR+, 25 °C) show linear dependence on the Hammett σ constants, the ρ constant values being -0.86 to -0.40 and -2.50, respectively. These negative values suggest that the both processes are influenced by the same effects and confirm the mechanism proposed earlier for oxidation of alcohols with ferrocenyl substituent by action of bis(triphenylsilyl) chromate in aprotic solvents.

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