One-Pot Synthesis of Biologically Important Spiro-2-amino-4H-pyrans,Spiroacenaphthylenes, and Spirooxindoles Using DBU as a Green and Recyclable Catalyst in Aqueous Medium

We have reported DBU-catalyzed one-pot synthesis of biologically and pharmacologically important spiropyrans from condensation of malononitrile/ethyl cyanoacetate, 1,3-dicarbonyl compounds, and ninhydrin/acenaphthequinone/istain in good yields. This new protocol employing DBU, which is a green, recyclable, and inexpensive catalyst, offers advantages such as mild reaction conditions, short reaction times, and easy isolation of products. The structures have been confirmed by x-ray analysis.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Generalised strip-saturation zone models for piezoelectric strip weakened by non-centric semi-permeable crack

Meccanica - In this paper, we have proposed generalised strip-saturation zone models for non-centric semi-permeable straight hairline crack weakening a piezoelectric strip. Strip-saturation zone...     

2-Phosphaindolizines

Abstract

An overview of 2-phosphaindolizines, i.e. 1,3-azaphospholo[1,5-a]pyridines along with their 1-aza-, 3-aza- and 1,3-diaza analogues has been presented. It includes their methods of syntheses, characterization and reactions. Under reactions, electrophilic substitutions, N-alkylation, Diels-Alder (DA) reactions with the >C=P- functionality in the absence of the catalyst and also in the presence of the catalyst, other 1,2-additions across the >C=P- functionality, cheletropic cycloaddition of tetrachloro-o-benzoquinone (TCQ) with the phosphorus atom and co-ordination with the metal pentacarbonyls and other derivatives have been described.     

A mononuclear cobalt(II) hydroxo complex: synthesis,molecular structure,and reactivity studies

A novel Co(II) hydroxo complex Co{HB(3-^tBu-5-ⁱPrpz)₃}(OH) 4 {where HB(3-^tBu-5-ⁱPrpz)₃ = hydrotris(3-tert-butyl-5-isopropylpyrazol-l-yl)borate} has been prepared and its molecular structure has been determined by X-ray crystallography. This complex is mononuclear with distorted tetrahedral geometry. The reaction of CO₂ with Co{HB(3-^tBu-5-ⁱPrpz)₃}(OH) resulted in the formation of a μ-carbonato bridged binuclear complex [Co{HB(3-^tBu-5-ⁱPrpz)₃}]₂(CO₃) wherein the carbonate group is bound to both metal centers in an asymmetrical manner. In order to explore the role of labile metal complexes in promoting ester hydrolysis, complexes [Co{HB(3,5-ⁱPr₂pz)₃}]₂(OH)₂ and Co{HB(3-^tBu-5-ⁱPrpz)₃}(OH) have been used as catalysts in the hydrolysis of both carboxylate as well as phosphate esters. The product of 4-nitrophenylacetate hydrolysis with Co{HB(3-^tBu-5-ⁱPrpz)₃}(OH) was isolated as four coordinate Co{HB(3-^tBu-5-ⁱPrpz)₃}(OC₆H₄-4-NO₂) 6, whereas the reaction of 4-nitrophenyltrifluoroacetate with [Co{HB(3,5-ⁱPr₂pz)₃}]₂(OH)₂ resulted the formation of the six coordinate Co{HB(3,5-ⁱPr₂pz)₃}(OC₆H₄-4-NO₂)(MeCN)₂ species. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

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A glycan shield for bacterial sphingolipids

In this issue of Chemistry & Biology, Kinjo et al. (2008) propose that the addition of oligosaccharides to the core outer membrane glycosphingolipid in Sphingomonas spp. may be an adaptation that allows bacteria to evade recognition by Natural Killer T cells, thus suggesting a remarkable process of host/pathogen coevolution.     

Dye Degradation and Sulfur Oxidation of Methyl Orange and Thiophenol via Newly Designed Nanocomposite GQDs/NiSe-NiO Photocatalyst Under Homemade LED Light

Photocatalytic processes triggered by graphene-based photocatalysts under solar light have sparked interest as a new sort of instrument for solar chemical synthesis. Herein we investigated self-assembled graphene quantum dots (GQDs)/NiSe-NiO composite photocatalyst for organic transformation as well as dye degradation. The synthesized GQDs/NiSe-NiO composite photocatalyst has an excellent suitable band gap, high molar extinction coefficient, low toxicity and chemical/thermal stability. The GQDs/NiSe-NiO composite photocatalyst emerges as a new standard for sulfur oxidation and dye degradation reactions under homemade LED light with high yield.     

Peptide Cysteine Thiols Act as Photostabilizer of Avobenzone through Stabilizing the Transition State of Keto-Enol Tautomerization

Photostabilizers have been used to impart stability to an FDA-approved chemical UV-A filter avobenzone against the UV-A radiations and sunlight. The thiol group of glutathione plays a critical role in imparting the photostabilization activity of glutathione on avobenzone. The current report aims to evaluate the photostabilization activity of multiple thiols containing cysteine peptides on avobenzone. Cysteine-tripeptide and cysteine-pentapeptide were chemically synthesized and characterized using mass spectrometry. Synthetic peptides were assessed for their photostabilization activity on the enolic-form of the avobenzone under natural sunlight using UV spectroscopy in both protic and aprotic solvents. Unlike glutathione, which has pronounced activity in protic solvents, cysteine-pentapeptide exhibits similar photoprotection activity in both protic and aprotic solvents. Computational calculations using DFT suggest that peptide cysteine thiols may assist in the reversal of the photoketonization process of avobenzone thereby exhibiting the photoprotection activity to the enolic-form of avobenzone. Peptide cysteine thiols lower the activation energy barrier of keto-to-enol tautomerization of avobenzone by 30 kcal mol⁻¹ by assisting the proton shuttle through a six-membered transition state. The current report emphasizes the applications of peptide thiols in cosmetics and may help in the development of peptides as aesthetic medicines.     

Phase switching in Hindmarsh-Rose relay neurons

A system of Hindmarsh-Rose relay neurons with time delay coupling is considered in which the relay (central) neuron has an additional feedback term that represents the interaction activity with a local environment. The strength of environmental coupling with the central neuron plays an important role in inducing synchronization and de-synchronization between the outer neurons. The strength of feedback developed from the environmental coupling has created a gradual quenching in the oscillations of the central neuron. At a higher feedback coupling strength, oscillation of the central neuron is suppressed drastically and a transition from a regime of synchronization to out-of-phase synchronization take place between the oscillations of the two outer neurons.     

Microsphere based continuous-flow immunoassay in a microfluidic device for determination of clinically relevant insulin levels

This paper describes a miniaturized microsphere-based immunoassay integrated into a microfluidic device for rapid quantitation of insulin. Analysis of bionic pancreas studies have revealed that the rates of absorption of insulin analogs vary from patient to patient, and even within patients on different occasions. Thus development of an approach to monitor insulin continuously allows the pharmacokinetic characteristics of insulin analogs to be determined in real-time. The authors have developed a microsphere-based continuous flow assay in a microfluidic chip that allows for the detection of insulin within seconds with high sensitivity and specificity. The method was applied to near real-time monitoring of clinical samples. Calibration plot were established for different insulin analogs such as insulin aspart (Novolog), insulin lispro (Humalog), and regular human insulin (RHI) and the insulin detection limit was 0.26 ng.mL^?1 (44 pM). This sensitivity allows to detect the fasting insulin levels of T1D patients, which are reported in the range of 50–180 pM (0.3–1 ng.mL^?1), after treatment with subcutaneous insulin administration. This fast approach was also applied to sera collected in intervals from T1D patients after a bolus of insulin aspart delivery. The insulin profile obtained by this method is similar to the basal and peak insulin levels as determined using the standard non-continuous ELISA reference method. In our perception, this assay will improve healthcare by personalizing diagnostics for better clinical outcome and provide real-time feedback on sensing and actuation.

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Graphical abstract Schematic illustration of the microfluidic microsphere based Microfluidic Lab-On-Chip device for near real-time insulin monitoring.