Electronic properties of Chevrel phases by positron angular correlation

A comparative study of the Chevrel phases Mo₆S₈, Mo₆Se₈, PbMo₆S₈ and Cu_1.8Mo₆S₈ is made by the positron angular correlation technique at room temperature. Electronic properties like the number of conduction electrons per cluster, the density of states at the Fermi level, the electron effective masses and the Fermi velocities are obtained within the framework of the free electron model. The results are discussed in terms of available theoretical and other experimental data.     

Hofmann rearrangement of primary carboxamides and cyclic imides using DCDMH and application to the synthesis of gabapentin and its potential peptide prodrugs

Two protocols for the efficient transformation of aromatic as well as aliphatic primary carboxamides to the corresponding carbamates and aromatic as well as aliphatic cyclic imides to the corresponding anthranilic acid derivatives & amino acid derivatives, respectively, are described. We also developed a novel methodology to the multigram scale synthesis of gabapentin and (S)-pregabalin. The gabapentin methyl carbamate was converted to novel potential peptide prodrugs of gabapentin.     

Interpreting non-random signatures in biomedical signals with Lempel-Ziv complexity

Lempel-Ziv complexity (LZ) [J. Ziv, A. Lempel, On the complexity of finite sequences, IEEE Trans. Inform. Theory 22 (1976) 75-81] and its variants have been used widely to identify non-random patterns in biomedical signals obtained across distinct physiological states. Non-random signatures of the complexity measure can occur under nonlinear deterministic as well as non-deterministic settings. Surrogate data testing have also been encouraged in the past in conjunction with complexity estimates to make a finer distinction between various classes of processes. In this brief letter, we make two important observations (1) Non-Gaussian noise at the dynamical level can elude existing surrogate algorithms namely: Phase-randomized surrogates (FT) amplitude-adjusted Fourier transform (AAFT) and iterated amplitude-adjusted Fourier transform (IAAFT). Thus any inference nonlinear determinism as an explanation for the non-randomness is incomplete (2) Decrease in complexity can be observed even across two linear processes with identical auto-correlation functions. The results are illustrated with a second-order auto-regressive process with Gaussian and non-Gaussian innovations. AR(2) processes have been used widely to model several physiological phenomena, hence their choice. The results presented encourage cautious interpretation of non-random signatures in experimental signals using complexity measures.     

Active Intermediates in Copper Nitrite Reductase Reactions Probed by a Cryotrapping‐Electron Paramagnetic Resonance Approach

Redox active metalloenzymes catalyse a range of biochemical processes essential for life. However, due to their complex reaction mechanisms, and often, their poor optical signals, detailed mechanistic understandings of them are limited. Here, we develop a cryoreduction approach coupled to electron paramagnetic resonance measurements to study electron transfer between the copper centers in the copper nitrite reductase (CuNiR) family of enzymes. Unlike alternative methods used to study electron transfer reactions, the cryoreduction approach presented here allows observation of the redox state of both metal centers, a direct read‐out of electron transfer, determines the presence of the substrate/product in the active site and shows the importance of protein motion in inter‐copper electron transfer catalyzed by CuNiRs. Cryoreduction‐EPR is broadly applicable for the study of electron transfer in other redox enzymes and paves the way to explore transient states in multiple redox‐center containing proteins (homo and hetero metal ions).     

Expedition on surface adsorption of N-nitrosodiethylamine from rubber fumes on blue phosphorene sheets – a first-principles insight

In recent days, humans are easily exposed to many work-related health issues. N-nitrosodiethylamine (NDE), which is considered to be a harmful carcinogenic agent released from rubber-based industries imparts a long-lasting effect on human health and immunity system. The current research investigates the ability of the two-dimensional nanomaterial, blue phosphorene nanosheet (BPNS) to detect the presence of NDE in the environment. Besides, the electronic and structural characteristics of BPNS are initially explored and NDE target vapour is permitted to interact with the chief component, BPNS. We have also designed blue phosphorene device to study the adsorption properties of NDE vapours based on current–voltage characteristics. The adsorption attributes are accounted for the target vapour adsorbed chief component, the results suggest that BPNS can be employed in detecting NDE vapours.     

Reversal Diastereoselectivity Between the Organomagnesium and Organolithium Reagents on Chiral N-Tert-Butylsulfinylaldimines for the Preparation of Chiral Amines

The asymmetric synthesis of both the enantiomer of chiral amines from the single chiral source of N-tert-butylsulfinylaldimines (3) by simply changing the organometallic reagents through diastereoselective addition. An efficient enantioselective synthesis of chiral amines including (S)-3-methyl-1-(2-piperidin-1-yl-phenyl)butyl amine (6a), a key intermediate to prepare antidiabetic drug repaglinide (1), is reported.     

Synthesis and Crystal Structure of an Anionic Linear Trinuclear Copper(Ⅱ) Complex Containing 2-Thenoyltrifluoroacetonato and Acetato Ligands

A novel anionic trinuclear linear copper(Ⅱ) complex {[Et3NH][Cu1.5(CH3COO)-(TTA)3]}2(1,TTA = 2-thenoyltrifluoroacetonate) has been synthesized in a direct reaction involving copper(Ⅱ) acetate monohydrate,TTA and excess triethylamine base in dichloromethane solvent.Green colored X-ray quality crystals of 1 were grown from n-hexane solvent at room temperature.The data were collected at 100 K.Compound 1 crystallizes in the monoclinic P21/n space group(a = 11.2141(8),b = 19.0965(13),c = 17.3680(14) ,β = 90.225(2)°,V = 3719.3(5) 3,Mr = 1840.14,Dc = 1.643 Mg/m3,F(000) = 1866,μ = 1.129 mm-1 and Z = 2).The asymmetric unit of 1 contains two copper atoms,one of which lies on a crystallographic inversion center with 50% occupancy.     

Correction to: Effect of Basil antioxidant additive on the performance,combustion and emission characteristics of used cooking oil biodiesel in CI engine

Journal of Thermal Analysis and Calorimetry - The solid–liquid equilibria (SLE) of two binary mixtures of organic stabilizers for energetic materials, viz....     

Synthesis of highly functionalized strained bicyclic dilactam derivatives

An efficient and modest protocol has been utilized for the synthesis of bicyclic dilactam derivatives through one-pot multicomponent domino reaction starting from various cyclic ketones under mild condition. The synthesized motif shows four stereogenic centers with two quaternary amine functionalities and such molecular arrangements are very fascinating and rare to obtain. We propose a mechanism for the formation of bicyclic dilactams through aldol condensation/condensation of cyanoacetamides/cyclization of condensed intermediate.