Synthesis,structure and spectroscopic properties of some thiosemicarbazone complexes of platinum

Reaction of salicyldehyde thosemicarbazone (H₂L¹), 2-hydroxyacetophenone thiosemicarbazone (H₂L²) and 2-hydroxynapthaldehyde thiosemicarbazone (H₂L³) (general abbreviation H₂L, where H₂ stands for the two dissociable protons, one phenolic proton and one hydrazinic proton) with K₂[PtCl₄] afforded a family of polymeric complexes of type [{Pt(L)}_n]. Reaction of the polymeric species with two monodentate ligands (D), viz. triphenylphosphine (PPh₃) and 4-picoline (pic), yielded complexes of the type [Pt(L)(D)]. These mixed-ligand complexes were also obtained from the reaction of the thiosemicarbazones with [Pt(PPh₃)₂Cl₂] and [Pt(pic)₂Cl₂]. The crystal structure of [Pt(PPh₃)(L²)] has been determined. The thiosemicarbazone ligands are coordinated, via dissociation of the two protons, as dianionic tridentate O,N,S-donors. The [Pt(L)(D)] complexes show characteristic ¹H NMR spectra and intense absorptions in the visible and ultraviolet region. They also fluoresce in the visible region at ambient temperature.     

Regioselective addition of 1,3-dicarbonyl dianion to N-sulfonyl aldimines: an expedient route to N-sulfonyl piperidines and N-sulfonyl azetidines

A simple route for the synthesis of δ-amino-β-keto esters and δ-amino-β-diketones is reported. This involves regioselective addition of 1,3-dianions derived from ethyl acetoacetate and acetyl acetone to N-sulfonyl aldimines. The δ-amino-β-keto ester derivatives were further converted into the corresponding N-sulfonyl piperidines and N-sulfonyl azetidines.     

Poly[μ4‐sulfido‐tris(thiocyanato‐κN)tris(μ3‐1,2,4‐triazolato‐κ3N1:N2:N4)tetrazinc(II)]: a three‐dimensional zinc sulfide coordination polymer

The title compound, [Zn₄(C₂H₂N₃)₃(NCS)₃S]_n, is a three‐dimensional coordination polymer consisting of tetrahedral SZn₄ clusters bridged by triazole ligands. In the tetrahedral unit, three Zn atoms are connected to six bridging triazolate ligands, whereas the fourth Zn atom (site symmetry 3m) is bonded to three terminal thiocyanate anions that protrude into the void space created by the Zn–triazolate network. The network prototype is simple cubic, but a strong distortion along a body diagonal and the imposition of a polar direction by the arrangement of the molecular constituents lead to the trigonal space group R3m. This study demonstrates the use of the 3‐mercapto‐1,2,4‐triazole ligand as an effective source for sulfide ions in the synthesis of sulfide‐based coordination polymers.     

A Robust Electrochemical Sensor Based on Butterfly-shaped Silver Nanostructure for Concurrent Quantification of Heavy Metals in Water Samples

Heavy metals in drinking water have become a severe threat to human health. Detection of heavy metals has been achieved by electrochemical sensors that are modified with complex nanocomposites; however, reproducibility of these sensors is still a big challenge when applied in commercial settings. Here, a simple, very robust, and sensitive electrochemical sensor based on a screen-printed carbon electrode modified with butterfly-shaped silver nanostructure (AgNS/SPCE) has been developed for the concurrent determination of cadmium (II), lead (II), copper (II), and mercury (II) in water samples. The electrochemical behavior of the modified electrodes was investigated using cyclic voltammetry and differential pulse anodic stripping voltammetry. The AgNS/SPCE showed distinct peak potentials and a significant increase in the peak currents for all heavy metals, attributed to the high electrical conductivity and electrocatalytic activity of the synthesized butterfly-shaped AgNS. Moreover, the excellent stability and sensitivity towards simultaneous quantification of heavy metals have been obtained with detection limits of 0.4 ppb, 2.5 ppb, 7.3 ppb, and 0.7 ppb for Cd (II), Pb (II), Cu (II), and Hg (II), respectively. Besides, the constructed sensor was successfully applied to simultaneously quantify target heavy metals in spiked water samples. Owing to excellent sensitivity, high robustness, affordability, and fast response, the presented electrochemical sensor could be incorporated into a portable and miniaturized potentiostat device, making it a promising method for on-site water analysis.     

Density of Deep Eutectic Solvents: The Path Forward Cheminformatics-Driven Reliable Predictions for Mixtures

Deep eutectic solvents (DES) are often regarded as greener sustainable alternative solvents and are currently employed in many industrial applications on a large scale. Bearing in mind the industrial importance of DES—and because the vast majority of DES has yet to be synthesized—the development of cheminformatic models and tools efficiently profiling their density becomes essential. In this work, after rigorous validation, quantitative structure-property relationship (QSPR) models were proposed for use in estimating the density of a wide variety of DES. These models were based on a modelling dataset previously employed for constructing thermodynamic models for the same endpoint. The best QSPR models were robust and sound, performing well on an external validation set (set up with recently reported experimental density data of DES). Furthermore, the results revealed structural features that could play crucial roles in ruling DES density. Then, intelligent consensus prediction was employed to develop a consensus model with improved predictive accuracy. All models were derived using publicly available tools to facilitate easy reproducibility of the proposed methodology. Future work may involve setting up reliable, interpretable cheminformatic models for other thermodynamic properties of DES and guiding the design of these solvents for applications.     

Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Germanium substrate

We have described Stranski–Krastanow growth of multilayer In(Ga)As/GaAs QDs on Ge substrate by MBE. The growth technique includes deposition of a thin germanium buffer layer followed by migration-enhanced epitaxy (MEE) grown GaAs layer at 350°C. The MEE layer was overgrown by a thin low-temperature (475°C) grown GaAs layer with a subsequent deposition of a thick GaAs layer grown at 590°C. The sample was characterized by AFM, cross-sectional TEM and temperature-dependent PL measurements. The AFM shows dense formation of QDs with no undulation in the wetting layer. The XTEM image confirms that the sample is free from structural defects. The 8 K PL emission exhibits a 1051 nm peak, which is similar to the control sample consisting of In(Ga)As/GaAs QDs grown on GaAs substrate, but the observed emission intensity is lower. The similar slopes of Arrhenius plot of the integrated PL intensity for the as-grown QD sample grown on Ge substrate as well as for a reference QD sample grown on GaAs substrate are found to be identical, indicating a similar carrier emission process for both the samples. This in turn indicates coherent formation of QDs on Ge substrate. We presume due to the accumulated strain associated with the self-assembled growth of nanostructures on Ge that nonradiative recombination centers are introduced in the GaAs barrier in between the QD layers, which in turn degrades the overall optical quality of the sample.     

Correlation between structural and superconducting properties of nano-granular disordered Nb thin films

We report on low temperature transport measurements on nano-granular Nb thin films deposited on Si (1 0 0) substrates using DC magnetron sputtering. The superconducting transition temperature (T_c) is found to decrease monotonically with the increase of the lattice parameter (a) irrespective of its thickness and grain size. The superconducting transition temperature is found to depend only on the lattice parameter whereas the normal state resistivity depends both on lattice parameter and the details of the sample morphology. We have modeled this T_c variation with lattice expansion in terms of Debye temperature reduction using Morse potential as the interatomic potential in Nb.     

Self-starting harmonic mode-locked Tm-Bi co-doped germanate fiber laser with carbon nanotube-based saturable absorber

We report a ring cavity passively harmonic mode-locked fiber laser using a newly developed thuliumbismuth co-doped fiber(TBF) as a gain medium in conjunction with a carbon nanotube(CNT)-based saturable absorber.The TBF laser generates a third harmonic mode-locked soliton pulse train with a high repetition rate of 50 MHz and a pulse duration of 1.86 ps.The laser operates at 1 901.6 nm with an average power of 6.6 mW,corresponding to a pulse energy of 0.132 nJ,at a 1 552 nm pump power of 723.3 mW.