Layered Crystalline and Amorphous Platinum Disulfide (PtS2): Contrasting Electrochemistry

Group 6 transition metal dichalcogenides (TMDs), such as MoS₂ and WS₂ have been extensively studied for various applications while few studies have delved into other TMDs such as platinum dichalcogenides. In this work, layered crystalline and amorphous platinum disulfide (PtS₂) were synthesized, characterised and their fundamental electrochemical properties were investigated. Both materials exhibited inherent oxidation and reduction reactions which would limit their operating potential window for sensing applications. Amorphous phase materials are considered to be promising electrocatalysts due to the porous, and nanostructured morphology with high concentration of unsaturated active sites. The electrocatalytic performances towards oxygen reduction (ORR) and hydrogen evolution reactions (HER) of crystalline and amorphous PtS₂ were analysed. Amorphous PtS₂ was found to exhibit superior electrocatalytic performances towards ORR and HER as compared to crystalline PtS₂. For HER, amorphous and crystalline PtS₂ have overpotential values of 0.30 V and 0.70 V (vs. RHE) at current density of 10 mA cm⁻², respectively. The influence of electrochemical reduction pre-treatment on their catalytic behaviours was also investigated. Electrochemical reduction pre-treatment on both crystalline and amorphous PtS₂ removed the oxidized sulfate groups and increased the proportion of Pt⁰ oxidation state which exposed more catalytic sites. As such, these materials were activated and displayed improved ORR and HER performances. Electrochemically reduced amorphous PtS₂ outperformed the untreated counterparts and exhibited the best HER performance with overpotential of 0.17 V (vs. RHE) at current density of −10 mA cm⁻². These findings provide insights into the electrochemical properties of noble metal PtS₂ in both crystalline and amorphous states which can be activated by electrochemical reduction pre-treatment.     

Metal contamination in Sunairi Point sediment core along Karachi coast,Pakistan

Journal of Radioanalytical and Nuclear Chemistry - This paper describes the pollution level in sediment core collected from Sunairi Point of Karachi coastal area Pakistan. The sediment was...     

Recent trends in the chemistry of Sandmeyer reaction: a review

Metal-catalyzed reactions play a vital part to construct a variety of pharmaceutically important scaffolds from past few decades. To carry out these reactions under mild conditions with low-cost easily available precursors, various new methodologies have been reported day by day. Sandmeyer reaction is one of these, first discovered by Sandmeyer in 1884. It is a well-known reaction mainly used for the conversion of an aryl amine to an aryl halide in the presence of Cu(I) halide via formation of diazonium salt intermediate. This reaction can be processed with or without copper catalysts for the formation of C–X (X?=?Cl, Br, I, etc.), C-CF₃/CF₂, C–CN, C–S, etc., linkages. As a result, corresponding aryl halides, trifluoromethylated compounds, aryl nitriles and aryl thioethers can be obtained which are effectively used for the construction of biologically active compounds. This review article discloses various literature reports about Sandmeyer-related transformations developed during 2000–2021 which give different ideas to synthetic chemists about further development of new and efficient protocols for Sandmeyer reaction.

Graphical abstract

An updated compilation of new approaches for Sandmeyer reaction is described in this review to construct a variety of carbon-halogen, carbon-phosphorous, carbon-sulfur, carbon-boron etc. linkages.

     

Influence of thyroid volume reduction on absorbed dose in 131I therapy studied by using Geant4 Monte Carlo simulation

A simulation study has been performed to quantify the effect of volume reduction on the thyroid absorbed dose per decay and to investigate the variation of energy deposition per decay due to β- and γ-activity of 131I with volume/mass of thyroid, for water, ICRP- and ICRU-soft tissue taken as thyroid material. A Monte Carlo model of the thyroid, in the Geant4 radiation transport simulation toolkit was constructed to compute the β- and γ-absorbed dose in the simulated thyroid phantom for various values of its volume. The effect of the size and shape of the thyroid on energy deposition per decay has also been studied by using spherical, ellipsoidal and cylindrical models for the thyroid and varying its volume in 1-25 cm3 range. The relative differences of Geant4 results for different models with each other and MCNP results lie well below 1.870%. The maximum relative difference among the Geant4 estimated results for water with ICRP and ICRU soft tissues is not more than 0.225%. S-values for ellipsoidal, spherical and cylindrical thyroid models were estimated and the relative difference with published results lies within 3.095%. The absorbed fraction values for beta particles show a good agreement with published values within 2.105% deviation. The Geant4 based simulation results of absorbed fractions for gammas again show a good agreement with the corresponding MCNP and EGS4 results （±6.667%） but have 29.032% higher values than that of MIRD calculated values. Consistent with previous studies, the reduction of the thyroid volume is found to have a substantial effect on the absorbed dose. Geant4 simulations confirm dose dependence on the volume/mass of thyroid in agreement with MCNP and EGS4 computed values but are substantially different from MIRD8 data. Therefore, inclusion of size/mass dependence is indicated for 131I radiotherapy of the thyroid.     

Griffith–Kelly–Sherman Correlation Inequalities for Generalized Potts Model

Inspired by the work of D.G.Kelly and S.Sherman on general Griffiths inequalities on correlations in Ising ferromagnets, we formulate and prove Griffith–Kelly–Sherman-type inequalities for the ferromagnetic Potts model with a general number q of local states. We take as local state space for the q-state Potts model the set F ^c  = { − l, − l + 1, ⋯ ,l − 1,l},where l=\fracq-12l=\frac{q-1}{2}. The important properties of F ^c for what follows are that |F ^c | = q and F ^c  = − F ^c .     

Wavelet neural network based on islanding detection via inverter‐based DG

In this article, a passive neurowavelet based on islanding detection technique for grid‐connected inverter‐based distributed generation has been developed. Connecting distributed generator to the distribution network has many benefits such as increasing the capacity of the grid and enhancing the power quality. However, it gives rise to many problems. This is mainly due to the fact that distribution networks are designed without any generation units at that level. Hence, integrating distributed generators into the existing distribution network is not problem‐free. Unintentional islanding is one of the encountered problems. Islanding is the situation where the distribution system containing both distributed generator and loads is separated from the main grid as a result of many reasons such as electrical faults and their subsequent switching incidents, equipment failures, or preplanned switching events like maintenance. The proposed method utilizes and combines wavelet analysis and artificial neural network to detect islanding. Discrete wavelet transform is capable of decomposing the signals into different frequency bands. It can be utilized in extracting discriminative features from the acquired voltage signals. Passive schemes have a large nondetection zone (NDZ) and concern has been raised on active method due to its degrading power quality effect. The main emphasis of the proposed scheme is to reduce the NDZ to as close as possible and to keep the output power quality unchanged. The simulations results, performed by MATLAB/Simulink, shows that the proposed method has a small NDZ. Also, this method is capable of detecting islanding accurately within the minimum standard time. © 2014 Wiley Periodicals, Inc. Complexity 21: 309–324, 2015     

A practical approach for linearity assessment of calibration curves under the International Union of Pure and Applied Chemistry (IUPAC) guidelines for an in-house validation of method of analysis

Linearity assessment as required in method validation has always been subject to different interpretations and definitions by various guidelines and protocols. However, there are very limited applicable implementation procedures that can be followed by a laboratory chemist in assessing linearity. Thus, this work proposes a simple method for linearity assessment in method validation by a regression analysis that covers experimental design, estimation of the parameters, outlier treatment, and evaluation of the assumptions according to the International Union of Pure and Applied Chemistry guidelines. The suitability of this procedure was demonstrated by its application to an in-house validation for the determination of plasticizers in plastic food packaging by GC.     

New ceramides from Platytaenia multicaule

Phytochemical investigation of Platytaenia multicaule resulted in the isolation of two new ceramides, N-triacontylpentadecanamide and 1,3,4-trihydroxy-2,dodecanoylamino-(24E)-unacotenene, along with two known compounds, beta-sitosterol and beta-sitosterol glycoside. The structure elucidation of the isolated compounds was based primarily on 1D and 2D NMR analyses, including COSY, NOESY, HMQC, and HMBC correlations.