Prediction of thermodynamic and surface properties of Pb−Hg liquid alloys at different temperatures

The thermodynamic properties, such as free energy of mixing, heat of mixing, activity and structural properties, such as concentration fluctuation in long wavelength limit, short-range order parameter of Pb–Hg liquid alloy at 600 K have been calculated using theoretical modelling. It has then been correlated with modified Butler model to compute the surface tension of the alloys at different temperatures. The Pb–Hg system at 600 K is found to be ordering at higher concentration of Pb.     

Enantiopure Calcium Iminophosphonamide Complexes: Synthesis,Photoluminescence, and Catalysis

The synthesis of calcium complexes ligated by three different chiral iminophosphonamide ligands, L- H ( L =[Ph₂P{N(R)CH(CH₃)Ph}₂]), L′ -H ( L′ =[Ph₂P{NDipp}{N(R)CH(CH₃)Ph}]), (Dipp=2,6-ⁱPr₂C₆H₃), and L′′ -H ( L′′ =[Ph₂P{N(R)CH(CH₃)naph}₂]), (naph=naphthyl) is presented. The resulting structures [ L ₂Ca], [ L′ ₂Ca], and [ L′′ ₂Ca] represent the first examples of enantiopure homoleptic calcium complexes based on this type of ligands. The calcium complexes show blue–green photoluminescence (PL) in the solid state, which is especially bright at low temperatures. Whereas the emission of [ L′′ ₂Ca] is assigned to the fluorescence of naphthyl groups, the PL of [ L ₂Ca] and [ L′ ₂Ca] is contributed by long-lived phosphorescence and thermally activated delayed fluorescence (TADF), with a strong variation of the PL lifetimes over the temperature range of 5–295 K. Furthermore, an excellent catalytic activity was found for these complexes in hydroboration of ketones at room temperature, although no enantioselectivity was achieved.     

Application of the Redox-Transmetalation Procedure to Access Divalent Lanthanide and Alkaline-Earth NHC Complexes**

Divalent lanthanide and alkaline-earth complexes supported by N-heterocyclic carbene (NHC) ligands have been accessed by redox-transmetalation between air-stable NHC-AgI complexes and the corresponding metals. By using the small ligand 1,3-dimethylimidazol-2-ylidene (IMe), two series of isostructural complexes were obtained: the tetra-NHC complexes [LnI₂(IMe)₄] (Ln=Eu and Sm) and the bis-NHC complexes [MI₂(IMe)₂(THF)₂] (M=Yb, Ca and Sr). In the former, distortions in the NHC coordination were found to originate from intermolecular repulsions in the solid state. Application of the redox-transmetalation strategy with the bulkier 1,3-dimesitylimidazol-2-ylidene (IMes) ligand yielded [SrI₂(IMes)(THF)₃], while using a similar procedure with Ca metal led to [CaI₂(THF)₄] and uncoordinated IMes. DFT calculations were performed to rationalise the selective formation of the bis-NHC adduct in [SrI₂(IMe)₂(THF)₂] and the tetra-NHC adduct in [SmI₂(IMe)₄]. Since the results in the gas phase point towards preferential formation of the tetra-NHC complexes for both metal centres, the differences between both arrangements are a result of solid-state effects such as slightly different packing forces.     

Investigating microcrystalline cellulose crystallinity using Raman spectroscopy

Cellulose - Microcrystalline cellulose (MCC) is a semi-crystalline material with inherent variable crystallinity due to raw material source and variable manufacturing conditions. MCC crystallinity...     

Stereoselective synthesis of trans-3-functionalized-4-pyrazolo[5,1-b]thiazole-3-carboxylate substituted β-lactams: Potential synthons for diverse biologically active agents

Abstract

An efficient protocol for the stereoselective synthesis of pyrazolo[5,1-b]thiazole-3-carboxylate tethered β-lactam conjugates 8a–j from novel pyrazolo [5,1-b]thiazole-3-carboxylate substituted Schiff’s bases 6a–f is reported here. The reaction between various ketene precursors and novel Schiff’s bases 6a–f afforded exclusive formation of trans-β-lactams 8a–j. The substrate scope of this approach was investigated extensively by varying different groups (R, Z). All the novel compounds were characterized using various spectroscopic techniques, such as FT-IR, ¹H NMR, ¹³C NMR, elemental analysis, ¹³C NMR (DEPT-135), and mass spectrometry in representative cases. Single crystal X-ray crystallographic study of trans-ethyl 7-(1-(4-methoxyphenyl)-4-oxo-3-phenoxyazetidin-2-yl)-6-methyl-2-(methylthio)pyrazolo[5,1-b]thiazole-3-carboxylate 8a has confirmed the molecular structure and the stereochemical outcome. To the best of our knowledge, the synthesis of such types of Schiff’s bases and β-lactam conjugates has not been reported so far.     

Recent strategy(ies) for the electrocatalytic reduction of CO2: Ni single-atom catalysts for the selective electrochemical formation of CO in aqueous electrolytes

To decrease the global carbon footprint concerns and to diminish the energy crisis, electrocatalytic reduction of CO₂ which results in the formulation of value-added chemicals is a potential solution. In this review, single-atom catalysts (SACs) which are rapidly growing and being developed as the stimulating catalytic materials for electrocatalytic reduction of CO₂ with improved selectivity, efficiency, and stability are considered. Various factors which are responsible for the efficient CO₂ reduction are discussed. The pyrolytic approach for the preparation of Ni-based SACs and the maximum atom utilization efficiency for the desirable production of CO from CO₂ are highlighted.     

Bergenia Genus: Traditional Uses,Phytochemistry and Pharmacology

Bergenia (Saxifragaceae) genus is native to central Asia and encompasses 32 known species. Among these, nine are of pharmacological relevance. In the Indian system of traditional medicine (Ayurveda), “Pashanabheda” (stone breaker) is an elite drug formulation obtained from the rhizomes of B. ligulata. Bergenia species also possess several other biological activities like diuretic, antidiabetic, antitussive, insecticidal, anti-inflammatory, antipyretic, anti-bradykinin, antiviral, antibacterial, antimalarial, hepatoprotective, antiulcer, anticancer, antioxidant, antiobesity, and adaptogenic. This review provides explicit information on the traditional uses, phytochemistry, and pharmacological significance of the genus Bergenia. The extant literature concerned was systematically collected from various databases, weblinks, blogs, books, and theses to select 174 references for detailed analysis. To date, 152 chemical constituents have been identified and characterized from the genus Bergenia that belong to the chemical classes of polyphenols, phenolic-glycosides, lactones, quinones, sterols, tannins, terpenes, and others. B. crassifolia alone possesses 104 bioactive compounds. Meticulous pharmacological and phytochemical studies on Bergenia species and its conservation could yield more reliable compounds and products of pharmacological significance for better healthcare.     

Comparative computational appraisal of supercritical CO2-based natural circulation loop: effect of heat-exchanger and isothermal wall

Journal of Thermal Analysis and Calorimetry - Natural circulation loop (NCL) is a geometrically simple heat transfer device in which fluid flow occurs due to density gradient of loop fluid, induced...     

Unusual Surface Latent Heat Flux Variations and Their Critical Dynamics Revealed before Strong Earthquakes

We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock.     

Palladium-catalyzed selective C–C bond cleavage and stereoselective alkenylation between cyclopropanol and 1,3-diyne: one-step synthesis of diverse conjugated enynes

The stereoselective synthesis of 1,3-enynes from 1,3-diynes is demonstrated by palladium-catalyzed selective C–C bond cleavage of cyclopropanol. Exclusive formation of mono-alkenylated adducts was achieved by eliminating the possibility of di-functionalization with high stereoselectivity. Indeed, this protocol worked very well with electronically and sterically diverse substrates. Several studies, including deuterium labeling experiments and intermolecular competitive experiments, were carried out to understand the mechanistic details. The atomic-level mechanism followed in the catalytic process was also validated using DFT calculations, and the rate-controlling states in the catalytic cycle were identified. Furthermore, preliminary mechanistic investigations with radical scavengers revealed the non-involvement of the radical pathway in this transformation.

Palladium-catalyzed tandem activation and functionalization of readily accessible cyclopropanols have been demonstrated to access valuable conjugated enynes from 1,3-diynes with high stereo-selectivity.