First X-ray structure of discrete anion [HgBr5]: Synthesis, characterization and single crystal X-ray structure determination of [Co(NH3)6][HgBr5]

A new cobalt(III) complex salt, [Co(NH₃)₆][HgBr₅](1) was crystallized from a solution of hexaamminecobalt(III)bromide and potassium tetrabromomercurate(II) in aqueous medium in 1:1 molar ratio. This complex salt has been characterized by elemental analyses, spectroscopic techniques (e.g. UV/Visible, IR), solubility product and conductance measurements. The complex salt crystallizes in Orthorhombic crystal system with space group Pnma. Single crystal X-ray structure determination revealed the presence of discrete ions: [Co(NH₃)₆]³⁺ cation and a new anion [HgBr₅]³⁻. This is the first structural report of a complex salt containing this new anion. The structure consists of stacks of cations and anions demonstrating supramolecular arrangements through N–HBr hydrogen-bond interactions. The crystal lattice is stabilized by these non-covalent interactions besides electrostatic interaction.     

DRIFT Studies of Adsorbed CO Over Sulfided K–Rh–Mo/Al2O3 Catalysts: Detection of Rh–Mo–S Phase

Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was used to study the nature of active species in K–Rh–Co–MoS₂/Al₂O₃ catalyst by means of probing with CO molecule. The effects of K addition to Rh and interaction between Mo and Rh were studied with varying K and Mo loadings over 1 wt% Rh/Al₂O₃ catalyst. In sulfided Rh–Mo/Al₂O₃, the formation of Rh–Mo–S phase was evidenced first time by a band at 2,095 cm^?1. The introduction of Co to K–Rh–MoS₂/Al₂O₃ catalyst showed the existence of both Rh and Co promoted MoS₂ sites, but the CO absorption frequencies in DRIFT spectra are significantly at lower side compared to Co free Rh–Mo catalyst. The stabilities of CO band from Rh and Co promoted and unpromoted MoS₂ sites are studied at different temperatures. When activated carbon used as support, bands for both promoted and unpromoted MoS₂ sites were appeared, but the intensity of these bands were decreased largely compared to alumina based catalyst, resulted from the coverage of added K not only on the support surface but also on the active metal components due to the neutral nature of activated carbon.     

Methyl acrylate/1‐octene copolymers: Lewis acid‐mediated polymerization

Copolymerization of methyl acrylate (MA) with 1‐octene (1‐Oct) was conducted in the presence of free radical initiator, 2,2′‐azobis(2‐methylpropionitrile) (AIBN) using heterogeneous Lewis acid, acidic alumina. The polymers obtained were transparent and highly viscous liquids. The copolymer composition calculated from ¹H NMR showed alkene incorporation in the range of 10–61%. The monomodal nature of chromatographic curves corresponding to the molecular weight distribution in gel permeation chromatography (GPC) further confirmed that the polymers obtained are true copolymers. The number–average molecular weights (M_n) of the copolymers were in the range of 1.1 × 10⁴–1.6 × 10⁴ with polydispersity index of 1.75–2.29. The effects of varying the acidic alumina amount, time of polymerization, and monomer infeed on the incorporation of 1‐Oct in the polymer chain were studied. Increased 1‐Oct infeed led to its higher inclusion in the copolymer chain as elucidated by NMR. DEPT‐135 NMR spectral analysis was used to explicate the nature of arrangement of monomer sequences in the copolymer chain. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Study of nitric acid leachout characteristics from weak base anion exchanger to maintain a specified pH regime during Gd(NO3)3 removal from moderator system of 540 MWe PHWRs

Nitric acid leachout characteristics from weak base anion exchanger (WBA) have been experimentally evaluated as a function of total nitric acid loading at a given flow velocity. An empirical first order model is used to explain the column outlet behaviour. Based on the experimental evaluation, a column configuration of a strong acid cation exchanger (SAC) topped mixed bed of SAC and WBA followed by a 5% nitric acid loaded WBA as the bottom layer of the column has been used to remove Gd(NO₃)₃ from water while maintaining the column outlet pH in the range of 5.0–5.5.     

Biodiesel production from mixtures of canola oil and used cooking oil

Used cooking oil (UCO) was mixed with canola oil at various ratios in order to make use of used cooking oil for production of biodiesel and also lower the cost of biodiesel production. Methyl and ethyl esters were prepared by means of KOH-catalyzed transesterification from the mixtures of both the oils. Water content, acid value and viscosity of most esters met ASTM standard except for ethyl esters prepared from used cooking oil. Canola oil content of at least 60% in the used cooking oil/canola oil feedstock is required in order to produce ethyl ester satisfying ASTM specifications. Although ethanolysis was proved to be more challenging, ethyl esters showed reduced crystallization temperature (−45.0 to −54.4 °C) as compared to methyl esters (−35.3 to −43.0 °C). A somewhat better low-temperature property of ester was observed at higher used cooking oil to canola oil ratio in spite of similar fatty acid compositions of both oils.     

Electroanalytical studies on cadmium(II) selective potentiometric sensors based on t-butyl thiacalix[4]arene and thiacalix[4]arene in poly(vinyl chloride)

Cd²⁺-selective sensors have been fabricated from poly(vinyl chloride) (PVC) matrix membranes containing t-butyl thiacalix[4]arene (I) and thiacalix[4]arene (II) as electroactive materials. The addition of sodium tetraphenylborate and the plasticizer 2-nitrophenyl octyl ether has been found to improve the performance of the sensors substantially. The membranes of various compositions of the two thiacalixarenes have been investigated and it was found that the best performance was obtained for the membrane of composition II:PVC:NaTPB:NPOE in the ratio 5:120:3:150. The sensor shows a linear potential response for Cd²⁺ over a wide activity range 3.2 × 10⁻⁶ to 1.0 × 10⁻¹ M with Nernstian compliance (29.5 mV decade⁻¹ of activity) in pH range 4.5-6.5 and a fast response time of ∼8 s. The potentiometric selectivity coefficient values determined by matched potential method indicate excellent selectivity for Cd²⁺ ions over mono-, di- and trivalent interfering cations. The sensor exhibits adequate shelf life (∼3 months) with good reproducibility (S.D. ±0.2 mV) and can also be used in partially non-aqueous media having up to 20% (v/v) methanol, ethanol or acetone content with no significant change in the value of slope or working activity range. The sensor has been used in the potentiometric titration of Cd²⁺ with EDTA. The sensor could be successfully used for the quantification of cadmium in river water samples.     

Identification of Natural Products as Potential Pharmacological Chaperones for Protein Misfolding Diseases

Defective protein folding and accumulation of misfolded proteins is associated with neurodegenerative, cardiovascular, secretory, and metabolic disorders. Efforts are being made to identify small-molecule modulators or structural-correctors for conformationally destabilized proteins implicated in various protein aggregation diseases. Using a metastable-reporter-based primary screen, we evaluated pharmacological chaperone activity of a diverse class of natural products. We found that a flavonoid glycoside ( C-10 , chrysoeriol-7-O-β-D-glucopyranoside) stabilizes metastable proteins, prevents its aggregation, and remodels the oligomers into protease-sensitive species. Data was corroborated with additional secondary screen with disease-specific pathogenic protein. In vitro and cell-based experiments showed that C-10 inhibits α-synuclein aggregation which is implicated in synucleinopathies-related neurodegeneration. C-10 interferes in its structural transition into β-sheeted fibrils and mitigates α-synuclein aggregation-associated cytotoxic effects. Computational modeling suggests that C-10 binds to unique sites in α-synuclein which may interfere in its aggregation amplification. These findings open an avenue for comprehensive SAR development for flavonoid glycosides as pharmacological chaperones for metastable and aggregation-prone proteins implicated in protein conformational diseases.     

Impact behavior of aminosilane functionalized nanosilica based shear thickening fluid impregnated Kevlar fabrics

In the present work, two types of shear thickening fluids have been synthesized by using neat and aminosilane functionalized silica nanoparticles and their viscosity curves have been obtained by the rheometer. Based on the values of peak viscosity of synthesized shear thickening fluids, the surface functionalized nanosilica based shear thickening fluid has been chosen as a best candidate due to the high viscosity for impregnation into the neat Kevlar of different layers viz. four (04) and eight (08) layers for velocity impact study. The experimental investigations reveal high energy absorption of shear thickening fluid impregnated Kevlar as compared to the neat Kevlar. The maximum energy absorption 62 J is achieved corresponding to the initial velocity 154 m∙s⁻¹ for 08 layers shear thickening fluid impregnated Kevlar specimen. The data have also been analytically determined and validated with the experimental data. The experimental data have good agreement with the analytical data within the accuracy of around 15 to 20%. The present findings can have significant inferences towards the fabrication of shear thickening fluids using nanomaterials for numerous applications such as soft armors, dampers, nanofinishing and so forth.