New barium,strontium and strontium‐doped barium squarates: synthesis,crystal structures and DNA/BSA binding,antioxidant and in vitro cytotoxicity studies

A new set of differently hydrated barium and strontium squarates, namely poly[[triaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)barium] monohydrate], {[Ba(C₄O₄)(H₂O)₃]·H₂O}_n ( 1 ), poly[[diaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)strontium] monohydrate], {[Sr(C₄O₄)(H₂O)₂]·H₂O}_n ( 2 ), and poly[[triaqua(μ‐1,2‐dioxocyclobut‐3‐ene‐1,2‐diolato)barium/strontium(0.85/0.15)] monohydrate], {[Ba_0.85Sr_0.15(C₄O₄)(H₂O)₃]·H₂O}_n ( 3 ), is reported. The study of their crystal structures indicates that all the complexes crystallize in the triclinic space group P. Complexes 1 and 3 have a rare combination of squarate units coordinated through monodentate O atoms to two different metal atoms and through two bidentate O atoms to three different metal atoms. Furthermore, they have three coordinated water molecules to give a coordination number of nine. The squarate ligands in complex 2 exhibit two different coordination modes: (i) monodentate O atoms coordinated to four different Sr atoms and (ii) two monodentate O atoms coordinated to two different metal atoms with the other two O atoms bidentate to four different Sr atoms. All the compounds decompose to give the respective carbonates when heated to 800 °C, as evidenced by thermogravimetry/differential thermal analysis (TG‐DTA), which are clusters of nanoparticles. Complexes 1 and 3 show additional endothermic peaks at 811 and 820 °C, respectively, indicating the phase transition of BaCO₃ from an orthorhombic (α‐Pmcn) to a trigonal phase (β‐R3m). All three complexes have significant DNA‐binding constants, ranging from 2.45 × 10⁴ to 9.41 × 10⁴ M^?1 against EB‐CT (ethidium bromide–calf thymus) DNA and protein binding constants ranging from 1.1 × 10⁵ to 8.6 × 10⁵ with bovine serum albumin. The in vitro cytotoxicity of the complexes is indicated by the IC₅₀ values, which range from 128.8 to 261.3 µg ml^?1. Complex 3 shows better BSA binding, antioxidant activity against the DPPH radical and cytotoxicity than complexes 1 and 2 .     

Supramolecular gels: functions and uses

In recent years there has been immense interest in studying gels derived from low molecular mass gelators (supramolecular, or simply molecular gels). The motivation for this is not only to understand the fundamental aggregate structures in the gels at different length scales, but also to explore their potential for futuristic technological applications. Gels have been made sensitive to external stimuli like light and chemical entities by incorporating a spectroscopically active or a receptor unit as part of the gelator molecule. This makes them suitable for applications such as sensing and actuating. The diversity of gel structural architectures has allowed them to be utilized as templates to prepare novel inorganic superstructures for possible applications in catalysis and separation. Gels derived from liquid crystals (anisotropy gels) that can act as dynamically functional materials have been prepared, for example, for (re-writable) information recording. Supramolecular gels can be important in controlled release applications, in oil recovery, for gelling cryogenic fuels etc. They can also serve as media for a range of applications. This tutorial review highlights some of the instructive work done by various groups to develop smart and functional gels, and covers a wide spectrum of scientific interest ranging from medicine to materials science.     

Equilibrium and kinetic studies of adsorption of phosphate onto ZnCl2 activated coir pith carbon

Phosphate removal from aqueous solution was investigated using ZnCl₂-activated carbon developed from coir pith, an agricultural solid waste. Studies were conducted to delineate the effect of contact time, adsorbent dose, phosphate concentration, pH, and temperature. The adsorption equilibrium data followed both Langmuir and Freundlich isotherms. Langmuir adsorption capacity was found to be 5.1 mg/g. Adsorption followed second-order kinetics. The removal was maximum in the pH range 3–10. pH effect and desorption studies showed that adsorption occurred by both ion exchange and chemisorption mechanisms. Adsorption was found to be spontaneous and endothermic. Effect of foreign ions on adsorption shows that perchlorate, sulfate, and selenite decreased the percent removal of phosphate.     

Small‐Angle X‐Ray Scattering and Near‐Infrared Vibrational Spectroscopy of Water Confined in Aerosol‐OT Reverse Micelles

The state of water confined in Aerosol‐OT–hydrocarbon–water reverse micelles with cyclohexane, n‐pentane, n‐octane, and n‐dodecane as apolar solvents is investigated by small‐angle X‐ray scattering and near‐infrared vibrational spectroscopy of the first overtone of the OH stretching mode of water. The experiments focus on water/AOT molecular ratios W₀=2–20, where water is strongly affected by the confinement and surface–water interactions. The pair‐distance distribution functions derived from the small‐angle scattering patterns allows a detailed characterization of the topology of these systems, and they indicate deviations from monodisperse, spherical water pools for some of these hydrocarbon systems. In contrast to a common assumption, the pool size does not scale linearly with W₀ in going from dry reverse micelles (W₀→0) to essentially bulk‐like water (W₀>20). The first overtone of the OH‐stretching vibration exhibits highly structured spectra, which reveal significant changes in the hydrogen bonding environment upon confinement. The spectra are rationalized by a core/shell model developed by Fayer and co‐workers. This model subdivides water into core water in the interior of the micelle and shell water close to the interface. Core water is modelled by the properties of bulk water, while the properties of shell water are taken to be those of water at W₀=2. The model allows the representation of the spectra at any hydration level as a linear combination of the spectra of core and shell water. Different approaches are critically reviewed and discussed as well.     

Stability-indicating method for the determination of assay and quantification of impurities in amlodipine–atorvastatin combination dosage form by RP-HPLC

A simple stability-indicating RP-HPLC method was developed and validated for quantification of amlodipine, atorvastatin, and its impurities on Waters HPLC using Unisol C₁₈ 5?µm, 250?×?4.6?mm column in their combined tablet dosage as per ICH guidelines. The gradient (T/%B) at 0/42, 18/42, 22/75, 30/75, 32/42, and 35/42 of 40?mM 4.7 pH ammonium acetate as mobile phase A and acetonitrile as mobile phase B of flow rate 1.5?mL/min and 240?nm wavelength. Peak purity compiled for amlodipine and atorvastatin in all stressed conditions. For impurities: Precision was found in between 1.5 and 3.6%. The limit of detection and quantification for amlodipine, amlodipine impurity A, and atorvastatin was found to be 0.06 and 0.18?µg/mL, for atorvastatin Impurity A, B, C, and H was determined as 0.04 and 0.11?µg/mL, for Atorvastatin Impurity D was measured as 0.11 and 0.28?µg/mL, respectively. The linear regression achieved >0.9999 from 0.22 to 7.5?µg/mL. Recovery was observed in between 97 and 101%. For assay: Precision was determined in between 0.1 and 0.2%. The linear regression achieved >0.9999 for amlodipine and atorvastatin. Recovery ranged from 100 to 101%. The validated method was found to be accurate, precise, reliable, and robust to determine the assay as well as impurities in amlodipine–atorvastatin combination dosage formulation.     

Development of sulfonated poly (ether ether ketone) electrolyte membrane for applications in hydrogen sensor

The future economy is projected as hydrogen economy and fuel cells are set to become the energy source either replacing or augmenting the present oil based technology. A sulfonated poly ether ether ketone (SPEEK) membrane as the electrolyte for hydrogen sensor that operates at room temperature was developed in our lab. The electrolyte used was SPEEK, which is a proton conducting solid polymer membrane. The membranes were characterized using various available techniques like TGA, XRD, SEM, etc. The durability was studied using the Fenton’s reagent. The proton conducting ability was analyzed using impedance spectroscopy. The catalysts considered were platinum for the cathode and three different catalysts (Pt, Pt/Pd and Pd) for the anode. The MEAs were evaluated for their performance in hydrogen sensor and the one with platinum catalyst at the anode gave the best response among the three indicating its suitability for the SPEEK membrane for hydrogen sensor.     

Copper(II) complexes containing a CuN4O2 coordination sphere assembled via pyridine-imine-amide coordination: Synthesis,structure and properties

Copper(II) complexes [CuL₂] of pyridine-N, imine-N and amide-O donor Schiff bases (HL) are reported. The Schiff bases Hpabh, Hpamh and Hpadh were prepared by condensation of 2-pyridinecarboxaldehyde with benzhydrazide, 4-methoxybenzhydrazide and 4-dimethylaminobenzhydrazide, respectively. The complexes were synthesised in MeOH media by reacting Cu(OAc)₂ · H₂O with HL in a 1:2 mole ratio. The X-ray structure of [Cu(pabh)₂] was determined. The rhombically distorted octahedral CuN₄O₂ coordination sphere is formed by two mononegative meridionally spanning pyridine-N, imine-N and deprotonated amide-O donor ligands. Electronic spectra of the complexes display two d–d bands at ca. 700 and ca. 1300 nm and two strong absorptions due to charge transfer transitions in the 450–268 nm range. Room temperature (298 K) solid state magnetic moments (1.90–2.08 _B) suggest an S = 1/2 spin state in each complex. The powder e.p.r. spectra of [Cu(pabh)₂] and [Cu(pamh)₂] at room temperature are consistent with a rhombic distortion of the N₄O₂ octahedron around the metal centre. However the spectrum of [Cu(padh)₂] suggests a tetragonal elongation of the CuN₄O₂ octahedron.     

Hole-shape optimization in a finite plate in the presence of auxiliary holes

Minimizing the stress concentration around holes in uniaxially loaded finite plates is an important consideration in engineering design. One method for reducing the stress concentration around a central circular hole in a uniaxially loaded plate is to introduce smaller auxiliary holes on either side of the original hole to help smooth the flow of the tensile principal-stress trajectories past the original hole. This method has been demonstrated by Heywood and systematically studied by Erickson and Riley. Erickson and Riley show that for a central-hole diameter-to-plate width ratio of 0.222, the maximum stress reduction is up to 16 percent. In recent work, Durelliet al. show that the stress concentrations around holes in uniaxially loaded plates can be minimized by changing the hole shape itself till an optimum hole profile with constant stress values respectively on the tensile and compressive segments of the hole boundary is reached. By this technique the maximum stress reduction obtained for the above case is up to 20 percent. In the present work, starting with the optimum sizes and locations of central and auxiliary circular holes for a finite plate given by Erickson and Riley, a systematic study of the hole-shape optimization is undertaken. A two-dimensional photoelastic method is used. For a central-hole diameter-to-plate width ratio of 0.222, the reduction in stress-concentration factor obtained after hole-shape optimization is about 30 percent. It is also shown that it is possible to introduce the ‘equivalent ellipse’ concept for optimized holes.