Preparation and Characterization of Chitosan Thin Films on Mixed-Matrix Membranes for Complete Removal of Chromium

Herein we present a new approach for the complete removal of Cr^VI species, through reduction of Cr^VI to Cr^III, followed by adsorption of Cr^III. Reduction of chromium from water is an important challenge, as Cr^IV is one of the most toxic substances emitted from industrial processes. Chitosan (CS) thin films were developed on plain polysulfone (PSf) and PSf/TiO₂ membrane substrates by a temperature-induced technique using polyvinyl alcohol as a binder. Structure property elucidation was carried out by X-ray diffraction, microscopy, spectroscopy, contact angle measurement, and water uptake studies. The increase in hydrophilicity followed the order: PSf < PSf/TiO₂ < PSf/TiO₂/CS membranes. Use of this thin-film composite membrane for chromium removal was investigated with regards to the effects of light and pH. The observations reveal 100 % reduction of Cr^VI to Cr^III through electrons and protons donated from OH and NH₂ groups of the CS layer; the reduced Cr^III species are adsorbed onto the CS layer via complexation to give chromium-free water.     

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network,X‐pcu‐5‐Zn,by Pillar‐Ligand Substitution

Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu ‐topology MOF, X‐pcu‐5‐Zn , have been prepared: X‐pcu‐6‐Zn , 6 =1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn , 7 =1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn , 8 =4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N₂, CO₂, C₂H₂, and C₂H₄ adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6 , afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.     

Tuning the Gate‐Opening Pressure in a Switching pcu Coordination Network,X‐pcu‐5‐Zn,by Pillar‐Ligand Substitution

Coordination networks that reversibly switch between closed and open phases are of topical interest since their stepped isotherms can offer higher working capacities for gas‐storage applications than the related rigid porous coordination networks. To be of practical utility, the pressures at which switching occurs, the gate‐opening and gate‐closing pressures, must lie between the storage and delivery pressures. Here we study the effect of linker substitution to fine‐tune gate‐opening and gate‐closing pressure. Specifically, three variants of a previously reported pcu ‐topology MOF, X‐pcu‐5‐Zn , have been prepared: X‐pcu‐6‐Zn , 6 =1,2‐bis(4‐pyridyl)ethane (bpe), X‐pcu‐7‐Zn , 7 =1,2‐bis(4‐pyridyl)acetylene (bpa), and X‐pcu‐8‐Zn , 8 =4,4′‐azopyridine (apy). Each exhibited switching isotherms but at different gate‐opening pressures. The N₂, CO₂, C₂H₂, and C₂H₄ adsorption isotherms consistently indicated that the most flexible dipyridyl organic linker, 6 , afforded lower gate‐opening and gate‐closing pressures. This simple design principle enables a rational control of the switching behavior in adsorbent materials.     

Water Molecules in Hydrotalcite‐like Layered Double Hydroxides: Interplay between the Hydration of the Anions and the Metal Hydroxide Layer

Layered double hydroxides comprise positively charged metal hydroxide layers and intercalated anions. These materials are obtained from aqueous medium both in nature and in the laboratory. Consequently the layered double hydroxides include a considerable amount of water. The presented study was designed to determine the proportion of water associated with the hydration sphere of the anion as opposed to that of the metal hydroxide slab. Among the two differently bound water species observed in all layered double hydroxides, the weakly bound water is associated with the metal hydroxide layer and is lost at 100 °C, whereas the strongly bound water is in the hydration sphere of the anion and is lost at higher temperatures (100 °C ≤ T ≤ 250 °C). This is in contrast to the better known cationic clays, wherein all the intercalated water is generally found to be in the hydration sphere of the cations. Further the water molecules in layered double hydroxides also bond to each other, leading to the incorporation of water in excess of what is predicted by the Miyata formula (Miyata, 1975) based on crystal chemical considerations. The excess water is one of the reasons for the poor crystallinity of layered hydroxides.     

A sterically congested cis‐stilbene and its phosphonium salt precursor

Triphenyl(2,4,5‐trimethoxybenzyl)phosphonium chloride is formed in solvent‐free form by the reaction under anhydrous conditions between triphenylphosphane and 2,4,5‐trimethoxybenzyl chloride, but when it is crystallized from a mixture of ethyl acetate and chloroform in the presence of air it forms a stoichiometric monohydrate, C₂₈H₂₈O₃P⁺·Cl⁻·H₂O, (I). The reactions between the anhydrous phosphonium salt and alkoxy‐substituted benzaldehydes, using Wittig reactions in the presence of potassium tert‐butoxide, provide a series of multiply substituted stilbenes, most of which were assigned the Z configuration on the basis of their NMR spectra. However, no such deduction could be made for the symmetrically substituted (Z)‐2,2′,4,4′,5,5′‐hexamethoxystilbene, C₂₀H₂₄O₆, (II). Compound (II) does in fact have the Z configuration and the molecular geometry provides evidence for steric congestion around the central double bond; in particular, the central alkene fragment is nonplanar, with a C—C=C—C torsion angle of 7.8 (4)°. In hydrated salt (I), the chloride anions and water molecules are linked by O—H...Cl hydrogen bonds to form C₂¹(4) chains; each cation is linked by C—H...O hydrogen bonds to two different chains, so forming a sheet structure. There are no direction‐specific intermolecular interactions in the structure of (II).     

Crossover Sorption of C2H2/CO2 and C2H6/C2H4 in Soft Porous Coordination Networks

Porous sorbents are materials that are used for various applications, including storage and separation. Typically, the uptake of a single gas by a sorbent decreases with temperature, but the relative affinity for two similar gases does not change. However, in this study, we report a rare example of “crossover sorption,” in which the uptake capacity and apparent affinity for two similar gases reverse at different temperatures. We synthesized two soft porous coordination polymers (PCPs), [Zn₂(L1)(L2)₂]_n (PCP-1) and [Zn₂(L1)(L3)₂]_n (PCP-2) (L1= 1,4-bis(4-pyridyl)benzene, L2=5-methyl-1,3-di(4-carboxyphenyl)benzene, and L3=5-methoxy-1,3-di(4-carboxyphenyl)benzene). These PCPs exhibits structural changes upon gas sorption and show the crossover sorption for both C₂H₂/CO₂ and C₂H₆/C₂H₄, in which the apparent affinity reverse with temperature. We used in situ gas-loading single-crystal X-ray diffraction (SCXRD) analysis to reveal the guest inclusion structures of PCP-1 for C₂H₂, CO₂, C₂H₆, and C₂H₄ gases at various temperatures. Interestingly, we observed three-step single-crystal to single-crystal (sc-sc) transformations with the different loading phases under these gases, providing insight into guest binding positions, nature of host–guest or guest-guest interactions, and their phase transformations upon exposure to these gases. Combining with theoretical investigation, we have fully elucidated the crossover sorption in the flexible coordination networks, which involves a reversal of apparent affinity and uptake of similar gases at different temperatures. We discovered that this behaviour can be explained by the delicate balance between guest binding and host–guest and guest-guest interactions.     

Shape-Memory Effect Enabled by Ligand Substitution and CO2 Affinity in a Flexible SIFSIX Coordination Network

We report that linker ligand substitution involving just one atom induces a shape-memory effect in a flexible coordination network. Specifically, whereas SIFSIX-23-Cu, [Cu(SiF₆)(L)₂]_n, (L=1,4-bis(1-imidazolyl)benzene, SiF₆²⁻=SIFSIX) has been previously reported to exhibit reversible switching between closed and open phases, the activated phase of SIFSIX-23-Cu^N, [Cu(SiF₆)(L^N)₂]_n (L^N=2,5-bis(1-imidazolyl)pyridine), transformed to a kinetically stable porous phase with strong affinity for CO₂. As-synthesized SIFSIX-23-Cu^N, α, transformed to less open, γ, and closed, β, phases during activation. β did not adsorb N₂ (77 K), rather it reverted to α induced by CO₂ at 195, 273 and 298 K. CO₂ desorption resulted in α′, a shape-memory phase which subsequently exhibited type-I isotherms for N₂ (77 K) and CO₂ as well as strong performance for separation of CO₂/N₂ (15/85) at 298 K and 1 bar driven by strong binding (Q_st=45–51 kJ/mol) and excellent CO₂/N₂ selectivity (up to 700). Interestingly, α′ reverted to β after re-solvation/desolvation. Molecular simulations and density functional theory (DFT) calculations provide insight into the properties of SIFSIX-23-Cu^N.     

Reversible Switching between Highly Porous and Nonporous Phases of an Interpenetrated Diamondoid Coordination Network That Exhibits Gate‐Opening at Methane Storage Pressures

Herein, we report that a new flexible coordination network, NiL₂ (L=4‐(4‐pyridyl)‐biphenyl‐4‐carboxylic acid), with diamondoid topology switches between non‐porous (closed) and several porous (open) phases at specific CO₂ and CH₄ pressures. These phases are manifested by multi‐step low‐pressure isotherms for CO₂ or a single‐step high‐pressure isotherm for CH₄. The potential methane working capacity of NiL₂ approaches that of compressed natural gas but at much lower pressures. The guest‐induced phase transitions of NiL₂ were studied by single‐crystal XRD, in situ variable pressure powder XRD, synchrotron powder XRD, pressure‐gradient differential scanning calorimetry (P‐DSC), and molecular modeling. The detailed structural information provides insight into the extreme flexibility of NiL₂ . Specifically, the extended linker ligand, L , undergoes ligand contortion and interactions between interpenetrated networks or sorbate–sorbent interactions enable the observed switching.     

Bioimaging of Peroxynitrite in MCF-7 Cells by a New Fluorescent Probe Rhodamine B Phenyl Hydrazide

Peroxynitrite is a potent oxidizing and nitrating agent which has detrimental effects on cells by altering the structure and function of biomolecules present within. A fluorescent probe rhodamine B phenyl hydrazide (RBPH) has been proposed for peroxynitrite (ONOO^?) imaging in MCF-7 cells based on its oxidation property, which converts RBPH to pink colored and highly fluorescent rhodamine B. The fluorescence emission intensity of the rhodamine B produced in the above process is linearly related to the concentration of peroxynitrite. The method obeys Beer’s law in the concentration range 2–20 nM and the detection limit has been found to be 1.4 nM. The possible reaction mechanism of peroxynitrite with RBPH to produce rhodamine B has been discussed with spectroscopic evidence. The Probe is selective to the peroxynitrite in the pH range 6–8 which is near physiological pH. Fluorescence microscopic studies suggest that the probe is cell permeable and hence peroxynitrite was imaged in MCF-7 cells.     

Nuclear techniques to investigate source and origin of groundwater pollutants and their flow path at Indian Rare Earths Ltd., Cochin,Kerala

Hydrochemical, environmental isotope and injected radiotracer investigations were carried out in order to investigate the possible source of contaminants and their movement in groundwater at Indian Rare Earths (IRE) site. Water samples were collected from piezometers, dug wells and river in and around IRE site for measurement of physical parameters, chemistry and isotopes. Chemical results show high fluoride, nitrate, sulphate and phosphate concentrations in piezometers whereas dug wells and river samples are free from contamination. Isotope data indicate that the contaminated groundwaters are enriched in δ²H and δ¹⁸O compared to dug well and river samples. Radiotracer experiments were carried out using single-well and multi-well techniques (radiotracers: ⁸²Br and ³H) for determining groundwater filtration velocity and flow direction, respectively. Groundwater filtration velocity was found to be about 1.3 cm/day and flow direction is from south to north. Based on the investigations it can be concluded that groundwater is getting contamination from southern part of IRE campus and the possible source for these contaminants could be the Fertilizer and Chemical of Travancore (FACT) industry.