Effect of lithium chloride on the palisade layer of the Triton-X-100 micelle: two sites for lithium ions as revealed by solvation and rotational dynamics studies

Dynamic Stokes' shift measurements using coumarin 153 as the fluorescence probe have been carried out to explore the effect of added electrolyte, lithium chloride (LiCl), on solvation dynamics in the Triton-X-100 (TX-100) micelle and thus to understand the changes in micellar Palisade layer, especially the entrapped water structures in the Palisade layer. At all concentrations of LiCl, the spectral shift correlation function shows biexponential decay. At lower LiCl concentrations, the longer solvation time is seen to decrease, although the shorter solvation time is not affected much. At higher LiCl concentrations, both longer and shorter solvation times increase with electrolyte concentration. The present observations have been rationalized assuming two possible modes of interaction of the Li+ ions in the micellar palisade layer. For LiCl concentrations below about 1.5 M, the Li+ ions appear to bind preferably to the ether groups of surfactant molecules, and the increased micellar hydration with the added salt effectively makes the solvation dynamics faster. At higher LiCl concentrations, available ether binding sites for the Li+ ions seem to get occupied effectively and the excess Li+ ions start remaining in the Palisade layer as strongly hydrated free ions. Because of strong hydration of the Li+ ions, the mobility of the entrapped water molecules in the micellar Palisade layer decreases significantly, causing the solvation dynamics to slow at higher LiCl concentrations. The fluorescence anisotropy results in the present systems are also in support of the above inferences drawn from solvation dynamics results. The present results with LiCl salt are found to be substantially different than those obtained in our earlier study (Kumbhakar et al. J. Phys. Chem. B 2005, 109, 14168) with salts such as NaCl, KCl, and CsCl. These differences are attributed mainly to the binding of the Li+ ions with the surfactant ether groups, which seems to be unlikely for the other alkali cations.     

A Thiazole-linked Covalent Organic Framework for Lithium-Sulphur Batteries

Lithium-sulphur (Li−S) batteries are a promising alternative power source, as they can provide a higher energy density than current lithium-ion batteries. Porous materials are often used as cathode materials as they can act as a host for sulphur in such batteries. Recently, covalent organic frameworks (COFs) have also been used, however they typically suffer from stability issues, resulting in limited and thus insufficient durability under practical conditions and applications. Herein, we report the synthesis of a crystalline and porous imine-linked triazine-based dimethoxybenzo-dithiophene functionalized COF (TTT-DMTD) incorporating high-density redox sites. The imine linkages were further post-synthetically transformed to yield a robust thiazole-linked COF (THZ-DMTD) by utilizing a sulphur-assisted chemical conversion method, while maintaining the crystallinity. As a synergistic effect of its high crystallinity, porosity and the presence of redox-active moieties, the thiazole-linked THZ-DMTD exhibited a high capacity and long-term stability (642 mAh g⁻¹ at 1.0 C; 78.9 % capacity retention after 200 cycles) when applied as a cathode material in a Li−S battery.     

Tunable infrared generation in KTA and applications

Noncollinear difference frequency mixing of dye laser and Nd:YAG second harmonic (fundamental) radiation from a commercial laser system is employed for the generation of 2.7–5.3 μm (1.6–1.7 μm) radiations in a flux-grown KTiOAsO₁ crystal. The generated radiation is used to scan the methane absorption in the fundamental (v ₃) and its first overtone (2v ₃) band at pressure 90 torr in a laboratory made single pass gas cell of length 33 cm.     

Tunable near-infrared radiation by difference frequency mixing in a lithium tetraborate crystal

Non-collinear difference frequency mixing is reported for the first time in a lithium tetraborate (Li₂B₄O₇) crystal, and is used to generate near-infrared radiation in the range 1700–2300 nm. Received: 13 July 2000 / Published online: 10 January 2001     

Generation of ultraviolet radiation with wide angular tolerance in cesium lithium borate crystal

Tangential phase-matching has been realised in cesium lithium borate (CLBO) crystal for the first time for the generation of fourth harmonic (266 nm) of Nd:YAG and third harmonic (226.7 nm) of a dye laser radiation by second harmonic generation and sum-frequency mixing with the angular tolerance as large as 22 mrad and 21 mrad respectively, over one of the interacting beams. An energy conversion efficiency of 15% for fourth harmonic generation is obtained with a 5.5 mm thick crystal and with the average pump powers only 170 and 70 mW. A set of Sellmeier dispersion equations for the CLBO crystal have also been formulated.     

Third harmonic generation of CO2 laser radiation in AgGaSe2 crystal

Generation of third harmonic of CO₂ laser radiation has been obtained in a type-II, ϑ=57° cut 9 mm thick AgGaSe₂ crystal for the first time by sum-frequency-mixing of the fundamental with its second harmonic, the latter being obtained using another type-I, ϑ=55° cut 11 mm thick AgGaSe₂ crystal. The energy conversion efficiencies obtained for second harmonic and third harmonic generations are 6.3% and 2.4% respectively with the input fundamental pump power density of 5.9 MW/cm² only. The wavelength of the fundamental CO₂ laser radiation used for the generation of harmonics is 10.6 μm, P(20) line. A compact TEA CO₂ laser source has been built in the laboratory.     

Effects of block size of pluronic polymers on the water structure in the corona region and its effect on the electron transfer reactions

Effects of constituent block size of triblock copolymers on the nature of the water molecules in the corona region of their micelles have been investigated using time-resolved fluorescence measurements. The physical nature of the water molecules in the micellar corona region of the block copolymer, Pluronic F88 ([ethylene oxide (EO)]103-[propylene oxide (PO)]39-EO103), has been studied using a solubilized coumarin dye. Solvent reorientation time and rotational correlation time have been measured and compared with another block copolymer, Pluronic P123 (EO20-PO70-EO20), which has a different composition of the constituent PO and EO blocks. It is noted that due to the presence of larger number of EO blocks in F88 as compared with P123, the corona region of the former micelle is more hydrated than that of the latter. The solvent reorientation time and rotational correlation time are found to be relatively shorter for F88 as compared with P123. This indicates that the water molecules in the corona of the F88 micelle are more labile than those of P123, which is also supported from the estimated number of water molecules associated with each EO unit, measured from the size of each type of micelle and its aggregation number. To understand the effect of block size on the chemical reactions in these microheterogeneous media, electron transfer reactions have been carried out between different coumarin acceptors and N, N-dimethylaniline donor. The electron transfer results obtained in F88 micelles have been compared with those obtained in P123, and the results are rationalized on the basis of the relative hydration of the two triblock copolymer micelles.     

Cyclometalated complexes derived from calix[4]arene bisphosphites and their catalytic applications in cross-coupling reactions

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p-tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p-tert-butyl- or p-H-calix[4]arene are connected to a P(OR) (R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C-C or C-H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd-P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C-C cross-coupling reactions but, on an average, the yields are only modest.     

Gel Sculpture: Moldable,Load‐Bearing and Self‐Healing Non‐Polymeric Supramolecular Gel Derived from a Simple Organic Salt

An easy access to a library of simple organic salts derived from tert‐butoxycarbonyl (Boc)‐protected L ‐amino acids and two secondary amines (dicyclohexyl‐ and dibenzyl amine) are synthesized following a supramolecular synthon rationale to generate a new series of low molecular weight gelators (LMWGs). Out of the 12 salts that we prepared, the nitrobenzene gel of dicyclohexylammonium Boc‐glycinate ( GLY.1 ) displayed remarkable load‐bearing, moldable and self‐healing properties. These remarkable properties displayed by GLY.1 and the inability to display such properties by its dibenzylammonium counterpart ( GLY.2 ) were explained using microscopic and rheological data. Single crystal structures of eight salts displayed the presence of a 1D hydrogen‐bonded network (HBN) that is believed to be important in gelation. Powder X‐ray diffraction in combination with the single crystal X‐ray structure of GLY.1 clearly established the presence of a 1D hydrogen‐bonded network in the xerogel of the nitrobenzene gel of GLY.1 . The fact that such remarkable properties arising from an easily accessible (salt formation) small molecule are due to supramolecular (non‐covalent) interactions is quite intriguing and such easily synthesizable materials may be useful in stress‐bearing and other applications.