Synthesis and characterisation of bis(pentafluorophenyl)antimony(V) cations, [(C6F5)2SbL3]

Pentacoordinate complex cations of the general formula [(C₆F₅)₂SbL₃]³⁺ stabilized as solid salts in combination with tetraphenylborate (BPh₄), tetrafluorobroate (BF₄) anions, where L=DMSO, Ph₃AsO, PyO, DMF, α-, β- and γ-picoline have been isolated. The newly formed complexes were characterized by elemental analysis, molar conductance measurements, solid-state IR and and NMR. From these results, a five-fold coordination around antimony was required.     

On the Control of Magnetic Anisotropy through an External Electric Field

The effect of an external electric field on the magnetic anisotropy of a single‐molecule magnet has been investigated, for the first time, with the help of DFT. The application of an electric field can alter the magnetic anisotropy from “easy‐plane” to “easy‐axis” type. Excitation analysis performed through time‐dependent DFT predicts that the external electric field facilitates metal to π‐acceptor ligand charge transfer, leading to uniaxial magnetic anisotropy and concomitant spin Hall effect in a single molecule.     

Synthesis and evaluation of thermal, photophysical and magnetic properties of novel starlike fullerene–organosilane macromolecules

Thermal, photophysical and magnetic properties of some novel fullerenol–silane adducts are described. Excellent improvement of thermal stability and high char yield due to the presence of silicon is the key feature of these adducts. Highest luminescence quenching due to maximum π–π electronic interactions between phenyl ring and fullerene are observed in the aromatic-silane adducts and the quenching ability of the aromatic ring reduces with further delocalization of the π-electrons as in naphthyl silane. The alkyl vinyl silane, on the other hand, records better fluorescence intensity owing to increase population of the electron density (+I effect) and non-effective charge transfer complex formation between isolated vinylic double bond and fullerene. Emission peak positions of these adducts are comparable to fullerenol because of control derivatization of fullerene ring causing less perturbation of the symmetric π-electronic system. These adducts are paramagnetic in nature with peaks around 3515 G and higher g-values (2.005–2.009) compared to fullerenol (1.985). The fullerenol–silane adducts are synthesized using fullerenol as substrate and different chloro and alkoxy silanes as silylating agents adopting simple nucleophilic displacement and transesterification reactions. All the fullerenol–silane adducts are characterized spectroscopically.     

MAS-NMR study of lithium zinc silicate glasses and glass-ceramics with various ZnO content

Lithium zinc silicate glasses of composition (mol%): 17.5Li₂O-(72−x)SiO₂-xZnO−5.1Na₂O−1.3P₂O₅−4.1B₂O₃, 5.5?x?17.7, were prepared by conventional melt-quenched technique and converted to glass-ceramic by controlled crystallization process. ²⁹Si and ³¹P MAS-NMR was used to characterize the structure of both glass and glass-ceramic samples. Despite the complex glass composition, Q², Q³ and Q⁴ sites are identified from ²⁹Si MAS-NMR, which relative intensities are found to vary with the ZnO content, indicating a network depolymerization by ZnO. Moreover, well separated Q³ and Q⁴ resonances for low ZnO content indicates the occurrence of phase separation. From ³¹P MAS-NMR, it is seen that phosphorus is mainly present in the form of ortho-(Q⁰) and pyro-phosphate (Q¹) structural units and variation of ZnO content did not have much effect on these resonances, which provides an additional evidence for phase separation in the glass. On conversion to glass-ceramics, lithium disilicate (Li₂Si₂O₅), lithium zinc ortho-silicate (Li₃Zn_0.5SiO₄), tridymite (SiO₂) and cristobalite (SiO₂) were identified as major silicate crystalline phases. Using ²⁹Si MAS-NMR, quantification of these silicate crystalline phases is carried out and correlated with the ZnO content in the glass-ceramics samples. In addition, ³¹P spectra unambiguously revealed the presence of crystalline Li₃PO₄ and (Na,Li)₃PO₄ in the glass-ceramics.     

In vivo lifetimes of the three color-sectors in bioluminescence emissions of the firefly Luciola praeusta at different temperatures

Bioluminescence emissions from fireflies have been well-studied for over a century. From the apparent features of the emitted light, conclusions have been drawn and hypotheses put forward on the characteristics of the highly efficient light emitting system. The basic emitter oxyluciferin, being chemically unstable, is difficult to study in isolation and, therefore, its analogs have been prepared and analyzed. In this letter, the lifetimes of the excited-state emitter oxyluciferin are measured, and an inference is drawn on the chemiluminescence reaction in vivo. The light from the Indian species of firefly Luciola praeusta contains three color-sectors: green, yellow, and red, and hence three optical filters are used to study time-resolved emissions from these sectors at different temperatures. All the three color-sectors are observed to be temperature sensitive in the time domain. An exponential variation of lifetime with temperature is observed for the emissions in these three regions.     

Upper Bounds on Liouville First-Passage Percolation and Watabiki's Prediction

Given a planar continuum Gaussian free field h^𝒰 in a domain 𝒰 with Dirichlet boundary condition and any δ > 0, we let be a real-valued smooth Gaussian process where is the average of h^𝒰 along a circle of radius δ with center v. For γ > 0, we study the Liouville first-passage percolation (in scale δ), i.e., the shortest path distance in 𝒰 where the weight of each path P is given by . We show that the distance between two typical points is for all sufficiently small but fixed γ > 0 and some constant c^* > 0. In addition, we obtain similar upper bounds on the Liouville first-passage percolation for discrete Gaussian free fields, as well as the Liouville graph distance, which roughly speaking is the minimal number of euclidean balls with comparable Liouville quantum gravity measure whose union contains a continuous path between two endpoints. Our results contradict some reasonable interpretations of Watabiki's prediction (1993) on the random distance of Liouville quantum gravity at high temperatures.© 2019 Wiley Periodicals, Inc.     

A turn on ESIPT probe for rapid and ratiometric fluorogenic detection of homocysteine and cysteine in water with live cell-imaging

5(Benzothiazol-2-yl)-4-hydroxyisophthalaldehyde (BHI), an intense ESIPT containing molecule in mixed media loses its properties due to resonance-assisted H-bond (RAHB) in absolute water. Due to resonance-assisted H-bond the o-aldehyde is more reactive than the other one. With addition of cysteine/homocysteine into this solution the o-aldehyde group gets transformed into thiazolidine/thiazine ring, respectively, and the phenolic proton becomes free enough for transfer to nitrogen of the benzothiazole ring in excited state, that is, the ESIPT of BHI is turned on. Thus we can detect cysteine/homocysteine in water as well as in live cells.     

Study of indoor radon and thoron progeny levels in surrounding areas of Nalbari, Assam, India

With the growing understanding of the role of radon and its daughter products as major sources of radiation exposure, the importance of large number of estimation of radon concentration in various parts of the country is realized. Inhalation of radon, thoron and their decay products is the major source of the total radioactive dose received by the human population from natural radiation. The indoor radon and thoron progeny levels in Nalbari area of Assam are studied by using the LR-115 (type II) Solid State Nuclear Track Detector in Plastic Twin Chamber dosimeter. Radon and thoron progeny levels in different types of dwellings for one full calendar year are presented in this paper. For Assam Type (A.T.) houses, indoor radon progeny concentrations vary from 0.17 to 0.64 mWL with an annual geometric mean of 0.27 mWL and that for Reinforced Cement Concrete (R.C.C.) houses vary from 0.22 mWL to 0.60 mWL with the annual geometric mean of 0.37 mWL. The thoron progeny levels in A.T. houses also vary from 0.01 to of 0.05 mWL with an annual geometric mean of 0.02 mWL and that for R.C.C. houses vary from 0.02 to 0.08 mWL with the annual geometric mean of 0.04 mWL.