Selectivity in Garratt-Braverman cyclization: an experimental and computational study

Bispropargyl sulfones equipped with aromatic rings of dissimilar nature were synthesized. Under basic conditions, these sulfones isomerized to the bisallenic sulfones, creating a competitive scenario between two alternate Garratt-Braverman (GB) cyclization pathways. The observed product distribution ruled out the involvement of any ionic intermediate and supported the diradical mechanism with greater involvement of the electron-rich aromatic ring via the more nucleophilic radical. DFT-based calculations supported the diradical mechanism along with the observed selectivity.     

Colored non-gaussian noise driven open systems: generalization of Kramers' theory with a unified approach

In this paper we have calculated escape rate from a meta stable state in the presence of both colored internal thermal and external nonthermal noises. For the internal noise we have considered usual gaussian distribution but the external noise may be gaussian or non-gaussian in characteristic. The calculated rate is valid for low noise strength of non-gaussian noise such that an effective gaussian approximation of non-gaussian noise wherein the higher order even cumulants of order "4" and higher are neglected. The rate expression we derived here reduces to the known results of the literature, as well as for purely external noise driven activated rate process. The latter exhibits how the rate changes if one switches from non-gaussian to gaussian character of the external noise.     

Click-reagent version of Sonogashira coupling protocol to conjugated fluorescent alkynes with no or reduced homocoupling

A click-reagent version of the Sonogashira-coupling protocol has been developed. Diarylalkynes with donor and/or acceptor substituents have been synthesized via this protocol at moderate to excellent yields and with no or drastically reduced quantities of undesired homocoupled side products. This protocol is green-solvent compatible, air-insensitive, and effective under microwave conditions.     

Barrier crossing dynamics of a charged particle in the presence of a magnetic field: a new turnover phenomenon

In this paper we have investigated the effect of a magnetic field on the barrier crossing rate of a charged particle. At the low friction regime we have observed a new turnover phenomenon for the variation of rate as a function of field strength. Thus although the force due to the magnetic field is not dissipative in nature, it plays a role in the steady state barrier crossing rate similar to that of a dissipative force in the weak damping regime. For appreciable damping strength, the rate monotonically decreases with the increase of field strength. We have demonstrated an interesting resonance effect due to the variation of frequency of the harmonic oscillator associated with the y-component motion at low damping and magnetic field strength.     

Water induced chromogenic and fluorogenic signal modulation in a bi-fluorophore appended acyclic amino-receptor system

An acyclic amino-receptor based bi-fluorophoric signaling system 3 exhibits water-induced simultaneous dual channel chromogenic and fluorogenic signal modulation. Its micromolar solution in various organic solvents exhibits an enhancement in absorption in the presence of water in trace amounts through the water-induced delactonization of rhodamine dye, rendering a visual perception as a function of colour change. The presence of water molecules also facilitates a fluorescence resonance energy transfer (FRET) from the excited nitro-benz-oxa-diazole fluorophore to rhodamine dye of 3 and leads to an enhancement of emission up to a second order of magnitude. The failure of the reference compounds 2 and 4 to respond under similar conditions reveals the role of structural variation of the receptor on the perturbation of photophysical processes.     

Alteration of selectivity in rhodamine based probes for Fe(III) and Hg(II) ion induced dual mode signalling responses

The probes for metal ion induced chromo- and fluorogenic signalling responses alter their selectivity depending upon the nature of substituent as well as a function of solvent medium. 2 has shown selectivity towards Fe(III) ion, 4 towards Hg(II) ion while 3 is responsive towards both Fe(III) and Hg(II) ions.     

Microstructural analysis of neutron-irradiation induced changes in polyester fibre studied using EPMA

Electron microscopy is an important characterization technique for the study of textile fibre as it gives more information on fabric wear, nature of fibre fracture, chemical degradation, abrasion, fatigue and many others. Electron Probe Micro Analyzer (EPMA) micrographs of virgin and some neutron-irradiated samples (graphite coated) are discussed. The filament diameter, D, of virgin PET fibre obtained from EPMA study was 12.5 μn. The surface topography of single filament distinctly reveals the core and sheath parts of the filament. The core diameter of the virgin fibre was estimated to be 1.43 μm. The fibre irradiated at fluence 1 × 10¹² n/cm² shows radiation induced sphere like polymer balls or spherulites of diameter 2.27 μm in the expanded core region. Due to irradiation, the sheath area crosslinks with expanded core region, which may be responsible for increase of strength and hardness of the polymer materials. Moreover, the micrograph at 3000 X magnifications clearly shows that there is no preferred orientation of the polymer in any direction confirming the isotropic nature of the sample.      

Identification of Putative Vaccine and Drug Targets against the Methicillin-Resistant Staphylococcus aureus by Reverse Vaccinology and Subtractive Genomics Approaches

Methicillin-resistant Staphylococcus aureus (MRSA) is an opportunistic pathogen and responsible for causing life-threatening infections. The emergence of hypervirulent and multidrug-resistant (MDR) S. aureus strains led to challenging issues in antibiotic therapy. Consequently, the morbidity and mortality rates caused by S. aureus infections have a substantial impact on health concerns. The current worldwide prevalence of MRSA infections highlights the need for long-lasting preventive measures and strategies. Unfortunately, effective measures are limited. In this study, we focus on the identification of vaccine candidates and drug target proteins against the 16 strains of MRSA using reverse vaccinology and subtractive genomics approaches. Using the reverse vaccinology approach, 4 putative antigenic proteins were identified; among these, PrsA and EssA proteins were found to be more promising vaccine candidates. We applied a molecular docking approach of selected 8 drug target proteins with the drug-like molecules, revealing that the ZINC4235426 as potential drug molecule with favorable interactions with the target active site residues of 5 drug target proteins viz., biotin protein ligase, HPr kinase/phosphorylase, thymidylate kinase, UDP-N-acetylmuramoyl-L-alanyl-D-glutamate-L-lysine ligase, and pantothenate synthetase. Thus, the identified proteins can be used for further rational drug or vaccine design to identify novel therapeutic agents for the treatment of multidrug-resistant staphylococcal infection.     

2,2'-Diaminodiphenyldisulphide-a new sensitive spectrophotometric reagent for platinum

2,2'-Diaminodiphenyldisulphide is a highly sensitive platinum chromogen. Platinum(IV) forms a complex with it in 50% aqueous ethanol at pH 5.0-6.0, having maximum absorption at 725 nm. The molar absorptivity of the complex is 5.48 x 10(4)1.mole(-1).cm(-1) at 725nm and the sensitivity is 0.0035 mug/cm(2). The colour system obeys Beer's law from 0.25 to 5 ppm with optimum concentration range 0.75-4 ppm of platinum. The relative error is 2.7%. The metal to reagent ratio is 1:2, and the stepwise formation constants K(1) and K(2) are 5.6 x 10(4) and 1.96 x 10(4) respectively.