Secondary-secondary diamine catalysts for the enantioselective Michael addition of cyclic ketones to nitroalkenes

Secondary-secondary diamines derived from S-proline are efficient catalysts for the ketone-nitroalkene Michael addition reaction. The stereoselectivity of the Michael addition is dependant on the pK_a of the N-substituted aminomethyl pendant in these diamines. N′-Aryl aminomethyl pyrrolidines provide γ-nitroketones with moderate to good enantiomeric excess (65-92%). Removal of the hydrogen-bond donor group by N-methylation results in a dramatic reduction of enantioselectivity (average ee 6%).     

In situ radiation measurement and estimation of U/Th ratio to reflect on the uranium bearing potential zone in metamorphic rocks of Mahendragarh district, Haryana

Gross gamma radiation survey was carried out using Nal(Tl) scintillator based portable gamma ray spectrometer (PGRS) around areas of Gaonri, Dholera, Pachnota and Meghot in Mahendragarh district, Haryana. Geologically the area forms part of north Delhi fold belt comprising calc-silicate, quartz biotite schist, impure marble, quartzite and pegmatite rocks. Equivalent uranium (eU₃O₈) concentration in ppm was estimated in situ on a regular grid pattern of 500 m (E-W) × 1000 m (N-S) and grab samples were collected at grid locations for analyzing in the laboratory for estimating the contents of eU₃O_s Ra_eq, ThO₂ and %K. A comparison with the laboratory analysed grab samples for eU₃0₈ data and in situ radiation measurements shows a good match of the two sets of data. The in situ measurements indicate higher concentration of eU₃O₈ in Chapra Bibipur in northeastern most corners, Maghot area in central part, Gaonri in western part and Pachnota in southwestern part of the study area. As index to uranium favorability, U(Ra_eq)-Th contour map (prepared using Surfer software with Krieging interpolation method for this grid size) based on the data on grab samples was generated which show three major clusters of relatively high U-Th ratio. The blocks delineated are enriched in sodic mineral albite which support albite hosted uranium mineralization potential in metamorphic rocks in Haryana.      

Enhanced Thermocatalytic Activity of Porous Yellow ZnO Nanoflakes: Defect‐ and Morphology‐Induced Perspectives

Herein, we report a simple and effective strategy for the synthesis of yellow ZnO (Y‐ZnO) nanostructures with abundant oxygen vacancies on a large scale, through the sulfidation of ZnO followed by calcination. The developed strategy allows retention of the overall morphology of Y‐ZnO compared with pristine ZnO and the extent of oxygen vacancies can be tuned. The influence of oxygen deficiencies, the extent of defect sites, and the morphology of ZnO on its solution‐phase thermocatalytic activity has been evaluated in the synthesis of 5‐substituted‐1H‐tetrazoles with different nitriles and sodium azide. A reasonable enhancement in the reaction rate was achieved by using Y‐ZnO nanoflakes (Y‐ZnO NFs) as a catalyst in place of pristine ZnO NFs. The reaction was complete within 6 h at 110 °C with Y‐ZnO NFs, whereas it took 14 h at 120 °C with pristine ZnO NFs. The catalyst is easy to recycle without a significant loss in catalytic activity.     

Dioxygen activation at non-heme diiron centers: characterization of intermediates in a mutant form of toluene/o-xylene monooxygenase hydroxylase

We report the generation and characterization of an intermediate in a mutant form of the toluene/o-xylene monooxygenase hydroxylase component from Pseudomonas stutzeri OX1. The reaction of chemically reduced I100W variant in the presence of the coupling protein, ToMOD, with dioxygen was monitored by stopped-flow UV/visible spectroscopy. Rapid-freeze quench (RFQ) samples were also generated for EPR and M?ssbauer spectroscopy. A transient species is observed in the UV/visible spectrum with an absorption maximum at 500 nm. EPR and M?ssbauer spectra of RFQ samples identified this species as a diiron(III,IV) cluster spin-coupled to a neutral W radical. A diamagnetic precursor to the mixed-valent diiron(III,IV) was also observed at an earlier time point, with M?ssbauer parameters typical of high-spin FeIII. We have tentatively assigned this antiferromagnetically coupled diiron(III) intermediate as a peroxo-bridged cluster, and this complex has also been observed in preliminary studies of the wild-type hydroxylase.     

Dose response and kinetic analysis of thermoluminescence of Li–Zn fluoroborate glass

The intention of this study is to explore the thermoluminescence properties of beta-irradiated Li–Zn fluoroborate glass. The glow-curve corresponding to 10?Gy shows two peaks when measured at 1°C/s. The dose response of the glass to beta irradiation was investigated. The trapping level parameters such as activation energy, frequency factor and order of kinetics associated with the observed glow-peak were determined using different methods. The thermoluminescence is affected by thermal quenching. A possible mechanism for the thermoluminescence is described.     

Analysis of vibrational spectra of nano-bio molecules： Application to metalloporphrins

In this paper, we have applied the Lie algebraic model to nano-bio molecules to determine the vibrational spectra of different stretching and bending vibrational modes. The determined vibrational energy levels by the Lie algebraic model are compared with the experimental data. The results from the theoretical mode[ are consistent with the experimental data. The vibrational energy levels are clustering in the excited states.     

Applications of Raman spectroscopy in dentistry part II: Soft tissue analysis

Raman spectroscopy is rapidly moving from an experimental technique for the analysis of biological molecules to a tool for the real-time clinical diagnosis and in situ evaluation of the oral tissue in medical and dental research. The purpose of this study is to identify various applications of Raman spectroscopy, to evaluate the contemporary status, and to explore future directions in the field of dentistry. Several in-depth applications are presented to illustrate Raman spectroscopy in early diagnosis of soft tissue abnormalities. Raman spectroscopy allows researchers to analyze histological and biochemical composition of biological tissues. The technique not only demonstrates its role in the disclosure of dysplasia and malignancy, but also in performing guided biopsies, diagnosing sialoliths, and assessment of surgical margins. Raman spectroscopy is used to identify the molecular structures and their components to give substantial information about the chemical structure properties of these molecules. In this article, we acquaint the utilization of Raman spectroscopy in analyzing the soft tissues in relation to dentistry.     

Study of energy transfer from capping agents to intrinsic vacancies/defects in passivated ZnS nanoparticles

The study of energy transfer mechanism from different capping agents to intrinsic luminescent vacancy centres of zinc sulphide (ZnS) has been reported in the present work. Nanoparticles of capped and uncapped ZnS are prepared by co-precipitation reaction. These nanoparticles are sterically stabilized using organic polymers—poly vinyl pyrrolidone, 2-mercaptoethanol and thioglycerol. Monodispersed nanoparticles were observed under TEM for both capped and uncapped ZnS nanopowders. However, for uncapped ZnS nanopowders, tendency for formation of nanorod like structure exists. Size of ZnS crystallites was calculated from X-ray diffraction pattern. The primary crystallite size estimated from X-ray diffraction pattern is 1.95–2.20 nm for capped nanostructures and 2.2 nm for uncapped nanostructures. FTIR spectra were conducted to confirm capping. Zeta potential measurements have been done to check the stability of dispersed nanoparticles. Band gap measurement was done by UV–visible spectrophotometer. Excitation and emission spectra are also performed in order to compare optical properties in various samples. Increase in emission intensity and band gap has been observed by adding different capping agents in comparison to uncapped ZnS nanoparticles. The results show that in capped ZnS nanoparticles the mechanism of energy transfer from capping layer to photoluminescent vacancy centres is more pronounced.