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81.
Rodriguez EE Poineau F Llobet A Sattelberger AP Bhattacharjee J Waghmare UV Hartmann T Cheetham AK 《Journal of the American Chemical Society》2007,129(33):10244-10248
Crystalline technetium dioxide was prepared and for the first time its crystal structure determined by neutron powder diffraction. In addition, electronic structure calculations using density functional theory were performed to further elucidate the bonding mechanisms in TcO2. The crystal structure determined by Rietveld analysis with the NPD data is of a distorted rutile type, similar to that of MoO2; space group P21/c, a = 5.6891(1), b = 4.7546(1), c = 5.5195(1) A, and beta = 121.453(1) degrees . The NPD analysis also establishes a new neutron scattering length of 6.00(3) fm for 99Tc. Our results clearly show metal-metal bonding between Tc pairs along the edge-sharing chains of TcO6 octahedra. The Tc-Tc bond was found to be 2.622(1) A from NPD profile analysis and 2.59 A from first-principles DFT calculations. The bond is somewhat longer than expected from earlier predictions, suggesting that the nature of the Tc-Tc interaction is weaker than anticipated for the Tc(IV) cation with three outer electrons. The NPD results supported by the DFT calculations suggest that the filling of antibonding orbitals and the influence of the crystal field stabilization of the d3 Tc cations lead to more regular TcO6 octahedra and diminish the metal-metal bond strength compared with closely related oxides such MoO2 and WO2. 相似文献
82.
Sanjay Dashrath Vaidya Bobba Venkata Siva Kumar Ramanatham Vinod Kumar Umesh Nanasaheb Bhise Uday Chandrakant Mashelkar 《Journal of heterocyclic chemistry》2007,44(3):685-691
83.
Agarwal Umesh P. Ralph Sally A. Baez Carlos Reiner Richard S. 《Cellulose (London, England)》2021,28(14):9069-9079
Cellulose - In cellulose materials, the cellulose II allomorph is often present either exclusively or in conjunction with cellulose I, the natural cellulose. Moreover, in regenerated and mercerized... 相似文献
84.
Chao Jia Liheng Chen Ziqiang Shao Umesh P. Agarwal Liangbing Hu J. Y. Zhu 《Cellulose (London, England)》2017,24(6):2483-2498
We fabricated cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) from different cellulose materials (bleached eucalyptus pulp (BEP), spruce dissolving pulp (SDP) and cotton based qualitative filter paper (QFP) using concentrated oxalic acid hydrolysis and subsequent mechanical fibrillation (for CNFs). The process was green as acid can be easily recovered, and the prepared cellulose nanomaterials were carboxylated and thermally stable. In detail, the CNC yield from the different materials was similar. After hydrolysis, the DP of the cellulose materials decreased substantially, whereas the mechanical fibrillation of the cellulosic solid residues (CSRs) did not dramatically reduce the DP of cellulose. CNCs with different aspect ratios were produced from different starting materials by oxalic acid hydrolysis. The CNCs and CNFs obtained from BEP and QFP possessed more uniform dimensions than those from SDP. On the other hand, CNFs derived from SDP presented the best suspension stability. FTIR analyses verified esterification of cellulose by oxalic acid hydrolysis. The results from both XRD and Raman spectroscopy indicated that whereas XRD crystallinity of CNCs from BEP and QFP did not change significantly, there was some change in Raman crystallinity of these samples. Raman spectra of SDP CNCs indicated that the acid hydrolysis preferably removed cellulose I portion of the samples and therefore the CNCs became cellulose II enriched. TGA revealed that the CNCs obtained from QFP exhibited higher thermal stability compared to those from BEP and SDP, and all the CNCs possessed better thermal stability than that of CNCs from sulfuric acid hydrolysis. The excellent properties of prepared cellulose nanomaterials will be conducive to their application in different fields. 相似文献
85.
Umesh A. Fegade Suban K. Sahoo Amanpreet Singh Narinder Singh Sanjay B. Attarde Anil S. Kuwar 《Analytica chimica acta》2015
A fluorescent based receptor (4Z)-4-(4-diethylamino)-2-hydroxybenzylidene amino)-1,2dihydro-1,5-dimethyl-2-phenylpyrazol-3-one (receptor 3) was developed for the highly selective and sensitive detection of Cu2+ and Zn2+ in semi-aqueous system. The fluorescence of receptor 3 was enhanced and quenched, respectively, with the addition of Zn2+ and Cu2+ ions over other surveyed cations. The receptor formed host-guest complexes in 1:1 stoichiometry with the detection limit of 5 nM and 15 nM for Cu2+ and Zn2+ ions, respectively. Further, we have effectively utilized the two metal ions (Cu2+ and Zn2+) as chemical inputs for the manufacture of INHIBIT type logic gate at molecular level using the fluorescence responses of receptor 3 at 450 nm. 相似文献
86.
Tailoring of Electronic Structure and Thermoelectric Properties of a Topological Crystalline Insulator by Chemical Doping
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Subhajit Roychowdhury Dr. U. Sandhya Shenoy Prof. Dr. Umesh V. Waghmare Dr. Kanishka Biswas 《Angewandte Chemie (International ed. in English)》2015,54(50):15241-15245
Topological crystalline insulators (TCIs) are a new quantum state of matter in which linearly dispersed metallic surface states are protected by crystal mirror symmetry. Owing to its vanishingly small bulk band gap, a TCI like Pb0.6Sn0.4Te has poor thermoelectric properties. Breaking of crystal symmetry can widen the band gap of TCI. While breaking of mirror symmetry in a TCI has been mostly explored by various physical perturbation techniques, chemical doping, which may also alter the electronic structure of TCI by perturbing the local mirror symmetry, has not yet been explored. Herein, we demonstrate that Na doping in Pb0.6Sn0.4Te locally breaks the crystal symmetry and opens up a bulk electronic band gap, which is confirmed by direct electronic absorption spectroscopy and electronic structure calculations. Na doping in Pb0.6Sn0.4Te increases p‐type carrier concentration and suppresses the bipolar conduction (by widening the band gap), which collectively gives rise to a promising zT of 1 at 856 K for Pb0.58Sn0.40Na0.02Te. Breaking of crystal symmetry by chemical doping widens the bulk band gap in TCI, which uncovers a route to improve TCI for thermoelectric applications. 相似文献
87.
H. Nagabhushana B.M. Nagabhushana B. Umesh H.B. Premkumar Nalina Anil T.K. Gundu Rao 《哲学杂志》2013,93(12):1567-1574
Enstatite (MgSiO3) ceramic powders were synthesised by a low-temperature initiated self-propagating, gas-producing solution combustion process. The prepared powders were characterised by powder X-ray diffraction, scanning electron microscopy and Brunauer–Emmer–Teller specific surface area measurements. Defect centres induced by radiation were studied using the techniques of thermoluminescence (TL) and electron spin resonance (ESR). A well-resolved glow with peak at 178°C and a shouldered peak at 120°C were observed. Two defect centres were identified by ESR measurements, which were carried out at room temperature, and these were assigned to an O? ion and F+ centre. The O? ion (hole centre) appears to correlate with the main TL peak at 178°C. 相似文献
88.
Umesh P. Gomes Yiqiao Chen Sanjib Kabi Peter Chow Dhrubes Biswas 《Current Applied Physics》2013,13(3):487-492
The performance of InAlAs/InGaAs quantum well field effect transistors are subject to high impact ionization and band-to-band tunneling (BTBT) due to its narrow bandgap feature. In this work, the energy gap is engineered using strain and quantization techniques to increase the effective energy gap leading to low impact ionization and BTBT leakage current. It is shown that the impact ionization is reduced in 5 nm channel device as compared to 13 nm device with onset at approximately Egeff/q. Also the band-to-band-tunneling current is reduced due to the increase in effective energy gap. We have also investigated the effects of quantum well engineering on the dc performance of InGaAs HEMTs. 相似文献
89.
Recent work in our laboratory has shown that the highly substituted, electronically rich 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (THIQ3CA) scaffold is a key building block for a novel class of promising anticoagulants (Al-Horani et al. J. Med. Chem.2011, 54, 6125-6138). The synthesis of THIQ3CA analogs, especially containing specific, electronically rich substituents, has been a challenge and essentially no efficient methods have been reported in the literature. We describe three complementary, glycine donor-based strategies for high yielding synthesis of highly substituted, electronically rich THIQ3CA esters. Three glycine donors studied herein include hydantoin 1, (±)-Boc-α-phosphonoglycine trimethyl ester 2 and (±)-Z-α-phosphonoglycine trimethyl ester 3. Although the synthesis of THIQ3CA analogs could be achieved using either of the three, an optimal, high yielding approach for the desired THIQ3CA esters was best achieved using 3 in three mild, efficient steps. Using this approach, a focused library of advanced N-arylacyl, N-arylalkyl, and bis-THIQ3CA analogs was synthesized. Variable temperature and solvent-dependent NMR chemical shift studies indicated the presence of two major conformational rotamers in 3:1 proportion for N-arylacyl-THIQ3CA analogs, which were separated by a high kinetic barrier of ~17 kcal/mol. In contrast, N-arylalkyl and bis-THIQ3CA variants displayed no rotamerism, which implicates restricted rotation around the amide bond as the origin for high-barrier conformational interconversion. This phenomenon is of major significance because structure-based drug design typically utilizes only one conformation. Overall, the work presents fundamental studies on the synthesis and conformational properties of highly substituted, electronically rich THIQ3CA analogs. 相似文献
90.
Naik AD Annigeri SM Gangadharmath UB Revankar VK Mahale VB 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(8):1713-1719
A new binucleating ligand containing phenoxide as an endogenous bridging group, 2,6-diformyl-p-cresol bis(2-furanthiocarboxyhydrazone) and its binuclear Co(II), Ni(II), Cu(II) and Zn(II) complexes with chloride ion as an exogenous bridge, have been obtained. The complexes were characterized by elemental analysis, molar conductivities, magnetic moment measurements at room temperature, electronic, IR, 1H-NMR, EPR, FAB spectral studies and thermal data. The copper complex assumes a tetranuclear structure composed of two binuclear units related by a center of symmetry. The dimeric nature of copper(II) complex is supported by FAB. This complex is EPR silent. Room temperature magnetic moment reveals the operation of a significant antiferromagnetic spin exchange between the metal centers. Ligand and its copper and zinc complexes exhibit fluorescence at room temperature in DMF. All the compounds show an appreciable antimicrobial activity. 相似文献