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91.
Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape 总被引:3,自引:0,他引:3
Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding. 相似文献
92.
Six polyamides with pendant 5-fluorouracil group were synthesized by the polycondensation ofdi-p-nitrophenyl N-(5-fluorouracil-1-acetyl)glutamate with a series of polymethylene diamines.All of the new polyamides obtained are soluble in water. Their chemical structures were confirmedby ~1H NMR, UV and IR spectra as well as elemental analyses. The antitumor activity of some ofthese polyamides were tested against Ehrlich Ascites Carcinoma in mice, III_a showed an inhibitionrate of 43%. 相似文献
93.
Elena S. Osipova Ekaterina S. Gulyaeva Evgenii I. Gutsul Vladislava A. Kirkina Alexander A. Pavlov Yulia V. Nelyubina Andrea Rossin Maurizio Peruzzini Lina M. Epstein Natalia V. Belkova Oleg A. Filippov Elena S. Shubina 《Chemical science》2021,12(10):3682
The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH2P(t-C4H9)2)2C6H4) and acidic [LWH(CO)3] (L = Cp (1a), Tp (1b); Cp = η5-cyclopentadienyl, Tp = κ3-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)2(μ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me2NHBH3, tBuNH2BH3) dehydrogenation. The combination of variable-temperature (1H, 31P{1H}, 11B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η1-borane complex [(PCP)Pd(Me2NHBH3)]+[LW(CO3)]− (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.Bimetallic complexes [LW(CO)2(μ-CO)⋯Pd(PCP)] cooperatively activate amine-boranes for their dehydrogenation via N–H proton tunneling at RDS and H2 evolution from two neutral hydrides. 相似文献
94.
Bakhmutova EV Bakhmutov VI Belkova NV Besora M Epstein LM Lledós A Nikonov GI Shubina ES Tomàs J Vorontsov EV 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(3):661-671
The interaction of [NbCp(2)H(3)] with fluorinated alcohols to give dihydrogen-bonded complexes was studied by a combination of IR, NMR and DFT methods. IR spectra were examined in the range from 200-295 K, affording a clear picture of dihydrogen-bond formation when [NbCp(2)H(3)]/HOR(f) mixtures (HOR(f) = hexafluoroisopropanol (HFIP) or perfluoro-tert-butanol (PFTB)) were quickly cooled to 200 K. Through examination of the OH region, the dihydrogen-bond energetics were determined to be 4.5+/-0.3 kcal mol(-1) for TFE (TFE = trifluoroethanol) and 5.7+/-0.3 kcal mol(-1) for HFIP. (1)H NMR studies of solutions of [NbCp(2)H(2)(B)H(A)] and HFIP in [D(8)]toluene revealed high-field shifts of the hydrides H(A) and H(B), characteristic of dihydrogen-bond formation, upon addition of alcohol. The magnitude of signal shifts and T(1) relaxation time measurements show preferential coordination of the alcohol to the central hydride H(A), but are also consistent with a bifurcated character of the dihydrogen bonding. Estimations of hydride-proton distances based on T(1) data are in good accord with the results of DFT calculations. DFT calculations for the interaction of [NbCp(2)H(3)] with a series of non-fluorinated (MeOH, CH(3)COOH) and fluorinated (CF(3)OH, TFE, HFIP, PFTB and CF(3)COOH) proton donors of different strengths showed dihydrogen-bond formation, with binding energies ranging from -5.7 to -12.3 kcal mol(-1), depending on the proton donor strength. Coordination of proton donors occurs both to the central and to the lateral hydrides of [NbCp(2)H(3)], the former interaction being of bifurcated type and energetically slightly more favourable. In the case of the strong acid H(3)O(+), the proton transfer occurs without any barrier, and no dihydrogen-bonded intermediates are found. Proton transfer to [NbCp(2)H(3)] gives bis(dihydrogen) [NbCp(2)(eta(2)-H(2))(2)](+) and dihydride(dihydrogen) complexes [NbCp(2)(H)(2)(eta(2)-H(2))](+) (with lateral hydrides and central dihydrogen), the former product being slightly more stable. When two molecules of TFA were included in the calculations, in addition to the dihydrogen-bonded adduct, an ionic pair formed by the cationic bis(dihydrogen) complex [NbCp(2)(eta(2)-H(2))(2)](+) and the homoconjugated anion pair (CF(3)COO...H...OOCCF(3))(-) was found as a minimum. It is very likely that these ionic pairs may be intermediates in the H/D exchange between the hydride ligands and the OD group observed with the more acidic alcohols in the NMR studies. 相似文献
95.
Thirteenα-methylene aromatic araminenone and fourα-methylene aromatic aminoketones were prepared by modified Mannich reaction.On the basis of isotopic labeling,a plausible way of cleavage was proposed for the formation of the M~ -17 fragment peak in the MS of theα-methylene aromatic araminenone and aminoketones.The characteristic chemical shift of the olefinic protons in ~1H NMR is also discussed. 相似文献
96.
介绍了一种相位开关型分频器电路的噪声分析方法。这种方法基于频率综合器的频域模型,能比较准确地预测分频器的相位噪声和它对整个频率综合器相位噪声的影响。分频器电路采用0.18μm CM O S工艺设计,用于W CDM A通讯系统中。在分析过程中,针对此电路的相位开关结构,提出了一些改进其噪声性能的方法。最后用仿真结果进行分析验证,仿真结果和理论相符合。 相似文献
97.
98.
只考虑腔长失调因素下建立了反射率模拟测量的理论模型。根据高斯光束传输规律分析了腔长失调对衰荡腔模式耦合的影响,推导了腔长失调与谐振腔输出脉冲信号、衰荡信号与反射率之间的关系,模拟了腔长失调在±10mm范围内的光脉冲衰荡现象。结果表明:对于光敏面直径为0.2mm的高速探测器,为了保证10-6的测量精度,腔长的失调量应控制在±1mm之间。在光路调节中采用具有对数变换功能的示波器和动态范围较大的探测器,可以提高测量精度。 相似文献
99.
1.3μm高增益偏振无关应变量子阱半导体光放大器 总被引:4,自引:2,他引:4
采用低压金属有机化学气相外延法 (LP MOVPE)生长并制作了 1 3μm脊型波导结构偏振无关半导体光放大器 (SOA) ,有源区为基于四个压应变量子阱和三个张应变量子阱交替生长的混合应变量子阱 (4C3T)结构 ,压应变阱宽为 6nm ,应变量 1 0 % ,张应变阱宽为 11nm ,应变量 - 0 95 % ;器件制作成 7°斜腔结构以有效抑制腔面反射。半导体光放大器腔面蒸镀Ti3 O5/Al2 O3 减反 (AR)膜以进一步降低腔面剩余反射率至 3× 10 -4以下 ;在 2 0 0mA驱动电流下 ,光放大器放大的自发辐射 (ASE)谱的 3dB带宽大于 5 0nm ,光谱波动小于 0 4dB ,半导体光放大器管芯的小信号增益近 30dB ,在 12 80~ 1340nm波长范围内偏振灵敏度小于 0 6dB ,饱和输出功率大于 10dBm ,噪声指数 (NF)为 7 5dB。 相似文献
100.
Youxiang Zhou Jianbiao Chen Lina Dong Liang Lu Fusheng Chen Dingjin Hu Xiaohong Wang 《Journal of luminescence》2012,132(6):1437-1445
Citrinin (CIT) is a nephrotoxic mycotoxin initially isolated from filamentous fungus Penicilliu citrinum. It was later isolated from several other species, such as Aspergillus and Monascus. It has a conjugated, planar structure that gives it a natural fluorescence ability, which can be used to develop sensitive methods for detecting CIT in food. In this paper, we used the spectro?uorescence technique to study the effects of pH value, β-cyclodextrin (β-CD) and organic solvents on the CIT fluorescence intensity. The results show that lower pH value, aceitc acid, β-CD and acetonitrile can induce a higher fluorescence intensity of CIT, but methanol or H2O has a decreasing effect on the fluorescence intensity of CIT. Findings in this study provide a theoretical basis for development of a high sensitivity fluorescence-based trace analysis for CIT detection. 相似文献