首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   99篇
  免费   0篇
化学   59篇
晶体学   1篇
数学   1篇
物理学   38篇
  2022年   4篇
  2021年   2篇
  2020年   2篇
  2019年   2篇
  2018年   1篇
  2016年   1篇
  2015年   3篇
  2014年   6篇
  2013年   7篇
  2012年   4篇
  2011年   8篇
  2010年   3篇
  2009年   7篇
  2008年   5篇
  2007年   3篇
  2006年   6篇
  2005年   9篇
  2004年   3篇
  2003年   3篇
  2002年   7篇
  2001年   5篇
  2000年   1篇
  1999年   1篇
  1993年   2篇
  1992年   1篇
  1991年   1篇
  1973年   1篇
  1962年   1篇
排序方式: 共有99条查询结果,搜索用时 15 毫秒
51.
    
Six-coordinate organotin derivatives L2SnR2 [L = 3-methyl-1-(4-trifluoromethylphenyl)-4-R3-C=O-5-pyrazolonato (R3 = CH3, L = L1; R3 = C6H5, L = L2; R3 = CF3, L = L3; R = CH3, n-C4H9, C6H5)] have been synthesized and characterized by analytical and spectroscopic (1H, 13C, 119Sn, and 19F NMR, IR) techniques. Partial dissociation of one ligand in chloro-hydrocarbon solvents gives rise to cationic five-coordinate L-(solvent)-diorganotin(IV) complexes. The X-ray crystal structure of bis[4-benzoyl-3-methyl-1-(4-trifluoromethylphenyl)pyrazolon-5-ato]diphenyltin ( 6 ) shows the metal in a distorted octahedron (skewed trapezoidal bipyramidal) with the two β-diketonato donors in syn positions, a C−Sn−C bond angle of 165.2(2)° and two sets of tin−oxygen bonds [2.141(5) and 2.139(3) Å for Sn−O(pyrazolonato) and 2.250(4) and 2.272(5) Å for Sn−O(acyl)]. Surprisingly, the recently reported dimethyltin derivative has the anti configuration, in contrast to expectations based on all previous experience. Large scale Hartree−Fock (HF) and Density Functional Theory (DFT) calculated structures for the anti configuration of bis[4-benzoyl3-methyl-1-(4-trifluoromethylphenyl)pyrazolon-5-ato]dimethyltin show good agreement with the experimental structure obtained from X-ray methods. The hypothetical syn configuration of bis[4-benzoyl-3-methyl-1-(4-trifluoromethylphenyl)pyrazolon-5-ato]dimethyltin was also studied theoretically and both methods also predict characteristic structural features, such as: (from HF) a C−Sn−C bond angle of 150.0°, Sn−O(pyrazolonato) bond lengths of 2.088 and 2.084 Å and Sn−O(acyl) bond lengths of 2.385 and 2.401 Å. Results from the syn calculated structures suggest that intramolecular repulsive F ··· F interactions contribute to the synanti conversion.  相似文献   
52.
    
Ester derivatives of 5-aminolevulinic acid (ALA-esters) have been proposed as alternative drugs for ALA in photodynamic therapy. After topical application of creams containing ALA, ALA methylester (ALA-Me), ALA hexylester (ALA-Hex) and ALA octylester (ALA-Oct) on mouse skin, typical fluorescence excitation and emission spectra of protoporphyrin IX (PpIX) were recorded, exhibiting a similar spectral shape for all the drugs in the range of concentrations (0.5-20%) studied. The accumulation kinetics of PpIX followed nearly a similar profile for all the drug formulations. The fluorescence of PpIX peaked at around 6-12 h of continuous cream application. Nevertheless, some differences in pharmacokinetics were noticed. For ALA cream, the highest PpIX fluorescence was achieved using 20% of ALA in an ointment. Conversely, 10% of ALA-Me and ALA-Hex, but not of ALA-Oct, in the cream was more efficient (P < 0.05) than was 20%. The cream becomes rather fluid when 20% of any of these ALA-esters is used in ointment, whereas 10% and lower concentrations of ALA-esters do not significantly increase fluidity of the cream. The dependence of PpIX accumulation on the concentration of ALA and ALA-ester in the applied cream followed (P < 0.002) kinetics as described by a mathematical model based on the Michaelis-Menten equation for enzymatic processes. Under the present conditions, the PpIX amount in the skin increased by around 50% by the application of ALA-Me, ALA-Hex or ALA-Oct for 4-12 h as compared with ALA for the same period. Observations of the mice under exposure to blue light showed that after 8-24 h of continuous application of ALA, the whole mouse was fluorescent, whereas in the case of ALA-Me, ALA-Hex and ALA-Oct the fluorescence of PpIX was located only at the area of initial cream application. The amount of the active compound in the applied cream necessary to induce 90% of the maximal amount of PpIX was determined for normal mouse skin. Optimal PpIX fluorescence can be attained using around 5% ALA, 10% ALA-Me and 5% ALA-Hex creams during short application times (2-4 h). Topical application of ALA-Oct may not gain optimal PpIX accumulation for short applications (<5 h). For long application times (8-12 h), it seems that around 1% ALA, 4% ALA-Me, 6% ALA-Hex and 16% ALA-Oct can give optimal PpIX fluorescence. But for long application times and high concentrations, systemic effect of ALA applied topically on relatively large areas should be considered.  相似文献   
53.
    
Diorganotin(IV) complexes of the β-diketonato benzoylacetonato ligand were synthesized and characterized with IR and multinuclear (H, C, Sn) NMR spectroscopy. The X-ray diffraction study of bis(benzoylacetonato)di-tert-butyltin(IV) shows two independent molecules in the crystallographic unit cell. The metal polyhedron is a distorted octahedral (Skewed Trapezoidal Bipyramidal) with the trans angle C−Sn−C of 151.5(5)°. Each ligand chelates the metal with different donor abilities [Sn−O bond lengths of 2.423(8) Å and 2.135(8) Å in one ligand, and 2.107(9) Å and 2.357(8) Å in the other]; results for the 2nd molecule are similar. The coordination arrangement differs from those of related bis(β-diketonato)diorganotin derivatives containing asymmetric ligands, which are characterized by an approximate Cs symmetry, in that both benzoylacetonato ligands point their methyl (and phenyl) substituents across (anti) the metal atom. Chelate planarity and some phenyl-chelate co-planarity was observed. Hartree−Fock (HF) and Density Functional Theory (DFT) calculated structures are in good agreement with those obtained using X ray analysis. DFT and HF calculated structures of bis(benzoylacetonato)diphenyltin(IV), having a similar connectivity as bis(benzoylacetonato)di-tert-butyltin(IV), differ markedly: the phenyls subtend a C−Sn−C bond angle of 180°, all Sn−O bond lengths are equal and the tin coordination sphere is a regular octahedron with the ligand bzac being isobidentate. This arrangement is caused by the phenyl electronic withdrawal effect. However, IR data for this compound show several Sn−O bands inconsistent with this configuration and suggest a different connectivity. Additional DFT structural calculations for (bzac)2SnPh2, performed on the connectivity resembling the “normal” syn geometry, show a conformational energy slightly lower than that of the centrosymmetric arrangement. Low temperature NMR spectra illustrate the possible rearrangements in solution. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)  相似文献   
54.
For the first time, the chemical composition of the seed essential oil of Rhododendron tomentosum was determined. Forty-seven compounds were identified, comprising 91.7% of the total oil. Palustrol (38.3%) and ledol (27.0%) were the predominant constituents. Some constituents, such as beta-pinene oxide, iso-menthyl acetate, nerolidyl acetate, cadalene and guaiazulene were characteristic only for the seeds and were identified for the first time in Rh. tomentosum oils. For comparison purposes, the essential oil isolated from the shoots of the same plant were analyzed [GC(FID) in combination with RIs, GC-MS and 13C NMR]. More than a half of the oil was comprised of ledol (36.5%) and palustrol (21.0%). Quantitative analysis of ascaridol, a heat-sensitive compound, was carried out by 13C NMR spectroscopy. Indeed, ascaridol undergoes partial thermal isomerization to iso-ascaridol during GC analyses.  相似文献   
55.
56.
57.
58.
Nonequilibrium molecular dynamics simulations are applied to the investigation of step-flow kinetics at crystal-melt interfaces of silicon, modeled with the Stillinger-Weber potential [Phys. Rev. B 31, 5262 (1985)]. Step kinetic coefficients are calculated from crystallization rates of interfaces that are vicinals of the faceted (111) orientation. These vicinal interfaces contain periodic arrays of bilayer steps, and they are observed to crystallize in a step-flow growth mode at undercoolings lower than 40 K. Kinetic coefficients for both [110] and [121] oriented steps are determined for several values of the average step separation, in the range of 7.7-62.4 A. The values of the step kinetic coefficients are shown to be highly isotropic, and are found to increase with increasing step separation until they saturate at step separations larger than approximately 50 A. The largest step kinetic coefficients are found to be in the range of 0.7-0.8 m(sK), values that are more than five times larger than the kinetic coefficient for the rough (100) crystal-melt interface in the same system. The dependence of step mobility on step separation and the relatively large value of the step kinetic coefficient are discussed in terms of available theoretical models for crystal growth kinetics from the melt.  相似文献   
59.
Research on the functions of the human brain requires that functional magnetic resonance imaging (MRI) moves towards producing images with less distortion and higher temporal and spatial resolution. This study compares passband balanced steady-state free precession (bSSFP) acquisitions with and without parallel imaging (PI) to investigate whether combining PI with this pulse sequence is a viable option for functional MRI. Such a novel combination has the potential to offer the distortion-free advantages of bSSFP with the reduced acquisition time of PI. Scans were done on a Philips 3T Intera, using the installed bSSFP pulse sequence, both with and without the sensitivity encoding (SENSE) PI option. The task was a visual flashing checkerboard, and the viewing window covered the visual cortex. Sensitivity comparisons with and without PI were done using the same manually drawn region of interest for each time course of the subject, and comparing the z-score summary statistics: number of voxels with z>2.3, the mean of those voxels, their 90th percentile and their maximum value. We show that PI greatly improves the temporal resolution in bSSFP, reducing the volume acquisition time by more than half in this study to 0.67 s with 3-mm isotropic voxels. At the same time, a statistically significant increase was found for the maximum z-score using bSSFP with PI as compared to without it (P=.02). This improvement can be understood in terms of physiological noise, as demonstrated by noise measurements. This produces observed increases in the overall temporal signal to noise of the functional time series, giving greater sensitivity to functional activations with PI. This study demonstrates for the first time the possibility of combining PI with bSSFP to achieve distortion-free functional images without loss of sensitivity and with high temporal resolution.  相似文献   
60.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号