全文获取类型
收费全文 | 394篇 |
免费 | 5篇 |
国内免费 | 2篇 |
专业分类
化学 | 283篇 |
晶体学 | 7篇 |
力学 | 11篇 |
数学 | 13篇 |
物理学 | 87篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 16篇 |
2020年 | 12篇 |
2019年 | 9篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 11篇 |
2015年 | 11篇 |
2014年 | 8篇 |
2013年 | 20篇 |
2012年 | 20篇 |
2011年 | 27篇 |
2010年 | 18篇 |
2009年 | 13篇 |
2008年 | 23篇 |
2007年 | 19篇 |
2006年 | 15篇 |
2005年 | 18篇 |
2004年 | 15篇 |
2003年 | 23篇 |
2002年 | 21篇 |
2001年 | 9篇 |
2000年 | 9篇 |
1999年 | 4篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 4篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 4篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有401条查询结果,搜索用时 15 毫秒
371.
It is shown that multiple scattering Xα calculations on Ni(CO)4 predict a strong back-donation effect contrary to what is stated in previous papers on the subject. 相似文献
372.
In this communication the authors report the HPLC SEPARATION OF 20 amino acids without derivatization. Separation was achieved by column swithing using a C-8 reversed-phase column and a cationic ion-exchange column. Detection of the underivatized amino acids was accomplished by means of an evaporative laser light-scattering (ELS) detector. The influence of the temperature of the diffusion tube and nebuolzation gas pressure on detector response is reported. The relationship of peak areas vs. mass show a good log-log linearity within a 1:10 range. Detechtion limit is in the order of 200 pmol for most amino acids under the conditions used. 相似文献
373.
374.
Summary Particulate-matter release into the stack effluents of a large coal-fired power station was characterized. Particulate samplings
were carried out in the chimney, downstream the electrostatic precipitation system, by means of an isokinetic probe. Concentration
and size distribution of total particulate mattern as well elemental composition as a function of particle size were detemined.
Concentrations of up to 24 elements were measured for whole filters by PIXE and AAS technique. Element enrichments in smaller
particles and in emitted ashes and their behaviours in combustion are also studied.
Work supported by ENEL-DSR. 相似文献
375.
Braga D Maini L Grepioni F Mota F Rovira C Novoa JJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(24):4536-4551
The (-)O-H...O(-) interaction formed by the anions HCO3-, HCO4, HC4O4 and HC5O5- (HA-), obtained upon monodeprotonation of the corresponding carbonic, oxalic, squaric and croconic acids (H2A), has been investigated theoretically and experimentally. The ring (RING) and chain (CHAIN) hydrogen bond motifs established between these anions have been analysed in terms of geometry and energy and their occurrence in crystalline salts investigated by searching the Cambridge Structural Database (CSD) and the Inorganic Chemistry Structural Database (ICSD). It has been shown that hydrogen carbonates form RINGs, with the notable exception of NaHCO3, while only CHAINs are known for hydrogen oxalates. Hydrogen squarates and hydrogen croconates can form both RINGs and CHAINs. The structures of Rb- and Cs- hydrogen croconates, which present the two alternative motifs, have been discussed together with that of the hydrated salt NaHC5O5.H2O. The relationship between RING and CHAIN has been examined in the light of ab initio calculations. A rigorous quantum chemical study of the nature of the interanionic (-)O-H...O(-) interaction in both vacuum and condensed phase has shown that the interaction energy is dominated by the electrostatic component which becomes attractive at short O...O distances (less than 2.5 A) if the net ionic charge on the anion is delocalised away from the -OH group. It has been demonstrated that the RING motif is slightly metastable with respect to dissociation in the gas phase, but becomes stable in the crystal owing to the influence of the Madelung field. However, the CHAIN motif is unstable both in the gas phase and in the crystal. It is argued that interanionic (-)O-H...O(-) interactions ought to be regarded as stabilising bonding interactions rather than proper intermolecular hydrogen bonds because the RING and CHAIN aggregates are not energetically stable on an absolute scale of bonding energy (i.e., in the absence of counterions). The presence of very short non-hydrogen-bridged O...O contacts resulting from charge compression of polyatomic anions bridged by alkali cations is also discussed. 相似文献
376.
377.
Braga D Polito M Dichiarante E Rubini K Grepioni F 《Chemical communications (Cambridge, England)》2007,(16):1594-1596
On heating the hydrated complexes 18-Crown[6].M[H(2)PO(4)].xH(2)O (x= 2 for M = K, Rb; x= 1.5 for M = Cs), quantitatively prepared by mechanical mixing of crystalline 18-Crown[6] and M[H(2)PO(4)], to ca. 60 degrees C, water loss takes place, accompanied by the extrusion of the crown ether from the crystalline complex and followed by reconstruction of the inorganic phase M[H(2)PO(4)](M = K, Rb, Cs); the resulting solid mixture reverts to 18-Crown[6].M[H(2)PO(4)].xH(2)O (x= 2 for M = K, Rb; x= 1.5 for M = Cs) upon grinding in air. 相似文献
378.
A variable selection methodology based on genetic algorithm (GA) was applied in a bilinear least squares model (BLLS) with second-order advantage, in three distinct situations, for determination by HPLC-DAD of the pesticides carbaryl (CBL), methyl thiophanate (TIO), simazin (SIM) and dimethoate (DMT) and the metabolite phthalimide (PTA) in wine. The chromatographic separation was carried out using an isocratic elution with 50:50 (v/v) acetonitrile:water as mobile phase. Preprocessing methods were performed for correcting the chromatographic time shifts, baseline variation and background. The optimization by GA provided a significant reduction of the errors, where for SIM and PTA a decrease of three times the value obtained using all variables, and an improvement in the distribution of them, reducing the observed bias in the results were observed. Comparing the RMSEP of the optimized model with the uncertainty estimates of the reference values it is observed that GA can be a very useful tool in second-order models. 相似文献
379.
Lillo V Fructos MR Ramírez J Braga AA Maseras F Díaz-Requejo MM Pérez PJ Fernández E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(9):2614-2621
The complexes [Cu(NHC)(NCMe)]BF4 (NHC=N-heterocyclic ligand), with bis(catecholato)diboron (B2(cat)2) as the boron source, efficiently catalyze the diboration of styrene with very high degrees of conversion. With the appropriate NHC ligand, the reaction proceeds quantitatively toward the diborated derivative PhCH(Bcat)--CH2(Bcat). The [styrene]/[B2(cat)2] ratio also has a strong effect on the selectivity: the use of an excess of styrene allows modification of the selectivity toward the formation solely of the monoborated derivative, PhCH2--CH2(Bcat). DFT calculations suggest that no oxidative addition processes take place at copper, but that intermediates containing coordinated sigma-bonds are involved in the catalytic cycle. 相似文献
380.
Braga PA Dos Santos DA Da Silva MF Vieira PC Fernandes JB Houghton PJ Fang R 《Natural product research》2007,21(1):47-55
The methanol extract from the stems and fruits of Swinglea glutinosa (Rutaceae) afforded 11 known acridone alkaloids and three N-phenylethyl-benzamide derivatives, glycocitrine-IV, 1,3,5-trihydroxy-4-methoxy-10-methyl-2,8-bis(3-methylbut-2-enyl)acridin-9(10H)-one, 1,3,5- trihydroxy-2,8-bis(3-methylbut-2-enyl)-10-methyl-9-acridone, citbrasine, citrusinine-II, citrusinine-I, 5-dihydroxyacronycine, pyranofoline, 3,4-dihydro-3,5,8-trihydroxy-6-methoxy-2,2,7-trimethyl-2H-pyrano[2,3-a]acridin-12(7H)-one, 2,3-dihydro-4,9-dihydroxy-2-(2-hydroxy-propan-2-yl)-11-methoxy-10-methylfuro[3,2-b]acridin-5(10H)-one, bis-5-hydroxyacronycine, N-(2-{4-[(3,7-dimethylocta-2,6-dien-1-yl)oxy]phenyl}ethyl)benzamide, N-(2-{4-[(3,7-dimethyl-4-acethyl-octa-2,6-dien-1-yl)oxy]phenyl}ethyl)benzamide, and severine acetate. All compounds isolated were examined for their activity against three cancer cell lines: human lung carcinoma (COR-L23), human breast adenocarcinoma (MCF7), human melanoma (C32), and normal human fetal lung cell line, MRC-5. The acridones tested exhibited weak cytotoxicity but the amides showed moderate nonselective cytotoxic activity. 相似文献