全文获取类型
收费全文 | 13310篇 |
免费 | 320篇 |
国内免费 | 74篇 |
专业分类
化学 | 8311篇 |
晶体学 | 133篇 |
力学 | 453篇 |
数学 | 1956篇 |
物理学 | 2851篇 |
出版年
2022年 | 103篇 |
2021年 | 144篇 |
2020年 | 181篇 |
2019年 | 174篇 |
2018年 | 135篇 |
2017年 | 116篇 |
2016年 | 277篇 |
2015年 | 245篇 |
2014年 | 310篇 |
2013年 | 682篇 |
2012年 | 635篇 |
2011年 | 708篇 |
2010年 | 361篇 |
2009年 | 419篇 |
2008年 | 652篇 |
2007年 | 657篇 |
2006年 | 620篇 |
2005年 | 562篇 |
2004年 | 530篇 |
2003年 | 436篇 |
2002年 | 385篇 |
2001年 | 240篇 |
2000年 | 246篇 |
1999年 | 141篇 |
1998年 | 137篇 |
1997年 | 139篇 |
1996年 | 187篇 |
1995年 | 138篇 |
1994年 | 195篇 |
1993年 | 195篇 |
1992年 | 197篇 |
1991年 | 141篇 |
1990年 | 142篇 |
1989年 | 150篇 |
1988年 | 120篇 |
1987年 | 139篇 |
1986年 | 126篇 |
1985年 | 223篇 |
1984年 | 183篇 |
1983年 | 128篇 |
1982年 | 157篇 |
1981年 | 136篇 |
1980年 | 157篇 |
1979年 | 144篇 |
1978年 | 150篇 |
1977年 | 128篇 |
1976年 | 144篇 |
1975年 | 117篇 |
1974年 | 143篇 |
1973年 | 132篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
161.
Resolution of freshly prepared and of commercially available (degraded) samples of cardiolipin into 15-30 components has been accomplished by reversed-phase high-performance liquid chromatography using a 3-micron particulate Microsorb C18 column irrigated with linear gradients of acetonitrile--methanol--10 mM phosphate buffer pH 7.4. Selected resolved components were crystallized and characterized by infrared absorption spectra. Saponification of other components and identification of component fatty acids by reversed-phase high-performance liquid chromatography demonstrated the presence of ten fatty acids (14:0, 14:1, 16:0, 16:1, 18:0, 18:1, 18:2, 18:3, 20:0, 20:4), with linoleic acid (18:2) identified in all resolved components. From fatty acid composition data it appears that several resolved fractions consist of single cardiolipin molecular species. 相似文献
162.
G. K. Bratspies J. F. Smith J. O. Hill P. J. Derrick 《Journal of Thermal Analysis and Calorimetry》1979,16(2):369-379
A new tin dithiocarbamate containing sulphur bridges, di--sulphidobis [bis(N,N-diethyldithiocarbamato)tin(IV)], has been isolated from the thermal decomposition of tetrakis(N,N-diethyldithiocarbamato)tin(IV). A dimeric structure is proposed on the basis of results from mass spectrometry, infrared spectroscopy, thermal analysis and vapour pressure osmometry.
The authors gratefully acknowledge the assistance given by Dr. A. G. Wedd with the vacuum sublimation technique. One of us, G. K. B., is grateful for a research scholarship provided by La Trobe University. 相似文献
Zusammenfassung Ein neues, Schwefelbrücken enthaltendes Zinn-Dithiocarbamat, Di--sulfidobis[bis(N,N-diäthyldithiocarbamato)Zinn(IV)], wurde bei der Zersetzung von Tetrakis(N,N-diäthyl-dithiocarbamato)Zinn(IV) isoliert. Aufgrund der Ergebnisse der Massenspektrometrie, der Infrarotspektroskopie, der Thermoanalyse und der Dampfdruck-Osmometrie wird eine Dimerstruktur vorgeschlagen.
Résumé Un nouveau dithiocarbamate d'étain contenant des ponts de soufre, le di--sulfidobis[bis(N,N-diéthyl-dithiocarbamato)é tain(IV)], a été isolé lors de la décomposition thermique du tétrakis(N,N-diethyl-dithiocarbamato) étain(IV). Une structure dimère est proposéeà partir des résultats obtenus par spectrométrie de masse, spectroscopie infrarouge, analyse thermique et osmométrie sous pression de vapeur.
—-- [/N,N- (/IV)], [/N,N- (/IV)], , (N,N- ) (IV). - , , .
The authors gratefully acknowledge the assistance given by Dr. A. G. Wedd with the vacuum sublimation technique. One of us, G. K. B., is grateful for a research scholarship provided by La Trobe University. 相似文献
163.
Very simple and selective methods are presented to determine the amino acid tryptophan (Trp) and the biogenic amine tryptamine (Tryp), both compounds with an indole-type molecular structure by the methodology named Heavy Atom Induced-Room Temperature Phosphorescence (HAI-RTP) which constitutes the first time that HAI-RTP has been used to detect compounds with non-naphthalenic structures in their molecules. Different variables affecting the phosphorescence signal (heavy atom perturber and sodium sulfite concentration) were carefully studied. The analytical curves give a linear dynamic range of 15-100 ng ml(-1) and a detection limit of 4 ng ml(-1) for Trp and 94-400 ng ml(-1) and 28 ng ml(-1) for Tryp. The methods have been successfully applied to the analysis of complex food matrices such as the presence of tryptophan in yoghurt and tryptamine in bottled beer. A single alkaline hydrolysis to release Trp from yoghurt proteins and two methods for extracting Tryp from beer samples are proposed and optimised. A total Trp content of 374 mg of Trp per kg of yoghurt was quantified by the standard addition method of calibration and a recovery of 90% was obtained for 250 ng ml(-1) of Tryp in spiked non-alcoholic beer samples. 相似文献
164.
Substoichiometric amorphous thin films of MoO3 in both the transparent and absorptive forms have been studied by X-ray electron spectroscopy. The transparent films can be colored blue (absorptive) electrically or by UV irradiation. The electron distribution curve of the blue film exhibits a small band near the Fermi edge which is absent in the transparent sample. This new band is attributed to electrons trapped in positively charged anion vacancies in the substoichiometric MoO3 lattice. This model provides an interpretation of the electrical conductivity and color of the films. 相似文献
165.
Abstract —Various low-potential viologen dyes enhance light-induced absorption changes in the near-infrared region (ΔA870) in chromatophore preparations from Rhodospirillum rubrum in the presence of dichlorophenol indophenol and a high concentration of ascorbate (DCPIP + asc). An increase in ΔA870 was also observed in large reaction-center preparations from R. rubrum with viologens in the presence of ascorbate. Our results indicate that E'0 , of the primary electron acceptor X may be as low as -0.37 V, as suggested recently by P. A. Loach (1973, personal communication). 相似文献
166.
Smith JT Tomfohr JK Wells MC Beebe TP Kepler TB Reichert WM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):8279-8286
A novel technique for the quantitative observation of cell migration along linear gradient substrates functionalized with adhesive proteins is presented. Gradients of the cell adhesion molecule fibronectin are generated by the cross diffusion of functionalizable alkanethiols on gold and characterized by X-ray photoelectron spectroscopy and surface plasmon resonance. Two distinct migration assays are described that characterize the movement of either sparsely populated noncontacting cells or a confluent monolayer of cells into free space. The drift speed of bovine aortic endothelial cells is measured and shown to increase along a fibronectin gradient when compared to a uniform control substrate using both assays. The results of these experiments establish reproducible conditions for studies of cell migration on gradients of surface-bound ligands. 相似文献
167.
The stereoselective total synthesis of (-)-microcarpalide, a recently discovered 10-membered lactone of fungal origin displaying a remarkable disrupting action on actin microfilaments, was accomplished by using ring-closing metathesis (RCM) as the key step for the formation of the medium-sized ring. The diene ester required for the macrocyclization reaction was assembled via DCC-mediated esterification of two suitable partners, each bearing a terminal alkene group. The alcohol fragment was synthesized from n-bromohexane through a seven-step sequence entailing two consecutive stereoselective homologations of chiral boronic esters as strategic transformations for the sequential insertion of the two stereocentres with the final S absolute configuration, using (+)-pinanediol as the chiral director; final elaboration to the desired C(11) framework envisaged treatment with an allyl Grignard reagent and oxidative cleavage of the boronic scaffold. In contrast, the acidic fragment was prepared in ten steps from d-tartaric acid, whose C(4) backbone was elongated to the required C(7) skeleton by means of two distinct Swern-Wittig oxidation-homologation sequences. 相似文献
168.
Douglas F. Foster Barry S. Nicholls Anthony K. Smith 《Journal of organometallic chemistry》1982,236(3):395-402
Reactions of Rh6(CO)16 with bis(diphenylphosphino)methane (dppm) gave Rh6(CO)14(dppm), Rh6(CO)12(dppm)2, or Rh6(CO)10(dppm)3, depending upon the reaction conditions. Rh4(CO)10(dppm) may be obtained from the reaction of Rh4(CO)12 with dppm, but this derivative rapidly decomposes in solution to give Rh4(CO)8(dppm)2, Rh6(CO)14(dppm), and Rh6(CO)12(dppm)2. Ir4(CO)10(dppm) and Ir4(CO)8(dppm)2 have also been prepared, and their structures are discussed on the basis of infrared and 31P NMR spectroscopic data. 相似文献
169.
A glucose biosensor with enzyme immobilised by sol–gel technology was constructed and evaluated. The glucose biosensor reported is based on encapsulated GOX within a sol–gel glass, prepared with 3-aminopropyltriethoxy silane, 2-(3,4-epoxycyclohexyl)-ethyltrimetoxy silane and HCl. A flow system incorporating the amperometric biosensor constructed was developed for the determination of glucose in the 1×10−4–5×10−3 mol l−1 range with a precision of 1.5%. The results obtained for the analysis of electrolytic solution for iv administration and human serum samples showed good agreement between the proposed method and the reference procedure, with relative error <5%. 相似文献
170.
A general stochastic theory of size exclusion chromatography (SEC) able to account for size dependence on both pore ingress and egress processes, moving zone dispersion and pore size distribution, was developed. The relationship between stochastic-chromatographic and batch equilibrium conditions are discussed and the fundamental role of the 'ergodic' hypothesis in establishing a link between them is emphasized. SEC models are solved by means of the characteristic function method and chromatographic parameters like plate height, peak skewness and excess are derived. The peak shapes are obtained by numerical inversion of the characteristic function under the most general conditions of the exploited models. Separate size effects on pore ingress and pore egress processes are investigated and their effects on both retention selectivity and efficiency are clearly shown. The peak splitting phenomenon and peak tailing due to incomplete sample sorption near to the exclusion limit is discussed. An SEC model for columns with two types of pores is discussed and several effects on retention selectivity and efficiency coming from pore size differences and their relative abundance are singled out. The relevance of moving zone dispersion on separation is investigated. The present approach proves to be general and able to account for more complex SEC conditions such as continuous pore size distributions and mixed retention mechanism. 相似文献