全文获取类型
收费全文 | 1668篇 |
免费 | 83篇 |
国内免费 | 10篇 |
专业分类
化学 | 1068篇 |
晶体学 | 4篇 |
力学 | 79篇 |
综合类 | 1篇 |
数学 | 366篇 |
物理学 | 243篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 25篇 |
2020年 | 25篇 |
2019年 | 24篇 |
2018年 | 28篇 |
2017年 | 21篇 |
2016年 | 54篇 |
2015年 | 53篇 |
2014年 | 52篇 |
2013年 | 100篇 |
2012年 | 97篇 |
2011年 | 116篇 |
2010年 | 74篇 |
2009年 | 71篇 |
2008年 | 91篇 |
2007年 | 111篇 |
2006年 | 96篇 |
2005年 | 88篇 |
2004年 | 97篇 |
2003年 | 86篇 |
2002年 | 72篇 |
2001年 | 27篇 |
2000年 | 24篇 |
1999年 | 30篇 |
1998年 | 14篇 |
1997年 | 20篇 |
1996年 | 24篇 |
1995年 | 13篇 |
1994年 | 18篇 |
1993年 | 13篇 |
1992年 | 11篇 |
1991年 | 16篇 |
1990年 | 16篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 6篇 |
1985年 | 12篇 |
1984年 | 11篇 |
1983年 | 10篇 |
1982年 | 12篇 |
1981年 | 11篇 |
1980年 | 11篇 |
1979年 | 5篇 |
1977年 | 11篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1974年 | 3篇 |
1970年 | 3篇 |
1967年 | 2篇 |
排序方式: 共有1761条查询结果,搜索用时 15 毫秒
21.
Vlekken J D'Olieslaeger M Knuyt G Vandervorst W De Schepper L 《Journal of the American Society for Mass Spectrometry》2000,11(7):650-658
In secondary ion mass spectrometry, the detection of MCs+ clusters (with M an element of the specimen) under a Cs bombardment is frequently used for the quantification of major elements. Despite some very good results obtained by this method, some problems still remain. In order to gain some more insight into these problems, the formation mechanism of the MCs+ clusters is investigated using a Monte Carlo model. It is shown that the majority of the constituent particles of the formed clusters are initially first or second neighbor atoms at the surface and that the velocity distribution of the MCs+ clusters becomes broader and peaked at higher velocities with increasing surface binding energy of the M atom. In addition, it is demonstrated that the interaction potential between the M and Cs+ particle has no influence on the velocity distribution of the MCs+ clusters. On the other hand, the cluster formation probability, defined as the probability that a sputtered M and Cs+ particle will form a MCs+ cluster, is extremely sensitive to this interaction potential. It is also shown that the cluster formation probability decreases with increasing surface binding energy. Finally, a good correspondence is obtained between the calculated and experimental velocity distributions of MCs+ clusters sputtered from different monoatomic materials. As a consequence, the Monte Carlo model and the discussed results can be validated. 相似文献
22.
Fuks-Janczarek I Luc J Sahraoui B Dumur F Hudhomme P Berdowski J Kityk IV 《The journal of physical chemistry. B》2005,109(20):10179-10183
We have revealed a substantial enhancement of third-order optical figure of merits by the synthesis of a compact molecule possessing the tetrathiafulvalene (TTF) group with two backside C=O groups. Addition of the saturated methylene chain substantially suppresses the third-order optical figure of merits and even local optical hyperpolarizabilities at lambda = 532 nm. Another TTF-derivative molecule possessing ethylenic and acetylenic chains demonstrates large hyperpolarizabilities; however, generally, the figure of merit factor decreases due to the increasing optical losses as a consequence of enhanced linear absorption. At the same time, both of the chromophores have a large nonlinear optical response. General approaches for search and design of the third-order optical materials with improved properties are given. 相似文献
23.
24.
Brunsveld L Watzke A Durek T Alexandrov K Goody RS Waldmann H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2756-2772
Prenylated proteins with non-native functionalities are generally very difficult to obtain by recombinant or enzymatic means. The semisynthesis of preparative amounts of prenylated Rab guanosine triphosphatases (GTPases) from recombinant proteins and synthetic prenylated peptides depends largely on the availability of functionalised prenylated peptides corresponding to the proteins' native structure or modifications thereof. Here, we describe and compare solution-phase and solid-phase strategies for the generation of peptides corresponding to the prenylated C terminus of Rab7 GTPase. The solid-phase with utilisation of a hydrazide linker emerges as the more favourable approach. It allows a fast and practical synthesis of pure peptides and gives a high degree of flexibility in their modification. To facilitate the analysis of semisynthetic proteins, the synthesised peptides were equipped with a fluorescent group. Using the described approach, we introduced fluorophores at several different positions of the Rab7 C terminus. The position of the incorporated fluorescent groups in the peptides did not influence the protein-ligation reaction, as the generated peptides could be ligated onto thioester-tagged Rab7. However, it was found that the positioning of the fluorescent group had an influence on the functionality of the Rab7 proteins; analysis of the interaction of the semisynthetic Rab7 proteins with REP (Rab escort protein) and GDI (guanosine diphosphate dissociation inhibitor) molecules revealed that modification of the peptide side chains or of the C-terminal isoprenoid did not significantly interfere with complex formation. However, functionalisation of the C terminus was found to have an adverse effect on complex formation and stability, possibly reflecting low structural flexibility of the Rab GDI/REP molecules in the vicinity of the lipid-binding site. 相似文献
25.
Mangelings D Tanret I Matthijs N Maftouh M Massart DL Vander Heyden Y 《Electrophoresis》2005,26(4-5):818-832
The effect of five factors on the capillary electrochromatographic enantioseparation of acidic compounds was studied using an experimental design. The studied factors were pH, acetonitrile content in the mobile phase, temperature, buffer concentration, and applied voltage. These experiments allowed defining a generic separation strategy applicable on acidic compounds with chemical and structural diversity. The starting screening conditions consist of a 45 mM ammonium formate electrolyte at pH 2.9 mixed with 65% acetonitrile, an applied voltage of 15 kV, and a temperature of 25 degrees C. The screening phase occasionally can be followed by an optimization procedure. Evaluation of the proposed strategy pointed out that it allows achieving baseline resolution within a relatively short time when a beginning of separation is obtained at the starting conditions. This strategy revealed enantioselectivity for 11 compounds out of 15, of which 10 could be baseline-separated after the proposed optimization steps. 相似文献
26.
E. M. Azaroual P. Luc R. Vetter 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,24(2):161-164
The use of an effusive beam of titanium atoms crossed with a CW single-mode tunable dye laser has allowed the high-resolution, Doppler-free study of the isotope shifts between50Ti,48Ti and46Ti, for seven 3d
2 4s
2 a3
F
J
3d
2 4s 4p z
5
D
J
, visible transitions of Ti I. The measurements show without ambiguity the existence of a non-negligible field shift. Using the values of the nuclear radii of titanium (coming from muonic X-ray measurements), it is possible to determine the respective values of the field and mass shifts. 相似文献
27.
A way of using gravity flow to induce a linear convection within a microfluidic system is presented. It is shown and mathematically supported that tilting a 1 cm long covered microchannel is enough to generate flow rates up to 1000 nL.min(-1), which represents a linear velocity of 2.4 mm.s(-1). This paper also presents a method to monitor the microfluidic events occurring in a covered microchannel when a difference of pressure is applied to force a solution to flow in said covered microchannel, thanks to electrodes inserted in the microfluidic device. Gravity-induced flow monitored electrochemically is applied to the performance of a parallel-microchannel enzyme-linked immunosorbent assay (ELISA) of the thyroid-stimulating hormone (TSH) with electrochemical detection. A simple method for generating and monitoring fluid flows is described, which can, for instance, be used for controlling parallel assays in microsystems. 相似文献
28.
29.
30.
Gerrit L'Abbé Luc Van Meervelt Sabine Emmers Wim Dehaen Suzanne Toppet 《Journal of heterocyclic chemistry》1992,29(7):1765-1768
Structural data were obtained by X-ray crystallography for the title compounds which show that they are essentially planar and exhibit an approximately linear N2-S1-N8 arrangement. In compound 3 the separation between the sulfur atom and the pyridine nitrogen atom (2.61 Å) is larger than the Huggins constant energy distance (2.58 Å), suggesting that there is little or no bonding between them. The methylated salt 4 , on the contrary, has a closer S…N(pyridine) distance (2.19 Å) with an estimated bond dissociation energy of 6 kcal/mole. 相似文献