全文获取类型
收费全文 | 2682篇 |
免费 | 123篇 |
国内免费 | 14篇 |
专业分类
化学 | 1632篇 |
晶体学 | 7篇 |
力学 | 102篇 |
综合类 | 10篇 |
数学 | 522篇 |
物理学 | 368篇 |
无线电 | 178篇 |
出版年
2023年 | 14篇 |
2022年 | 27篇 |
2021年 | 40篇 |
2020年 | 44篇 |
2019年 | 35篇 |
2018年 | 51篇 |
2017年 | 38篇 |
2016年 | 82篇 |
2015年 | 73篇 |
2014年 | 82篇 |
2013年 | 158篇 |
2012年 | 149篇 |
2011年 | 166篇 |
2010年 | 109篇 |
2009年 | 105篇 |
2008年 | 141篇 |
2007年 | 148篇 |
2006年 | 140篇 |
2005年 | 127篇 |
2004年 | 130篇 |
2003年 | 133篇 |
2002年 | 106篇 |
2001年 | 39篇 |
2000年 | 35篇 |
1999年 | 40篇 |
1998年 | 28篇 |
1997年 | 35篇 |
1996年 | 43篇 |
1995年 | 22篇 |
1994年 | 28篇 |
1993年 | 31篇 |
1992年 | 20篇 |
1991年 | 26篇 |
1990年 | 22篇 |
1989年 | 14篇 |
1988年 | 12篇 |
1987年 | 12篇 |
1985年 | 25篇 |
1984年 | 26篇 |
1983年 | 18篇 |
1982年 | 35篇 |
1981年 | 26篇 |
1980年 | 27篇 |
1979年 | 17篇 |
1978年 | 12篇 |
1977年 | 25篇 |
1976年 | 18篇 |
1975年 | 11篇 |
1974年 | 11篇 |
1973年 | 11篇 |
排序方式: 共有2819条查询结果,搜索用时 15 毫秒
31.
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
32.
Colette Deschamps-Vallet Jean-Baptiste Ilots Michle Meyer-Dayan Darius Molho 《Journal of heterocyclic chemistry》1982,19(1):97-101
3-Phenyl-1-benzopyrylium percholorates 1a, 1i react exculusively at C-2 with ethanol and isopropyl alcohol, affording mixed acetals 2a, 3a, 3i . Aqueous ammonia gives symmetrical secondary amines 4a, 4b or bis(3-phenyl-2H-1-benzopyran-2-yl)amines, while with aqueous aliphatic amines (40%) bis-acetals 5a, 5b or 2,2′-oxy-bis(3-phenyl-2H-1-benzopyrans) are characterized. In some other acidic conditions, 5a and 5b are also obtained. 相似文献
33.
Peter Lindemann Silvia E. Braslavsky Marie-Michle Cordonnier Lee H. Pratt Kurt Schaffner 《Photochemistry and photobiology》1993,58(3):417-424
Abstract–Thc kinetics of the microsecond phototransformation intermediates of 124 kDa Avena phytochrome (17001,2) were studied in the prcsence of bound monoclonal antibodies at various temperatures. A global analysis was applied to the decays at all wavelengths at each temperature in order to derive the rate constants and the decay-associated spectra of the three decay components. Monoclonal antibodies bound to specific epitopes altered the Arrhenius parameters of both 17001,2 decay components. The strongest influence on these parameters was observed with OAT 8 (epitope between residues 624 and 686), which decreased by more than 50% the activation parameters of both components. This decrease is interpreted to result from an increased flexibility induced by this antibody in the ground state or in the transition state of bonds changing during the decay of both 1700 transients. Thus, the OAT 8 cpitope appears to be functionally important during the decay of the 17001,2 intermediates. For the case of 11001 bound OAT 23 and OAT 25 (epitopes between residues 1 and 66) reduced even further the relatively small flexibility of these bonds in the red light-absorbing form of phytochrome (P1) without antibodies, as reflected by the high preex-ponential factors for its decay. This resulted also in higher activation energies for this decay in the presence of the antibodies. Thus, the amino-terminus should act as a rigid spacer of the chromophore cavity without affecting it during the microsecond transformation, because the Arrhenius parameters for these decays are similar to those for small phytochrome. The possible implications of the influence of the various antibodies on the bleaching remaining after the decay of 17001,2 are discussed. 相似文献
34.
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
35.
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
36.
37.
Vincent Lapinte Laurent Fontaine Vronique Montembault Irne Campistron Danile Reyx 《Journal of molecular catalysis. A, Chemical》2002,190(1-2):117-129
ROMP and retro-acyclic diene metathesis (ADMET) were used for the synthesis of new functional polymers and functional oligomers, respectively. Purely exo and enantiomerically pure norbornene and 7-oxanorbornene derivatives were prepared using stereospecific synthesis, effective fractionation and high yield condensation reactions. Successful ROMPs of those monomers were performed using either the new carbenic Schrock’s or Grubb’s catalysts or in some cases a classical bicomponent catalyst. New functional polymers such as optically active poly(norbornene-2-carboxylic acid), reactive poly(norbornene-2-azlactone), and side-chain liquid crystal polyoxanorbornenes were fully characterized. On the other hand, successful depolymerizations of 1,4-polyisoprene and of epoxidized 1,4-polybutadiene via cross-metathesis with 4-octene were performed using a stabilized bicomponent catalyst and the Grubb’s catalyst, respectively. Conditions for the controlled synthesis of epoxidized oligobutadienes and of epoxydienic monomers via retro-ADMET were clearly defined. 相似文献
38.
39.
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
40.
Supercritical fluid chromatography of carbohydrates 总被引:1,自引:0,他引:1
Michel Lafosse Bernard Herbreteau Luc Morin-Allory 《Journal of chromatography. A》1996,720(1-2):61-73
Supercritical fluid chromatography (SFC) is a relatively new technique applied to polar solutes such as carbohydrates about 10 years ago. The developments in the SFC of carbohydrates are summarized and a comparison between capillary and packed column SFC is presented. High-efficiency capillary columns are suitable only for derivatized carbohydrates since various packed columns are well adapted for non derivatized mono-, di- and trisaccharides and provide complementary selectivities. 相似文献