全文获取类型
收费全文 | 24079篇 |
免费 | 4006篇 |
国内免费 | 3114篇 |
专业分类
化学 | 18753篇 |
晶体学 | 230篇 |
力学 | 939篇 |
综合类 | 215篇 |
数学 | 1434篇 |
物理学 | 9628篇 |
出版年
2024年 | 49篇 |
2023年 | 221篇 |
2022年 | 483篇 |
2021年 | 961篇 |
2020年 | 1055篇 |
2019年 | 761篇 |
2018年 | 707篇 |
2017年 | 896篇 |
2016年 | 1149篇 |
2015年 | 993篇 |
2014年 | 1329篇 |
2013年 | 2169篇 |
2012年 | 1451篇 |
2011年 | 1405篇 |
2010年 | 1173篇 |
2009年 | 1417篇 |
2008年 | 1588篇 |
2007年 | 1550篇 |
2006年 | 1409篇 |
2005年 | 1358篇 |
2004年 | 1324篇 |
2003年 | 1174篇 |
2002年 | 914篇 |
2001年 | 793篇 |
2000年 | 787篇 |
1999年 | 668篇 |
1998年 | 614篇 |
1997年 | 504篇 |
1996年 | 412篇 |
1995年 | 384篇 |
1994年 | 317篇 |
1993年 | 205篇 |
1992年 | 217篇 |
1991年 | 129篇 |
1990年 | 106篇 |
1989年 | 100篇 |
1988年 | 68篇 |
1987年 | 56篇 |
1986年 | 49篇 |
1985年 | 50篇 |
1984年 | 42篇 |
1983年 | 15篇 |
1982年 | 21篇 |
1981年 | 35篇 |
1980年 | 23篇 |
1979年 | 16篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 521 毫秒
991.
Sergey?P.?BabailovEmail author Lubov?D.?Nikulina 《Journal of inclusion phenomena and macrocyclic chemistry》2005,51(1-2):103-109
1H and 13C NMR measurements are reported for the CDCl3 and CD2Cl2 solutions of [La(NO3)3(18-crown-6)] (I), [Pr(NO3)3(18-crown-6)] (II) and [Ce(NO3)3(18-crown-6)] (III) complexes. Temperature dependencies of the 1H NMR spectra of II have been analyzed using the dynamic NMR methods for multi-site exchange. Two types of conformational dynamic processes in II were identified (the first one with activation enthalpy ΔH
‡=26 ± 4 kJ/mol is conditioned by interconversion of complex enantiomeric form and pseudorotation of macrocycle molecule upon the C
2 symmetry axis, the second one with ΔH
‡=46 ± 5 kJ/mol is conditioned by macrocycle molecule inversion). Studies of the values of the lanthanide-induced shifts revealed that the structure of complexes in solution is similar to that reported for the complex I in the crystal state.This revised version was published online in July 2005 with a corrected issue number. 相似文献
992.
S. V. Fedorov A. Yu. Rulev N. N. Chipanina A. M. Shulunova V. G. Nenajdenko E. S. Balenkova D. A. Tyurin V. K. Turchaninov 《Russian Chemical Bulletin》2005,54(1):103-107
The molecular structures of β-amino-α-bromovinyl trifluoromethyl ketones was studied by UV, IR, 1H, 13C, and 15N NMR spectroscopy and using the density functional (B3LYP/6-31G(d,p) and PBE/QZ3P) and ab initio riMP2/cc-pVTZm quantum-chemical calculations. Factors affecting stabilization of the EZE-conformation of the molecules, which is atypical of analogous unsubstituted amino enones, are considered.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 102–106, January, 2005. 相似文献
993.
Hydrogen bond complex stability between adenine (A) and hydrogen bond equivalents of uracil: 2-pyridone derivatives (UX
X2O) and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives (UX
SO2) was studied, and as the result, the hydrogen bond energy of UX
X2O-A and a complex of UXX
SO2-A, was about 1.5 kcal/mol more stable than that of the corresponding adenine-uracil derivatives complex, respectively. The energy difference between the imide tautomer and enol tautomer was smaller than those of uracil derivatives. UF
SO2 can form a stable complex with A, and its imide tautomer is stable. 相似文献
994.
Christian K. Riener Andreas Ebner Alex A. Gall Yuri L. Lyubchenko Hermann J. Gruber 《Analytica chimica acta》2003,479(1):59-75
We have established an easy-to-use test system for detecting receptor-ligand interactions on the single molecule level using atomic force microscopy (AFM). For this, avidin-biotin, probably the best characterized receptor-ligand pair, was chosen. AFM sensors were prepared containing tethered biotin molecules at sufficiently low surface concentrations appropriate for single molecule studies. A biotin tether, consisting of a 6 nm poly(ethylene glycol) (PEG) chain and a functional succinimide group at the other end, was newly synthesized and covalently coupled to amine-functionalized AFM tips. In particular, PEG800 diamine was glutarylated, the mono-adduct NH2-PEG-COOH was isolated by ion exchange chromatography and reacted with biotin succinimidylester to give biotin-PEG-COOH which was then activated as N-hydroxysuccinimide (NHS) ester to give the biotin-PEG-NHS conjugate which was coupled to the aminofunctionalized AFM tip. The motional freedom provided by PEG allows for free rotation of the biotin molecule on the AFM sensor and for specific binding to avidin which had been adsorbed to mica surfaces via electrostatic interactions. Specific avidin-biotin recognition events were discriminated from nonspecific tip-mica adhesion by their typical unbinding force (∼40 pN at 1.4 nN/s loading rate), unbinding length (<13 nm), the characteristic nonlinear force-distance relation of the PEG linker, and by specific block with excess of free d-biotin. The convenience of the test system allowed to evaluate, and compare, different methods and conditions of tip aminofunctionalization with respect to specific binding and nonspecific adhesion. It is concluded that this system is well suited as calibration or start-up kit for single molecule recognition force microscopy. 相似文献
995.
996.
PANG Jie YE Bing-Hong HUANG Yong-Mei LIN Qiong ZENG Cui SUN Yuan-Ming 《结构化学》2007,26(8):924-928
In order to prove up the interaction between konjac glucomannan (KGM) and other amyloses, by using KGM, guaran gum and carrageenan as materials, their blending in different external conditions was modeled by means of molecular dynamics (MD) method. The result showed that 323 K was a significant turning point for the formation of hydrogen bond, and KGM and guaran gum were just juxtaposed together via intermolecular hydrogen bond; but with the addition of carrageenan, KGM, guaran gum and carrageenan were spirally twisted together, and when their blending proportion is 3:2:9 the combination was the most compact. Moreover, the research result has provided the sequent studies afterwards on amyloses with some references. 相似文献
997.
In many polymers under corrosive liquids, degradation followed after permeation of environmental solution for a long period. The permeation rate of environmental solution, in many cases, is very low in corrosion-resistant polymeric materials. Therefore, the observation of the permeation of environmental solution and degradation of polymeric materials are very difficult in practical application. A simulation of permeation of solution is required in order to understand the permeation behavior of environmental solution and polymer degradation. A detailed analysis of the permeation behavior of solution accompanied by chemical reaction is important to study for improving the lifetime of polymers. Polyamide 66 (PA66) and sulfuric acid solution were used to investigate the quantitative study of permeation of environmental solution and its relation to degradation of polymeric materials. Correlation between diffusion process and degradation of PA66 related to the decrease of weight average molecular weight was defined. The diffusion rate of sulfuric acid solution was found to increase by decreasing weight average molecular weight of PA66 due to the established chain scission by hydrolysis reaction. The permeation of sulfuric acid solution that affected the decomposition reaction was modeled and quantitative evaluation of permeation of sulfuric acid was established. 相似文献
998.
Aiming to develop a high performance fiber reinforced rubber of SBR, a special technique using electron beam (EB) irradiation-induced graft-polymerization was applied to ultra-high molecular-weight polyethylene (UHMWPE) fibers. Although UHMWPE is chemically inert, N-vinyl formamide (NVF) could be graft-polymerized onto the UHMWPE fiber surface with this special technique. A maximum grafting percentage of 23.6% was achieved. The composite of SBR and grafted UHMWPE fibers with maximum grafting indicated a linear increase in the initial modulus and strength with the fiber content. At the fiber content of 10%, the initial modulus was improved about five times with respect to that of the pure SBR, while the strength was done about twice. At this moment, only a small reduction could be observed in the strain compared with that of pure SBR. The fiber reinforced rubber with a good performance was obtained in the system of SBR and grafted UHMWPE fibers. 相似文献
999.
F. Meyer J. Dupré C. Meyer C. Lambeau M. De Vleeschouwer J. -G. Lahaye A. Fayt 《International Journal of Infrared and Millimeter Waves》1982,3(1):83-95
The 5 band of methylacetylene has been studied simultaneously by means of CO2 Laser Stark spectroscopy and high resolution infrared absorption spectroscopy (0.012 cm–1). The primary aim of this work was to assign all the Stark coïncidences. Effective vibration-rotation parameters and the dipole moment of the v5=1 state have been determined. 相似文献
1000.
YingChunLIU GuoZhenXIAO QiWANG 《中国化学快报》2004,15(7):879-882
The diffusivity and viscosity of water confined in micropores were studied by molecular dynamics simulations. The effects of pore width and density were analyzed at pore widths from 0.9 to 2.6nm. The diffusivity in micropores is lower than that of the bulk, and it decreases as pore width decreases and as density increases. But the viscosity in micropores is much larger than that of the bulk, and it increases as pore width decreases and as density increases. The diffusivity in channel parallel direction is obviously larger than that in channel perpendicular directions. 相似文献