全文获取类型
收费全文 | 58272篇 |
免费 | 6360篇 |
国内免费 | 7168篇 |
专业分类
化学 | 23500篇 |
晶体学 | 659篇 |
力学 | 1666篇 |
综合类 | 457篇 |
数学 | 3521篇 |
物理学 | 11719篇 |
综合类 | 30278篇 |
出版年
2024年 | 167篇 |
2023年 | 737篇 |
2022年 | 1399篇 |
2021年 | 1572篇 |
2020年 | 1666篇 |
2019年 | 1592篇 |
2018年 | 1415篇 |
2017年 | 1594篇 |
2016年 | 1894篇 |
2015年 | 2447篇 |
2014年 | 3286篇 |
2013年 | 3795篇 |
2012年 | 4355篇 |
2011年 | 4603篇 |
2010年 | 4063篇 |
2009年 | 4143篇 |
2008年 | 4442篇 |
2007年 | 4310篇 |
2006年 | 3757篇 |
2005年 | 3206篇 |
2004年 | 2446篇 |
2003年 | 2066篇 |
2002年 | 2132篇 |
2001年 | 1898篇 |
2000年 | 1674篇 |
1999年 | 1332篇 |
1998年 | 820篇 |
1997年 | 761篇 |
1996年 | 667篇 |
1995年 | 609篇 |
1994年 | 547篇 |
1993年 | 409篇 |
1992年 | 350篇 |
1991年 | 344篇 |
1990年 | 308篇 |
1989年 | 252篇 |
1988年 | 210篇 |
1987年 | 157篇 |
1986年 | 126篇 |
1985年 | 77篇 |
1984年 | 36篇 |
1983年 | 33篇 |
1982年 | 29篇 |
1981年 | 10篇 |
1980年 | 15篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1957年 | 4篇 |
1955年 | 5篇 |
1936年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
961.
Yan YG Li QX Huo SJ Ma M Cai WB Osawa M 《The journal of physical chemistry. B》2005,109(16):7900-7906
A versatile two-step wet process to fabricate Pt, Pd, Rh, and Ru nanoparticle films (simplified as nanofilms hereafter) for in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study of electrochemical interfaces is presented, which incorporates an initial chemical deposition of a gold nanofilm on the basal plane of a silicon prism with the subsequent electrodepostion of desired platinum group metal overlayers. Galvanostatic electrodeposition of Pt, Rh, and Pd from phosphate or perchloric acid electrolytes, or potentiostatic electrodeposition of Ru from a sulfuric acid electrolyte, yields sufficiently "pinhole-free" overlayers as evidenced by electrochemical and spectroscopic characterizations. The Pt group metal nanofilms thus obtained exhibit strongly enhanced IR absorption. In contrast to the corresponding metal films electrochemically deposited directly on glassy carbon and bulk metal electrodes, the observed enhanced absorption for the probe molecule CO exhibits normal unipolar band shapes. Scanning tunneling microscopic (STM) images reveal that fine nanoparticles of Pt group metals are deposited around wavy and stepped bunches of Au nanoparticles of relatively large sizes. This ubiquitous strategy is expected to open a wide avenue for extending ATR surface-enhanced IR absorption spectroscopy to explore molecular adsorption and reactions on technologically important transition metals, as exemplified by successful real-time spectroscopic and electrochemical monitoring of the oxidation of CO at Pd and that of methanol at Pt nanofilm electrodes. The spectral features of free water molecules coadsorbed with CO on Pt, Pd, Rh, and Ru are also discussed. 相似文献
962.
963.
Ben‐Yong Lou Yan‐Bin Huang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):o246-o248
4,4′‐Bipyridyl N,N′‐dioxide crystallizes with 3‐hydroxy‐2‐naphthoic acid to give a centrosymmetric three‐component adduct, C10H8N2O2·2C11H8O3, which is engineered into a two‐dimensional layer structure by two kinds of π–π interactions. Weak C—H⋯O interactions further link the two‐dimensional structure into a three‐dimensional structure. 相似文献
964.
965.
Yan J Kline AD Mo H Shapiro MJ Zartler ER 《Magnetic resonance in chemistry : MRC》2004,42(11):962-967
A novel methodology using the order matrix calculation to determine the absolute sign of spin-spin couplings based on the structure of organic compounds is presented. The sign of the residual dipolar coupling (RDC) depends on the sign of corresponding scalar spin-spin coupling constant and the sign of the RDC has a dramatic influence on the order matrix calculation. Therefore, the sign of the spin-spin coupling constant can be obtained by an order matrix calculation through the corresponding RDC. Six types of spin-spin coupling constants, including 2J(H,H), 1J(C,F), 2J(C,F), 3J(C,F), 2J(F,H) and 3J(F,H), were obtained simultaneously. Except for 3J(C,F) where the measured RDCs have very small magnitudes, the signs were determined unambiguously. 相似文献
966.
A two-dimensional liquid chromatography/capillary electrophoresis technique was developed for rapid and comprehensive mapping of cell extracts. The cell extracts were first separated by reversed-phase HPLC based on hydrophobicity. Fractions of the effluent from the HPLC system were collected into 96-well microtiter plates and dried under vacuum. The fractions were reconstituted with deionized water, separated by capillary array electrophoresis based on charge-to-size ratio, and detected by UV absorption at 214 nm. Prior to analysis by multiplexed capillary electrophoresis, the reconstituted fractions were concentrated on-column using large volume sample stacking with polarity switching. In this way, high-resolution analysis of even the minor components in the complicated mixture was possible. 相似文献
967.
动力学光度法测定痕量钴的研究 总被引:6,自引:0,他引:6
催化动力学法测定微量Co~(2+)已有报道,方法灵敏度一般在10~(-6)~10~(-10g)数量级,多数用于测定水、血液和高纯物质中的Co~(2+),而测定中药內的痕量CO~(2+)还未见报道。本文研究了氨水介质中Co~(2+)催化二苯偶氮酰肼氧化褪色的新指示反应及动力学条 相似文献
968.
CTMAB胶束体系中反离子缔合度的测定 总被引:2,自引:0,他引:2
对十六烷基三甲基淡化按(CTMAB)水胶束体系,不同方法测得其反离子缔合度产值不同【‘-\且很高于由股团电化学理论所得q值0.67问.本文以离子选择性电极法测定CTMAB水胶束体系中反离子缩合度(仁0.65),并研究了外加盐和乙醇的影响·1实验部分1.工试剂和仪器十六烷基三甲基漠化技(CP)在无水乙醇中重结晶两次,纯化物经帕环法测其表面张力在CMC附近无最低声、·淡化钾(AR),水为。次蒸馏水,PXJIC型离子计,302型PB,电极(响应范围为PB,=1.6~3.3,响应时间为5分钟)222型甘汞电极·1.2实验方法在CMCV/de的稀… 相似文献
969.
The present paper employed density function theory to investigate two reaction pathways for isomerization of enol ester proposed by Yang(path a) and the present authors(path a), respectively. The base catalytic effects of solvent triethylamine on these two reactions were also evaluated. It is demonstrated that path B is more preferable than path a due to low barrier height for the rate-determining step. 相似文献
970.
Fa-Kun Zheng A-Qing Wu Yan Li Guo-Cong Guo Ming-Sheng Wang Qiang Li Jin-Shun Huang 《Journal of Molecular Structure》2005,740(1-3):147-151
Three new metal complexes, Cu(4-Hcba)2(4-cba)2(Py)2 (4-Hcba=4-cyanobenzoic acid) 1 and M[H(4-cba)2]2(Py)2 (M=Ni 2, Co 3), have been prepared by the treatment of 4-Hcba with the respective metal nitrate M(NO3)2 (M=Cu, Ni, Co) in the presence of pyridine (Py). Single-crystal X-ray diffraction analyses (3 is isostructural to 2) show that the obtained complexes are of isolated mononuclear and the metal atoms have distorted octahedral coordination environment. Two different types of intramolecular hydrogen bonds exist: asymmetrical O–HO for 1 and symmetrical OHO for 2 and 3. The crystal packing between the molecular complexes is controlled mainly by T-shaped C–Hπ interactions between pyridine and phenyl rings. Preliminary discussions on IR, UV–VIS and fluorescent spectra have also been carried out. 相似文献