全文获取类型
收费全文 | 3157篇 |
免费 | 61篇 |
国内免费 | 330篇 |
专业分类
化学 | 2238篇 |
晶体学 | 2篇 |
力学 | 111篇 |
综合类 | 3篇 |
数学 | 1058篇 |
物理学 | 136篇 |
出版年
2024年 | 2篇 |
2023年 | 59篇 |
2022年 | 67篇 |
2021年 | 36篇 |
2020年 | 58篇 |
2019年 | 75篇 |
2018年 | 80篇 |
2017年 | 80篇 |
2016年 | 71篇 |
2015年 | 52篇 |
2014年 | 129篇 |
2013年 | 275篇 |
2012年 | 200篇 |
2011年 | 185篇 |
2010年 | 163篇 |
2009年 | 235篇 |
2008年 | 258篇 |
2007年 | 250篇 |
2006年 | 211篇 |
2005年 | 171篇 |
2004年 | 172篇 |
2003年 | 77篇 |
2002年 | 100篇 |
2001年 | 60篇 |
2000年 | 44篇 |
1999年 | 54篇 |
1998年 | 61篇 |
1997年 | 52篇 |
1996年 | 52篇 |
1995年 | 40篇 |
1994年 | 37篇 |
1993年 | 16篇 |
1992年 | 26篇 |
1991年 | 24篇 |
1990年 | 6篇 |
1989年 | 16篇 |
1988年 | 8篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
排序方式: 共有3548条查询结果,搜索用时 500 毫秒
71.
Daoxing Xia 《Proceedings of the American Mathematical Society》1996,124(6):1743-1753
The generalized cyclic cohomology is introduced which is associated with -deformed commutators . Some formulas related to the trace of the product of -deformed commutators are established. The Chern character of odd dimension associated with -deformed commutators is studied.
72.
Rigol C Olea-Azar C Mendizábal F Otero L Gambino D González M Cerecetto H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2933-2938
Cyclic voltammetry and electron spin resonance (ESR) techniques were used in the investigation of several potential antiprotozoal thiosemicarbazones nitrofurane derivatives. A self-protonation process involving the protonation of the nitro group due to the presence of an acidic proton in the thiosemicarbazone moiety was observed in the first step of a CEE(rev) reduction mechanism of these derivatives. ESR spectra of the free radicals obtained by electrolytic reduction were characterized and analyzed. AM1 methodology was used to obtain the optimized geometries and UB3LYP calculations were performed to obtain the theoretical hyperfine coupling constants. The theoretical study exhibited an unusual assignment of the spin densities showing a free radical centered in the thiosemicarbazone moiety rather than the nitro which are in agreement with the experimental hyperfine pattern. 相似文献
73.
《Electroanalysis》2006,18(22):2225-2231
The mechanism of electrochemical behavior of catechol in the presence of thiaproline is investigated by cyclic voltammetry, controlled‐potential coulometry and spectrophotometric tracing of the reaction coordinate. The results indicate that thiaproline participate in with an ECEC mechanism in a nucleophilic (Michael) addition to o‐quinone. Effect of pH of buffer solution on reaction pathway is studied and showed that addition of thiaproline to the o‐quinone is performed only in solutions with pHs higher than 5. These results indicate that the addition of thiaproline is occurred first from amine functional group. In the second step, the addition of carboxylate group of thiaproline to C‐5 of catechol results the final product with a lactone ring in its structure. Observation of two isosbestic point in absorption spectrum during the progress of the electrolysis together with the FT‐IR results for final product can be presented as evidence for two step addition of thiaproline to catechol. Final product, due to the electron donor property of thiaproline, more easily oxidized respect to the former catechol and as a result, a new redox couple is obtained for this compound in lower potentials. The easier anodic oxidation of addition product (relative to catechol) caused to an increase in anodic current for catechol, which is proportional to the thiaproline concentration. The differential pulse voltammetry (DPV) is applied as a sensitive voltammetric method for the detection of thiaproline. A linear range from 5×10?8 to 5×10?6 M with a detection limit of 1×10?8 M is resulted for thiaproline. With respect to the reversibility of the electrochemical reactions in the mechanism, and also more facile oxidation of the addition products, the square‐wave voltammetry is presented as a method with considerably more sensitivity for the detection of sub‐micromolar amounts of thiaproline. The advantageous properties of the voltammetric method for thiaproline detection lie in its excellent catalytic activity, sensitivity and simplicity. 相似文献
74.
环戊二烯热聚产物及二聚环戊二烯加氢产物的质谱 总被引:1,自引:0,他引:1
本实验用色谱-质谱-计算机联用仪测定了环戊二烯热聚产物及双环戊二烯加氢产物的质谱,讨论了环状化合物的开裂规律,有开环断裂反应及骨架重排等问题。 相似文献
75.
采用直流极谱和循环伏安等多种手段研究了卟啉配位剂(H_2TCPP)在汞电极上的极谱性质。在碱性介质中,H_2TCPP的电极反应具有以下三个特性:(1)第一步为受扩散控制的2e并有2H~+参与的可逆还原过程,第二和第三步为不可逆各为2e的还原反应;(2)H_2TCPP在汞电极上存在强吸附性;(3)第一步电极反应产物可发生随后的化学反应,即前两步还原经由ECE机理进行。 相似文献
76.
Waldemar Adam 《Angewandte Chemie (International ed. in English)》1974,13(10):619-627
The photodecarboxylation of malonyl peroxides into α-lactones[1] and the thermal conversion of the 1,4-endo-peroxide 4,5-epoxy-3,6-epidioxy-1-cyclohexene into the novel benzene trioxide[2] are two recent examples of the potential of cyclic peroxides in the synthesis of unusual organic molecules. The former transformation entails a fragmentation, the latter a rearrangement process. Most reported examples fall into one of these two gross reaction types. Of the numerous examples that have been reported in the literature during the last two decades, only those shall be focused on that lead to unusual compounds or constitute efficient syntheses of known compounds, in order to stress the convenience of cyclic peroxides in the synthesis of organic compounds. 相似文献
77.
Yong Zhu Jin-lian Hu Kwok-wing Yeung Hao-jun Fan Ye-qiu 《高分子科学》2006,(2):173-186
SMPU (shape memory polyurethane) non-ionomers and ionomers, synthesized with poly(c-caprolactone) (PCL), 4, 4'-diphenylmethane diisocyanate (MDI), 1,4-butanediol (BDO), dimethylolpropionic acid (DMPA) were measured with cyclic tensile test and strain recovery test. The relations between the structure and shape memory effect of these two series were studied with respect to the ionic group content and the effect of neutralization. The resulting data indicate that, with the introduction of asymmetrical extender, the stress at 100% elongation is decreased for PU non-ionomer and ionomer series, especially lowered sharply for non-ionomer series; the fixation ratio of ionomer series is not affected obviously by the ionic group content; the total recovery ratio of ionomer series is decreased greatly. After sufficient relaxation time for samples stretched beforehand, the switching temperature is raised slightly, whereas the recovery ratio measured with strain recovery test method is lowered with increased DMPA content. The characterization with FT-IR, DSC, DMA elucidated that, the ordered hard domain of the two series is disrupted with the introduction of DMPA which causes more hard segments to dissolve in soft phase; ionic groups on hard segment enhance the cohesion between hard segments especially at high ionic group content and significantly facilitate the phase separation compared with the corresponding non-ionomer at moderate ionic group content. 相似文献
78.
环状碳酸酯低聚物的合成及其开环聚合的研究 总被引:4,自引:0,他引:4
环状碳酸酯低聚物的合成及其开环聚合的研究陈雨萍魏玮李革(中国科学院化学研究所工程塑料国家重点实验室北京100080)关键词环状碳酸酯低聚物,聚碳酸酯,开环聚合环状单体的开环聚合在合成高聚物方面具有突出的优点,即在聚合过程中没有副产物、热效应低、聚合... 相似文献
79.
A comparison is made between dichlorosilanes and cyclic siloxanes as starting materials in the synthesis of stationary phases for capillary gas chromatography (CGC) and supercritical fluid chromatography (SFC). Siloxanes containing one or more of the side groups methyl, vinyl, phenyl, and cyanoethyl in various ratios were synthesized and compared. These phases were characterized by chromatographic (gel permeation, GPC), spectroscopic (IR, 1H NMR, 29Si NMR), and thermal (DSC) methods. Coated fused silica columns were evaluated with respect to polarity, crosslinkability with several free-radical initiators, and thermal stability. A new liquid phase, 7% cyanoethyl, 7% phenyl, 1% vinyl methyl polysiloxane is shown to be more polar than OV-1701, more temperature stable, easily crosslinked and suitable for use in supercritical fluid chromatography. 相似文献
80.
Voltammetric behaviour and determination of moxifloxacin in pharmaceutical products and human plasma
Erk N 《Analytical and bioanalytical chemistry》2004,378(5):1351-1356
The oxidative behaviour of moxifloxacin was studied at a glassy carbon electrode in different buffer systems using cyclic, differential pulse, and Osteryoung square-wave voltammetry. The oxidation process was shown to be irreversible over the entire pH range studied (2.0–10.0) and was diffusion-controlled. The methods were performed in Britton–Robinson buffer and the corresponding calibration graphs were constructed and statistical data were evaluated. When the proposed methods were applied at pH 6.0 linearity was achieved from 4.4×10–7 to 1.0×10–5 mol L–1. Applicability to tablets and human plasma analysis was illustrated. Furthermore, a high-performance liquid chromatographic method with diode-array detection was developed. A calibration graph was established from 4.0×10–6 to 5.0×10–5 mol L–1 moxifloxacin. The described methods were successfully employed with high precision and accuracy for estimation of the total drug content of human plasma and for pharmaceutical dosage forms of moxifloxacin. 相似文献