全文获取类型
收费全文 | 83512篇 |
免费 | 13352篇 |
国内免费 | 8767篇 |
专业分类
化学 | 58352篇 |
晶体学 | 956篇 |
力学 | 5054篇 |
综合类 | 563篇 |
数学 | 10067篇 |
物理学 | 30639篇 |
出版年
2024年 | 171篇 |
2023年 | 1643篇 |
2022年 | 2096篇 |
2021年 | 2958篇 |
2020年 | 3411篇 |
2019年 | 3195篇 |
2018年 | 2701篇 |
2017年 | 2571篇 |
2016年 | 3847篇 |
2015年 | 3827篇 |
2014年 | 4644篇 |
2013年 | 6035篇 |
2012年 | 7551篇 |
2011年 | 7598篇 |
2010年 | 5275篇 |
2009年 | 4938篇 |
2008年 | 5298篇 |
2007年 | 4730篇 |
2006年 | 4334篇 |
2005年 | 3663篇 |
2004年 | 2902篇 |
2003年 | 2287篇 |
2002年 | 2078篇 |
2001年 | 1686篇 |
2000年 | 1530篇 |
1999年 | 1801篇 |
1998年 | 1490篇 |
1997年 | 1376篇 |
1996年 | 1440篇 |
1995年 | 1292篇 |
1994年 | 1122篇 |
1993年 | 964篇 |
1992年 | 853篇 |
1991年 | 739篇 |
1990年 | 634篇 |
1989年 | 464篇 |
1988年 | 385篇 |
1987年 | 350篇 |
1986年 | 293篇 |
1985年 | 285篇 |
1984年 | 215篇 |
1983年 | 203篇 |
1982年 | 130篇 |
1981年 | 96篇 |
1980年 | 77篇 |
1979年 | 49篇 |
1977年 | 37篇 |
1976年 | 45篇 |
1975年 | 51篇 |
1972年 | 37篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
用超临界流体干燥法制备出大孔高比表面高分散态Fe/ZrO_2气凝胶超细粒子催化剂,研究了在其制备过程中织构性质、颗粒大小、体相和表面结构的变化,并与普通浸渍法制备的Fe/ZrO_2催化剂作了对比。对几种Fe/ZrO_2催化剂的F-T反应性能考察表明,Fe/ZeO_2气凝胶超细催化剂显示出高的反应活性;随载体ZrO_2颗粒尺寸减小,活性组分铁的分散度变大,其颗粒尺寸变小,催化剂比表面积增大,反应活性增大,甲烷和低碳烃生成量增加,重质组分减少,认为产物烃分布主要受催化剂活性相颗粒尺寸效应制约。 相似文献
992.
A series of Fe-P-B ultrafine amorphous alloy particles has been prepared by the chemical reduction method The composition and size of the particles have been effectively adjusted.Mossbauer spectroscopy in addition to sonic other techniques has been used to investigate the reaction process,the factors that influence the preparation,the crystallization of the particles,and the interactions between the components within them.The results indicate that the co-deposition of iron,phosphorus and boron atoms in the solution at room temperature forms Fe-P-B amorphous alloy particles,and a preferential bonding of Fe-P bond to Fe-B one exists in the particles. 相似文献
993.
Mian Chang Jiayou Yu Shaojun Wang Liping Yang Yi Yang Shihao Cai Shouheng Shi Yan Wang P. W. Zhu 《中国科学B辑(英文版)》1997,40(5):529-534
A synthetical equation is proposed to characterize the essential features of the inverse “S” type curve on the basis of summing-up
simulation approach of “S” type curve. The two physical variables in the model obtained are discussed and the detailed method
used to determine the parameters is given. The model is then presented to describe the crystallization of poly(caryleher ether
ketone) (PEEK) and thermal decomposition of poly(amide-imide) (PAI) respectively. It is found that some thermal characteristic
parameters can be well estimated from the model simu-lated in computer. 相似文献
994.
通过分子设计,合成了一种新颖的双β-二酮有机配体9-乙基-3,6-二(乙酰基-3-苯甲酰基)咔唑(H2L)及其铕配合物,红外光谱和电子光谱表明Eu^3+与H2L发生配位。配合物的溶液荧光光谱不仅有613 nm处的中心离子Eu^3+的特征红光,属^5D0→^7F2跃迁带,还有445nm处配体的宽带蓝色发光,属H2L^*→H2L跃迁带,而配合物的光致发光光谱只有611 nm处为中心离子Eu^3+的特征红光,属^5D0→^7F2跃迁带,峰形尖锐,半峰宽仅7 nm,单色性好,表明该固体铕双β-二酮配合物是一种潜在的红色发光材料。 相似文献
995.
The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H2O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper. 相似文献
996.
We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521]. 相似文献
997.
采用化学溶液分解法(CSD)在p—Si(111)衬底上制备了(Bi0.9Nd0.1)2Ti2o7薄膜。用X射线衍射技术分析了薄膜的结构和结晶性,结果显示,在600℃退火10min得到了结晶性较好、表面致密的多晶薄膜;用原子力显微镜描述了薄膜的表面形貌,与在XRD中观察到的择优取向是一致的;同时还研究了薄膜的电学性能。结果表明,在0~6V范围内,薄膜的漏电流小于1.53×10^10A;在室温100kHz下,其介电常数为166,介电损耗因子为0.227,显示出薄膜具有较好的绝缘性和介电性能。 相似文献
998.
Jia Rui Wang Chu Ting Yang Lei Liu Qing Xiang Guo Department of Chemistry University of Science Technology of China Hefei China 《中国化学快报》2007,18(2):133-136
Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view. 相似文献
999.
Study of urinary nucleosides as biological marker in cancer patients analyzed by micellar electrokinetic capillary chromatography 总被引:10,自引:0,他引:10
Thirteen normal and modified nucleosides, primarily degradation products of transfer ribonucleic acid (tRNA), were evaluated as potential tumor markers for cancer patients. Their urinary concentrations were determined by means of micellar electrokinetic capillary chromatography (MEKC) in the urine from 54 healthy adults and 70 cancer patients, then quantitatively expressed as a function of creatinine excretion. It was found that urinary nucleosides for cancer patients were on the average significantly higher than those for healthy controls, however, no significant differences were found between male and female or between different ages. Based on 13 urinary nucleoside concentrations, principal component analysis (PCA) could be used to classify 72% of cancer patients from the healthy controls. The present study shows that the precise measurement of urinary nucleosides by MEKC in combining with PCA technique may provide a clinically useful approach for diagnosis of cancer. 相似文献
1000.
Yang LI Yu ZHANG Xiao Long WANG Zhi HUANG Xiao Ping CAOState Key Laboratory of Applied Organic Chemistry College of Chemistry Chemical Engineering Lanzhou University Lanzhou 《中国化学快报》2004,(6)
A convenient and rapid approach for the synthesis of piperamide alkaloids la ~ h by the recently developed one-flask Ramberg-Backlund reaction was described. The synthesis of 1e was reported for the first time. 相似文献