全文获取类型
收费全文 | 8158篇 |
免费 | 885篇 |
国内免费 | 2072篇 |
专业分类
化学 | 8329篇 |
晶体学 | 48篇 |
力学 | 459篇 |
综合类 | 82篇 |
数学 | 996篇 |
物理学 | 1201篇 |
出版年
2024年 | 33篇 |
2023年 | 157篇 |
2022年 | 303篇 |
2021年 | 411篇 |
2020年 | 589篇 |
2019年 | 395篇 |
2018年 | 336篇 |
2017年 | 333篇 |
2016年 | 428篇 |
2015年 | 348篇 |
2014年 | 509篇 |
2013年 | 762篇 |
2012年 | 491篇 |
2011年 | 480篇 |
2010年 | 404篇 |
2009年 | 450篇 |
2008年 | 477篇 |
2007年 | 469篇 |
2006年 | 435篇 |
2005年 | 383篇 |
2004年 | 362篇 |
2003年 | 409篇 |
2002年 | 394篇 |
2001年 | 248篇 |
2000年 | 209篇 |
1999年 | 181篇 |
1998年 | 155篇 |
1997年 | 123篇 |
1996年 | 135篇 |
1995年 | 105篇 |
1994年 | 104篇 |
1993年 | 85篇 |
1992年 | 84篇 |
1991年 | 47篇 |
1990年 | 38篇 |
1989年 | 26篇 |
1988年 | 35篇 |
1987年 | 26篇 |
1986年 | 33篇 |
1985年 | 31篇 |
1984年 | 23篇 |
1983年 | 10篇 |
1982年 | 21篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 406 毫秒
151.
手性胺醇稀土配合物的合成、荧光性质及其催化芳香酮的不对称氢化反应 总被引:2,自引:0,他引:2
合成了三种新的含C2-对称轴的手性胺醇(PhOHCHCH2)2NCH2C6H4R (R=OCH3, L1; R=CH3, L2; R=Cl, L3), 将其与无水氯化稀土LnCl3•4THF (Ln=La, Sm, Gd)反应生成了九个新的胺醇类稀土配合物LLnCl•2THF (L=L1, L2, L3; Ln=La, Sm, Gd). 用元素分析、热重分析、红外和紫外光谱等手段对它们进行了表征. 荧光光谱显示一些配合物具有荧光性能. 原位催化芳香酮的不对称氢化反应表明: L1/SmCl3•4THF体系催化苯乙酮不对称氢化反应的转化率达71%, 相应的对映体过量值达32%. 相似文献
152.
Cathodic reduction of -azidocinnamic ester under aprotic conditions on Hg, Pt, or graphite electrodes can be directed to high yields of N,N-diacylated dehydroaminoacid derivates (f.i. addition of acetic anhydride) or to almost quantitative yields of -aminocinnamic ester in very pure form by careful addition of H+-donors. The dehydroamino compounds in turn can be further reduced to the corresponding saturated compounds by following H+-addition and changed electrolysis potential. Almost no dimerization occurs. 相似文献
153.
Byeong Hyo Kim Rongbi HanFengyu Piao Young Moo JunWoonphil Baik Byung Min Lee 《Tetrahedron letters》2003,44(1):77-79
N-Arylacetamides were prepared in excellent yields from nitroarenes in the presence of acetic anhydride, acetic acid and indium by a one-pot procedure. 相似文献
154.
γ-芳基取代烯丙醇菊酯的合成及杀虫活性陈亚娟,黄润秋,马军安(南开大学元素有机化学研究所,天津,300071)关键词γ-芳基取代烯丙醇,拟除虫菊酯,杀虫活性第一个人工合成除虫菊酯烯丙菊酯保留了天然除虫菊酯醇部分的环戊烯醇酮结构,至今仍广泛用作卫生杀虫... 相似文献
155.
Pt3Co核-Pt壳型纳米粒子的制备及磁性 总被引:1,自引:1,他引:1
Pt3Co alloy nanoparticles were prepared by the reduction of H2PtCl6 and Co(OOCCH3)2 using NaBH4 as a reducing agent. The Pt3Co core-Pt shell nanoparticles (Pt3Co@Pt) were synthesized using hydrogen absorption reduction and characterized by plasma-atomic emission spectrometry (ICP), transmission electron microscopy (TEM), X-ray diffraction (XRD) and SQUID magnetometer. The results show that average size of Pt3Co@Pt nanoparticles is 3.6 nm with a standard deviation of 0.9 nm. Heating Pt3Co nanoparticles in air at 700 ℃ for 1 h, Co in Pt3Co nanoparticles was oxidized to Co3O4 and CoO; while no oxidation tendency was detected for Pt3Co@Pt nanoparticles. The crystallize structure of Pt3Co@Pt changed from the face centered cube (fcc) to the face centered tetragonal (fct) after the heating treatment. The coercivity of the heated Pt3Co@Pt reached to 276 Oe at room temperature. 相似文献
156.
Chemical Reduction of CO2 to Different Products during Photo Catalytic Reaction on TiO2 under Diverse Conditions: an Overview 下载免费PDF全文
The chemical reduction of CO_2 remains a challenge with respect to the reversal of the oxidative degradation of any organic materials.The conversion of CO_2 into useful substances is essential in developing al- ternative fuels and various raw materials for different in- dustries.This also aids in preventing the continuous rise in tropospheric temperature due to the green house effect of CO_2.In this article an overview of the growth taken place so far in the field of CO_2 chemical reduction is pre- sented.The discussion comprises of photochemical meth- ods for the development of different products,viz.CO, CH_3O_H and CH_4,through chemical reduction of CO_2. This includes the use of photo catalysts,mainly TiO_2, and the role of a hole scavenger(such as 2-propanol)for this purpose. 相似文献
157.
As an adjunct to the regression analysis of differential capacitance curves, which allows refining the adsorption parameters, a program, which takes into account possible errors in volume concentrations of organic substances, is developed. Using this procedure, the earlier data on the differential capacitance of a mercury electrode in aqueous solutions of normal butanol (1-BuOH) containing either 0.1 M NaF or 0.05 and 0.5 M Na2SO4 as the supporting electrolyte are analyzed. This allows obtaining the most accurate values of adsorption parameters for the systems mentioned above within the framework of the model of two parallel capacitors and the Frumkin isotherm. It is shown that, when a linear dependence of the intermolecular interaction parameter on the electrode potential is taken into account, the standard deviation of experimental capacitance values from those calculated using the mentioned model is 6.8–8.8%, which points to very high accuracy of this phenomenological model. 相似文献
158.
S. Yu. Kukushkin P. Yu. Ivanov L. M. Alekseeva V. I. Levina K. I. Kobrakov N. B. Grigor'ev V. G. Granik 《Russian Chemical Bulletin》2005,54(8):1887-1891
The half-wave potentials of polarographic reduction of the carbonyl group in unsubstituted and N-methyl- and N-phenylsulfonyl-substituted 1- and 4-oxotetrahydrocarbazoles and their reactivities in reactions with nucleophilic (NaBH4, malonodinitrile, and cyanoacetamide) and electrophilic (DMF dimethyl acetal) reagents were compared. 4-Oxotetrahydrocarbazoles
are much less reactive than 1-oxotetrahydrocarbazoles.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1832–1836, August, 2005. 相似文献
159.
利用化学键合和“瓶中造船”方法,成功地将酒石酸钛配合物接枝到HMS(heragonal mesoporous silicas)上或包络合于微孔NaY内.FT-IR表征表明酒石酸钛在HMS上是通过与载体表面羟基发生交换作用而被固载的;在NaY载体上则是通过包络合被封装在载体的超笼内.UV-Vis可见漫反射表征表明两类固载型催化剂有着相似的钛配位环境.在催化肉桂醇环氧化反应中,HMS键合型催化剂的反应转化率比NaY包络型催化剂的高;但后者在环氧化选择性上要高于前者.回收样品的重复使用实验结果表明,两类固载型催化剂在重复使用过程中均存在不同程度的失活. 相似文献
160.
In this work, surface-enhanced Raman scattering (SERS)-active gold substrates were first developed by combining the technologies of oxidation–reduction cycles (ORCs) and plasmas treatments in roughening metal substrates. First, a gold substrate was treated by argon plasmas. Then the treated gold substrate was further roughened by triangular-wave ORCs in an aqueous solution containing 0.1 M HCl. Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on this roughened gold substrate modified by argon plasmas pretreatment exhibits a higher intensity by 10-fold of magnitude and a better resolution, as compared with the SERS of R6G adsorbed on an unmodified roughened gold substrate. Meanwhile, the probing concentration of R6G adsorbed on the modified substrate can be reduced by one order. It was also found that the pretreatment of argon plasmas demonstrates a positive effect on the (2 2 0) face of Au partly changing into the (1 1 1) face with the lowest surface energy after the ORCs roughening, which is contributive to the improved SERS observed. 相似文献