全文获取类型
收费全文 | 11777篇 |
免费 | 1354篇 |
国内免费 | 2002篇 |
专业分类
化学 | 7715篇 |
晶体学 | 522篇 |
力学 | 88篇 |
综合类 | 59篇 |
数学 | 4139篇 |
物理学 | 2610篇 |
出版年
2024年 | 11篇 |
2023年 | 167篇 |
2022年 | 194篇 |
2021年 | 244篇 |
2020年 | 354篇 |
2019年 | 437篇 |
2018年 | 363篇 |
2017年 | 443篇 |
2016年 | 429篇 |
2015年 | 400篇 |
2014年 | 513篇 |
2013年 | 948篇 |
2012年 | 597篇 |
2011年 | 876篇 |
2010年 | 679篇 |
2009年 | 854篇 |
2008年 | 865篇 |
2007年 | 858篇 |
2006年 | 710篇 |
2005年 | 579篇 |
2004年 | 586篇 |
2003年 | 499篇 |
2002年 | 478篇 |
2001年 | 363篇 |
2000年 | 350篇 |
1999年 | 365篇 |
1998年 | 275篇 |
1997年 | 222篇 |
1996年 | 196篇 |
1995年 | 205篇 |
1994年 | 165篇 |
1993年 | 120篇 |
1992年 | 141篇 |
1991年 | 84篇 |
1990年 | 70篇 |
1989年 | 46篇 |
1988年 | 43篇 |
1987年 | 34篇 |
1986年 | 41篇 |
1985年 | 31篇 |
1984年 | 31篇 |
1983年 | 23篇 |
1982年 | 33篇 |
1981年 | 33篇 |
1980年 | 25篇 |
1979年 | 33篇 |
1978年 | 35篇 |
1977年 | 27篇 |
1976年 | 23篇 |
1975年 | 15篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
101.
102.
Prof. Dr. Holger Braunschweig Charlotte Brückner Dr. Mehmet Ali Celik Dr. Klaus Dück Dr. Florian Hupp Dr. Thomas Kramer Johannes Krebs Dr. Ivo Krummenacher 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11056-11064
Taking advantage of an improved synthesis of [Ti(η6‐C6H6)2], we report here the first examples of ansa‐bridged bis(benzene) titanium complexes. Deprotonation of [Ti(η6‐C6H6)2] with nBuLi in the presence of N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (pmdta) leads to the corresponding 1,1′‐dilithio salt [Ti(η6‐C6H5Li)2] ? pmdta that enables the preparation of the first one‐ and two‐atom‐bridged complexes by simple salt metathesis. The ansa complexes were fully characterized (NMR spectroscopy, UV/Vis spectroscopy, elemental analysis, and X‐ray crystallography) and further studied electrochemically and computationally. Moreover, [Ti(η6‐C6H6)2] is found to react with the Lewis base 1,3‐dimethylimidazole‐2‐ylidene (IMe) to give the bent sandwich complex [Ti(η6‐C6H6)2(IMe)]. 相似文献
103.
Topochemical Transformations of CaX2 (X=C,Si, Ge) to Form Free‐Standing Two‐Dimensional Materials 下载免费PDF全文
Saied Md. Pratik A. Nijamudheen Prof. Dr. Ayan Datta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18454-18460
Topochemical transformations of layered materials CaX2 (X=Si, Ge) are the method of choice for the high‐yield synthesis of pristine, defect‐free two‐dimensional systems silicane and germanane, which have advanced electronic properties. Based on solid‐state dispersion‐corrected calculations, mechanisms for such transformations are elucidated that provide an in‐depth understanding of phase transition in these layered materials. While formation of such layered materials is highly favorable for silicane and germanane, a barrier of 1.2 eV in the case of graphane precludes its synthesis from CaC2 topochemically. The energy penalty required for distorting linear acetylene into a trans‐bent geometry accounts for this barrier. In contrast it is highly favorable in the heavier analogues, resulting in barrierless topochemical generation of silicane and germanane. Photochemical generation of the trans‐bent structure of acetylene in its first excited state (S1) can directly generate graphane through a barrierless condensation. Unlike the buckled structure of silicene, the phase‐h of CaSi2 with perfectly planar silicene layers exhibits the Dirac cones at the high symmetry points K and H. Interestingly, topochemical acidification of the cubic phase of calcium carbide is predicted to generate the previously elusive platonic hydrocarbon, tetrahedrane. 相似文献
104.
Magnetically separable CuO nanoparticles supported on graphene oxide (Fe3O4 NPs/GO-CuO NPs) is synthesized and characterized for the preparation of propargylamines in EtOH, at 90℃. Fe3O4 NPs/GO-CuO NPs is found to be an efficient catalyst for the A3-coupling of aldehydes, amines, and alkynes through C-H activation. Both aromatic and aliphatic aldehydes and alkynes are combined with secondary amines to provide a wide range of propargylamines in moderate to excellent yields. 相似文献
105.
Selective oxidation of sulfides to sulfoxides was successfully performed by employing readily available Fe(NO3)3·9H2O as the active catalyst with oxygen as the oxidant in 2,2,2-trifluoroethanol (TFE) without the formation of sulfones. Nitrate anion could play a crucial role in promoting the reaction due to the oxidation capacity under acidic media. High yields of sulfoxides were exclusively obtained from the corresponding sulfides. Furthermore, both aromatic and aliphatic sulfides gave moderate to high yields of sulfoxides with this protocol. 相似文献
106.
107.
Surekha S. Jogdand Abhishek Das Akshay Dhayagude Sudhir Kapoor Satyawati S. Joshi 《先进技术聚合物》2015,26(9):1114-1122
Polymeric materials have been found to be ideal candidates for the synthesis of organic–inorganic nanomaterials. We have obtained Co3O4‐decorated graphene oxide (GO) nanocomposites by a simple polymer combustion method. Polyvinyl alcohol (PVA) of two different molecular weights, 14,000 and 125,000, was used for the synthesis. The pristine sample was annealed at 300, 500, and 800°C. PVA has played an important role in the formation of GO and Co3O4 nanoparticles. Synthesized Co3O4–GO nanocomposites were characterized by X‐ray diffraction, Fourier transform infrared, Raman, electron paramagnetic resonance, transmission electron microscopy, and vibrating sample magnetometry. Reflection peaks at 12° and 37° in an X‐ray study confirm the formation of Co3O4–GO. Raman study validates the presence of GO in nanocomposites of Co3O4–GO. Room temperature ferromagnetism was observed in all annealed samples. The highest coercivity of 462 G was observed for 300°C annealed samples as compared with bulk Co3O4. On the basis of the results obtained, a mechanism of formation is proposed. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
108.
中孔MCM-41锚合Zr(IV)-salen催化剂制备及用于硫化物氧化制亚砜和Knoevenagel缩合反应 总被引:1,自引:0,他引:1
通过NH2-MCM-41与水杨醛反应得到席夫碱配体,然后加入八水氧氯化锆形成络合物,制得Zr(IV)-salen-MCM-41催化剂。采用X射线衍射、N2吸附-脱附、热重、红外光谱、电感耦合等离子体发射光谱和能量散射谱等分析手段对催化剂结构进行了表征。在含有该催化剂的体系中进行了硫化物选择氧化为亚砜以及醛与丙二腈和氰乙酸乙酯的Knoveonagel缩合反应,并考察了催化剂的循环使用性能。 相似文献
109.
110.
文章合成了Lu(NO3)3(C2H5O2N)4.H2O,用红外和元素分析对其进行了表征。用高精度全自动绝热量热仪,测定了该配合物80-382 K温区的热容, 利用实验热容数据, 根据热容与焓、熵的热力学关系, 求出了配合物85-350 K温区内每隔5 K相对于298.15K的标准热力学函数(HT - H298.15)m和(ST - S298.15)m.在80-350 K温度区间内,配合物的热容随温度升高而增大,没有相转移点和热力学吸收峰的出现,该配合物在此温度区间内是稳定存在的。 相似文献