全文获取类型
收费全文 | 2016篇 |
免费 | 474篇 |
国内免费 | 192篇 |
专业分类
化学 | 2296篇 |
晶体学 | 43篇 |
力学 | 16篇 |
综合类 | 10篇 |
数学 | 3篇 |
物理学 | 314篇 |
出版年
2024年 | 8篇 |
2023年 | 32篇 |
2022年 | 69篇 |
2021年 | 68篇 |
2020年 | 122篇 |
2019年 | 97篇 |
2018年 | 85篇 |
2017年 | 79篇 |
2016年 | 186篇 |
2015年 | 145篇 |
2014年 | 121篇 |
2013年 | 216篇 |
2012年 | 157篇 |
2011年 | 101篇 |
2010年 | 111篇 |
2009年 | 108篇 |
2008年 | 107篇 |
2007年 | 113篇 |
2006年 | 113篇 |
2005年 | 108篇 |
2004年 | 69篇 |
2003年 | 85篇 |
2002年 | 82篇 |
2001年 | 32篇 |
2000年 | 18篇 |
1999年 | 24篇 |
1998年 | 13篇 |
1997年 | 41篇 |
1996年 | 28篇 |
1995年 | 34篇 |
1994年 | 8篇 |
1993年 | 17篇 |
1992年 | 19篇 |
1991年 | 9篇 |
1990年 | 9篇 |
1989年 | 13篇 |
1988年 | 9篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1978年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1970年 | 1篇 |
排序方式: 共有2682条查询结果,搜索用时 15 毫秒
1.
《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(2):600-606
A series of α,ω‐boryl(bromo)alkanes of the general formula R2B? (CH2)n? Br (n=3, 4, 5, 6) was obtained in high yield following a standard hydroboration protocol. Upon treatment with Mg turnings and formation of the respective Grignard species, all alkanes with n=4 to 6 underwent an unprecedented boron‐centered cyclisation reaction with formation of boratacyclopentanes, ‐hexanes, and ‐heptanes, respectively. All new compounds were isolated in high yields as colourless, crystalline materials and characterised in solution by multinuclear NMR spectroscopy. Four representative examples were chosen for X‐ray diffraction studies, thus providing the first structurally characterised ring systems of that size at a tetraalkyl borate centre. 相似文献
2.
Alpeshkumar K. Malde Santosh A. Khedkar Evans C. Coutinho 《Journal of Physical Organic Chemistry》2007,20(2):151-160
Modification of peptides to produce peptidomimetics is of great interest, with the aim of designing potent, selective, and metabolically stable analogs having certain conformational properties. Organoboranes have been reported in the literature with a wide range of therapeutic applications. One of the therapeutically important class of molecules is amine‐carboxyboranes derived from amino acids by replacement of the Cα atom of an amino acid/peptide by boron. The conformational preferences of these peptides, with respect to backbone ω, ?, and ψ torsion angles, have been investigated by theoretical calculations. The amide bond in these molecules has the same geometry in the ground and transition states as the natural peptides. However, the boron isosteres of glycine and alanine peptides are less structured than their natural derivatives, but are distinguished by structures with a positive value for the ? angle, which is normally disfavored for natural peptides. This property could be used to build peptides with a geometry not usually seen in natural peptides. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
3.
S. Vepřek 《Plasma Chemistry and Plasma Processing》1992,12(3):219-235
Impurity release from the first wall and components facing the hot plasma in Tokamak devices for controlled fusion research and the concomitant pollution of the plasma lead to enhanced energy losses and deuterium-tritium luel dilution. Both these effects can prevent reaching the ignition conditions. The recently developed technique for large areain situ deposition of boron carbide protective coatings by means of plasma-induced chemical vapor deposition enables one to significantly improve the purity of the fusion plasma. The prospects of approaching the scientific break-even in the large machines of the Tokarnak type has been increased.Extended version of an invited paper presented at the 10th International Symposium on Boron, Borides, and Related Compounds, Albuquerque, New Mexico, August 1990.The term Tokarnak is an abbreviation of the Russian name toroidal magnetic chamber. 相似文献
4.
A. A. Korlyukov K. A. Lyssenko M. Yu. Antipin A. G. Shipov O. A. Zamyshlyaeva E. P. Kramarova Vad. V. Negrebetsky S. A. Pogozhikh Yu. E. Ovchinnikov Yu. I. Baukov 《Russian Chemical Bulletin》2004,53(9):1924-1931
The reaction of 4-(2-hydroxybenzoyl)-2,2,6,6-tetramethyl-2,6-disilamorpholine with BF3Et2O afforded (O-B)-chelate 4-[2-(difluoroboroxy)benzoyl]-2,2,6,6-tetramethyl-2,6-disilamorpholine. Treatment of the latter with BF3Et2O or SOCl2 gave rise to products of the disilamorpholine ring opening, viz., (O-B) chelate 2-(difluoroboroxy)-N,N-bis(dimethylfluorosilylmethyl)benzamide or 2-(difluoroboroxy)-N, N-bis(dimethylchlorosilylmethyl)benzamide, respectively. The structures of the compounds synthesized were confirmed by X-ray diffraction analysis and 1H, 13C, and 29Si NMR spectroscopy. High-precision X-ray diffraction study and quantum-chemical calculations demonstrated that the coordination OSi bond is absent in the two last-mentioned compounds.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1846–1853, September, 2004. 相似文献
5.
Hiroto Yoshida Yasuhito YamaryoJoji Ohshita Atsutaka Kunai 《Tetrahedron letters》2003,44(8):1541-1544
Base-free oxidative homocoupling reaction of arylboronic esters has been found to proceed using a catalytic amount of a palladium-1,3-bis(diphenylphosphino)propane (DPPP) complex under an oxygen atmosphere, affording a variety of biaryls in modest to excellent yields. Even arylboronic esters bearing a base-sensitive functional group are applicable to the reaction. 相似文献
6.
Revital Sasson 《Tetrahedron》2005,61(5):1083-1086
A variety of 2-alkyl-1,3-dithiane-2-carboxylic acids was prepared from the appropriate alkyl halides, 1,3-dithiane and CO2. These acids were reacted with BrF3 to form the trifluoromethylalkyl derivatives via a combination of ionic and radical trifluorodecarboxylation in about 50-60% yield. 相似文献
7.
The new isocyanato carborane anion, [7-OCN-7-CB10H12]− was prepared by the reaction of 7-H3N-7-CB10H12 with triphosgene in the presence of triethylamine. The structure of this compound was established by 1H, 11B and 13C NMR as well as IR spectroscopy. The reactivigty of this compound with a series of organic amines was investigated. The resulting ureas were obtained in good to excellent yields. This approach is suitable for development of compounds for use in tumor selective Boron Neutron Capture Therapy (BNCT). 相似文献
8.
M. Röder J. Hahn U. Falke S. Schulze F. Richter M. Hietschold 《Mikrochimica acta》1997,125(1-4):283-286
A series of BN films was deposited by means of r.f. magnetron sputtering of a h-BN target onto Si(1OO) surfaces. Hereby, the substrate bias voltage was varied. Special interest is focussed to the influence of the deposition parameters on the orientation of the growing hexagonal BN film with respect to the substrate. For structural investigation, cross section samples were prepared. In addition to HRTEM and diffraction investigations, especially electron energy loss spectroscopy (EELS) was applied successfully for phase identification. For negative bias voltages of U
B
=–300 V and U
B
=–350V, we found a phase system consisting of a first-grown 25 nm thick layer of hexagonal structure with the c axis parallel to the substrate surface followed by the cubic phase.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday 相似文献
9.
10.
葡萄糖异构酶加速葡萄糖与果糖的平衡,平衡时果糖含量为42%左右,体系中加入一些硼酸盐,果糖的含量提高到80%左右,究其原因可能是由于葡萄糖和果糖与硼酸盐形成不同稳定性的配合物。虽然Roy,Conner,Daris,Belcher,Lorand等都已报导了这些配合物的稳定常数,概括结果分歧较大。Belcher曾首次报导了硼酸与D-果糖的配位数为 相似文献