全文获取类型
收费全文 | 1555篇 |
免费 | 51篇 |
国内免费 | 4篇 |
专业分类
化学 | 1118篇 |
晶体学 | 8篇 |
力学 | 27篇 |
数学 | 181篇 |
物理学 | 276篇 |
出版年
2023年 | 10篇 |
2022年 | 15篇 |
2021年 | 19篇 |
2020年 | 23篇 |
2019年 | 19篇 |
2018年 | 10篇 |
2017年 | 10篇 |
2016年 | 31篇 |
2015年 | 33篇 |
2014年 | 32篇 |
2013年 | 72篇 |
2012年 | 91篇 |
2011年 | 124篇 |
2010年 | 63篇 |
2009年 | 63篇 |
2008年 | 106篇 |
2007年 | 99篇 |
2006年 | 102篇 |
2005年 | 95篇 |
2004年 | 70篇 |
2003年 | 60篇 |
2002年 | 67篇 |
2001年 | 34篇 |
2000年 | 18篇 |
1999年 | 14篇 |
1998年 | 25篇 |
1997年 | 18篇 |
1996年 | 18篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 12篇 |
1992年 | 7篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 9篇 |
1985年 | 26篇 |
1984年 | 12篇 |
1982年 | 10篇 |
1981年 | 14篇 |
1979年 | 10篇 |
1978年 | 12篇 |
1977年 | 14篇 |
1976年 | 10篇 |
1975年 | 15篇 |
1974年 | 13篇 |
1973年 | 6篇 |
1970年 | 6篇 |
排序方式: 共有1610条查询结果,搜索用时 15 毫秒
31.
Tugarinov V Kay LE Ibraghimov I Orekhov VY 《Journal of the American Chemical Society》2005,127(8):2767-2775
An approach for recording four-dimensional (4D) methyl (1)H-(13)C-(13)C-(1)H NOESY spectra with high resolution and sensitivity is presented and applied to Malate Synthase G (723 residues, 82 kDa). Sensitivity and resolution have been optimized using a highly deuterated, methyl-protonated sample in concert with methyl-TROSY, sparse data sampling in the three indirect dimensions, and 4D spectral reconstruction using multidimensional decomposition (MDD). A sparse data acquisition protocol is introduced that ensures that sufficiently long indirect acquisition times can be employed to exploit the decreased relaxation rates associated with methyl-TROSY, without increasing the duration of the 4D experiment beyond acceptable measurement times. In this manner, only a fraction ( approximately 30%) of the experimental data that would normally be needed to achieve a spectrum of high resolution is acquired. The reconstructed 4D spectrum is of similar resolution and sensitivity to three-dimensional (3D) (13)C-edited NOE spectra, is straightforward to analyze, and resolves ambiguities that emerge when 3D data sets only are considered. 相似文献
32.
33.
Novel products from attempted michael addition to 1-methyl-1,2,5,6-tetrahydropyridine-4-carbonitrile
Graeme L. Butt Leslie W. Deady Maureen F. Mackay Maruse Sadek 《Tetrahedron letters》1982,23(43):4485-4488
The reaction of some phenols with the title compound, in the presence of sodium, gives 2-(2-hydroxyaryl_piperidine derivatives. Geometrical isomers have been separated, which differ in having an equatorial (A) or axial (B) cyano group on the piperidine chair (the methyl and aryl groups are equatorial in both forms). The x-ray crystallographic structures of an example of each of A and B are reported and the proton NMR spectra are assigned. 相似文献
34.
A sensitive 3D NMR pulse scheme, (H)C(CA)NH-COSY, is presented for the assignment of (13)C(delta)(1) Ile chemical shifts in large perdeuterated, methyl-protonated proteins. The nonlinearity of branched amino acids, such as Ile, significantly degrades the quality of TOCSY schemes which transfer magnetization from methyl carbons to the backbone (13)C(alpha) positions, and in applications to high molecular weight proteins (correlation times on the order of 40-50 ns), this compromises the sensitivity of spectra used for methyl assignment. The experiment presented utilizes COSY-based transfer steps and refocuses undesirable (13)C-(13)C scalar couplings that degrade the efficiency of TOCSY transfers. The (H)C(CA)NH-COSY scheme is tested on an (15)N,(13)C,(2)H-[Leu, Val, Ile (delta 1 only)]-methyl-protonated maltose binding protein (MBP)/beta-cyclodextrin complex at 5 degrees C (molecular tumbling time 46 +/- 2 ns), facilitating the assignment of (13)C(delta 1) chemical shifts for 18 of the 19 Ile residues for which backbone assignments were previously obtained. Both sensitivity and resolution of the resulting spectra are shown to be significantly better than those for a similar TOCSY-based approach. 相似文献
35.
In a combination of cobalt-mediated cationic and free radical chemistry, treatment of the allyl silane substituted β-hydroxycobaloxime 13 with pTSA led predominantly to the trans-disubstituted cyclopentane 14, which on irradiation with TEMPO produced 15. In a similar manner, the cobaloxime 18 was cyclised to 19 in the presence of pTSA which, on irradiation with a sunlamp then underwent radical mediated cyclisation to the substituted indane 20. 相似文献
36.
W. Russell Bowman Anthony J. Fletcher Peter J. Lovell Elena Hernández López Graeme B.S. Potts 《Tetrahedron》2007,63(1):191-203
Amides have been successfully used as precursors of imidoyl radicals for radical cyclisation. The amides have been converted to imidoyl selanides via reaction with phosgene to yield imidoyl chlorides followed by reaction with potassium phenylselanide. Imidoyl selanides were reacted with tributyltin hydride (Bu3SnH) as the radical mediator with triethylborane or AIBN as initiators to yield imidoyl radicals for cyclisation reactions. Imidoyl radicals have been cyclised onto alkenes to yield 2,3-substituted-indoles and -quinolines and also onto pyrroles and indoles to give bi- and tricyclic heteroarenes. 相似文献
37.
Graeme D. McAllister 《Tetrahedron》2007,63(49):12123-12130
A concise route to the anti-tumour natural product (−)-varitriol, together with its novel isomer (−)-3′-epi-varitriol, is described using a Horner-Wadsworth-Emmons (HWE)/conjugate addition/Ramberg-Bäcklund sequence as the cornerstone. The flexibility of the synthetic route has been demonstrated by the preparation of novel varitriol analogues. 相似文献
38.
Miles S. CongreveCorinne Kay Jan J. ScicinskiSteven V. Ley Geoffrey WilliamsPeter J. Murray Stephen C. McKeownStephen P. Watson 《Tetrahedron letters》2003,44(21):4153-4156
The development of a versatile amine releasing linker based on the modified o-nitrobenzene sulfonamide protective group is described. This new N-Boc-o-nitrobenzenesulfonamide (Boc-ONBS) linker enables the elaboration on resin of primary and secondary amines by sequential substitution of the sulfonamide moiety using the Mitsunobu reaction. A 16-member array of secondary and Boc protected primary amines was then prepared using this linker. 相似文献
39.
Severin K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(7):1515-1519
Several methods to synthesize bimetallic complexes in which two different metal fragments are connected by halide bridges are described. Using simple starting materials a large pool of structurally defined bimetallic complexes with unique chemical reactivities can be prepared in short time. Applications in organometallic synthesis and homogeneous catalysis are discussed. 相似文献
40.
Bernard S. Kay 《Communications in Mathematical Physics》1978,62(1):55-70
We give mathematically rigorous results on the quantization of the covariant Klein Gordon field with an external stationary scalar interaction in a stationary curved space-time. We show how, following Segal, Weinless etc., the problem reduces to finding a “one particle structure” for the corresponding classical system. Our main result is an existence theorem for such a one-particle structure for a precisely specified class of stationary space-times. Byproducts of our approach are:
- A discussion of when a given “equal-time” surface in a given stationary space-time is Cauchy.
- A modification and extension of the methods of Chernoff [3] for proving the essential self-adjointness of certain partial differential operators.