全文获取类型
收费全文 | 28500篇 |
免费 | 797篇 |
国内免费 | 230篇 |
专业分类
化学 | 19356篇 |
晶体学 | 132篇 |
力学 | 654篇 |
综合类 | 1篇 |
数学 | 5458篇 |
物理学 | 3926篇 |
出版年
2022年 | 184篇 |
2021年 | 278篇 |
2020年 | 347篇 |
2019年 | 314篇 |
2018年 | 276篇 |
2017年 | 292篇 |
2016年 | 600篇 |
2015年 | 624篇 |
2014年 | 660篇 |
2013年 | 1412篇 |
2012年 | 1415篇 |
2011年 | 1717篇 |
2010年 | 958篇 |
2009年 | 821篇 |
2008年 | 1474篇 |
2007年 | 1480篇 |
2006年 | 1556篇 |
2005年 | 1396篇 |
2004年 | 1332篇 |
2003年 | 1104篇 |
2002年 | 1051篇 |
2001年 | 457篇 |
2000年 | 413篇 |
1999年 | 396篇 |
1998年 | 388篇 |
1997年 | 434篇 |
1996年 | 398篇 |
1995年 | 364篇 |
1994年 | 394篇 |
1993年 | 347篇 |
1992年 | 323篇 |
1991年 | 320篇 |
1990年 | 283篇 |
1989年 | 280篇 |
1988年 | 260篇 |
1987年 | 220篇 |
1986年 | 248篇 |
1985年 | 363篇 |
1984年 | 372篇 |
1983年 | 319篇 |
1982年 | 350篇 |
1981年 | 316篇 |
1980年 | 341篇 |
1979年 | 272篇 |
1978年 | 304篇 |
1977年 | 282篇 |
1976年 | 227篇 |
1975年 | 200篇 |
1974年 | 197篇 |
1973年 | 169篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
11.
Dr. Sebastian Lars Müller Xinglong Zhou Dr. Peter Leonard Oxana Korzhenko Dr. Constantin Daniliuc Prof. Dr. Frank Seela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3077-3090
Silver-mediated α-dC–Ag+–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong Tm increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag+–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology. 相似文献
12.
Ieva
Dauickait Amos S. Lawless Jennifer A. Scott Peter Jan van Leeuwen 《Numerical Linear Algebra with Applications》2020,27(5)
We consider the large sparse symmetric linear systems of equations that arise in the solution of weak constraint four‐dimensional variational data assimilation, a method of high interest for numerical weather prediction. These systems can be written as saddle point systems with a 3 × 3 block structure but block eliminations can be performed to reduce them to saddle point systems with a 2 × 2 block structure, or further to symmetric positive definite systems. In this article, we analyse how sensitive the spectra of these matrices are to the number of observations of the underlying dynamical system. We also obtain bounds on the eigenvalues of the matrices. Numerical experiments are used to confirm the theoretical analysis and bounds. 相似文献
13.
Peter T. Smith Younghoon Kim Dr. Bahiru Punja Benke Prof. Kimoon Kim Prof. Christopher J. Chang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(12):4932-4937
We report a supramolecular strategy for promoting the selective reduction of O2 for direct electrosynthesis of H2O2. We utilized cobalt tetraphenylporphyrin (Co-TPP), an oxygen reduction reaction (ORR) catalyst with highly variable product selectivity, as a building block to assemble the permanently porous supramolecular cage Co-PB-1(6) bearing six Co-TPP subunits connected through twenty-four imine bonds. Reduction of these imine linkers to amines yields the more flexible cage Co-rPB-1(6). Both Co-PB-1(6) and Co-rPB-1(6) cages produce 90–100 % H2O2 from electrochemical ORR catalysis in neutral pH water, whereas the Co-TPP monomer gives a 50 % mixture of H2O2 and H2O. Bimolecular pathways have been implicated in facilitating H2O formation, therefore, we attribute this high H2O2 selectivity to site isolation of the discrete molecular units in each supramolecule. The ability to control reaction selectivity in supramolecular structures beyond traditional host–guest interactions offers new opportunities for designing such architectures for a broader range of catalytic applications. 相似文献
14.
15.
16.
Peter Imkeller 《Probability Theory and Related Fields》1996,106(1):105-135
Summary. The analytic treatment of problems related to the asymptotic behaviour of random dynamical systems generated by stochastic
differential equations suffers from the presence of non-adapted random invariant measures. Semimartingale theory becomes accessible
if the underlying Wiener filtration is enlarged by the information carried by the orthogonal projectors on the Oseledets spaces
of the (linearized) system.
We study the corresponding problem of preservation of the semimartingale property and the validity of a priori inequalities
between the norms of stochastic integrals in the enlarged filtration and norms of their quadratic variations in case the random
element F enlarging the filtration is real valued and possesses an absolutely continuous law. Applying the tools of Malliavin’s calculus,
we give smoothness conditions on F under which the semimartingale property is preserved and a priori martingale inequalities are valid.
Received: 12 April 1995 / In revised form: 7 March 1996 相似文献
17.
18.
Stefan Peterli Dieter Hubmann Urs Squin Helmut Mett Peter Traxler 《Helvetica chimica acta》1994,77(1):59-69
β-Nitrostyrene derivatives of adenosine 5′-glutarates are potent and selective bisubstrate-type inhibitors of the epidermal growth factor receptor protein tyrosine kinase (EGF-R PTK). In an attempt to improve the inhibitory activity, this type of compounds was modified with alkyl spacers of varying length between the nitrostyrene and the glutaryl units. The spacers consisted of 1, 3, 4, and 5 atoms to give compounds of the benzyl, oxyethyl, oxypropyl, and oxybutyl series, respectively (Schemes 1 and 2). Adenosine 5′-esters were prepared in the benzyl and oxypropyl series only. Compared to the compounds in the parent series without spacer (IC50 = 0.7–12 μM ), most of the modified compounds inhibited the EGF-R PTK only marginally or were inactive (IC50 ≥ 100 μM ). The only exceptions were the free acids 19 and 20 with IC50 values of ca. 5 μM . It is noteworthy that esterification of these two hydrogen glutarates with either MeOH or adenosine yielded inactive compounds, which is in contrast to the corresponding substances without spacers. 相似文献
19.
Ralf Freund Christos Allagiannis Peter Schnholzer Karl Bernauer 《Helvetica chimica acta》1994,77(3):615-621
A crude hydrate 6 and a crystalline hemiacetal 7 of glyoxylamide 4 were prepared from crotonamide 5 (Scheme 2). Particularly hemiacetal 7 , but also 6 and the ‘dimer’ 8 (obtained from 7 ) may serve as homochiral auxiliaries. The structure of 8 was determined by X-ray analysis. By arenesulfonyl halides, tryptimines 12–14 of 4 were diastereoselectively transformed into spirotricycles 15–17 and 19 . 相似文献
20.
Helmut Schmidhammer Eva Scherb-Bukowiecki Thomas A. Mayer Peter Schnholzer 《Helvetica chimica acta》1994,77(6):1590-1594
The synthesis of benzazepine analogues of the opium alkaloid noscapine ( 1 ) is described. The benzazepines 2 and 3 were prepared starting from nornarceine ethyl ester ( 4 ; readily available from 1 ) in several steps. X-Ray analysis of compound 2 revealed that it is not a diastereosisomer mixture but a racemate of the threo-form and thus has the same configuration as 1 . 相似文献