全文获取类型
收费全文 | 3517篇 |
免费 | 101篇 |
国内免费 | 15篇 |
专业分类
化学 | 2171篇 |
晶体学 | 15篇 |
力学 | 195篇 |
数学 | 751篇 |
物理学 | 501篇 |
出版年
2023年 | 16篇 |
2022年 | 39篇 |
2021年 | 98篇 |
2020年 | 73篇 |
2019年 | 52篇 |
2018年 | 65篇 |
2017年 | 57篇 |
2016年 | 111篇 |
2015年 | 104篇 |
2014年 | 80篇 |
2013年 | 187篇 |
2012年 | 207篇 |
2011年 | 247篇 |
2010年 | 145篇 |
2009年 | 122篇 |
2008年 | 201篇 |
2007年 | 220篇 |
2006年 | 164篇 |
2005年 | 154篇 |
2004年 | 145篇 |
2003年 | 117篇 |
2002年 | 98篇 |
2001年 | 45篇 |
2000年 | 25篇 |
1999年 | 38篇 |
1998年 | 34篇 |
1997年 | 34篇 |
1996年 | 36篇 |
1995年 | 26篇 |
1994年 | 30篇 |
1993年 | 47篇 |
1992年 | 18篇 |
1991年 | 27篇 |
1990年 | 29篇 |
1989年 | 17篇 |
1988年 | 26篇 |
1987年 | 22篇 |
1986年 | 23篇 |
1985年 | 46篇 |
1984年 | 41篇 |
1983年 | 23篇 |
1982年 | 25篇 |
1981年 | 30篇 |
1980年 | 27篇 |
1979年 | 24篇 |
1978年 | 26篇 |
1977年 | 23篇 |
1976年 | 24篇 |
1975年 | 13篇 |
1974年 | 21篇 |
排序方式: 共有3633条查询结果,搜索用时 46 毫秒
41.
An automated procedure for correcting the interference due to mixing the reagents in the determination of ATP by a bioluminescent
technique is described. The measurements were performed by an in-house interfaced PC photometer. An automated procedure based
on a robust regression method and outliers detection was applied to exclude the time of the mixing of the reagents from the
global time of reaction. In fact the mixing of the reagents is responsible of the poor analytical precision (RSD%>25) and
low sensitivity (limit of detection≈2×10-8 mol/l). By this procedure, the precision (RSD%<7) and sensitivity (limit of detection≈8×10-10 mol/l) were improved. The method was applied to the determination of ATP in marine sediments and good recovery within 90–108%
was obtained. For non-polluted samples the measurement can be carried out by direct comparison with standard solutions. The
standard addition procedure is recommended for polluted samples.
Received: 25 April 1996/Revised: 28 June 1996/Accepted: 3 July 1996 相似文献
42.
Mondello L Shellie R Casilli A Quinto Tranchida P Marriott P Dugo G 《Journal of separation science》2004,27(9):699-702
A 5 m x 50 microm capillary column with 0.05 microm stationary phase film thickness, with a calculated efficiency of almost 20,000 plates per metre (under optimum conditions), was used for very fasthigh resolution GC analysis of lime essential oil. The total analysis time of this volatile essential oil was less than 90 s. Fast GC is shown to be appropriate for essential oil quality assurance analysis, and quantitative results of key components are comparable with those obtained by using conventional GC analysis. The fast GC analysis is approximately 33 times faster than the conventional GC method. 相似文献
43.
Sanna D Micera G Kallay C Rigo V Sovago I 《Dalton transactions (Cambridge, England : 2003)》2004,(17):2702-2707
Copper(II) complexes of peptides containing two or three histidyl residues (Ac-HisGlyHis-OH, Ac-HisGlyHis-NHMe, Ac-HisHisGlyHis-OH and Ac-HisHisGlyHis-NHMe) have been studied by potentiometric, UV-Vis, EPR and CD spectroscopic measurements. The imidazole nitrogen atoms are described as the primary metal binding sites of all ligands resulting in the formation of various macrochelates in the pH range 4 to 7. The (Nim, N-, Nim)-co-ordinated [CuH-1L]0+ complexes were mainly detected in samples containing free carboxylates at the C-termini, whilst the [CuH-2L]-(0) complexes were the predominant species in slightly alkaline solution and their binding modes were described via 4N-co-ordination (Nim, N-, N-, Nim) in (7,5,6)-membered fused chelate rings. Deprotonation and co-ordination of the third amide nitrogens were detected above pH approximately 9 in all cases. 相似文献
44.
Cordaro M Di Donna L Grassi G Maiuolo L Mazzotti F Perri E Sindona G Tagarelli A 《European journal of mass spectrometry (Chichester, England)》2004,10(5):691-697
An evaluation of the gas-phase ion chemistry of rotenone (1) by electrospray ionisation (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS2) is presented, aiming at providing tools for its determination in natural and biological matrices. The behaviour of its cycloadducts with benzonitrile-N-oxide (2) and 2,4,6-trimethylbenzonitrile-N-oxide (3) was also evaluated and the MS data thus obtained have provided evidence into the mechanism of formation of the key product ion at m/z 192 which can be considered a marker in the MS and MS2 spectra of rotenone and its derivatives. 相似文献
45.
NMR data have been used to assign the stereochemistry to some new (E)- and (Z)-α-phenyl-β-[2-(N-methyl)nitropyrrolyl]acrylic acids. The (E)-molecules are biased in the s-cis conformation showing NMR spectroscopic features strictly depending on the conformation.The analysis of the NMR spectra reveals that the (Z)-isomers exist also in the s-cis conformation. 相似文献
46.
47.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献
48.
Angelo Mugnoli Domenico Spinelli Giovanni Consiglio Renato Noto 《Journal of heterocyclic chemistry》1988,25(1):177-183
The geometry obtained by a crystal structure determination of the title compounds, as compared with that of the analogous benzene derivatives, along with results of ab initio calculations, is used to interpret the different SNAr reactivities in some thiophene and benzene compounds. The smaller rotation of the nitro groups with respect to the aromatic rings observed in thiophene derivatives should be considered a relevant factor in the higher reactivity in the thiophene series. 相似文献
49.
Antonia Sacchi Paolo De Caprariis Luciano Mayol Giovanni De Martino 《Journal of heterocyclic chemistry》1995,32(3):1067-1069
4-Hydroxy-3-phenylprolines were synthesized via 1-acetyl-2,2-diethoxycarbonyl-2,3-dihydro-3-phenyl-1H-pyrrole. Reversed phase hplc resulted in the isolation of the products which were characterized by 1H and 13C nmr spectroscopy. 相似文献
50.
Giovanni Monegato 《Numerical Algorithms》1996,11(1):271-283
We consider the numerical solution of second kind integral equations of the form $$u(y) - \int\limits_0^1 {k(y/x)\frac{{u(x)}}{x}dx = f(y), 0 \le y \le 1,} $$ for some given kernelk(t). These equations, usually indicated as of Mellin type, arise in a variety of applications. In particular, we examine a Nyström interpolant based on the following product quadrature rule: $$\int\limits_0^1 {k(y/x)\frac{{u(x)}}{x}dx \approx \sum\limits_{i = 0}^n {w_{ni} (y)u(x_{mi} ).} } $$ This rule is obtained by interpolatingu(x) by the Lagrange polynomial associated with the set of Gauss-Radau nodes {x ni}. Under certain assumptions on the kernelk(t), we are able to prove the stability of our interpolant and derive convergence estimates. 相似文献