全文获取类型
收费全文 | 31119篇 |
免费 | 4966篇 |
国内免费 | 9120篇 |
专业分类
化学 | 23696篇 |
晶体学 | 1083篇 |
力学 | 1741篇 |
综合类 | 906篇 |
数学 | 5100篇 |
物理学 | 12679篇 |
出版年
2024年 | 62篇 |
2023年 | 282篇 |
2022年 | 1018篇 |
2021年 | 1072篇 |
2020年 | 1005篇 |
2019年 | 952篇 |
2018年 | 927篇 |
2017年 | 1237篇 |
2016年 | 1168篇 |
2015年 | 1496篇 |
2014年 | 1766篇 |
2013年 | 2440篇 |
2012年 | 2563篇 |
2011年 | 2864篇 |
2010年 | 2591篇 |
2009年 | 2586篇 |
2008年 | 2855篇 |
2007年 | 2783篇 |
2006年 | 2618篇 |
2005年 | 2289篇 |
2004年 | 1811篇 |
2003年 | 1222篇 |
2002年 | 1234篇 |
2001年 | 1141篇 |
2000年 | 1170篇 |
1999年 | 702篇 |
1998年 | 380篇 |
1997年 | 336篇 |
1996年 | 327篇 |
1995年 | 279篇 |
1994年 | 299篇 |
1993年 | 258篇 |
1992年 | 233篇 |
1991年 | 142篇 |
1990年 | 144篇 |
1989年 | 154篇 |
1988年 | 98篇 |
1987年 | 102篇 |
1986年 | 81篇 |
1985年 | 71篇 |
1984年 | 76篇 |
1983年 | 50篇 |
1982年 | 45篇 |
1981年 | 45篇 |
1980年 | 31篇 |
1979年 | 40篇 |
1978年 | 22篇 |
1976年 | 10篇 |
1974年 | 16篇 |
1965年 | 11篇 |
排序方式: 共有10000条查询结果,搜索用时 203 毫秒
991.
Feng G Mareque-Rivas JC Torres Martín de Rosales R Williams NH 《Journal of the American Chemical Society》2005,127(39):13470-13471
The activity of a Zn(II) complex of a tetradentate, tripodal ligand for catalyzing phosphodiester cleavage is enhanced 750-fold by introducing three hydrogen bond donors to the ligand. Inhibition studies show that the Zn-aqua complex is the kinetically active form and that it binds the transition state with a formal dissociation constant of 3 x 108 M-1. The effect of these ligand modifications on the transition-state affinity is comparable to the rate acceleration provided by the metal ion itself. Overall, this mononuclear complex is more active than the most reactive dinuclear Zn(II) complexes reported to date. 相似文献
992.
993.
Voltammetric behavior of zaleplon and its differential pulse polarographic determination in capsules
Larenas G Bollo S Rodriguez M Lemus I Nuñez-Vergara LJ Squella JA Alvarez-Lueje A 《Journal of AOAC International》2005,88(4):1135-1141
In this work both the electrochemical behavior and the analysis of the hypnotic pyrazolopyrimidine derivative zaleplon were studied. Zaleplon in ethanol-0.1M Britton Robinson buffer solution (30-70) showed 2 irreversible, well-defined cathodic responses in the pH range of 2-12 using differential pulse polarography (DPP), tast polarography, and cyclic voltammetry. From chronocoulometric studies, it was possible to conclude that one electron was transferred in each reduction peak or wave. For analytical purposes, the DPP technique working at pH 4.5 for peak I was selected, which exhibited adequate repeatability, reproducibility, and selectivity. The recovery was 99.97 +/- 1.52%, and the detection and quantitation limits were 5.13 x 10(-7)M and 1.11 x 10(-6)M, respectively. The DPP method was applied successfully to the individual assay of capsules in order to verify the content uniformity of zaleplon. Treatment of the sample is not required because the excipients do not interfere, the method is not time consuming, and it is less expensive than column liquid chromatography. 相似文献
994.
Quéméner B Cabrera Pino JC Ralet MC Bonnin E Thibault JF 《Journal of mass spectrometry : JMS》2003,38(6):641-648
Partially acetylated and methylated oligogalacturonides produced by enzymatic hydrolysis of sugar beet pectin were analysed by negative electrospray ionization ion trap mass spectrometry (ESI-ITMS). The (18)O labelling of the oligomer reducing end allowed the precise assignment of the fragments resulting from glycosidic bond and cross-ring cleavages. The collisional-induced dissociation of the C(i) and Z(j) fragment ions through sequential MS(n) experiments always displayed (0, 2)A-type cross-ring cleavage ions which were related to C(2)H(4)O(2) losses. These (0, 2)A ions appeared to be highly diagnostic ions allowing the precise location of the acetyl groups to the O-2 and/or O-3 of the acetylated galacturonic acid residues. 相似文献
995.
通过分子模拟方法研究了手性金属配合物[Rh(bpy)2Chrysi]^3+(bpy=2,2’-bipyridineChrysi=5,6-chrysenequinonediimine)对包含C:T错配碱基对的B-DNA序列的识别作用.结合类似的针对含G:A错配的和正常的B-DNA序列的识别作用研究,发现配合物I-Rh(bpy)zChrysi]^3+可以对错配B-DNA序列进行序列特异性的识别.能量对比计算结果表明,该经典插入识别作用倾向于在错配碱基对附近进行,其中△-[Rh(bpy)2chrysi]^3+比其手性异构体更占优势.这同Barton教授工作组的实验结果是一致的.另外插入作用倾向于在错配序列中的正常双碱基对C3A4/G3T4(错配碱基对附近)中从小沟进行.与该配合物对含G:A错配的和正常的B-DNA序列的识别作用不同的是,对包含C:T错配碱基对的B-DNA序列的识别作用倾向于从小沟进行.这一点可能源于C:T碱基对结构的不同. 相似文献
996.
1INTRODUCTION Over the past decades,olefin oligomerization and polymerization based on late transition metal catalysts have been the most exciting developments in the area of organometallic chemistry and polymer science[1~3].In this broad context,neutral nickel(II)complexes have attracted much attention for their less sensitivity to protonic solvents and polar mon-mers.The most typical one is the SHOP-type cata-lyst[4~6],which contains an anionic[P,O]chelate ring and shows high activ… 相似文献
997.
Serdar Öğüt Juan C. Idrobo Julius Jellinek Jinlan Wang 《Journal of Cluster Science》2006,17(4):609-626
We examine low-energy isomeric forms, static polarizabilities, and optical absorption spectra of Ag
n
, n = 2–8, and Au
n
, n = 2–3, clusters using first principles computations within the static and time-dependent versions of the density functional theory. The noticeable decrease in the static polarizabilities of Ag7 and Ag8 compared to the values characteristic of Ag
n
, n = 2–6, is correlated with the transition from two-dimensional to three-dimensional structures at n = 7. The optical spectra computed within the time-dependent local density approximation for the most stable structures are in good agreement with the available experimental data and the results of earlier theoretical studies. Optical spectra of higher-energy isomers typically present features that are not observed in the experimental spectra. The d electrons affect the spectra of noble metal clusters by quenching the oscillator strengths through screening of the s electrons and by getting directly involved in the excitations. Due to the larger s–d hybridization in Au compared to Ag, these effects are more pronounced in Au
n
clusters. 相似文献
998.
Juan Grotewold Marcello M. Hirschler 《Journal of polymer science. Part A, Polymer chemistry》1977,15(2):383-391
The yield of methyl methacrylate (MMA) polymerization as a function of triethylaluminum (TEA) concentration for a constant azobisisobutyronitrile (AIBN) concentration at 50°C has been measured. The polymerization yield does not differ markedly from that with AIBN alone as long as the initial TEA concentration is held smaller than four times the initial AIBN concentration. A sudden decrease in yield and molecular weight is observed at TEA/AIBN concentration ratios between 4 and 5. A plot of M?w?1 vs. TEA gives a rate-transfer constant of 89 1./mole-sec. If the reaction mixture is vacuum-evaporated with a previous addition of water, instead of precipitating the polymer, the formation of a considerable amount of MMA oligomer is detected for TEA/AIBN concentration ratios larger than 4. On the average, each TEA molecule in excess of four times the initial amount of AIBN yields one oligomer molecule. The data are consistent with a radical polymerization mechanism for the high molecular weight polymer and with a nonradical one for the oligomer formation. 相似文献
999.
1000.
Mínguez JM Castellote MI Vaquero JJ García-Navio JL Alvarez-Builla J Castaño O Andrés JL 《The Journal of organic chemistry》1996,61(14):4655-4665
A new synthesis of the pyrrolo[1,2-a]pyrazine system from pyrrole is described. In light of the ab initio calculations carried out on this heterocyclic system some of its basic chemistry was investigated and included electrophilic substitution, addition of organolithium reagents, metalation with lithium diisopropylamide and subsequent reaction with electrophiles, and formation of salts by quaternization of the nonbridgehead nitrogen. N-ylides obtained from these salts undergo 1,3-dipolar cycloaddition with suitable dipolarophiles to give dipyrrolo[1,2-a]pyrazines, pyrazolo[1,5-a]-pyrrolo[2,1-c]pyrazines, and heterobetaines. Examples of intramolecular 1,3-dipolar cycloadditions are also reported. 相似文献