全文获取类型
收费全文 | 4774篇 |
免费 | 247篇 |
国内免费 | 26篇 |
专业分类
化学 | 3400篇 |
晶体学 | 18篇 |
力学 | 110篇 |
数学 | 704篇 |
物理学 | 815篇 |
出版年
2023年 | 31篇 |
2022年 | 29篇 |
2021年 | 70篇 |
2020年 | 89篇 |
2019年 | 95篇 |
2018年 | 86篇 |
2017年 | 85篇 |
2016年 | 214篇 |
2015年 | 166篇 |
2014年 | 149篇 |
2013年 | 331篇 |
2012年 | 310篇 |
2011年 | 357篇 |
2010年 | 205篇 |
2009年 | 154篇 |
2008年 | 305篇 |
2007年 | 258篇 |
2006年 | 214篇 |
2005年 | 225篇 |
2004年 | 188篇 |
2003年 | 184篇 |
2002年 | 165篇 |
2001年 | 87篇 |
2000年 | 66篇 |
1999年 | 62篇 |
1998年 | 62篇 |
1997年 | 39篇 |
1996年 | 44篇 |
1995年 | 28篇 |
1994年 | 40篇 |
1993年 | 54篇 |
1992年 | 34篇 |
1991年 | 37篇 |
1990年 | 31篇 |
1989年 | 28篇 |
1988年 | 28篇 |
1987年 | 32篇 |
1986年 | 21篇 |
1985年 | 44篇 |
1984年 | 31篇 |
1983年 | 27篇 |
1982年 | 28篇 |
1981年 | 21篇 |
1980年 | 28篇 |
1979年 | 33篇 |
1978年 | 29篇 |
1977年 | 25篇 |
1975年 | 21篇 |
1974年 | 25篇 |
1973年 | 29篇 |
排序方式: 共有5047条查询结果,搜索用时 31 毫秒
41.
42.
43.
44.
Production and characterisation of polyclonal antibodies to a derivative of 3-amino-2-oxazolidinone, a metabolite of the nitrofuran furazolidone 总被引:6,自引:0,他引:6
Kevin M. Cooper Anthony Caddell Christopher T. Elliott D. Glenn Kennedy 《Analytica chimica acta》2004,520(1-2):79-86
Polyclonal antibodies were produced to detect 3-amino-2-oxazolidinone (AOZ), a stable metabolite of the nitrofuran antibiotic furazolidone, following derivatisation with o-nitrobenzaldehyde. A carboxyphenyl derivative of AOZ was prepared, purified and conjugated to immunogenic carrier protein. Six antisera were produced from the immunisation of seven rabbits using various immunogen doses and time-scales. IC50 values, as determined by competitive enzyme-linked immunosorbent assay (ELISA) suggested that reducing immunogen dose from 0.3 to 0.05 mg, while lengthening rest periods between booster immunisations from 2 to 8 weeks, increased the sensitivity of the antibodies to 3-{[(2-nitrophenyl)methylene]amino}-2-oxazolidinone (NPAOZ) from 3.8 to 0.3 μg l−1. An IC50 of 0.065 μg l−1 (AOZ in the form of NPAOZ) was achieved with antiserum R670 by altering ELISA conditions. This antibody was highly specific for NPAOZ and did not cross-react with various nitrofuran metabolites, their nitrophenyl derivatives or a range of veterinary drugs. Antibody R670 is suitable for incorporation into an immunoassay for AOZ with sufficient sensitivity to satisfy current criteria for monitoring of veterinary drug residues. This is the first publication of an antibody for detection of a nitrofuran metabolite. 相似文献
45.
46.
Barriga S Fuertes P Marcos CF Rakitin OA Torroba T 《The Journal of organic chemistry》2002,67(18):6439-6448
We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system. 相似文献
47.
Heterobinuclear oxometalate anions based upon [CrMoO7]2-, [CrWO7]2-, and [MoWO7]2- were generated and transferred to the gas phase by the electrospray process from acetonitrile solutions containing two of the salts (Bu4N)2[MO4] (M = Cr, Mo, W). Their reactivities were examined and compared with those of the related homobinuclear anions based upon [M2O7]2- (M = Cr, Mo, W). Particular emphasis was placed upon reactions relevant to gas-phase catalytic cycles described previously for oxidation of alcohols by [Mo2O6(OH)]- (Waters, T.; O'Hair, R. A. J.; Wedd, A. G. J. Am. Chem. Soc. 2003, 125, 3384-3396). The protonated anions [MM'O6(OH)]- each reacted with methanol with loss of water to form [MM'O6(OCH3)]- at a rate that was intermediate between those of [M2O6(OH)]- and [M'2O6(OH)]-. The butylated anions [MM'O6(OBu)]- were generated by collisional activation of the ion-pairs {Bu4N+ [MM'O7]2-}-. Collisional activation of [MM'O6(OBu)]- resulted in either the loss of butanal (redox reaction) or the loss of butene (elimination reaction), with the detailed nature of the observations depending on the nature of both M and M'. Selective 18O labeling indicated that the butoxo ligands of [CrMoO6(OBu)]- and [CrWO6(OBu)]- were located on molybdenum and tungsten, respectively. This structural insight allowed a more detailed comparison of reactivity with the homobinuclear species, and highlighted the importance of the neighboring metal center in these reactions. 相似文献
48.
Basurto S García S Neo AG Torroba T Marcos CF Miguel D Barberá J Ros MB de la Fuente MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5362-5376
Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties. 相似文献
49.
Summary The general objective is to provide an alternative methodology based on capillary electrophoresis (CE) to characterize flavonoids from honey and hence determine its botanical origin. The specific objective is to compare the separation of flavonoids by CE with those achieved by HPLC to assess CE as an alternative technique for the determination of honey flavonoids. Fourteen different flavonoids isolated from honey were analysed by MECC and compared to the HPLC separations. It was difficult to find specific experimental conditions to separate all the flavonoids from honey in a single MEKC run. Three chromatographic conditions are optimized and, depending on the flavonoid markers sought in honey, the appropriate detection method should be chosen. Compared to the HPLC results, it is clear that CE could be an alternative technique in honey flavonoids analysis and particularly in the study of its geographical and floral origin. 相似文献
50.
Virgil Percec Brian C. Auman Hildeberto Nava Joseph P. Kennedy 《Journal of polymer science. Part A, Polymer chemistry》1988,26(3):721-741
Alternating—i.e., -(A-B)n- type—block copolymers of polyisobutylene (PIB) and aromatic polyether sulfone (PSU) have been prepared by phase transfer catalyzed Williamson polyetherification of α,ω-di(phenol)PIB with α,ω-di(chloroallyl)- or -(bromobenzyl)PSU. Block copolymers of the two prepolymers were also synthesized by the phase transfer catalyzed polyetherification of methylene chloride with α,ω-di(phenol)PIB and α,ω-di(phenol)PSU (bisphenol-A-terminated PSU). This method leads to -[(A)x-(B)y]n- block copolymers with formal linkages between segments. At sufficiently high segment lengths, both types of block copolymers exhibit two distinct Tgs, indicating phase separation into rubbery PIB and glassy PSU domains. 相似文献