全文获取类型
收费全文 | 3247篇 |
免费 | 200篇 |
国内免费 | 44篇 |
专业分类
化学 | 2301篇 |
晶体学 | 41篇 |
力学 | 141篇 |
综合类 | 2篇 |
数学 | 396篇 |
物理学 | 610篇 |
出版年
2024年 | 34篇 |
2023年 | 60篇 |
2022年 | 187篇 |
2021年 | 307篇 |
2020年 | 182篇 |
2019年 | 172篇 |
2018年 | 156篇 |
2017年 | 128篇 |
2016年 | 197篇 |
2015年 | 135篇 |
2014年 | 153篇 |
2013年 | 244篇 |
2012年 | 224篇 |
2011年 | 252篇 |
2010年 | 140篇 |
2009年 | 131篇 |
2008年 | 140篇 |
2007年 | 133篇 |
2006年 | 97篇 |
2005年 | 83篇 |
2004年 | 54篇 |
2003年 | 54篇 |
2002年 | 52篇 |
2001年 | 18篇 |
2000年 | 22篇 |
1999年 | 9篇 |
1998年 | 12篇 |
1997年 | 9篇 |
1996年 | 17篇 |
1995年 | 11篇 |
1994年 | 5篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1976年 | 3篇 |
1973年 | 2篇 |
1970年 | 1篇 |
1964年 | 1篇 |
1961年 | 1篇 |
排序方式: 共有3491条查询结果,搜索用时 31 毫秒
21.
Conjugate additions of amino alcohols derived from alpha-amino acids to vinyl sulfones, followed by N-benzylation, chlorination, and intramolecular alkylation, provide a convenient route to substituted pyrrolidines. The process is accompanied by the stereospecific rearrangement of substituents from the alpha-position of the amine to the beta-position of the product and takes place via the corresponding aziridinium ion intermediates. Another type of rearrangement was observed during the reaction of (2-piperidine)methanol or 2-(2-piperidine)ethanol with phenyl trans-1-propenyl sulfone, in which the methyl group appears to migrate from the beta- to the alpha-position of the sulfone moiety. This process involves the isomerization of phenyl trans-1-propenyl sulfone to phenyl 2-propenyl sulfone by the addition-elimination of catalytic benzenesulfinate anion to the former vinyl sulfone, followed by conjugate addition of the amino group to the latter sulfone. Chlorination and intramolecular alkylation then afford the corresponding rearranged indolizidine and quinolizidine derivatives, respectively. 相似文献
22.
Muhammad Mufazzal Saeed 《Journal of Radioanalytical and Nuclear Chemistry》2006,267(2):427-433
Summary The sorption of microquantities of Tm(III) ions on washed polyurethane foam (PUF) from a mixture of aqueous solution and ethanol
containing PAN was examined. The maximum sorption of 3.18. 10-6M solution of Tm(III) ions was observed at pH 8 with 30-minute equilibration time. The optimum ratio of aqueous-ethanol phase
for the sorption of Tm(III) ions was found to be 3:1 v/v, respectively. The sorption rate of metal ions on PUF is followed a first order kinetics and obeyed the equation for an intra
particle diffusion process. The equilibrium concentration data of Tm(III) ions could be described satisfactorily by several
adsorption isotherms. The Freundlich adsorption isotherm constants 1/nand KFare 0.66±0.02 and (5.7±0.3). 10-3mol. g-1, respectively. The Langmuir isotherm constants for monolayer coverage (Q) and binding strength of sorption (b) are (2.5±0.7). 10-5mol. g-1and (1.6±0.1). 104l. mol-1, respectively. The sorption capacity derived from Dubinin-Radushkevich (D-R) isotherm is (1.7±0.2). 10-4mol. g-1and the sorption free energy (E) is 9.8±0.2 kJ. mol-1indicating chemisorption phenomena. The thermodynamic parameters indicate that the sorption of Tm(III) ions onto PUF is endothermic,
entropy driven and spontaneous in nature. 相似文献
23.
Nizakat Bib Misal Khan Amal Badshah Muhammad Ashraf Chaudry 《Radiation Physics and Chemistry》2005,73(6):362-364
Minimally processed cauliflower samples were irradiated, stored at 5 °C for 2 weeks and analyzed for sensory, physicochemical and microbiological qualities at 0th, 7th and 14th days. The data showed highest mean values of 7.93 and 7.57 for appearance and flavor, respectively, for 1.0 kGy treated samples. The D10 values of contaminating microorganisms on cauliflower were 0.20 (Escherischia coli) and 0.24 kGy (Salmonella paratyphae A.) and the resulting 5D10 value was 1.2 kGy. The study revealed that a dose of 1.5 kGy is enough for retention of quality and reduction of microbial load to 5D10 values in cauliflower during 2 weeks storage at refrigerated temperature. 相似文献
24.
Ahmad VU Khan A Farooq U Kousar F Khan SS Nawaz SA Abbasi MA Choudhary MI 《Chemical & pharmaceutical bulletin》2005,53(4):378-381
Three new tricyclic cis-clerodane type diterpenoids trivially named as limbatolide A (1), limbatolide B (2) and limbatolide C (3) have been isolated from the roots of Otostegia limbata along with two known compounds; oleanic acid and beta-sitosterol. The structure elucidation of the new compounds was based primarily on two-dimensional (2D) NMR techniques. Compounds 1-3 displayed inhibitory potential in a concentration-dependent manner against acetylcholinesterase (AChE; EC 3.1.1.7) and butyrylcholinesterase (BChE; EC 3.1.1.8) enzymes, respectively. 相似文献
25.
We have demonstrated that the readily available amido-keto compounds 5, with prearranged carbonyl and glycine moieties, under strongly basic conditions easily undergo complete and highly diastereoselective cyclization, affording a generalized and practical access to the conformationally constrained phenylserine derivatives 4. High chemical yields, virtually complete diastereoselectivity combined with the operational convenience of the experimental procedures render this method useful for preparation of these diastereomerically pure derivatives. 相似文献
26.
Tahir AA Molloy KC Mazhar M Kociok-Köhn G Hamid M Dastgir S 《Inorganic chemistry》2005,44(25):9207-9212
Ba(dmae)2 (dmaeH=N,N-dimethylaminoethanol, C4H11NO) reacts with Co(acac)2 (acac=2,4-pentanedionate) to produce the trinuclear coordination complex [Ba2Co(acac)4(dmae)3(dmaeH)] in an 85% yield. Spectroscopic and single-crystal X-ray diffraction experiments indicate that the complex possesses a structure in which two barium atoms and a cobalt atom are bridged by acac and dmae groups. The barium centers are eight and nine coordinate with BaO7N and BaO7N2 coordination spheres while the cobalt is a more regular CoO5N octahedron. This 2:1 heterobimetallic molecular complex was investigated as precursor for the deposition of thin film by AACVD. The film was characterized by SEM and XRD. TGA shows that the complex starts thermal decomposition upon heating in nitrogen atmosphere at 105 degrees C to produce barium cobalt oxide material of a Ba2CoO3 composition with an orthorhombic structure. The synthetic approach detailed here represents a unique route to the formation of a heterobimetallic barium cobalt coordination complex. 相似文献
27.
Ahmad VU Zubair M Athar Abbasi M Abid Rashid M Rasool N Nahar Khan S Iqbal Choudhary M Kousar F 《Magnetic resonance in chemistry : MRC》2005,43(6):486-488
The investigation of the chemical constituents of Symplocos racemosa Roxb led to the isolation of two new glycosides, symcomoside A (1) and symcomoside B (2), together with one known glycoside, tortoside C (3), which is reported for the first time from this plant. The structures of the new compounds were determined by 1D and 2D homonuclear and heteronuclear NMR spectroscopy, from chemical evidence and by comparison with published data for closely related compounds. Symcomoside B (2) showed potent inhibitory activity against alpha-glucosidase in a concentration-dependent fashion with an IC50 value of 0.733 +/- 0.033 mM whereas symcomoside A (1) showed very weak inhibitory activity against alpha-glucosidase (9.90% in 0.70 mM). 相似文献
28.
The dependence of the diffusion parameters including slowing down area, neutron diffusion length and migration length on the voided volume fraction in water has been studied experimentally. For this purpose, the PIEAS Neutron Transport Facility (PNTF) comprised of a 10 Ci Am–Be neutron source and a water filled aluminum tank with Perspex voided tubes has been designed and fabricated. A BF3 detector was used for the neutron counting. The slowing down area was determined at the cadmium cutoff level. The diffusion parameters were determined first in the absence of voids. The experimentally measured values of the slowing down area, the diffusion length and the migration length have been found in good agreement with the corresponding values determined by other workers. By varying void volume fraction from 0% to 7.5%, the experimental measurements show a monotonic increase in the slowing down area from 58.71±2.6 to 71.28±3.2 cm2, in the diffusion length from 2.95±0.13 to 3.11±0.13 cm and in the migration length from 8.21±0.165 to 8.99±0.169 cm. Our measurements show that the diffusion parameters exhibit a quadratic dependence on the void volume fraction. 相似文献
29.
Marine brown alga Dictyota dichotoma (Dictyotaceae) collected from Karachi coast of Arabian Sea yielded two new (1 and 2) enones (dolastane-diterpenoids) named: dichotenone-A and -B along with an olide (loliolide, 3) as a new source. Their structures have been characterized with the aid of 2D-NMR spectroscopic techniques. 相似文献
30.
Khan KM Shujaat S Rahat S Hayat S Atta-ur-Rahman Choudhary MI 《Chemical & pharmaceutical bulletin》2002,50(11):1443-1446
Eight new beta-N-substituted acyl hydrazides along with their corresponding acyl derivatives were synthesized and screened for in vitro beta-glucuronidase inhibition and found to be active against the enzyme. All of these compounds were found to be noncompetitive inhibitors except for N'-(2-cyanoethyl)-4-hydroxy benzohydrazide (10), which was found to be an uncompetitive inhibitor. Structure-activity relationship studies indicated that the benzyloxy group present in compounds 12 and 13 is responsible for the beta-glucuronidase inhibition activity. 相似文献