全文获取类型
收费全文 | 6600篇 |
免费 | 172篇 |
国内免费 | 28篇 |
专业分类
化学 | 4786篇 |
晶体学 | 71篇 |
力学 | 82篇 |
数学 | 402篇 |
物理学 | 1459篇 |
出版年
2023年 | 42篇 |
2022年 | 49篇 |
2021年 | 60篇 |
2020年 | 109篇 |
2019年 | 103篇 |
2018年 | 52篇 |
2017年 | 44篇 |
2016年 | 115篇 |
2015年 | 127篇 |
2014年 | 141篇 |
2013年 | 347篇 |
2012年 | 344篇 |
2011年 | 387篇 |
2010年 | 216篇 |
2009年 | 215篇 |
2008年 | 399篇 |
2007年 | 397篇 |
2006年 | 404篇 |
2005年 | 362篇 |
2004年 | 310篇 |
2003年 | 268篇 |
2002年 | 287篇 |
2001年 | 139篇 |
2000年 | 153篇 |
1999年 | 114篇 |
1998年 | 78篇 |
1997年 | 82篇 |
1996年 | 88篇 |
1995年 | 69篇 |
1994年 | 53篇 |
1993年 | 61篇 |
1992年 | 83篇 |
1991年 | 57篇 |
1990年 | 49篇 |
1989年 | 58篇 |
1988年 | 73篇 |
1987年 | 56篇 |
1986年 | 56篇 |
1985年 | 87篇 |
1984年 | 85篇 |
1983年 | 40篇 |
1982年 | 62篇 |
1981年 | 59篇 |
1980年 | 57篇 |
1979年 | 54篇 |
1978年 | 43篇 |
1977年 | 54篇 |
1976年 | 32篇 |
1975年 | 36篇 |
1974年 | 37篇 |
排序方式: 共有6800条查询结果,搜索用时 0 毫秒
51.
An automatic method for the determination of metabolites of Ropivacaine in urine was set up. It utilizes supported liquid membrane extraction for sample clean-up and enrichment, followed by ion-pair chromatography determination using UV detection. The extraction was very selective with no observed interfering compounds from the urine matrix, permitting simple isocratic chromatographic analysis. The detection limits for spiked urine samples were 2–18 nM for the different compounds. The repeatability was 1–3% (RSD) with an internal standard that was also extracted, and about twice without this standard. A throughput of 3.3 samples per hour was achieved and the liquid membrane was stable for more than a week. 相似文献
52.
S. Takahashi H. Morimoto E. Murata S. Kataoka K. Sonogashira N. Hagihara 《Journal of polymer science. Part A, Polymer chemistry》1982,20(2):565-573
Metal-polyyne polymers consisting of palladium and conjugated acetylenic systems, where PD and R represent the —Pd(PBu3)2—moiety and alkyl groups, respectively, were prepared by polycondensation between palladium chlorides and α,ω-diethynyl compounds in amines using a catalytic amount of cuprous iodide. The molecular weights of the polymers formed were greatly affected by the basicity of the amines and the addition of free phosphines to the polymerization system. Under the optimum conditions, i.e., in the presence of CuI and PBu3 (in molar ratio 1/4) in piperidine at room temperature, polymer Ia (R1 = R2 = H) having M?w = 29,000 was obtained. 相似文献
53.
Toshikazu Kurosaki Osamu Takahashi Makoto Okawara 《Journal of polymer science. Part A, Polymer chemistry》1974,12(7):1407-1420
Polymers having stable pendant . radicals were synthesized through their precursor polymers by oxidizing them in air or by H2O2–Na2WO4. Hydrochlorides and sulfates of 4-methacryloylamino- and 4-methacryloyloxy-1-hydroxy-2,2,6,6-tetramethylpiperidines were synthesized as precursor monomers and polymerized by using α,α′-azobisisobutyronitrile under appropriate conditions to precursor polymers of high molecular weight: poly-4-methacryloylamino-/oxy-1-hydroxy-2,2,6,6-tetramethylpiperidinehydrochlorides and sulfates. The precursor polymers were converted to polymers having nitroxyl stable radicals, i.e., poly-4-methacryloylamino-/oxy-2,2,6,6-tetramethylpiperidine-1-oxyls, by oxidation in air or with H2O2–Na2WO4 without any main-chain scission. The structure of the resultant stable radical polymers was determined by infrared, ultraviolet, and ESR spectroscopy. Based on the results of spectroscopic analysis and Kjeldahl analysis, the transformation from precursors to nitroxyl stable radical polymers was found to be quantitative. Investigations on the applicability of polymeric nitroxyl radicals to oxidation-reduction reactions were attempted by means of polarography; the reduction half-wave potential was found to be ?1.16 V for the mercury pool. 相似文献
54.
55.
Masahiro Manabe Asako Tokunaga Hideo Kawamura Hajime Katsuura Masaki Shiomi Koichi Hiramatsu 《Colloid and polymer science》2002,280(10):929-935
In the micellar solution of SDS, the partition coefficient (Kx) of following branched alkanols at infinite dilution was determined by applying a differential conductivity method: the alkanols used were i-CmH2m+1OH (m=4-9, i=1-5) in which the position of OH group (i) shifts from an end to the center of a hydrocarbon chain. The method provides two significant quantities, d!/dXam and dCsf/dCaf in addition to Kx. The following results have been obtained. (1) The dependence of Kx on i indicates that the hydrophobicity of alkanol is weakened with increasing i, whereas the increase in m strengthens the hydrophobicity. (2) The degree of counterion disossiation of micelles (!) is accelerated by the solubilized alkanols in micelles (mole fraction: Xam) and the acceleration rate, d!/dXam (=0.17), depends on neither m nor i. (3) In the bulk water, the monomerically dissolved alkanols (concentration: Caf) depresses the concentration of free monomer surfactant (Csf), and the depressing rate, dCsf/dCaf, in micellar solution is identical with the corresponding quantity, ((CMC/(Ca)o at CMC. 相似文献
56.
Contrary to the precedents, 1,3-anti stereoselection was found in the intramolecular Michael addition of ethyl ,5-carbamoyloxy-4-trialkylsilyloxy-2-hexenoate to culminate in a synthesis of N-benzoyl-,-daunosomine. The antiperiplanar effect due to the group at 4-position was revealed to play a major role in the stereoselection in this type of reactions. N-benzoyl-,-3-epidaunosamine was also synthesized by 1,2-syn asymmetric induction. 相似文献
57.
Tadamasa Shida Yasufumi Takahashi Hiroyuki Hatano Masashi Imamura 《Chemical physics letters》1975,33(3):491-494
Radical-anions of iodine, bromine, and monoiodochloride are produced in γ-irradiated amorphous solids at 77 K, and their electronic and ESR spectra measured. On limited warming of the irradiated solution dimerization by the reaction I2? + I2 → I4? occurs to produce the same species as reported by Fornier de Violet et al. The electronic structure of the dimeric anion is discussed in comparison with the monomeric anion. 相似文献
58.
Masahiro Toyoda Yukio Hamaji Kunisaburo Tomono 《Journal of Sol-Gel Science and Technology》1997,9(1):71-84
The sol-gel processing was applied to the fabrication of PbTiO3 fibers. Pb(CH3COO)2·3H2O and Ti(OC3H
7
i
)4 were refluxed with stirring in 2-methoxyethanol to form Pb-methoxyethoxide and Ti-methoxyethoxide, respectively, followed
by mixing with stirring in 2-methoxyethanol to form Pb−Ti double alkoxide. The hydrolysis and polycondensation reaction of
this double alkoxide gave polymerized products, and as a result the viscosity of the solution increased, suggesting that linear
polymers were produced through the hydrolysis and polycondensation reaction. Homogeneous PbTiO3 gel fibers were drawn from the spinnable viscous solutions, which were wellcrystallized into perovskite type PbTiO3 at 650°C. The heat-treated fibers were a few centimeters long and from 10 to 100 μm in diameter. The fiber was made up of
extremely uniform grains. Electron diffraction revealed a preferred growth of (101) planes along the fiber axis, which might
be due to the linear molecular characteristics of the alkoxide. 相似文献
59.
Masahiro Yoshida 《Tetrahedron letters》2004,45(29):5573-5575
The direct coupling of propargylic alcohols with arylboronic acids has been achieved using palladium catalyst. Various propargylic alcohols and arylboronic acids can be coupled to afford the corresponding allenic and propargylic arenes, which are selectively produced depending on the substituent on the propargylic alcohol, respectively. 相似文献
60.
Masahiro Kurokawa Hidemasa Yamaguchi Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1979,17(2):485-492
l-Menthyl vinyl ether (l-MVE) was homopolymerized and copolymerized with the monomers indene (IN) and acenaphthylene (ANp) by BF3OEt2 as a catalyst. The chiral menthyl substituent was cloven from the homopolymers and copolymers using dry-hydrogen bromide gas. After the removal of optically active menthyl group, poly(vinyl alcohol) (PVA) from l-MVE homopolymer was optically inactive, and copolymers (VA-IN, VA-ANp) from l-MVE-IN and l-MVE-ANp copolymers were still optically active. Hence, in the case of l-MVE homopolymer, it was concluded that asymmetric induction in the polymer main chain can only produce pseudoasymmetry. In the case of l-MVE-IN and l-MVE-ANp copolymers, it was found that asymmetric induction proceeded in the copolymer main chain and was caused by the influence of chiral menthyl group. 相似文献