全文获取类型
收费全文 | 60478篇 |
免费 | 11394篇 |
国内免费 | 2223篇 |
专业分类
化学 | 61306篇 |
晶体学 | 870篇 |
力学 | 1560篇 |
综合类 | 19篇 |
数学 | 5347篇 |
物理学 | 4993篇 |
出版年
2024年 | 2篇 |
2023年 | 17篇 |
2022年 | 93篇 |
2021年 | 268篇 |
2020年 | 594篇 |
2019年 | 2411篇 |
2018年 | 2287篇 |
2017年 | 2734篇 |
2016年 | 3022篇 |
2015年 | 5321篇 |
2014年 | 5020篇 |
2013年 | 6893篇 |
2012年 | 5528篇 |
2011年 | 5153篇 |
2010年 | 4221篇 |
2009年 | 3988篇 |
2008年 | 4323篇 |
2007年 | 3648篇 |
2006年 | 3386篇 |
2005年 | 3216篇 |
2004年 | 2660篇 |
2003年 | 2423篇 |
2002年 | 3062篇 |
2001年 | 1546篇 |
2000年 | 1399篇 |
1999年 | 593篇 |
1998年 | 40篇 |
1997年 | 25篇 |
1996年 | 29篇 |
1995年 | 27篇 |
1994年 | 18篇 |
1993年 | 25篇 |
1992年 | 11篇 |
1991年 | 17篇 |
1990年 | 7篇 |
1989年 | 13篇 |
1988年 | 15篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 8篇 |
1977年 | 2篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 20 毫秒
881.
A practicable and selective liquid chromatography-mass spectrometry assay for the determination of two cyclooxygenase-2 inhibitors, etoricoxib and valdecoxib, in human plasma is presented. The analytical technique is based on reversed-phase high-performance liquid chromatography (HPLC) coupled to atmospheric pressure chemical ionisation (APCI) mass spectrometry (Finnigan Mat LCQ ion trap). Mass analysis was performed in the positive ion mode. The ion trap was operated in the tandem MS mode (MS2) and the transitions of etoricoxib (m/z 359.2 --> 280.3) and valdecoxib (m/z 315.1 --> 235.1) were followed by selected reaction monitoring. Retention times of etoricoxib and valdecoxib were 1.05 and 1.08 min, respectively. The method was validated over a linear range 10-2500 and 5-1000 microg/L using the other substrate as internal standard. After validation, the method was used to study the pharmacokinetic pro fi le of etoricoxib or valdecoxib in a healthy volunteer after administration of a single oral dose (valdecoxib, 20 mg; etoricoxib, 90 mg). The presented method was suf fi cient to cover more than 90% of the area under the plasma concentration time curve. 相似文献
882.
1 INTRODUCTION The reactivity of activated alumina adsorbent is closely related to its specific surface area: the larger the specific surface area, the better its activity and adsorbent capability are. However, in reality, the prac- tically available specific surface area or effective spe- cific area has relationship with its pore structure[1]. Since many reactant molecules are difficult to enter the pores to react with whose radius is shorter than certain critical value, the increase of p… 相似文献
883.
J. G. Liu M. H. He H. W. Zhou Z. G. Qian F. S. Wang S. Y. Yang 《Journal of polymer science. Part A, Polymer chemistry》2002,40(1):110-119
Organosoluble polyimides were synthesized with the alicyclic dianhydride 1,8‐dimethylbicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride and aromatic diamines. The polyimides possessed good solubility both in strong dipolar solvents and in common solvents; the thermal decomposition temperature of the polyimides exceeded 420 °C. Strong and flexible films of the polyimides, with the cutoff of ultraviolet–visible absorption lower than 310–320 nm, exhibited good features as the alignment layers for nematic liquid crystals with pretilt angles of 1.5–2.9°. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 110–119, 2002 相似文献
884.
Robert Liska 《Journal of polymer science. Part A, Polymer chemistry》2002,40(10):1504-1518
The synthesis of new water‐soluble photoinitiators (PIs) based on hydroxyalkylphenones, benzophenones, and thioxanthones with carbohydrate residues such as glucose, cellobiose, and 1‐amino‐1‐deoxy‐D ‐glucitol (glucamine) is described. In addition, selected initiators were reacted with methacryloyl chloride to obtain copolymerizable initiators with improved migration stability. Results from photo differential scanning calorimetry and gel‐content measurements in commercially available water‐thinnable and emulsion‐type resins as well as 2‐hydroxyethyl acrylate are included. Glucose‐modified PIs gave the best results with respect to compatibility with the resin, reactivity, and gel content. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1504–1518, 2002 相似文献
885.
氧化物、盐类在氧化物载体表面的自发分散是一种广泛存在的现象,文献中已报导过大量氧化物和盐类在高比表面载体上分散的研究结果['-3]TIO。作为一种较新型的载体,与Y-AI。O。、硅胶等传统载体相比,有许多不同特性.活性组分在TIO。表面的分散状态及所得催化剂的性能已有不少报导['-'],但所用的TIOZ主要是较高比表面的锐钛矿型TIOZ(刘金红石型TIO。(r)和锐钛矿型TIOZ(a)的结构不同,它是高温生成相,比表面较小['].氧化物在金红石上的分散行为仍未见报导.我们制备了三种具有不同比表面的TIO水),系统地研… 相似文献
886.
Thermally induced phase separation technique was utilized to fabricate biodegradable poly(l ‐lactic acid) (PLLA) macrocellular foams which were capable of being applied in tissue engineering. The block copolymer Pluronic F127 composed of (polyethyleneoxide)‐(polypropyleneoxide)‐(polyethyleneoxide) [(PEO)‐(PPO)‐(PEO)] was used as a porogen. Water/dioxane mixtures with different volume ratios were used as solvents. The addition of Pluronic F127 could induce an appearance of large pores (50–200 μm) besides small pores (10–20 μm) or a change from a solid–liquid phase separation to a liquid–liquid phase separation. The role of Pluronic F127 depends on the water/dioxane ratios in the PLLA/dioxane/water system. The X‐ray diffraction patterns and porosity measurement results showed that Pluronic F127 was crystallized and existed on the pore wall. The effect of Pluronic F127 on changing pore structure is attributed to the occurrence of the interaction of the lipophilic PPO blocks in Pluronic F127 with PLLA clews, consequently, this results in PLLA aggregation and early phase separation on cooling. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
887.
Hans‐Peter Kormann Günter Schmid Katrin Pelzer K. Philippot Bruno Chaudret 《无机化学与普通化学杂志》2004,630(12):1913-1918
Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 109 ‐ 1011 pores per cm2, all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane. 相似文献
888.
889.
Protocatechuic acid esters (= 3,4‐dihydroxybenzoates) scavenge ca. 5 equiv. of radical in alcoholic solvents, whereas they consume only 2 equiv. of radical in nonalcoholic solvents. While the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents as compared to that in nonalcoholic solvents is due to a nucleophilic addition of an alcohol molecule at C(2) of an intermediate o‐quinone structure, thus regenerating a catechol (= benzene‐1,2‐diol) structure, it is still unclear why protocatechuic acid esters scavenge more than 4 equiv. of radical (C(2) refers to the protocatechuic acid numbering). Therefore, to elucidate the oxidation mechanism beyond the formation of the C(2) alcohol adduct, 3,4‐dihydroxy‐2‐methoxybenzoic acid methyl ester ( 4 ), the C(2) MeOH adduct, which is an oxidation product of methyl protocatechuate ( 1 ) in MeOH, was oxidized by the DPPH radical (= 2,2‐diphenyl‐1‐picrylhydrazyl) or o‐chloranil (= 3,4,5,6‐tetrachlorocyclohexa‐3,5‐diene‐1,2‐dione) in CD3OD/(D6)acetone 3 : 1). The oxidation mixtures were directly analyzed by NMR. Oxidation with both the DPPH radical and o‐chloranil produced a C(2),C(6) bis‐methanol adduct ( 7 ), which could scavenge additional 2 equiv. of radical. Calculations of LUMO electron densities of o‐quinones corroborated the regioselective nucleophilic addition of alcohol molecules with o‐quinones. Our results strongly suggest that the regeneration of a catechol structure via a nucleophilic addition of an alcohol molecule with a o‐quinone is a key reaction for the high radical‐scavenging activity of protocatechuic acid esters in alcoholic solvents. 相似文献
890.
A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %). 相似文献