全文获取类型
收费全文 | 8191篇 |
免费 | 885篇 |
国内免费 | 2072篇 |
专业分类
化学 | 8360篇 |
晶体学 | 48篇 |
力学 | 459篇 |
综合类 | 82篇 |
数学 | 996篇 |
物理学 | 1203篇 |
出版年
2024年 | 33篇 |
2023年 | 157篇 |
2022年 | 336篇 |
2021年 | 411篇 |
2020年 | 589篇 |
2019年 | 395篇 |
2018年 | 336篇 |
2017年 | 333篇 |
2016年 | 428篇 |
2015年 | 348篇 |
2014年 | 509篇 |
2013年 | 762篇 |
2012年 | 491篇 |
2011年 | 480篇 |
2010年 | 404篇 |
2009年 | 450篇 |
2008年 | 477篇 |
2007年 | 469篇 |
2006年 | 435篇 |
2005年 | 383篇 |
2004年 | 362篇 |
2003年 | 409篇 |
2002年 | 394篇 |
2001年 | 248篇 |
2000年 | 209篇 |
1999年 | 181篇 |
1998年 | 155篇 |
1997年 | 123篇 |
1996年 | 135篇 |
1995年 | 105篇 |
1994年 | 104篇 |
1993年 | 85篇 |
1992年 | 84篇 |
1991年 | 47篇 |
1990年 | 38篇 |
1989年 | 26篇 |
1988年 | 35篇 |
1987年 | 26篇 |
1986年 | 33篇 |
1985年 | 31篇 |
1984年 | 23篇 |
1983年 | 10篇 |
1982年 | 21篇 |
1981年 | 12篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
171.
Conversion of sulphur compounds in reduced, contaminated sediments that are brought in upland conditions may largely affect the potential mobility of heavy metal contaminants. We applied selected methods for the determination of total sulphur and sulphur fractions in a contaminated sediment in the reduced state and after gradual drying and oxidation during 1 month. Dry ashing, followed by ion chromatographic detection, was reliable for the determination of total sulphur. Good recoveries were obtained in both reference samples and spiked samples. Total sulphur was 14.5±0.6 g kg−1 relative to dry sediment. Wet chemical methods that involve the determination of acid-volatile, Zn–HCl-reducible, chromium-reducible, acetone-soluble and HI-reducible sulphur were used to estimate specific sulphur forms. Results for acetone-soluble sulphur were to high and not consistent with results for other fractions. Major part of sulphur in the sediment (90%) was inorganic. Sulphides were converted partially to sulphate and to intermediary oxidised sulphur compounds upon oxidation of the sediment. The results suggested that the intermediary oxidised sulphur pool in the reduced sediment (2.5 g kg−1) mainly consisted of pyrite, that was not converted during drying and oxidation. No significant changes in organic sulphur were detected. 相似文献
172.
Based on density functional calculations, the mechanism and the energetic course of the chemical vapor deposition (CVD) reaction of TiCl4 with NH3 were studied at the level of B3LYP with 6-311g(d) basis set. Furthermore, the polymerization processes of dimerization, trimerization and tetramerization were investigated. The calculation results indicate that the formation of polymers is favored at the elimination reaction. On the basis of the calculated energetics, a possible mechanism of the reduction reaction has been proposed. 相似文献
173.
Glukhareva T. V. Morzherin Yu. Yu. Dyudya L. V. Malysheva K. V. Tkachev A. V. Padva A. Bakulev V. A. 《Russian Chemical Bulletin》2004,53(6):1311-1317
A method for the synthesis of previously inaccessible 5-dialkylamino-substituted 1,2,3-thiadiazole-4-carbaldehydes was developed. Ring transformation in these compounds induced by primary aliphatic and aromatic amines, hydroxylamines, and N-substituted hydrazines resulted in the synthesis of a broad range of 1,2,3-triazole-4-carbothioamide. 相似文献
174.
Ken-ichi Ogu 《Journal of fluorine chemistry》2003,124(1):69-80
Treatment of allylic alcohols with hexafluoropropene-diethylamine adduct (PPDA) afforded N,N-diethyl-2-fluoro-2-trifluoromethyl-4-alkenamides which were formed by the Claisen rearrangement of intermediary 2-alkenyl-1-diethylamino-2,3,3,3-tetrafluoro-1-propenyl ethers. Although (E)-allylic alcohols gave two diastereomeric products in about 1:1 ratio, (Z)-allylic alcohols gave the corresponding product as a single diastereomer. 相似文献
175.
To make clear the reason of unsuitability of poly(vinyl alcohol) (PVA) protective colloid for the emulsion polymerization
of conjugated monomers, a model experiment of emulsion polymerization of methyl methacrylate (MMA) was carried out with ammonium
persulfate (APS) or azobis(isobutyronitrile) (AIBN) initiators, where a small amount of MMA (1/100th of the concentration
compared with ordinary emulsion polymerization) was employed. This corresponds to the initial stage of the emulsion polymerization.
Grafting of MMA onto PVA took place remarkably irrespective of the kind of the initiators. Formation of homo-poly(MMA) was
observed to a small extent. The formation of new emulsion particles smaller than 100 nm continued to increase to almost the
end of the polymerization. PVA molecules in the grafted polymer are supposed to act as stabilizers of newly formed particles.
From kinetic treatment using the experimental data, the important issues were derived as follows. Firstly, the sulfate anion
radical from APS is much more reactive than the isobutyronitrile radical from AIBN in terms of hydrogen abstraction from PVA.
Secondly, high grafting ability of the latter initiator system, notwithstanding the much lower reactivity in the hydrogen
abstraction compared with the APS system, is attributed to the relative reactivity of the primary radicals, i.e., hydrogen
abstraction reaction from PVA to initiation reaction with MMA. The much slower rate of addition of the isobutyronitrile radical
to the monomer compared with that of hydrogen abstraction from PVA facilitates the grafting, although the rate constant of
hydrogen abstraction is far smaller than that with the sulfate anion radical by 10−4 times.
Received: 26 April 2001 Accepted: 6 September 2001 相似文献
176.
锌和锡参与下末端环氧化物的选择性烯丙基化反应 总被引:1,自引:0,他引:1
烯丙基溴和金属辛或锡成功地将末端环氧化合物1一锅法合成高烯丙基醇2和双高烯丙基醇3. 还研究了环氧化合物取代基的影响, 并提出了此烯丙基化的反应途径 . 相似文献
177.
Jörg Fridgen Georg Eickerling Ana M. Santos 《Journal of organometallic chemistry》2004,689(17):2752-2761
Novel chiral 2′-pyridinyl alcohols derived from isopropylidene-protected carbohydrates are reported. They show different characteristics at the hydroxy group, but are all suitable ligands for chiral molybdenum(VI) complexes of the type MoO2L2 (L = chiral 2′-pyridinyl alcoholate). MoO2(acac)2 served as starting material in the complex syntheses. The structure of one ligand and one dioxo complex were exemplary established by X-ray crystallography. For catalytic runs in the enantioselective epoxidation catalysis trans-methylstyrene was used as model substrate, tert-butylhydroperoxide and cumolhydroperoxide, resp., as the oxidant. 相似文献
178.
Ahmed Abd El-Fattah Mohamad Nageeb Hassan Ahmad Rashad Mona Marei Sherif Kandil 《International Journal of Polymer Analysis and Characterization》2020,25(5):362-373
Abstract An injectable composite hydrogel composed of polyvinyl alcohol (PVA) and bioactive glass (BG) particles were synthesized by a physical crosslinking approach. The morphology, mechanical properties, and viscoelasticity of the PVA/BG composite hydrogel were characterized. Scanning electronic microscopy (SEM) showed uniform and homogeneous distribution of BG particles throughout the composite hydrogel. The incorporation of 2.5?wt% of BG particles in the composite hydrogel formulations, enhanced the static compressive strength and static elastic modulus by 325% and 150%, respectively. The storage molds (G′) was greater than the loss modules (G′′) at all the frequency range studied, which revealed a self-standing elastic composite hydrogel with a smooth injectability. The PVA/BG composite hydrogel was also implanted subcutaneously in the dorsal region of adult male rats. After 4?weeks of implantation, no inflammatory cells were seen within and around the implant, which indicated that the composite hydrogel was biocompatible. The properties of the synthesized injectable PVA/BG composite hydrogel demonstrate its capability toward bone regeneration. 相似文献
179.
The kinetics of electroreduction of Pd(II) complexes with -alanine, Pd(ala)2, is studied on a rotating Pd disk electrode in solutions of pH 8–13 containing large excess of -alanine and various supporting electrolytes (NaF, Na2SO4, NaClO4). On a Pd electrode, complexes Pd(ala)2 undergo reduction at potentials much more negative than on an Hg electrode. This is attributed to the chemisorption of water on the Pd electrode, which hampers adsorption of Pd(ala)2 that take part in the slow electrochemical stage. As with the Hg electrode, perchlorate ions hinder the Pd(ala)2 reduction on a Pd electrode. Studying adsorption of Pd(ala)2 on a Pd electrode is hampered by parallel processes of hydrogen adsorption and absorption. 相似文献
180.
在358K下用200ml/min的空气氧化碱性悬浮液合成了MFe_2O_(4+δ)(δ≥0,M=Fe、Co、Ni、Mn),并在573K下用40ml/min的H_2还原MFe_2O_(4+δ)制备了氧缺位铁酸盐MFe_2O_(4-δ)(δ>0)。用XRD、Mssbauer谱等测试方法对铁酸盐的结构进行了表征,考察了铁酸盐的组成及第二金属组分(Co、Ni、Mn)对铁酸盐还原性能的影响。在H_2还原3h内,铁酸盐氧缺位程度随还原时间增加而增大,晶格常数也相应增大;5h以上,铁酸盐将被还原为MO-FeO或α-Fe,晶格常数几乎不变。按Fe、Co、Ni、Mn顺序,MO与FeO的相互作用能力、MO-FeO固溶体的稳定性及铁酸盐还原为MO-FeO的能力均增强,MO-FeO进一步还原为α-Fe的能力却减弱。 相似文献