全文获取类型
收费全文 | 24043篇 |
免费 | 1328篇 |
国内免费 | 3452篇 |
专业分类
化学 | 19553篇 |
晶体学 | 1057篇 |
力学 | 221篇 |
综合类 | 192篇 |
数学 | 3688篇 |
物理学 | 4112篇 |
出版年
2024年 | 17篇 |
2023年 | 189篇 |
2022年 | 815篇 |
2021年 | 739篇 |
2020年 | 542篇 |
2019年 | 539篇 |
2018年 | 426篇 |
2017年 | 562篇 |
2016年 | 592篇 |
2015年 | 550篇 |
2014年 | 818篇 |
2013年 | 1781篇 |
2012年 | 1291篇 |
2011年 | 1489篇 |
2010年 | 1483篇 |
2009年 | 1678篇 |
2008年 | 1625篇 |
2007年 | 1643篇 |
2006年 | 1555篇 |
2005年 | 1342篇 |
2004年 | 1309篇 |
2003年 | 1109篇 |
2002年 | 946篇 |
2001年 | 710篇 |
2000年 | 701篇 |
1999年 | 530篇 |
1998年 | 520篇 |
1997年 | 426篇 |
1996年 | 361篇 |
1995年 | 367篇 |
1994年 | 323篇 |
1993年 | 303篇 |
1992年 | 286篇 |
1991年 | 213篇 |
1990年 | 122篇 |
1989年 | 153篇 |
1988年 | 136篇 |
1987年 | 89篇 |
1986年 | 61篇 |
1985年 | 71篇 |
1984年 | 90篇 |
1983年 | 23篇 |
1982年 | 44篇 |
1981年 | 60篇 |
1980年 | 51篇 |
1979年 | 38篇 |
1978年 | 27篇 |
1977年 | 22篇 |
1976年 | 11篇 |
1975年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
191.
A series of 2-benzyl-1,3-dicabonyl derivatives was synthesized.Their insulin-sensitizing activity was evaluated in 3T3-L1 preadipocyte cells.Compounds3,26 and 27 were found to possess strong insulin-sensitizing activity in vitro and were selected for further hypoglycemic evaluation in vivo. 相似文献
192.
FFC-1离子交换纤维对酸碱有害气体吸附性能的研究 总被引:8,自引:0,他引:8
系统考察了不同直径及反离子形式的FFC-1聚羧酸离子交换纤维对酸碱有害气体的穿透吸附,各种温、湿度条件下的吸水率,以及作为有害气体吸附滤除材料的重复使用与再生性能。研究表明:FFC-1纤维直径的减小有利于提高对有害气体的动态吸附容量。在体系温度、相对湿度分别为15℃、50%时,以3D腈纶为起始原料的钠型FFC-1离子交换纤维的吸水率≥350mg/g.纤维;对SO2的穿透吸附容量可达200mg/g.纤维。FFC-1离子交换纤维具有良好的重复使用与再生能力,经20次再生循环使用后,纤维交换容量未见明显变化。 相似文献
193.
Determination of 1-aminocyclopropane-1-carboxylic acid in apple extracts by capillary electrophoresis with laser-induced fluorescence detection 总被引:1,自引:0,他引:1
A rapid and sensitive method for the determination of 1-aminocyclopropane-1-carboxylic acid (ACC) in apple tissues has been described. This method is based on the derivatization of ACC with 3-(2-furoyl)quinoline-2-carboxaldehyde (FQ), and separation and quantification of the resulting FQ-ACC derivative by capillary electrophoresis coupled to laser-induced fluorescence detection (CE-LIF). Our results indicated that ACC derivatized with FQ could be well separated from other interfering amino acids using 20 mM borate buffer (pH 9.35) containing 40 mM sodium dodecyl sulfate and 10 mM Brij 35. The linearity of ACC was determined in the range from 0.05 to 5 microM with a correlation of 0.9967. The concentration detection limit for ACC was 10 nM (signal-to-noise = 3). The sensitivity and selectivity of this described method allows the analysis of ACC in crude apple extracts without extra purification and enrichment procedure. 相似文献
194.
α,ω-Difluoropolydimethylsiloxanes F[(CH3)2SiO]n(CH3)2SiF have been prepared by reaction of (CH3)2SiF2 with cyclic dimethylsiloxanes [(CH3)2SiO]n (n = 3 or 4). An equilibrium is reached in the redistribution of fluorine vs. oxygen atoms after ca. 24 h at 200°C or 15 days at 150°C when catalysed by AlCl3. 16 equilibrated samples of varied (R = F/Si) overall compositions have been analysed by 1H and 19F NMR and by VPC. The presence of rings has been established for the lower values of R. The molecular constitution of the equilibrated samples is described by a set of constants. The abundance of the end units is slightly larger than expected from random distribution. The good resolution of the spectra permits the distinguishing of the 9th order of environment of the end units and the 5th order for the middle units and the verification that there is no preferential association among the building units, and thus the proportion of chains of various lengths obeys Flory's random distribution mode. The equilibrium molecular constitution of these α,ω-difluorosiloxanes is close to that of their dichloro analogs; the substitution of chlorine by fluorine atoms at the end of the chains thus appears to cause little perturbation. On the other hand, the kinetic evolution of the reaction appears to be different, since the first species which forms is always the pyro moleculeinstead of long chains and large rings as in the case of the chloro analogs. 相似文献
195.
H. Yasemin Yenilmez 《Journal of organometallic chemistry》2007,692(5):940-945
Phthalocyanines (M = Co, Zn or 2H) with four ({4-[(Z or E)-phenylazo]-1-naphthyl}oxy) substituents on the periphery have been synthesized to enlarge the absorbing range of the dyestuffs. Cyclopalladation of the azobenzene groups lead to network-type oligomeric products by formation of binuclear palladium (II) complexes and they have been further converted into monomeric species by treatment with acetylacetonate. The electronic spectra clearly indicate the absorptions resulting from phenylazo and naphthyl groups along with the Q and B bands of the phthalocyanines. The consequence of the palladation is a relatively intense broad absorption due to LMCT with maxima around 520 nm. 相似文献
196.
Optimisation of Supercritical Carbon Dioxide Systems for Complexation of Naproxen : Beta-Cyclodextrin 总被引:1,自引:0,他引:1
Susana Junco Teresa Casimiro Nuno Ribeiro Manuel Nunes Da Ponte Helena M. Cabral Marques 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):69-73
Supercritical carbon dioxide (scCO2)offers several attractive scenarios for thepharmaceutical processing as an alternativeto aqueous and organic solvents. In thiswork naproxen, a widely used non steroidalanti-inflammatory drug with analgesic andanti-inflammatory properties, was chosenas a model drug. Its complexation with cyclodextrinsimproves the rate and extent of dissolutionof the drug, increase its rate of absorption and mayreduce the unpleasant side-effects of the drug.The interest in using this supercritical technologyled us to develop an experimental unit for the useof supercritical CO2 as a processing medium forthe complexation of naproxen with beta cyclodextrin (CD). 相似文献
197.
Tsutomu Oishi Kensoh Kagawa Minoru Fujimoto 《Journal of polymer science. Part A, Polymer chemistry》1995,33(8):1341-1352
Two types of optically active N-[N′-(α-methylbenzyl)amino/carbonyl-n-alkyl]maleimides (MBAC) were synthesized from maleic anhydride, 6-amino-n-caproic acid (or 12-amino-n-dodecanoic acid), and (R)-(+)-α-methylbenzylamine. Radical homopolymerizations of MBAC were performed in several solvents at 60 and 110°C for 24 h to give optically active polymers. Radical copolymerizations of MBAC were performed with styrene (ST) and methyl methacrylate (MMA) in dioxane at 60°C. The monomer reactivity ratios and the Alfrey-Price Q-e values were determined. Chiroptical properties of the polymers and copolymers were investigated. © 1995 John Wiley & Sons, Inc. 相似文献
198.
使用双沸点仪测定了丙酮、乙酸乙酯、对二氧六环、乙腈或三乙胺与甲醇或1,2→二氯乙烷以及二者混合物等十一组二元体系在99.3 kPa下的汽液平衡数据(T,x,p), 计算了有关体系的过量吉布斯自由能。结果表明, 六种非质子溶剂与甲醇组成的二元系GE>0; 乙腈或三乙胺与1,2-二氯乙烷组成的二元系GE>0, 而丙酮、乙酸乙酯或对二氧六环与1,2-二氯乙烷的二元混合物GE<0。从同种分子间或不同种分子间的缔合作用对上述结果进行了讨论。本文还在固定极性非质子溶剂(第三组分)物质的量浓度的条件下, 测定了非质子溶剂+1,2-二氯乙烷+甲醇三元混合物的汽液平衡数据, 考察了非质子溶剂的加入对甲醇+1,2-二氯乙烷二元系GE的影响。 相似文献
199.
Tadashi Kawai Masako Komaki Tomokazu Iyoda 《Journal of molecular catalysis. A, Chemical》2002,190(1-2):45-53
Metathesis of 2-vinyl aromatic heterocycles such as furan, thiophene, pyrrole and pyridine in the presence of a molybdenum-based Schrock catalyst has been investigated from a synthetic point of view. The self-metathesis of 2-vinyl aromatic heterocycles was not successful. However, in cross-metathesis of thiophene, furan and styrene with 1-octene, the cross-metathesis product, heterodimer, was readily obtained selectively, together with only small amounts of the two corresponding self-metathesis products. The origin of the surprisingly high selectivity of heterodimer formation was elucidated through metallacyclobutane intermediate mechanism, observations of carbenes by in situ 1H NMR, and reaction products. 相似文献
200.
利用紫外-可见吸收和荧光发射光谱, 结合非线性最小二乘法拟合曲线以及分子力学(MM2)模拟系统地研究了手性分子N-[4-(1-芘基)]丁酰-D/L-苯丙氨酸(PDP和PLP, 总称PPs)与β-环糊精(β-CD)、 2-位硒桥联双β-CD(2-SeCD)和2-位碲桥联双β-CD(2-TeCD)的包结能力大小及这3个环糊精对PPs手性识别能力的差异和识别机理. 研究结果表明, PPs不能与单疏水空腔的β-CD形成很好的包结复合物, 与具有较长桥联链的2-TeCD结合能力最强. 2-TeCD与PDP和PLP的结合常数分别为2.33×104和6.07×103 L/mol, 对PPs的手性识别比达到KD/KL=3.84, 高于2-SeCD(KD/KL=2.61). 用MM2模拟得出了PPs与这两个双环糊精形成复合物的三维结构: PPs的绝大部分位于双环糊精两个空腔之间, 但是在这两个复合物中, 苯环与芘环所成的二面角不同. 此外, PPs与这两个双环糊精作用时均存在明显的氢键相互作用, 且2-TeCD强于2-SeCD. 相似文献