全文获取类型
收费全文 | 20338篇 |
免费 | 3614篇 |
国内免费 | 2756篇 |
专业分类
化学 | 15583篇 |
晶体学 | 235篇 |
力学 | 1744篇 |
综合类 | 127篇 |
数学 | 672篇 |
物理学 | 8347篇 |
出版年
2024年 | 54篇 |
2023年 | 214篇 |
2022年 | 522篇 |
2021年 | 619篇 |
2020年 | 805篇 |
2019年 | 660篇 |
2018年 | 542篇 |
2017年 | 643篇 |
2016年 | 862篇 |
2015年 | 891篇 |
2014年 | 1086篇 |
2013年 | 1856篇 |
2012年 | 1311篇 |
2011年 | 1551篇 |
2010年 | 1214篇 |
2009年 | 1389篇 |
2008年 | 1460篇 |
2007年 | 1395篇 |
2006年 | 1369篇 |
2005年 | 1143篇 |
2004年 | 1046篇 |
2003年 | 846篇 |
2002年 | 841篇 |
2001年 | 591篇 |
2000年 | 542篇 |
1999年 | 469篇 |
1998年 | 398篇 |
1997年 | 348篇 |
1996年 | 308篇 |
1995年 | 285篇 |
1994年 | 239篇 |
1993年 | 199篇 |
1992年 | 184篇 |
1991年 | 139篇 |
1990年 | 122篇 |
1989年 | 89篇 |
1988年 | 83篇 |
1987年 | 63篇 |
1986年 | 48篇 |
1985年 | 46篇 |
1984年 | 56篇 |
1983年 | 15篇 |
1982年 | 41篇 |
1981年 | 19篇 |
1980年 | 22篇 |
1979年 | 20篇 |
1978年 | 11篇 |
1977年 | 14篇 |
1976年 | 14篇 |
1973年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Polystyrene-supported N-phenyl-N-acyl sulfonamide resin was prepared by reacting polystyrene sulfonyl chloride resin with aniline and acylating in pyridine with either acid chlorides or anhydrides. Then, this resin was utilized as a new type of acyl transfer reagent to synthesize the amide library. It was approved to be a more effective acyl transfer reagent with higher amide yields than the polystyrene-supported N-methyl-N-acyl sulfonamide resin and N-benzyl-N-acyl sulfonamide resin. When the phenyl group bonded to the N atom on N-phenyl-N-acyl sulfonamide resin was substituted by the electron withdrawing group or electron donating group, a decreasing amide yield was obtained. N-phenyl-N-acyl sulfonamide resin could be regenerated many times. 相似文献
992.
HCl elimination in low ratio was first carried out from poly(vinyl chloride) to increase allylic chlorines. Partially dehydrochlorinated poly(vinyl chloride), having a macroinitiator effect, was grafted with tert‐butyl methacrylate via atom transfer radical polymerization in the presence of CuBr/2,2′‐bipyridine at 64°C in tetrahydrofuran. Original poly(vinyl chloride) was also grafted with tert‐butyl methacrylate under the same conditions to compare with that of partially dehydrochlorinated poly(vinyl chloride). The graft copolymers were characterized by elemental analysis, FTIR, 1H and 13C‐NMR, differential scanning calorimetry, and gel permeation chromatography (GPC). Thermal stabilities of the graft copolymers were investigated by thermogravimetric analysis as compared with those of the macroinitiators. 相似文献
993.
《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):1001-1010
Abstract Comb‐like polystyrene grafted silica nanoparticles (c‐PS‐SNs) were prepared by the following steps: (a) methacryloxypropyl silica nanoparticles (MPSNs) were used as macromonomer and free radical copolymerized with 4‐vinyl benzyl chloride (VBC) by a solution polymerization method; (b) the product of (A), poly(4‐vinyl benzyl chloride) grafted silica nanoparticle (PVBC‐SN) was separated and then used as a macroinitiator for the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of styrene catalyzed by the complex of Cu(I)Br and 2,2′‐bipyridyl (bipy) in toluene solutions. The structurally well‐defined polymer chains were grown from the nanoparticle surfaces to yield particles composed of a silica core and a well defined, densely grafted outer comb‐like PS layer. A percentage of grafting (PG%) (the weight ratio of the PS grafted with that of the silica charged) of more than 80% was achieved after a polymerizing time of 5?hr. 相似文献
994.
A series of fluorine‐containing diblock copolymers based on lauryl methacrylate and 1H,1H,2H,2H‐perfluoroalkyl acrylate have been prepared by atom transfer radical polymerization (ATRP). The preparation process of PLMA‐Br macroinitiators was controlled within a reasonable time corresponding to the ln [M0]/[Mt]~time plot of the reaction. FTIR, 1H‐NMR, GPC and fluorine‐element analysis (FEA) were used to characterize the synthesized block copolymers. The solid surface activity of these polymers was demonstrated by contact angle measurement. The polymer films prepared by block copolymers with more than three fluorinated units showed low dispersion force contributions to the surface energy indicating the presence of the fluorinated block at the surface. The surface activity in solutions was measured by drop‐weight method. Ii is interesting to find, when the fluorine weight percentage is controlled constant, that PLMA‐b‐PFAEA with larger molecular size is more prominent in exploiting the fluorinated structure to reduce the surface tension of solutions. The block copolymer's ability in reducing surface tension of solutions also depends on the type of solvent. 相似文献
995.
In this article, the poly(methyl methacrylate)/montmorillonite (PMMA/MMT) organic-inorganic hybrid materials were prepared by conventional free radical polymerization and reversible addition-fragmentation chain transfer (RAFT) polymerization, respectively. The kinetics comparison of these two polymerizations was studied. The PMMA/MMT hybrid materials were characterized by gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). According to these results, we knew that the polymerization behavior of MMA showed controlled/living radical polymerization (CLRP) characteristics under the control of RAFT agent. The incorporation of RAFT agent and MMT nanoparticles improved the thermal properties of polymers, and the thermal stability of polymers increased with increasing content of MMT nanoparticles. The structures and morphologies of PMMA/MMT hybrid materials were characterized by FT-IR, XRD and TEM. These results showed that the MMA monomer can be initiated and propagated in the clay layers of MMT via the control of RAFT agent, and then the exfoliated structure was obtained for the hybrid materials. 相似文献
996.
Silicon-containing condensation polymers were prepared starting from difunctional silicon-containing carboxylic acids or diols derived from long-chain fatty acids. Polyesters were synthesized by reaction of diacids containing siloxane linkages with diols, and diols containing siloxane linkages with various diacids. 1,3-Bis (10-carboxydecyl)tetramethyldisiloxane was condensed with various diamines to yield polyamides. 1,3-Bis(11-hydroxyundecyl)tetramethyldisiloxane and 1,3-bis [9(10)-hydroxyoctadecyl]tetramethyldisiloxane were condensed with diisocyanates to yield polyurethanes. Polycarbonates were synthesized by reacting the diols containing siloxane linkages with ethyl chloroformate. Some polybenzimidazols were synthesized by heating the diesters of the silicon-containing carboxylic acids with 3,3′ -diaminobenzidine. Some of the polyurethanes and polybenzimidazoles were thermally stable up to 300°C as indicated by TGA. 相似文献
997.
Ferhat Kaykal Haluk Bingol Ahmet B. Sariguney Ahmet Coskun 《Supramolecular chemistry》2013,25(8):570-578
The alkali metal ion transfers facilitated by a novel calix[4]arene derivative (OPEC) across the water/1,2-dichloroethane (1,2-DCE) micro-interface supported at the tip of a micropipette were presented. The well-defined voltammetric behaviours except Cs+ was obtained by cyclic voltammetry and differential pulse voltammetry. The bulk concentration of metal ions was much higher than that of OPEC in the performed measurements. The diffusion coefficient of OPEC in the 1,2-DCE phase was calculated as 5.18 ± 0.70 × 10? 6 cm2 s? 1. On the basis of the changes of the half-wave transfer potentials, the logarithms of the association constants having 1:1 ionophore–ion complex stoichiometry for Li+, Na+, K+ and Rb+ in 1,2-DCE were determined as 4.80, 4.62, 4.98 and 5.32, respectively. The facilitated ion transfers were also evaluated by the Randles equivalent circuit used for ac-impedance data analysis. 相似文献
998.
Three viologen derivatives with the ability to detect amines were synthesised. Upon interacting with amines, a rapid colour change caused by electron transfer and charge transfer between viologen derivatives and amines can be directly observed by naked eyes. With fluorine substituents, the detection sensitivity of these viologen derivatives for amines is remarkably enhanced to reach the level of ppm. 相似文献
999.
1000.
Prof. Dr. Horst Kisch 《Angewandte Chemie (International ed. in English)》2013,52(3):812-847
Preceding work on photoelectrochemistry at semiconductor single‐crystal electrodes has formed the basis for the tremendous growth in the three last decades in the field of photocatalysis at semiconductor powders. The reason for this is the unique ability of inorganic semiconductor surfaces to photocatalyze concerted reduction and oxidation reactions of a large variety of electron‐donor and ‐acceptor substrates. Whereas great attention was paid to water splitting and the exhaustive aerobic degradation of pollutants, only a small amount of research also explored synthetic aspects. After introducing the basic mechanistic principles, standard experiments for the preparation and characterization of visible light active photocatalysts as well as the investigation of reaction mechanisms are discussed. Novel atom‐economic C? C and C? N coupling reactions illustrate the relevance of semiconductor photocatalysis for organic synthesis, and demonstrate that the multidisciplinary field combines classical photochemistry with electrochemistry, solid‐state chemistry, and heterogeneous catalysis. 相似文献