全文获取类型
收费全文 | 54444篇 |
免费 | 6328篇 |
国内免费 | 3817篇 |
专业分类
化学 | 23740篇 |
晶体学 | 250篇 |
力学 | 3850篇 |
综合类 | 910篇 |
数学 | 17363篇 |
物理学 | 18476篇 |
出版年
2023年 | 428篇 |
2022年 | 705篇 |
2021年 | 1613篇 |
2020年 | 1352篇 |
2019年 | 1438篇 |
2018年 | 1148篇 |
2017年 | 1289篇 |
2016年 | 1576篇 |
2015年 | 1663篇 |
2014年 | 2352篇 |
2013年 | 4039篇 |
2012年 | 2690篇 |
2011年 | 3120篇 |
2010年 | 2750篇 |
2009年 | 3364篇 |
2008年 | 3548篇 |
2007年 | 3673篇 |
2006年 | 3040篇 |
2005年 | 2296篇 |
2004年 | 2152篇 |
2003年 | 2164篇 |
2002年 | 1922篇 |
2001年 | 1773篇 |
2000年 | 1399篇 |
1999年 | 1171篇 |
1998年 | 1104篇 |
1997年 | 898篇 |
1996年 | 843篇 |
1995年 | 753篇 |
1994年 | 693篇 |
1993年 | 682篇 |
1992年 | 667篇 |
1991年 | 469篇 |
1990年 | 384篇 |
1989年 | 337篇 |
1988年 | 324篇 |
1987年 | 277篇 |
1986年 | 271篇 |
1985年 | 392篇 |
1984年 | 315篇 |
1983年 | 183篇 |
1982年 | 356篇 |
1981年 | 523篇 |
1980年 | 479篇 |
1979年 | 518篇 |
1978年 | 395篇 |
1977年 | 309篇 |
1976年 | 267篇 |
1974年 | 85篇 |
1973年 | 162篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
Intermolecular Stetter reaction of aromatic aldehydes with (E)-(2-nitrovinyl)cyclohexane catalyzed by thiazolium A has been developed. The reaction rate and efficiency are profoundly impacted by the presence of thiourea B. The reaction affords moderate to good yields of the Stetter product. Some factors influencing yield were discussed. 相似文献
82.
Highly Efficient Copper(II) Ion Sorbents Obtained by Calcium Carbonate Mineralization on Functionalized Cross‐Linked Copolymers 下载免费PDF全文
Dr. Marcela Mihai Dr. Ion Bunia Florica Doroftei Dr. Cristian‐Dragos Varganici Prof. Bogdan C. Simionescu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5220-5230
A new type of CuII ion sorbents is presented. These are obtained by CaCO3 mineralization from supersaturated solutions on gel‐like cross‐linked polymeric beads as insoluble templates. A divinylbenzene–ethylacrylate–acrylonitrile cross‐linked copolymer functionalized with weakly acidic, basic, or amphoteric functional groups has been used, as well as different initial inorganic concentrations and addition procedures for CaCO3 crystal growth. The morphology of the new composites was investigated by SEM and compared to that of the unmodified beads, and the polymorph content was established by X‐ray diffraction. The beads, before and after CaCO3 mineralization, were tested as sorbents for CuII ions. The newly formed patterns on the bead surface after CuII sorption were observed by SEM, and the elemental distribution on the composites and the chemical structure of crystals after interaction with CuII were investigated by EDAX elemental mapping and by FTIR‐ATR spectroscopy, respectively. The sorption capacity increased significantly after CaCO3 crystals growth on the weak anionic bead surface (up to 1041.5 mg CuII/g sample) compared to that of unmodified beads (491.5 mg CuII/g sample). 相似文献
83.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification 下载免费PDF全文
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献
84.
Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide) 下载免费PDF全文
Ainhoa Lejardi Jose‐Ramon Sarasua Agustin Etxeberria Emilio Meaurio 《Journal of Polymer Science.Polymer Physics》2016,54(13):1217-1226
Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to 1H and 13C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226 相似文献
85.
“(Diphosphine)Nickel”‐Catalyzed Negishi Cross‐Coupling: An Experimental and Theoretical Study 下载免费PDF全文
Dr. Emmanuel Nicolas Alexia Ohleier Florian D'Accriscio Dr. Anne‐Frédérique Pécharman Dr. Matthieu Demange Dr. Philippe Ribagnac Dr. Jorge Ballester Dr. Corinne Gosmini Dr. Nicolas Mézailles 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(21):7690-7694
The use of a strongly donating “(bis‐dialkylphosphine)Ni” fragment promotes the catalytic coupling of a large range of ArCl and ArZnCl derivatives under mild conditions. Stoichiometric mechanistic investigations and DFT calculations prove that a Ni0/NiII cycle is operative in this system. 相似文献
86.
Redox‐responsive core cross‐linked micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) by Diels‐Alder reaction for doxorubicin release 下载免费PDF全文
Cuong M. Q. Le Hai Ha Pham Thi Xuan Thang Cao Gun‐Do Kim Chul‐Woong Oh Kwon Taek Lim 《Journal of polymer science. Part A, Polymer chemistry》2016,54(23):3741-3750
Redox‐responsive core cross‐linked (CCL) micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) (PEO‐b‐PFMA) block copolymers were prepared by the Diels‐Alder click‐type reaction. First, the PEO‐b‐PFMA amphiphilic block copolymer was synthesized by the reversible addition‐fragmentation chain transfer polymerization. The hydrophobic blocks of PFMA were employed to encapsulate the doxorubicin (DOX) drug, and they were cross‐linked using dithiobismaleimidoethane at 60 °C without any catalyst. Under physiological circumstance, the CCL micelles demonstrated the enhanced structural stability of the micelles, whereas dissociation of the micelles took place rapidly through the breaking of disulfide bonds in the cross‐linking linkages under reduction environment. The core‐cross‐linked micelles showed fine spherical distribution with hydrodynamic diameter of 68 ± 2.9 nm. The in vitro drug release profiles presented a slight release of DOX at pH 7.4, while a significant release of DOX was observed at pH 5.0 in the presence of 1,4‐dithiothreitol. MTT assays demonstrated that the block copolymer did not have any practically cytotoxicity against the normal HEK293 cell line while DOX‐loaded CCL micelles exhibited a high antitumor activity towards HepG2 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3741–3750 相似文献
87.
DOSY NMR as a tool for predicting optimal conditions for hydrogel formation: The case of a hyperbranched polyglycidol cross‐linked with boronic acids 下载免费PDF全文
Monika Gosecka Mateusz Gosecki Slawomir Kazmierski 《Journal of Polymer Science.Polymer Physics》2016,54(21):2171-2178
This article demonstrates the utility of DOSY NMR for the determination of the optimal conditions for the efficient covalent, reversible cross‐linking of macromolecules in water for hydrogel formation. The studied model system was hyperbranched polyglycidol (HbPGL) containing numerous diol groups in peripheral regions and two types of boronic acids, that is, B(OH)4? and benzene‐1,4‐boronic diacid, as cross‐linking agents. Diffusion coefficient changes of a polymer in solution, under the influence of various concentrations of cross‐linking agent and pH, which influences the equilibrium of the reaction between boronic acids and diols, were recorded. These data are consistent with the rheological properties, namely the G′max(ω) of hydrogels prepared under analogous conditions, from more concentrated solutions of HbPGL. This approach appears to be promising as it facilitates avoiding the loss of a large amount of polymer that is necessary for the elaboration of appropriate conditions for network formation in aqueous media. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2171–2178 相似文献
88.
Theoretical investigations on the insertion reaction mechanisms of three- membered-ring silylenoid H2 Si Li F with GeH 3R(R = F, OH, NH2) have been systematically carried out by combined density functional theory(DFT) and ab initio quantum chemical calculations. The geometries of all stationary points for these reactions were optimized using the B3 LYP method and then the QCISD method was used to calculate the single-point energies. The calculated results indicate that, there are one precursor complex(Q), one transition state(TS), and one intermediate(IM) which connect the reactants and the products along the potential energy surface. The insertion reactions of three-membered-ring silylenoid with Ge H3 R proceed in a concerted manner, forming H2RSi-Ge H3 and Li F. The calculated potential energy barriers of the three reactions are 29.17, 30.90, and 54.07 k J/mol, and the reaction energies for the three reactions are –127.05, –116.91, and –103.31 k J/mol, respectively. The insertion reactions in solvents are similar to those in vacuum. Under the same situation, the insertion reactions should occur easily in the following order: GeH 3-F GeH 3-OH GeH 3-NH2. The elucidations of the mechanism of these insertion reactions provided a new mode of silicon-germanium bond formation. 相似文献
89.
90.
We establish the uniqueness of semi-wavefront solution for a non-local delayed reaction–diffusion equation. This result is obtained by using a generalization of the Diekmann–Kaper theory for a nonlinear convolution equation. Several applications to the systems of non-local reaction–diffusion equations with distributed time delay are also considered. 相似文献