全文获取类型
收费全文 | 7532篇 |
免费 | 669篇 |
国内免费 | 1088篇 |
专业分类
化学 | 7133篇 |
晶体学 | 16篇 |
力学 | 63篇 |
综合类 | 54篇 |
数学 | 1390篇 |
物理学 | 633篇 |
出版年
2024年 | 3篇 |
2023年 | 65篇 |
2022年 | 95篇 |
2021年 | 163篇 |
2020年 | 309篇 |
2019年 | 258篇 |
2018年 | 213篇 |
2017年 | 218篇 |
2016年 | 305篇 |
2015年 | 274篇 |
2014年 | 284篇 |
2013年 | 819篇 |
2012年 | 396篇 |
2011年 | 429篇 |
2010年 | 413篇 |
2009年 | 430篇 |
2008年 | 565篇 |
2007年 | 527篇 |
2006年 | 510篇 |
2005年 | 490篇 |
2004年 | 470篇 |
2003年 | 405篇 |
2002年 | 334篇 |
2001年 | 213篇 |
2000年 | 142篇 |
1999年 | 147篇 |
1998年 | 111篇 |
1997年 | 99篇 |
1996年 | 88篇 |
1995年 | 93篇 |
1994年 | 92篇 |
1993年 | 96篇 |
1992年 | 63篇 |
1991年 | 48篇 |
1990年 | 32篇 |
1989年 | 21篇 |
1988年 | 17篇 |
1987年 | 8篇 |
1986年 | 12篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1974年 | 1篇 |
排序方式: 共有9289条查询结果,搜索用时 15 毫秒
21.
Jing Qu Xinran Luo Zhonggang Wang 《Journal of polymer science. Part A, Polymer chemistry》2016,54(13):1969-1977
Tetrakis(4‐(1‐bromoethyl)phenyl)silane is synthesized and utilized to initiate the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) to generate bromo‐terminated four‐armed PMMA macroinitiators, which further initiate the ATRP of methylacryloyloxyl‐2‐hydroxypropyl perfluorooctanoate (FGOA) to create fluorinated star‐shaped block copolymers PMMA‐b‐poly(FGOA)s with fluorine content ranging from 0 to 31.7 wt %. The polymerizations are well controlled with the polydispersity indices <1.30. The polymers readily dissolve in common organic solvents and show good film‐formation. Compared with the nonfluorinated sample, the fluorinated films exhibit significantly increased water contact angles owing to the enrichment of fluorine on the surface. The enhanced hydrophobicity is advantageous for the optical stability when the devices work under a moist environment. Moreover, the films possess high thermo‐optic coefficients, tunable refractive indices, and extremely low birefringence coefficients because of the presence of bulky and rigid tetraphenylsilane core and star‐shaped topological structure, showing potential application in optical waveguide devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1969–1977 相似文献
22.
Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions 下载免费PDF全文
Ing. Martin Holan Dr. Radek Pohl Dr. Ivana Císařová Dr. Blanka Klepetářová Prof. Dr. Peter G. Jones Dr. Ullrich Jahn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9877-9888
Densely functionalized cyclopentane derivatives with up to four consecutive stereocenters are assembled by a tandem Michael addition/single‐electron transfer oxidation/radical cyclization/oxygenation strategy mediated by ferrocenium hexafluorophosphate, a recyclable, less toxic single‐electron transfer oxidant. Ester enolates were coupled with α‐benzylidene and α‐alkylidene β‐dicarbonyl compounds with switchable diastereoselectivity. This pivotal steering element subsequently controls the diastereoselectivity of the radical cyclization step. The substitution pattern of the radical cyclization acceptor enables a switch of the cyclization mode from a 5‐exo pattern for terminally substituted olefin units to a 6‐endo mode for internally substituted acceptors. The oxidative anionic/radical strategy also allows efficient termination by oxygenation with the free radical 2,2,6,6‐tetramethyl‐1‐piperidinoxyl, and two C?C bonds and one C?O bond are thus formed in the sequence. A stereochemical model is proposed that accounts for all of the experimental results and allows the prediction of the stereochemical outcome. Further transformations of the synthesized cyclopentanes are reported. 相似文献
23.
Victoria A. Piunova Hans W. Horn Gavin O. Jones Julia E. Rice Robert D. Miller 《Journal of polymer science. Part A, Polymer chemistry》2016,54(4):563-569
This study reports an application of trichloroethanol (TCE) as a bifunctional initiator for the synthesis of block copolymers (BCPs) by organocatalyzed ring‐opening polymerization (OROP) and atom transfer radical polymerization (ATRP). TCE was employed to synthesize a low dispersity poly (valerolactone) macroinitiator, which was subsequently used for the ATRP of tert‐butyl methacrylate. While it is known that TCE can serve as an initiator in ATRP, the ability to induce polymerization under OROP is reported for the first time. The formation of well‐defined BCPs was confirmed by gel permeation chromatography and 1H NMR. Computational studies were performed to obtain a molecular‐level understanding of the ring‐opening polymerization mechanism involving TCE as initiator. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 563–569 相似文献
24.
Daniel J. Tao Dr. Mikko Muuronen Yuriy Slutskyy Alexander Le Prof. Filipp Furche Prof. Larry E. Overman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8786-8790
The stereochemical outcome of reactions of chiral nucleophilic trisubstituted acetonide radicals with electron‐deficient alkenes is dictated by a delicate balance between destabilizing non‐bonding interactions and stabilizing hydrogen‐bonding between substituents on the α and β carbons. 相似文献
25.
Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization 下载免费PDF全文
Haicun Yang Hongting Pu Fanghong Gong 《Journal of polymer science. Part A, Polymer chemistry》2016,54(11):1508-1516
The surface grafting of attapulgite (ATP) with polystyrene (PS) was established via a simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NIATRP). 4‐(chloromethyl)phenyltrimethoxysilane (CMPTMS) chemical bounded on the surface of ATP (ATP‐Cl, Cl‐I) was prepared via one‐step self‐assembly. SR&NI ATRP of styrene was conducted using CuCl2 complex tris(2‐(dimethylamino)ethyl)amine (Me6‐TREN) as the catalytic system, initiated by 2,2‐azobis(isobutyronitrile) (AIBN) and ATP‐Cl. FT‐IR, XRD, XPS, TGA and TEM data were consistent with the grafting of benzyl chloride groups and PS chains on ATP surface. The controllability of polymerization was investigated by the kinetics behavior under different molar ratio of AIBN and CuCl2. The obtained polymer possessed a uniform distribution of molecular weights with a lower polydispersity index of 1.2~1.4. The relationship between polymerization on the surface of ATP and in solution was discussed in detail based on TGA data of hybrid particles and GPC trace of free polymer in solution. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1508–1516 相似文献
26.
Well‐controlled ATRP of 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate for high‐density click functionalization of polymers and metallic substrates 下载免费PDF全文
The combination of atom transfer radical polymerization (ATRP) and click chemistry has created unprecedented opportunities for controlled syntheses of functional polymers. ATRP of azido‐bearing methacrylate monomers (e.g., 2‐(2‐(2‐azidoethyoxy)ethoxy)ethyl methacrylate, AzTEGMA), however, proceeded with poor control at commonly adopted temperature of 50 °C, resulting in significant side reactions. By lowering reaction temperature and monomer concentrations, well‐defined pAzTEGMA with significantly reduced polydispersity were prepared within a reasonable timeframe. Upon subsequent functionalization of the side chains of pAzTEGMA via Cu(I)‐catalyzed azide‐alkyne cycloaddition (CuAAC) click chemistry, functional polymers with number‐average molecular weights (Mn) up to 22 kDa with narrow polydispersity (PDI < 1.30) were obtained. Applying the optimized polymerization condition, we also grafted pAzTEGMA brushes from Ti6Al4 substrates by surface‐initiated ATRP (SI‐ATRP), and effectively functionalized the azide‐terminated side chains with hydrophobic and hydrophilic alkynes by CuAAC. The well‐controlled ATRP of azido‐bearing methacrylates and subsequent facile high‐density functionalization of the side chains of the polymethacrylates via CuAAC offers a useful tool for engineering functional polymers or surfaces for diverse applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1268–1277 相似文献
27.
Cover Picture: Mild and Low‐Pressure fac‐Ir(ppy)3‐Mediated Radical Aminocarbonylation of Unactivated Alkyl Iodides through Visible‐Light Photoredox Catalysis (Chem. Eur. J. 27/2016) 下载免费PDF全文
28.
Jingang Li Yixin Xiang Sixun Zheng 《Journal of polymer science. Part A, Polymer chemistry》2016,54(3):368-380
In this contribution, we reported the synthesis of a hyperbranched block copolymer composed of poly(ε‐caprolactone) (PCL) and polystyrene (PS) subchains. Toward this end, we first synthesized an α‐alkynyl‐ and ω,ω′‐diazido‐terminated PCL‐b‐(PS)2 macromonomer via the combination of ring‐opening polymerization and atom transfer radical polymerization. By the use of this AB2 macromonomer, the hyperbranched block copolymer (h‐[PCL‐b‐(PS)2]) was synthesized via a copper‐catalyzed Huisgen 1,3‐dipolar cycloaddition (i.e., click reaction) polymerization. The hyperbranched block copolymer was characterized by means of 1H nuclear magnetic resonance spectroscopy and gel permeation chromatography. Both differential scanning calorimetry and atomic force microscopy showed that the hyperbranched block copolymer was microphase‐separated in bulk. While this hyperbranched block copolymer was incorporated into epoxy, the nanostructured thermosets were successfully obtained; the formation of the nanophases in epoxy followed reaction‐induced microphase separation mechanism as evidenced by atomic force microscopy, small angle X‐ray scattering, and dynamic mechanical thermal analysis. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 368–380 相似文献
29.
Formation of Long,Multicenter π‐[TCNE]22− Dimers in Solution: Solvation and Stability Assessed through Molecular Dynamics Simulations
下载免费PDF全文
Dr. Marçal Capdevila‐Cortada Dr. Jordi Ribas‐Arino Dr. Alain Chaumont Prof. Georges Wipff Prof. Juan J. Novoa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(47):17037-17046
Purely organic radical ions dimerize in solution at low temperature, forming long, multicenter bonds, despite the metastability of the isolated dimers. Here, we present the first computational study of these π‐dimers in solution, with explicit consideration of solvent molecules and finite temperature effects. By means of force‐field and ab initio molecular dynamics and free energy simulations, the structure and stability of π‐[TCNE]22? (TCNE=tetracyanoethylene) dimers in dichloromethane have been evaluated. Although the dimers dissociate at room temperature, they are stable at 175 K and their structure is similar to the one in the solid state, with a cofacial arrangement of the radicals at an interplanar separation of approximately 3.0 Å. The π‐[TCNE]22? dimers form dissociated ion pairs with the NBu4+ counterions, and their first solvation shell comprises approximately 20 CH2Cl2 molecules. Among them, the eight molecules distributed along the equatorial plane of the dimer play a key role in stabilizing the dimer through bridging C?H???N contacts. The calculated free energy of dimerization of TCNE . ? in solution at 175 K is ?5.5 kcal mol?1. These results provide the first quantitative model describing the pairing of radical ions in solution, and demonstrate the key role of solvation forces on the dimerization process. 相似文献
30.
Dr. Jingjun Hao Prof. Arnold L. Rheingold Marzieh Kavand Dr. Kipp J. van Schooten Prof. Christoph Boehme Dr. Marçal Capdevila‐Cortada Prof. Juan J. Novoa Eva Wöss Prof. Günther Knör Prof. Joel S. Miller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12312-12315
The reaction of 2,3,5,6‐tetracyanopyridine (TCNPy) and Cr(C6H6)2 forms diamagnetic σ‐[TCNPy]22? possessing a 1.572(3) Å intrafragment sp3–sp3 bond. This is in contrast to the structurally related 1,2,4,5‐tetracyanobenzene and 1,2,4,5‐tetracyanopyrazine that form π‐dimer dianions possessing long, multicenter bonds. 相似文献