全文获取类型
收费全文 | 41555篇 |
免费 | 3175篇 |
国内免费 | 4116篇 |
专业分类
化学 | 29861篇 |
晶体学 | 299篇 |
力学 | 861篇 |
综合类 | 683篇 |
数学 | 6955篇 |
物理学 | 10187篇 |
出版年
2023年 | 297篇 |
2022年 | 550篇 |
2021年 | 1477篇 |
2020年 | 1139篇 |
2019年 | 1226篇 |
2018年 | 920篇 |
2017年 | 1152篇 |
2016年 | 1371篇 |
2015年 | 1376篇 |
2014年 | 1661篇 |
2013年 | 3146篇 |
2012年 | 2195篇 |
2011年 | 2235篇 |
2010年 | 2025篇 |
2009年 | 2510篇 |
2008年 | 2598篇 |
2007年 | 2767篇 |
2006年 | 2221篇 |
2005年 | 1578篇 |
2004年 | 1522篇 |
2003年 | 1344篇 |
2002年 | 1281篇 |
2001年 | 1238篇 |
2000年 | 838篇 |
1999年 | 722篇 |
1998年 | 689篇 |
1997年 | 494篇 |
1996年 | 573篇 |
1995年 | 609篇 |
1994年 | 610篇 |
1993年 | 628篇 |
1992年 | 539篇 |
1991年 | 362篇 |
1990年 | 294篇 |
1989年 | 236篇 |
1988年 | 264篇 |
1987年 | 211篇 |
1986年 | 221篇 |
1985年 | 334篇 |
1984年 | 250篇 |
1983年 | 149篇 |
1982年 | 314篇 |
1981年 | 476篇 |
1980年 | 426篇 |
1979年 | 467篇 |
1978年 | 375篇 |
1977年 | 279篇 |
1976年 | 237篇 |
1974年 | 74篇 |
1973年 | 151篇 |
排序方式: 共有10000条查询结果,搜索用时 24 毫秒
81.
82.
Synthesis of polymer with defined fluorescent end groups via reversible addition fragmentation transfer polymerization for characterizing the conformations of polymer chains in solutions 下载免费PDF全文
Ye Sha Qing Zhu Yuanxin Wan Linling Li Xiaoliang Wang Gi Xue Dongshan Zhou 《Journal of polymer science. Part A, Polymer chemistry》2016,54(15):2413-2420
A new type of chain transfer agent used in reversible addition fragmentation chain transfer (RAFT) polymerization named 9‐anthracenylmethyl (4‐cyano‐4‐(N‐carbazylcarbodithioate) pentanoate) (ACCP) was synthesized with a total yield over 75% by the incorporation of both fluorescent donor and acceptor chromophores. Polymerization of heterotelechelic α,ω end‐labeled dye‐functionalized polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(n‐butyl methacrylate) (PBMA) with adjustable molecular weights and narrow polydispersity could be conducted by a one‐pot procedure through RAFT polymerization with this bischromophore chain transfer agent. The polymerizations demonstrated “living” controlled characteristics. By taking advantage of the characteristic fluorescence resonance energy transfer (FRET) response between the polymer chain terminals, the variation of chain dimensions in solution from the dilute region to the semidilute region can be monitored by changes in the ratio of the fluorescence intensities of the carbazolyl group to the anthryl group, which lends itself to potential applications in characterizing chain dimensions in solutions for thermodynamic or dynamic studies. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2413–2420 相似文献
83.
84.
Effect of branched alkyl side chains on the performance of thin‐film transistors and photovoltaic cells fabricated with isoindigo‐based conjugated polymers 下载免费PDF全文
Gi Eun Park Jicheol Shin Dae Hee Lee Min Ju Cho Dong Hoon Choi 《Journal of polymer science. Part A, Polymer chemistry》2015,53(10):1226-1234
New isoindigo and di(thienyl)ethylene‐containing π‐extended conjugated polymers with different branched side chains were synthesized to investigate their physical properties and device performance in thin‐film transistors and photovoltaic cells. 11‐Butyltricosane (S3) and 11‐heptyltricosane (S6) groups were used as side‐chain moieties tethered to isoindigo units. The linking groups between the polymer backbone and bifurcation point in the branched side chain differ in the two polymers (i.e., PIDTE‐S3 and PIDTE‐S6 ). The polymers bearing S6 side chains showed much better charge transport behavior than those with S3 side chains. Thermally annealed PIDTE‐S6 film exhibited an outstanding hole mobility of 4.07 cm2 V?1 s?1 under ambient conditions. Furthermore, bulk heterojunction organic photovoltaic cells made from a blend film of PIDTE‐S3 and (6,6)‐phenyl C61‐butyric acid methyl ester demonstrated promising device performance with a power conversion efficiency in the range of 4.9–5.0%. © 2015 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 2015 , 53, 1226–1234 相似文献
85.
Specific Design of Titanium(IV) Phenolato Chelates Yields Stable and Accessible,Effective and Selective Anticancer Agents 下载免费PDF全文
Sigalit Meker Dr. Ori Braitbard Dr. Matthew D. Hall Prof. Jacob Hochman Prof. Edit Y. Tshuva 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):9986-9995
Octahedral titanium(IV) complexes of phenolato hexadentate ligands were developed and showed very high stability for days in water solutions. In vitro cytotoxicity studies showed that, whereas tetrakis(phenolato) systems are generally of low activity presumably due to inaccessibility, smaller bis(phenolato)bis(alkoxo) complexes feature high anticancer activity and accessibility even without formulations, also toward a cisplatin‐resistant cell line. An all‐aliphatic control complex was unstable and inactive. A leading phenolato complex also revealed: 1) high durability in fully aqueous solutions; accordingly, negligible loss of activity after preincubation for three days in medium or in serum; 2) maximal cellular accumulation and induction of apoptosis following 24–48 h of administration; 3) reduced impact on noncancerous fibroblast cells; 4) in vivo efficacy toward lymphoma cells in murine model; 5) high activity in NCI‐60 panel, with average GI50 of 4.6±2 μm . This newly developed family of TiIV complexes is thus of great potential for anticancer therapy. 相似文献
86.
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
87.
Generic applications of 13C‐detected NMR diffusion to formulated systems with suppression of thermal convection induced by proton decoupling 下载免费PDF全文
Jianbo Hou Yiyong He Paolo Sabatino Ling Yuan David Redwine 《Magnetic resonance in chemistry : MRC》2016,54(7):584-591
Fast and effective structural/compositional analysis on formulated systems represents one of the major challenges encountered in analytical science. 13C‐detected diffusion represents a promising tool to tackle the aforementioned challenges, particularly in industry. Toward exploring the generic applications of 13C‐detected diffusion, thermal convection induced by 1H decoupling has been identified as a key factor that resulted in significantly reduced resolution in the diffusion dimension. Optimization of experimental parameters and utilization of double‐stimulated echo‐based pulse sequence both can effectively suppress the thermal convection caused by the 1H decoupling, the success of which allows robust and generic applications of 13C‐detected diffusion to systems from mixtures of small molecules, polymer blends, and copolymers to actual complex formulated systems. The method is particularly powerful in differentiating small molecules from polymers, polymer blends from copolymers, and end‐group analysis. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
88.
Highly active polymeric organocatalyst: Chiral ionic polymers prepared from 10,11‐didehydrogenated cinchonidinium salt 下载免费PDF全文
Md. Mehadi Hassan Naoki Haraguchi Shinichi Itsuno 《Journal of polymer science. Part A, Polymer chemistry》2016,54(5):621-627
Since few examples of 10,11‐didehydrogenated (3‐ethynyl) cinchona alkaloids have been utilized as organocatalysts in asymmetric reaction, we synthesized 10,11‐didehydrogenated cinchonidine. The 3‐vinyl group of cinchonidine was transformed into a 3‐ethynyl functionality. Based on the resulting 10,11‐didehydrogenated cinchonidine, the corresponding quaternary ammonium salt and its dimers were prepared. The ion‐exchange reaction between the quaternary ammonium salt and sodium sulfonate produced the quaternary ammonium sulfonate as a stable ionic compound. Chiral ionic polymers were then synthesized by the ion‐exchange polymerization of the 10,11‐didehydrogenated cinchonidinium salt dimer and a disulfonate. The chiral ionic polymers were found to be capable of efficiently catalyzing the asymmetric alkylation of N‐(diphenylmethylene)glycine tert‐butyl ester. The enantioselectivities obtained with the polymeric catalysts were higher than those obtained with the corresponding monomeric catalyst. Dimers of 10,11‐didehydrogenated cinchonidinium salts were prepared. Treatment of the dimer with disodium disulfonate gave the chiral ionic polymers, which showed high catalytic activity in asymmetric benzylation of N‐(diphenylmethylen)glycine tert‐butyl ester. The polymeric catalysts were reused several times without the loss of catalytic activity. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 621–627 相似文献
89.
Single crystals of a new silicate carbonate, K2Ca[Si2O5](CO3), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6322) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P63/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO4) and the other of the high-temperature soda-like α-Na2CO3, Ca substituting for Na. The electro-neutral layer K2[Si2O5] (denoted K) as well as the layer Ca(CO3) (denoted S) may separately correspond to individual structures. In K2Ca[Si2O5](CO3) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability. 相似文献
90.
Li Zhang Dr. Julie Jung Dr. Peng Zhang Mei Guo Dr. Lang Zhao Prof. Dr. Jinkui Tang Prof. Dr. Boris Le Guennic 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1392-1398
Elaborate chemical design is of utmost importance in order to slow down the relaxation dynamics in single‐molecule magnets (SMMs) and hence improve their potential applications. Much interest was devoted to the study of distinct relaxation processes related to the different crystal fields of crystallographically independent lanthanide ions. However, the assignment of the relaxation processes to specific metal sites remains a challenging task. To address this challenge, a new asymmetric Dy2 SMM displaying a well‐separated two‐step relaxation process with the anisotropic centers in fine‐tuned local environments was elaborately designed. For the first time a one‐to‐one relationship between the metal sites and the relaxation processes was evidenced. This work sheds light on complex multiple relaxation and may direct the rational design of lanthanide SMMs with enhanced magnetic properties. 相似文献