全文获取类型
收费全文 | 19245篇 |
免费 | 3289篇 |
国内免费 | 2856篇 |
专业分类
化学 | 8995篇 |
晶体学 | 241篇 |
力学 | 852篇 |
综合类 | 194篇 |
数学 | 1704篇 |
物理学 | 5078篇 |
无线电 | 8326篇 |
出版年
2024年 | 84篇 |
2023年 | 397篇 |
2022年 | 678篇 |
2021年 | 716篇 |
2020年 | 772篇 |
2019年 | 734篇 |
2018年 | 646篇 |
2017年 | 698篇 |
2016年 | 786篇 |
2015年 | 1095篇 |
2014年 | 1257篇 |
2013年 | 1523篇 |
2012年 | 1778篇 |
2011年 | 1765篇 |
2010年 | 1563篇 |
2009年 | 1497篇 |
2008年 | 1529篇 |
2007年 | 1381篇 |
2006年 | 1266篇 |
2005年 | 1049篇 |
2004年 | 776篇 |
2003年 | 570篇 |
2002年 | 548篇 |
2001年 | 429篇 |
2000年 | 396篇 |
1999年 | 264篇 |
1998年 | 148篇 |
1997年 | 120篇 |
1996年 | 107篇 |
1995年 | 109篇 |
1994年 | 82篇 |
1993年 | 91篇 |
1992年 | 51篇 |
1991年 | 50篇 |
1990年 | 47篇 |
1989年 | 37篇 |
1988年 | 52篇 |
1987年 | 20篇 |
1986年 | 34篇 |
1985年 | 19篇 |
1984年 | 15篇 |
1983年 | 14篇 |
1982年 | 16篇 |
1981年 | 9篇 |
1980年 | 17篇 |
1979年 | 17篇 |
1978年 | 21篇 |
1977年 | 9篇 |
1973年 | 8篇 |
1971年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
131.
A Protic Ionic Liquid Catalyzes CO2 Conversion at Atmospheric Pressure and Room Temperature: Synthesis of Quinazoline‐2,4(1H,3H)‐diones 下载免费PDF全文
Dr. Yanfei Zhao Bo Yu Dr. Zhenzhen Yang Dr. Hongye Zhang Leiduan Hao Xiang Gao Prof. Zhimin Liu 《Angewandte Chemie (International ed. in English)》2014,53(23):5922-5925
The chemical fixation of CO2 under mild reaction conditions is of significance from a sustainable chemistry viewpoint. Herein a CO2‐reactive protic ionic liquid (PIL), [HDBU+][TFE?], was designed by neutralization of the superbase 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) with a weak proton donor trifluoroethanol (TFE). As a bifunctional catalyst for simultaneously activating CO2 and the substrate, this PIL displayed excellent performance in catalyzing the reactions of CO2 with 2‐aminobenzonitriles at atmospheric pressure and room temperature, thus producing a series of quinazoline‐2,4(1H,3H)‐diones in excellent yields. 相似文献
132.
Jian-Fen Zhang Bo Yang Weiqing Chen Jing Chen 《Applied biochemistry and biotechnology》2014,172(8):3913-3925
A soluble glucoside 3-dehydrogenase (G3DH) was purified from a newly isolated Sphingobacterium faecium ZJF-D6 CCTCC M 2013251. The enzyme was purified to 35.71-fold with a yield of 41.91 % and was estimated by sodium dodecyl sulphate–polyacrylamide gel electrophoresis with a molecular mass of 62 kDa. The sequences of two peptides of the enzyme were all contained in a GMC family oxidoreductase (EFK55866) by mass spectrometry analysis. The optimal pH of the enzyme was around 6.2. The enzyme was stable within a pH range of 5.0–6.6 and was sensitive to heat. G3DH from S. faecium exhibited extremely broad substrate specificity and well regioselectivity to validoxylamine A. The enzyme was completely inhibited by Hg2Cl2 and partly inhibited by Cu2+, Fe2+, Ca2+, and Cd2+. The apparent K m values for D-glucose, sucrose, and validoxylamine were calculated to be 1.1, 1.7, and 2.1 mM, respectively. With this purified enzyme, 3-keto sucrose was prepared at pH 5.0, 30 °C for 10 h with a yield of 28.7 %. 相似文献
133.
Polyurethane cationomer coats were synthesised on the basis of typical diisocyanates, properly selected polyether polyols, HO-tertiary amines and HCOOH as quaternisation reagents. The values of their surface free energy (SFE) parameters were obtained by the van Oss-Good method, with the use of the contact angle values which had been found by the goniometric method. Based on the obtained findings, empirical models were developed which made it possible to anticipate the effects of the raw material types on the SFE values of the produced coats. The possibility was noted to adjust the SFE values within 25–50 mJ/m2 by selecting carefully suitable parent substances. The principal consequences for the formation of improved hydrophobicity coats, applicable inter alia specialised protective coatings, were found to come not only from diisocyanate and polyol types but also from the alkylammonium cation structure which results from the use of different tertiary amines. The fundamental SFE lowering effect was noted when tertiary amines with 0–15 % of the 2,2,3,3-tetrafluoro-1,4-butanediol as a fluorinated chain extender was incorporated into polymer chains. 相似文献
134.
Haihong Zhang Dejun Zeng Bo Wang Jianfeng Yang 《Journal of Sol-Gel Science and Technology》2014,69(2):311-319
The spinning precursor sols for the continuous mullite-based fibers were prepared by adding nano-silica to substitute part of silica sol. The effect of SiO2 nanoparticles on the particle evolution models, polymerization degree and solid content of the sol,and the spinning length and sintering behavior of the fibers was investigated. The results were shown that the addition of nano silica enhanced the polymerization degree and extended the spinnable range of the sol. The appropriate polymerization degree (B value) for this sol system was 1.885–2.145. The grain diameter decreased from 39.6 to 25.9 nm with increasing the nano-silica content to 20 %, and then, it increased to 41.2 nm with increasing the nano-silica content to 100 %. The appropriate content of nano-silica powders would reduce the grain diameter. However, it had no influence on the linear growth model, homogeneity and solid content of the precursor sol. 相似文献
135.
利用L-谷氨酸苄酯开环聚合得到聚L-谷氨酸苄酯,对其进行表征,将聚L-谷氨酸苄酯溶于四氢呋喃后涂敷在3-氨丙基三乙氧基硅胶上制得液相色谱固定相,研究了正相色谱条件下聚L-谷氨酸苄酯涂敷型固定相对9种位置异构体及10种手性化合物的拆分能力。以不同比例的正己烷/异丙醇为流动相,有6种位置异构体(o,m,p-氯苯胺、o,m,p-溴苯胺、o,m,p-碘苯胺、o,m,p-硝基苯胺、o,m,p-二硝基苯和o,m,p-苯二胺)和4种手性化合物(1-(对氯苯基)乙醇、5-二硝基-N-(1-苯乙基)苯甲酰胺、华法林和四咪唑)得到不同程度的拆分,表明聚L-谷氨酸苄酯涂敷型固定相对位置异构体具有较好的识别作用,同时也表现出良好的手性拆分能力。 相似文献
136.
Yuanzhe Zhang Dr. Bo Li Prof. Dr. Shih-Yuan Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16062-16066
The first trans-selective cyanoboration reaction of an alkyne, specifically a 1,3-enyne, is described. The reported palladium-catalyzed cyanoboration of 1,3-enynes is site-, regio-, and diastereoselective, and is uniquely enabled by the 1,4-azaborine-based Senphos ligand structure. Tetra-substituted alkenyl nitriles are obtained providing useful boron-dienenitrile building blocks that can be further functionalized. The utility of our method has been demonstrated with the synthesis of Satigrel, an anti-platelet aggregating agent. 相似文献
137.
Chun-Dong Xue Zhong-Ping Sun Yong-Jiang Li Jian-Feng Chen Bo Liu Kai-Rong Qin 《Electrophoresis》2020,41(10-11):909-916
In the present study, we numerically demonstrate an approach for separation of micro and sub-micro diamagnetic particles in dual ferrofluid streams based on negative magnetophoresis. The dual streams are constructed by an intermediate sheath flow, after which the negative magnetophoretic force induced by an array of permanent magnets dominates the separation of diamagnetic particles. A simple and efficient numerical model is developed to calculate the motions of particles under the action of magnetic field and flow field. Effects of the average flow velocity, the ratio of sheath fluid flow to sample fluid flow, the number of the magnet pair as well as the position of magnet pair are investigated. The optimal parametric condition for complete separation is obtained through the parametric analysis, and the separation principle is further elucidated by the force analysis. The separation of smaller micro and sub-micro diamagnetic particles is finally demonstrated. This study provides an insight into the negative magnetophoretic phenomenon and guides the fabrication of feasible, low-cost diagnostic devices for sub-micro particle separation. 相似文献
138.
Saeromi Chung Mahmood H. Akhtar A. Benboudiaf Deog‐Su Park Yoon‐Bo Shim 《Electroanalysis》2020,32(3):520-527
An electrochemical sensor based on the conducting polymer composite with a palladium complex (Pd(C2H4N2S2)2) was developed for the detection of serotonin and dopamine simultaneously in the breast cancer cell and human plasma samples. The proposed sensor was fabricated using the Pd(C2H4N2S2)2 complex‐anchored poly2,2 : 5,2‐terthiophene‐3‐(p‐benzoic acid) (pTBA) layer on the AuNPs decorated reduced graphene oxide (AuNPs@rGO) substrate, which revealed the enhanced anodic current of the target species. The sensor probe was characterized by electrochemical and surface analysis methods. The experimental parameters affecting the sensor performance were optimized, in terms of AuNPs@rGO concentration, the number of electropolymerization cycle for pTBA, immobilization time of Pd(C2H4N2S2)2, and pH. The dynamic ranges for serotonin and dopamine were obtained from 0.02 to 200 μM, and from 0.1 to 200 μM with the detection limit of 2.5, and 24.0 nM, respectively. The reliability of proposed sensor was evaluated using cancer cell lines for the clinical applications. 相似文献
139.
The relative stability of the 3A2, 1A2, and 1A1 states of phenylnitrene is evaluated by means of ab initio calculations followed by difference-dedicated configuration interaction (DDCI). This approach is based on effective Hamiltonian theory at a low order of perturbation to select rationally the determinants which contribute to the energy difference. The CI space built on this criterion is then treated variationally. The method allows a considerable reduction of the CI space compared with a complete CAS*SDCI calculation (where CAS stands for complete active space). Depending on the concerned energy difference, different model spaces may be chosen, as illustrated in the 3A2 → 1A2 and the 3A2 → 1A1 transitions in phenylnitrene. Since the CI space may reach considerable dimensions, a direct CI algorithm for selected CI spaces, the SCIEL algorithm, has been used to perform the calculations. The results are in excellent agreement with previous calculations and with available experimental data. © 1996 by John Wiley & Sons, Inc. 相似文献
140.