全文获取类型
收费全文 | 13496篇 |
免费 | 2234篇 |
国内免费 | 1443篇 |
专业分类
化学 | 9260篇 |
晶体学 | 126篇 |
力学 | 924篇 |
综合类 | 88篇 |
数学 | 1659篇 |
物理学 | 5116篇 |
出版年
2024年 | 45篇 |
2023年 | 284篇 |
2022年 | 484篇 |
2021年 | 533篇 |
2020年 | 547篇 |
2019年 | 488篇 |
2018年 | 470篇 |
2017年 | 410篇 |
2016年 | 596篇 |
2015年 | 652篇 |
2014年 | 752篇 |
2013年 | 995篇 |
2012年 | 1139篇 |
2011年 | 1174篇 |
2010年 | 803篇 |
2009年 | 747篇 |
2008年 | 840篇 |
2007年 | 772篇 |
2006年 | 700篇 |
2005年 | 570篇 |
2004年 | 428篇 |
2003年 | 352篇 |
2002年 | 324篇 |
2001年 | 286篇 |
2000年 | 242篇 |
1999年 | 284篇 |
1998年 | 269篇 |
1997年 | 197篇 |
1996年 | 219篇 |
1995年 | 217篇 |
1994年 | 183篇 |
1993年 | 160篇 |
1992年 | 132篇 |
1991年 | 146篇 |
1990年 | 143篇 |
1989年 | 110篇 |
1988年 | 92篇 |
1987年 | 78篇 |
1986年 | 59篇 |
1985年 | 62篇 |
1984年 | 28篇 |
1983年 | 33篇 |
1982年 | 26篇 |
1981年 | 20篇 |
1980年 | 13篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1974年 | 6篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
Emamectin benzoate, a macrocyclic lactone, can be used in low quantities to control arthropod pests, effectively. However, its poor photostability prevents its further use. To delay its photodegradation, novel acrylate‐type polymeric nanoparticles were synthesized and tested as materials for improving pesticide photostability. N‐acylated emamectin benzoate was synthesized via bonding emamectin benzoate to acrylamide. The resulting pesticide, containing the double bond linkage –C=C–N–, was copolymerized with butyl acrylate and methyl methacrylate by the emulsion polymerization method. The refined polymers were characterized by Fourier transform infrared spectroscopy spectroscopy, and result illustrated the pesticide was conjugated to the polymers. Atomic force microscope and dynamic light scattering analyses were also used for determining the average particle diameters of pesticide–polymer conjugates. Photostability tests showed that the nanoparticles obtained exhibited greatly improved photostability. Additionally, the laboratory toxicity tests demonstrated that the insecticidal effects of the novel emamectin benzoate formulation were better than those of the control pesticide formulation (emamectin benzoate EC). Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
72.
73.
Lipid profiling of human plasma from peritoneal dialysis patients using an improved 2D (NP/RP) LC-QToF MS method 总被引:1,自引:0,他引:1
Min Li Baosheng Feng Yuan Liang Wei Zhang Yu Bai Wen Tang Tao Wang Huwei Liu 《Analytical and bioanalytical chemistry》2013,405(21):6629-6638
An improved online two-dimensional liquid chromatography-quadrupole time-of-flight mass spectrometry (2D LC-QToF MS) system was developed for the lipid profiling of human plasma, in which different lipid classes were separated by the first dimensional normal-phase (NP) LC and different lipid molecular species were separated by the second dimensional reversed-phase (RP) LC. This 2D LC-QToF MS system was built based on a ten-port, two-position valve as the interface, the conditions of which had been optimized and discussed in detail. As two loops were used to trap and transfer the first dimensional elute to the second dimension separately, this new interface suppressed the sample band broadening in the first dimensional column, increased the recovery and repeatability of 2D LC interface, and offered the possibility for the realization of not-stop-flow NP/RP 2D LC system. Finally, 190 endogenous lipid species out of 10 lipid classes were determined within a single run from the plasma of peritoneal patients. This method was also applied to identify the difference in lipid profile between plasma from peritoneal dialysis patients with bad volume status and peritoneal dialysis patients with good volume status. The discovery of 30 potential biomarkers would be helpful to the malnutrition, inflammation, and atherosclerosis syndrome investigation. 相似文献
74.
Qixin Dong Jiajun Zhu Qiang Sui Chao Tang Xiaomei Wang Yunqiu Yu 《Journal of separation science》2013,36(7):1200-1208
In this study, the objective was to investigate the degradation behavior of Esomeprazole under different recommended stress conditions according to International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use [1] by HPLC. Our research showed that the effect of mobile phase species on separation was significant for the determination of Esomeprazole and its related compounds. Successful separation of the drug from its related impurities and degradation products formed under different stress conditions was achieved using ammonium acetate buffer/ACN by a gradient elution. Compared with phosphate buffer/ACN, ammonium acetate buffer/ACN under same pH and gradient showed a great improvement in resolution due to the change of elution order. The drug was subjected to stress conditions including acidic, alkaline, oxidative, photolytic, and thermal conditions. Extensive degradation occurred in acidic and oxidative conditions, while mild degradation was observed in alkaline and photolytic conditions. Besides, it turned out the drug was extremely stable under thermal condition. The stability‐indicating LC–UV method was validated with respect to linearity, precision, accuracy, specificity, and robustness. The LC–MS method was also adopted for the characterization of degradation products. Based on the m/z values and fragmentation patterns, the degradation pathway of the drug has been proposed. 相似文献
75.
Total synthesis of α-elvucitabine was achieved in 26% overall yield by a concise nine-step procedure starting from L-lyxose, with trimethylsilyl trifluoromethaneoulfonate (TMSOTf)–mediated stereocontrolled α-N-glycosidation and olefination through Barton–McCombie deoxygenation being the key steps, and the stereochemistry of the product was determined by nuclear Overhauser effect spectroscopy. 相似文献
76.
Qian‐Lin Tang 《International journal of quantum chemistry》2013,113(16):1992-2001
Practical copper (Cu)‐based catalysts for the water–gas shift (WGS) reaction was long believed to expose a large proportion of Cu(110) planes. In this work, as an important first step toward addressing sulfur poisoning of these catalysts, the detailed mechanism for the splitting of hydrogen sulfide (H2S) on the open Cu(110) facet has been investigated in the framework of periodic, self‐consistent density functional theory (DFT‐GGA). The microkinetic model based on the first‐principles calculations has also been developed to quantitatively evaluate the two considered decomposition routes for yielding surface atomic sulfur (S*): (1) H2S → H2S* → SH* → S* and (2) 2H2S → 2H2S* → 2SH* → S* + H2S* → S* + H2S. The first pathway proceeding through unimolecular SH* dissociation was identified to be feasible, whereas the second pathway involving bimolecular SH* disproportionation made no contribution to S* formation. The molecular adsorption of H2S is the slowest elementary step of its full decomposition, being related with the large entropy term of the gas‐phase reactant under realistic reaction conditions. A comparison of thermodynamic and kinetic reactivity between the substrate and the close‐packed Cu(111) surface further shows that a loosely packed facet can promote the S* formation from H2S on Cu, thus revealing that the reaction process is structure sensitive. The present DFT and microkinetic modeling results provide a reasonably complete picture for the chemistry of H2S on the Cu(110) surface, which is a necessary basis for the design of new sulfur‐tolerant WGS catalysts. © 2013 Wiley Periodicals, Inc. 相似文献
77.
An atom-economic route to densely functionalized thiophenes has been developed via base-catalyzed rearrangement of 5-propargyl-2H-thiopyran-4(3H)-ones involving tandem retro-thio Michael addition, propargyl isomerization, and intramolecular thio-addition to allenes. 相似文献
78.
Chang Jun Zou Quan Wu Tang Gui Hong Lan Qiang Tian Tai Yu Wang 《Journal of inclusion phenomena and macrocyclic chemistry》2013,76(1-2):61-68
For the first time, hydroxypropyl-β-cyclodextrin (HP-β-CD) has been brought in to include 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTCA) in order to enhance inhibition efficiency of PBTCA, which leads a new approach to study oil–gas field corrosion inhibition in the process of acid treatment. Based on the host–guest inclusion reaction, the inclusion complex of PBTCA with HP-β-CD has been prepared in the laboratory. UV–Vis absorption spectrum was applied to study the inclusion behavior of PBTCA with HP-β-CD. The results revealed that PBTCA with HP-β-CD can form a 1:1 stoichiometry inclusion complex. The 1:1 inclusion complex synthesized by using lyophilization was further characterized by Fourier transform infrared spectroscopy. Besides, inhibition effect of the inclusion complex on the corrosion inhibition of Q235 carbon steel has been investigated in 0.1 M sulfuric acid (H2SO4) solution using potentiodynamic polarization, electrochemical impedance spectroscopy techniques and scanning electron microscopy (SEM). It was found that the presence of the inclusion complex better achieved the anti-corrosion property in aggressive medium than was the case with alone PBTCA and the highest inhibition efficiency of the inclusion complex over 90 % was obtained, which are suggestive of the active effect of the inclusion complex for improving inhibition efficiency of PBTCA. Meanwhile, the results obtained from SEM further showed that the inclusion complex acts as a more efficient corrosion inhibitor for Q235 carbon steel in H2SO4 medium. 相似文献
79.
C. P. Cheng M. H. Tang Z. H. Tang Y. C. Zhou 《Journal of Sol-Gel Science and Technology》2013,68(2):346-350
Magnetoelectric (ME) xLa0.6Ca0.4MnO3–(1 ? x)Bi3.4Nd0.6Ti3O12 (LCMO–BNT) composite thin films have been prepared by a sol–gel process and spin-coating technique. The effects of LCMO content on the microstructure, leakage current density, ferroelectric properties, fatigue endurance and ME voltage coefficient of LCMO–BNT thin films derived by sol–gel method were studied. It was found that the composite thin films have better fatigue endurance properties and lower leakage current densities compared with pure BNT thin films, as well as large ME voltage coefficients. 相似文献
80.
Conghui Tang Ning Jiao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(25):6646-6650
A novel copper‐catalyzed aerobic oxidative C(CO) C(alkyl) bond cleavage reaction of aryl alkyl ketones for C N bond formation is described. A series of acetophenone derivatives as well as more challenging aryl ketones with long‐chain alkyl substituents could be selectively cleaved and converted into the corresponding amides, which are frequently found in biologically active compounds and pharmaceuticals. 相似文献