全文获取类型
收费全文 | 14290篇 |
免费 | 2286篇 |
国内免费 | 2462篇 |
专业分类
化学 | 10599篇 |
晶体学 | 302篇 |
力学 | 919篇 |
综合类 | 216篇 |
数学 | 1678篇 |
物理学 | 5324篇 |
出版年
2024年 | 30篇 |
2023年 | 183篇 |
2022年 | 405篇 |
2021年 | 462篇 |
2020年 | 459篇 |
2019年 | 536篇 |
2018年 | 471篇 |
2017年 | 523篇 |
2016年 | 675篇 |
2015年 | 732篇 |
2014年 | 823篇 |
2013年 | 1082篇 |
2012年 | 1254篇 |
2011年 | 1267篇 |
2010年 | 944篇 |
2009年 | 1006篇 |
2008年 | 1086篇 |
2007年 | 1001篇 |
2006年 | 967篇 |
2005年 | 758篇 |
2004年 | 703篇 |
2003年 | 588篇 |
2002年 | 695篇 |
2001年 | 604篇 |
2000年 | 409篇 |
1999年 | 323篇 |
1998年 | 213篇 |
1997年 | 136篇 |
1996年 | 127篇 |
1995年 | 107篇 |
1994年 | 87篇 |
1993年 | 90篇 |
1992年 | 50篇 |
1991年 | 46篇 |
1990年 | 42篇 |
1989年 | 40篇 |
1988年 | 25篇 |
1987年 | 22篇 |
1986年 | 19篇 |
1985年 | 18篇 |
1984年 | 6篇 |
1983年 | 4篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 3篇 |
1975年 | 1篇 |
1957年 | 1篇 |
1936年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 12 毫秒
971.
Guo Zhang Xu Jian Hua Dong Kun Yuan Qiu 《Journal of polymer science. Part A, Polymer chemistry》1997,35(4):643-650
Several N-phenyl maleimides with different p-substituents have been synthesized from the maleic anhydride and relevant aromatic amine. In the presence of N,N-dimethyl-4-toluidine (DMT), the N-substituted phenyl maleimide (4-XPhMIs) could be polymerized under UV irradiation. It was observed that a new absorption appeared on the UV-Vis spectrum of the mixture solution of 4-XPhMI and DMT, which reveals the formation of charge-transfer complex in the ground state. It was found that the fluorescence of DMT was quenched by 4-XPhMI and the quenching constant of 4-XPhMI, obtained from the Stern–Volmer plot, increases with the electron-deficiency of ethylene double bond of 4-XPhMI. The dynamic quenching of the fluorescence of DMT by 4-XPhMI suggests the formation of exciplex in excited state between DMT and 4-XPhMI. The radicals formed in the systems have been detected by spin-trapping techniques and electron paramagnetic resonance (EPR) spectrometer. Based on all of these results, it has been proposed that the initiation process of the polymerization involves the formation of exciplex and the initial radicals were produced by proton-transfer in the exciplex from DMT to 4-XPhMI. © 1997 John Wiley & Sons, Inc. 相似文献
972.
Jian Ming Yu Philippe Dubois Robert Jerome 《Journal of polymer science. Part A, Polymer chemistry》1997,35(16):3507-3515
New block copolymers of the ABA type, where B stands for polybutadiene (PBD) and A for polyglycidylmethacrylate(PGMA), poly(methylmethacrylate(MMA)-co-GMA) and PMMA-b-PGMA, respectively, have been successfully synthesized by using the diadduct of tert-butyllithium (tert-BuLi) to meta-diisopropenylbenzene (m-DIB) as a difunctional initiator. The PBD midblock has been synthesized in a cyclohexane/diethylether (100/6, v/v) mixture at room temperature, whereas the methacrylate outer blocks have been synthesized in a cyclohexane/diethylether/THF (100/6/150, v/v/v) mixture at −78°C. Block copolymers of a very narrow molecular weight distribution (1.10) have been analyzed by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), and tensile testing. These materials are phase separated and can exhibit tensile strength up to 22 MPa together with very high elongation at break (1500%). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3507–3515, 1997 相似文献
973.
Hongsheng Wang Bingzheng Wang Sean-Thomas B. Lundin Hui Kong Bosheng Su Jian Wang 《Molecules (Basel, Switzerland)》2021,26(22)
To efficiently convert and utilize intermittent solar energy, a novel solar-driven ethanol steam reforming (ESR) system integrated with a membrane reactor is proposed. It has the potential to convert low-grade solar thermal energy into high energy level chemical energy. Driven by chemical potential, hydrogen permeation membranes (HPM) can separate the generated hydrogen and shift the ESR equilibrium forward to increase conversion and thermodynamic efficiency. The thermodynamic and environmental performances are analyzed via numerical simulation under a reaction temperature range of 100–400 °C with permeate pressures of 0.01–0.75 bar. The highest theoretical conversion rate is 98.3% at 100 °C and 0.01 bar, while the highest first-law efficiency, solar-to-fuel efficiency, and exergy efficiency are 82.3%, 45.3%, and 70.4% at 215 °C and 0.20 bar. The standard coal saving rate (SCSR) and carbon dioxide reduction rate (CDRR) are maximums of 101 g·m−2·h−1 and 247 g·m−2·h−1 at 200 °C and 0.20 bar with a hydrogen generation rate of 22.4 mol·m−2·h−1. This study illustrates the feasibility of solar-driven ESR integrated with a membrane reactor and distinguishes a novel approach for distributed hydrogen generation and solar energy utilization and upgradation. 相似文献
974.
Luyang Jian Ying Xue Yuefeng Gao Bo Wang Yanghua Qu Shuanghong Li Heqiong Li Zhen Li Bing Wang Hailing Luo 《Molecules (Basel, Switzerland)》2021,26(15)
(1) Background: the current research was conducted to investigate the potential non-antioxidant roles of vitamin E in the protection of hepatocysts from oxidative damage. (2) Methods: primary sheep hepatocytes were cultured and exposed to 200, 400, 600, or 800 μmol/L hydrogen peroxide, while their viability was assessed using a CCK-8 kit. Then, cells were treated with 400 μmol/L hydrogen peroxide following a pretreatment with 50, 100, 200, 400, and 800 μmol/L vitamin E and their intracellular ROS levels were determined by means of the DCF-DA assay. RNA-seq, verified by qRT-PCR, was conducted thereafter: non-treated control (C1); cells treated with 400 μmol/L hydrogen peroxide (C2); and C2 plus a pretreatment with 100 μmol/L vitamin E (T1). (3) Results: the 200–800 μmol/L hydrogen peroxide caused significant cell death, while 50, 100, and 200 μmol/L vitamin E pretreatment significantly improved the survival rate of hepatocytes. ROS content in the cells pretreated with vitamin E was significantly lower than that in the control group and hydrogen-peroxide-treated group, especially in those pretreated with 100 μmol/L vitamin E. The differentially expressed genes (DEGs) concerning cell death involved in apoptosis (RIPK1, TLR7, CASP8, and CASP8AP2), pyroptosis (NLRP3, IL-1β, and IRAK2), and ferroptosis (TFRC and PTGS2). The abundances of IL-1β, IRAK2, NLRP3, CASP8, CASP8AP2, RIPK1, and TLR7 were significantly increased in the C1 group and decreased in T1 group, while TFRC and PTGS2 were increased in T1 group. (4) Conclusions: oxidative stress induced by hydrogen peroxide caused cellular damage and death in sheep hepatocytes. Pretreatment with vitamin E effectively reduced intracellular ROS levels and protected the hepatocytes from cell death by regulating gene expression associated with apoptosis (RIPK1, TLR7, CASP8, and CASP8AP2) and pyroptosis (NLRP3, IL-1β, and IRAK2), but not ferroptosis (TFRC and PTGS2). 相似文献
975.
Xukai Jiang Nitin A. Patil Mohammad A. K. Azad Hasini Wickremasinghe Heidi Yu Jinxin Zhao Xinru Zhang Mengyao Li Bin Gong Lin Wan Wendong Ma Philip E. Thompson Kai Yang Bing Yuan Falk Schreiber Lushan Wang Tony Velkov Kade D. Roberts Jian Li 《Chemical science》2021,12(36):12211
Multidrug-resistant Gram-negative bacteria represent a major medical challenge worldwide. New antibiotics are desperately required with ‘old’ polymyxins often being the only available therapeutic option. Here, we systematically investigated the structure–activity relationship (SAR) of polymyxins using a quantitative lipidomics-informed outer membrane (OM) model of Acinetobacter baumannii and a series of chemically synthesized polymyxin analogs. By integrating chemical biology and all-atom molecular dynamics simulations, we deciphered how each residue of the polymyxin molecule modulated its conformational folding and specific interactions with the bacterial OM. Importantly, a novel designed polymyxin analog FADDI-287 with predicted stronger OM penetration showed improved in vitro antibacterial activity. Collectively, our study provides a novel chemical biology and computational strategy to expedite the discovery of new-generation polymyxins against life-threatening Gram-negative ‘superbugs’.Multidrug-resistant Gram-negative bacteria have been an urgent threat to global public health. Novel antibiotics are desperately needed to combat these ''superbugs''. 相似文献
976.
977.
978.
硅氮化合物的结构与水解稳定性的关系 总被引:1,自引:0,他引:1
采用硅氮化合物本体与水蒸汽直接作用的方法,研究了一系列硅氮化合物的结构与水解稳定性之间的关系.结果表明,空间位阻越大则硅氮化合物水解稳定性越好,环张力对硅氮烷的水解稳定性有一定的影响,但空间位阻的作用更为显著.带有苯基的环二硅氮烷、六苯基环三硅氮烷和含硅氮键的高分子聚合物具有较大的空间位阻,因此水解稳定性非常好. 相似文献
979.
Zhang Z Blom DA Gai Z Thompson JR Shen J Dai S 《Journal of the American Chemical Society》2003,125(25):7528-7529
One-dimensional (1D) magnetic nanomaterials have attracted much attention recently because of their applications in magnetic recording and spintronics. Nevertheless, it remains a challenge to prepare free-standing magnetic nanowires in high yield. This Communication reports the successful high-yield synthesis of an interesting 1D ferromagnetic CoPt alloy by direct decomposition of platinum acetylacetonate and cobalt carbonyl compound in ethylenediamine solvent through a solvothermal reaction. The CoPt alloy nanowires obtained have a tunable diameter of 10-50 nm and a length along the longitudinal axis of up to several microns, depending on crystallization temperature and reaction time. A unique formation mechanism involving coarsening and ripening under solvothermal conditions was discovered. This research opens new opportunities in synthesizing nanomaterials through low-temperature solvothermal processes. 相似文献
980.