首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   4289篇
  免费   213篇
  国内免费   18篇
化学   2764篇
晶体学   16篇
力学   86篇
数学   659篇
物理学   995篇
  2023年   31篇
  2022年   40篇
  2021年   63篇
  2020年   81篇
  2019年   78篇
  2018年   75篇
  2017年   78篇
  2016年   182篇
  2015年   147篇
  2014年   126篇
  2013年   237篇
  2012年   293篇
  2011年   317篇
  2010年   182篇
  2009年   132篇
  2008年   266篇
  2007年   230篇
  2006年   195篇
  2005年   214篇
  2004年   178篇
  2003年   163篇
  2002年   146篇
  2001年   58篇
  2000年   45篇
  1999年   54篇
  1998年   42篇
  1997年   33篇
  1996年   47篇
  1995年   26篇
  1994年   40篇
  1993年   46篇
  1992年   50篇
  1991年   30篇
  1990年   39篇
  1989年   35篇
  1988年   41篇
  1987年   29篇
  1986年   30篇
  1985年   57篇
  1984年   35篇
  1983年   23篇
  1982年   20篇
  1981年   25篇
  1980年   18篇
  1979年   26篇
  1977年   23篇
  1976年   17篇
  1975年   16篇
  1974年   23篇
  1973年   20篇
排序方式: 共有4520条查询结果,搜索用时 15 毫秒
901.
Optical absorption of vitreous GeSb2Se4 was studied in spectral region 0.7–25 μm. At low absorption levels near the edge the absorption coefficient K depends exponentially on energy. At high absorption levels the quadratical energy dependence of K is observed. In the present work we determined the optical energy gap Eoptg = 1.29 eV and discussed the temperature dependence of the absorption coefficient. Measured reflectivity curves were used to estimate the value of the refractive index of GeSb2Se4 (n = 3.13–3.56 ath?ω = 1.00–1.70 eV). Vitreous GeSb2Se4 is also transparent in the spectral interval 2–15.7 μm.  相似文献   
902.
We report the crystal structure of a new polymorph of l-tyrosine (denoted the β polymorph), prepared by crystallization from the gas phase following vacuum sublimation. Structure determination was carried out by combined analysis of three-dimensional electron diffraction (3D-ED) data and powder X-ray diffraction (XRD) data. Specifically, 3D-ED data were required for reliable unit cell determination and space group assignment, with structure solution carried out independently from both 3D-ED data and powder XRD data, using the direct-space strategy for structure solution implemented using a genetic algorithm. Structure refinement was carried out both from powder XRD data, using the Rietveld profile refinement technique, and from 3D-ED data. The final refined structure was validated both by periodic DFT-D calculations, which confirm that the structure corresponds to an energy minimum on the energy landscape, and by the fact that the values of isotropic 13C NMR chemical shifts calculated for the crystal structure using DFT-D methodology are in good agreement with the experimental high-resolution solid-state 13C NMR spectrum. Based on DFT-D calculations using the PBE0-MBD method, the β polymorph is meta-stable with respect to the previously reported crystal structure of l-tyrosine (now denoted the α polymorph). Crystal structure prediction calculations using the AIRSS approach suggest that there are three other plausible crystalline polymorphs of l-tyrosine, with higher energy than the α and β polymorphs.

A new polymorph of l-tyrosine is reported, with the crystal structure determined by combined analysis of 3D-ED data and powder XRD data, augmented by information from periodic DFT-D calculations and solid-state 13C NMR data.  相似文献   
903.
The use of nanomaterials rationally engineered to treat cancer is a burgeoning field that has reported great medical achievements. Iron-based polymeric nano-formulations with precisely tuned physicochemical properties are an expanding and versatile therapeutic strategy for tumor treatment. Recently, a peculiar type of regulated necrosis named ferroptosis has gained increased attention as a target for cancer therapy. Here, we show for the first time that novel iron oxide nanoparticles coated with gallic acid and polyacrylic acid (IONP–GA/PAA) possess intrinsic cytotoxic activity on various cancer cell lines. Indeed, IONP–GA/PAA treatment efficiently induces ferroptosis in glioblastoma, neuroblastoma, and fibrosarcoma cells. IONP–GA/PAA-induced ferroptosis was blocked by the canonical ferroptosis inhibitors, including deferoxamine and ciclopirox olamine (iron chelators), and ferrostatin-1, the lipophilic radical trap. These ferroptosis inhibitors also prevented the lipid hydroperoxide generation promoted by the nanoparticles. Altogether, we report on novel ferroptosis-inducing iron encapsulated nanoparticles with potent anti-cancer properties, which has promising potential for further in vivo validation.  相似文献   
904.
Nitrogen-containing heterocycles represent the majority of FDA-approved small-molecule pharmaceuticals. Herein, we describe a synthetic method to produce saturated N-heterocyclic drug scaffolds with an internal alkyne for elaboration. The treatment of N,N-dimethylhydrazinoalkenes with Et2Zn, followed by a Cu(I)-catalyzed cross-coupling with 1-bromoalkynes, results in piperidines and pyrrolidines with a good yield. Five examples are reported and a proposed mechanism for the Cu(I)-catalyzed cross-coupling is presented.  相似文献   
905.
With an ever-growing emphasis on sustainable synthesis, aerobic C–H activation (the use of oxygen in air to activate C–H bonds) represents a highly attractive conduit for the development of novel synthetic methodologies. Herein, we report the air mediated functionalisation of various saturated heterocycles and ethers via aerobically generated radical intermediates to form new C–C bonds using acetylenic and vinyl triflones as radical acceptors. This enables access to a variety of acetylenic and vinyl substituted saturated heterocycles that are rich in synthetic value. Mechanistic studies and control reactions support an aerobic radical-based C–H activation mechanism.

Herein we disclose a novel method for the aerobic C–H activation of ethereal-based heterocycles to generate various α-functionalised building blocks.  相似文献   
906.
The production of widely used polymers such as polyester currently relies upon the chemical separation of and transformation of xylene isomers. The least valuable but most prevalent isomer is meta-xylene which can be selectively transformed into the more useful and expensive para-xylene isomer using a zeolite catalyst but at a high energy cost. In this work, high-throughput screening of existing and hypothetical zeolite databases containing more than two million structures was performed, using a combination of classical simulation and deep neural network methods to identify promising materials for selective adsorption of meta-xylene. Novel anomaly detection techniques were applied to the heavily biased classification task of identifying structures with a selectivity greater than that of the best performing existing zeolite, ZSM-5 (MFI topology). Eight hypothetical zeolite topologies are found to be several orders of magnitude more selective towards meta-xylene than ZSM-5 which may provide an impetus for synthetic efforts to realise these promising materials. Moreover, the leading hypothetical frameworks identified from the screening procedure require a markedly lower operating temperature to achieve the diffusion seen in existing materials, suggesting significant energetic savings if the frameworks can be realised.

A combination of machine learning and high throughput simulation has identified several potential zeolite structures that appear to outperform the leading commercially used material and explained the key factors for high selectivity.  相似文献   
907.
Human telomeric DNA, in G-quadruplex (G4) conformation, is characterized by a remarkable structural stability that confers it the capacity to resist to oxidative stress producing one or even clustered 8-oxoguanine (8oxoG) lesions. We present a combined experimental/computational investigation, by using circular dichroism in aqueous solutions, cellular immunofluorescence assays and molecular dynamics simulations, that identifies the crucial role of the stability of G4s to oxidative lesions, related also to their biological role as inhibitors of telomerase, an enzyme overexpressed in most cancers associated to oxidative stress.  相似文献   
908.
909.
910.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号