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   1678篇
  免费   257篇
  国内免费   167篇
化学   1246篇
晶体学   19篇
力学   69篇
综合类   6篇
数学   176篇
物理学   586篇
  2024年   2篇
  2023年   41篇
  2022年   71篇
  2021年   73篇
  2020年   84篇
  2019年   72篇
  2018年   58篇
  2017年   58篇
  2016年   80篇
  2015年   92篇
  2014年   102篇
  2013年   121篇
  2012年   161篇
  2011年   179篇
  2010年   110篇
  2009年   96篇
  2008年   102篇
  2007年   98篇
  2006年   84篇
  2005年   68篇
  2004年   65篇
  2003年   32篇
  2002年   31篇
  2001年   10篇
  2000年   24篇
  1999年   27篇
  1998年   31篇
  1997年   19篇
  1996年   23篇
  1995年   15篇
  1994年   16篇
  1993年   5篇
  1992年   7篇
  1991年   7篇
  1990年   12篇
  1989年   2篇
  1988年   2篇
  1987年   6篇
  1986年   9篇
  1985年   1篇
  1984年   1篇
  1983年   3篇
  1982年   1篇
  1981年   1篇
排序方式: 共有2102条查询结果,搜索用时 15 毫秒
111.
The development of ultrastable carbon materials for potassium storage poses key limitations caused by the huge volume variation and sluggish kinetics. Nitrogen-enriched porous carbons have recently emerged as promising candidates for this application; however, rational control over nitrogen doping is needed to further suppress the long-term capacity fading. Here we propose a strategy based on pyrolysis–etching of a pyridine-coordinated polymer for deliberate manipulation of edge-nitrogen doping and specific spatial distribution in amorphous high-surface-area carbons; the obtained material shows an edge-nitrogen content of up to 9.34 at %, richer N distribution inside the material, and high surface area of 616 m2 g−1 under a cost-effective low-temperature carbonization. The optimized carbon delivers unprecedented K-storage stability over 6000 cycles with negligible capacity decay (252 mA h g−1 after 4 months at 1 A g−1), rarely reported for potassium storage.  相似文献   
112.
The colinearity of canonical modular polyketide synthases, which creates a direct link between multienzyme structure and the chemical structure of the biosynthetic end-product, has become a cornerstone of knowledge-based genome mining. Herein, we report genetic and enzymatic evidence for the remarkable role of an enoylreductase in the polyketide synthase for azalomycin F biosynthesis. This internal enoylreductase domain, previously identified as acting only in the second of two chain extension cycles on an initial iterative module, is shown to also catalyze enoylreduction in trans within the next module. The mechanism for this rare deviation from colinearity appears to involve direct cross-modular interaction of the reductase with the longer acyl chain, rather than back transfer of the substrate into the iterative module, suggesting an additional and surprising plasticity in natural PKS assembly-line catalysis.  相似文献   
113.
Ultraviolet B (UVB) radiation is known as a culprit in skin carcinogenesis. We have previously reported that bucillamine (N-[2-mercapto-2-methylpropionyl]-L-cysteine), a cysteine derivative with antioxidant and anti-inflammatory capacity, protects against UVB-induced p53 activation and inflammatory responses in mouse skin. Since MAPK signaling pathways regulate p53 expression and activation, here we determined bucillamine effect on UVB-mediated MAPK activation in vitro using human skin keratinocyte cell line HaCaT and in vivo using SKH-1 hairless mouse skin. A single low dose of UVB (30 mJ cm−2) resulted in increased JNK/MAPK phosphorylation and caspase-3 cleavage in HaCaT cells. However, JNK activation and casaspe-3 cleavage were inhibited by pretreatment of HaCaT cells with physiological doses of bucillamine (25 and 100 µm ). Consistent with these results, bucillamine pretreatment in mice (20 mg kg−1) inhibited JNK/MAPK and ERK/MAPK activation in skin epidermal cells at 6–12 and 24 h, respectively, after UVB exposure. Moreover, bucillamine attenuated UVB-induced Ki-67-positive cells and cleaved caspase-3-positive cells in mouse skin. These findings demonstrate that bucillamine inhibits UVB-induced MAPK signaling, cell proliferation and apoptosis. Together with our previous report, we provide evidence that bucillamine has a photoprotective effect against UV exposure.  相似文献   
114.
建立了毛细管电泳高频电导法同时测定地芬诺酯和阿托品的方法。探讨了缓冲溶液、有机溶剂添加剂、分离电压和进样条件以及毛细管内径和长度等因素对分离检测的影响。在电泳介质为10.0mmol/L乳酸-15.0?H5OH、分离电压20.0kV的优化条件下,6min内即可实现地芬诺酯和阿托品的同时分离检测,线性范围分别为5.00~500和2.00~320mg/L;检出限分别为3.0和1.0mg/L。  相似文献   
115.
Composite materials and their applications constitute a hot field of research nowadays due to the fact that they comprise a combination of the unique properties of each component of which they consist. Very often, they exhibit better performance and properties compared to their combined building blocks. Graphene oxide (GO), as the most widely used derivative of graphene, has attracted widespread attention because of its excellent properties. Abundant oxygen-containing functional groups on GO can provide various reactive sites for chemical modification or functionalization of GO, which in turn can be used to develop novel GO-based composites. This review outlines the most recent advances in the field of novel dyes and pigments encompassing GO as a key ingredient or as an important cofactor. The interactions of graphene with other materials/compounds are highlighted. The special structure and unique properties of GO have a great effect on the performance of fabricated hybrid dyes and pigments by enhancing the color performance of dyes, the anticorrosion properties of pigments, the viscosity and rheology of inks, etc., which further expands the applications of dyes and pigments in dyeing, optical elements, solar-thermal energy storage, sensing, coatings, and microelectronics devices. Finally, challenges in the current development as well as the future prospects of GO-based dyes and pigments are also discussed. This review provides a reference for the further exploration of novel dyes and pigments.  相似文献   
116.
The purpose of this paper was to investigate the effect of high-intensity ultrasonication (HIU) pretreatment before enzymolysis on structural conformations of walnut protein isolate (WPI) and antioxidant activity of its hydrolysates. Aqueous WPI suspensions were subjected to ultrasonic processing at different power levels (600–2000 W) and times (5–30 min), and then changes in the particle size, zeta (ζ) potential, and structure of WPI were investigated, and antioxidant activity of its hydrolysates was determined. The particle size of the particles of aqueous WPI suspensions was decreased after ultrasound, indicating that sonication destroyed protein aggregates. The ζ-potential values of a protein solution significantly changed after sonication, demonstrating that the original dense structure of the protein was destroyed. Fourier transform infrared spectroscopy indicated a change in the secondary structure of WPI after sonication, with a decrease in β-turn and an increase in α-helix, β-sheet, and random coil content. Two absorption peaks of WPI were generated, and the fluorescence emission intensity of the proteins decreased after ultrasonic treatment, indicating that the changes in protein tertiary structure occurred. Moreover, the degree of hydrolysis and the antioxidant activity of the WPI hydrolysates increased after sonication. These results suggest that HIU pretreatment is a potential tool for improving the functional properties of walnut proteins.  相似文献   
117.
为了给光锥与时间延迟积分电荷耦合器件耦合监控装置提供有效的被测运动条纹,分析了传统推扫成像实验装置的不足之处,设计了电子显示目标滚屏运动装置.采用光学相机对印刷条纹静止成像,并用TDI-CCD数字相机对监视器屏幕上的运动条纹动态成像.实验结果表明,该方案解决了高分辨率的鉴别率图样无法在监视器或投影仪上精确显示的困难.与传统的实验室模拟装置相比,该方案提高了鉴别率条纹的运动稳定性,减小了条纹运动速率与TDI-CCD扫描行频间的失配误差,不仅能够对耦合过程实施监控,而且还能用于耦合系统的像质评价.  相似文献   
118.
Effective hydrodeoxygenation (HDO) of aromatic alcohols is very attractive in both conventional organic synthesis and upgrading of biomass-derived molecules, but the selectivity of this reaction is usually low because of the competitive hydrogenation of the unsaturated aromatic ring and the hydroxyl group. The high activity of noble metal-based catalysts often leads to undesired side reactions (e.g., saturation of the aromatic ring) and excessive hydrogen consumption. Non-noble metal-based catalysts suffer from unsatisfied activity and selectivity and often require harsh reaction conditions. Herein, for the first time, we report chemoselective HDO of various aromatic alcohols with excellent selectivity, using porous carbon–nitrogen hybrid material-supported Co catalysts. The C–OH bonds were selectively cleaved while leaving the aromatic moiety intact, and in most cases the yields of targeted compounds reached above 99% and the catalyst could be readily recycled. Nitrogen doping on the carbon skeleton of the catalyst support (C–N matrix) significantly improved the yield of the targeted product. The presence of large pores and a high surface area also improved the catalyst efficiency. This work opens the way for efficient and selective HDO reactions of aromatic alcohols using non-noble metal catalysts.

Porous carbon–nitrogen hybrid material-supported Co catalysts can effectively promote the chemoselective hydrodeoxygenation reaction of a various of aromatic alcohols in ethanol and hydrogen atmosphere, under relatively mild conditions.  相似文献   
119.
Foaming effect strongly impacts the physical and mechanical properties of foam glass materials, but an understanding of its mechanism especially at the molecular level is still limited. In this study, the foaming effects of dextrin, a mixture of dextrin and carbon, and different carbon allotropes are investigated with respect to surface morphology as well as physical and mechanical properties, in which 1 wt.% carbon black is identified as an optimal choice for a well-balanced material property. More importantly, the different foaming effects are elucidated by all-atomistic molecular dynamics simulations with molecular-level insights into the structure–property relationships. The results show that smaller pores and more uniform pore structure benefit the mechanical properties of the foam glass samples. The foam glass samples show excellent chemical and thermal stability with 1 wt.% carbon as the foaming agent. Furthermore, the foaming effects of CaSO4 and Na2HPO4 are investigated, which both create more uniform pore structures. This work may inspire more systematic approaches to control foaming effect for customized engineering needs by establishing molecular-level structure–property–process relationships, thereby, leading to efficient production of foam glass materials with desired foaming effects.  相似文献   
120.
光纤生物传感器用于核酸的特异性检测   总被引:15,自引:2,他引:15  
为了利用光纤传感器实现对细菌核酸分子的特异性和相对快速检测,我们使用直径1mm的石英光纤和635nm激光二极管,利用倏逝波原理制作了光纤生物传感器。光纤经过处理后产生醛基化基团,然后与核酸分子进行共价结合。通过3个实验来验证传感器的特异性和灵敏度。蒌光素溶液直接检测,使用互补模式寡核苷酸分子(25mer)进行核酸杂交模式实验和设计嗜肺军团菌一段特异性探针一 光标记嗜肺军团菌染色体DNA杂交。结果表明:光纤检测荧光素的灵敏度可达0.01mmol/L,而生物芯片扫描仪最低可检测到1nmol/L的荧光素;模式寡 核苷酸杂交表明:光纤传感器可以特异地检出目的核酸分子,灵敏度可达纳克级水平;染色体杂交结果显示在正常检测浓度下,光纤检测军团菌之信噪比达到了6:1,同时具有较好的特异性。检测时间约需要3-4h。我们构建的光纤生物传感器可以用于核酸分子的特异性检测,并且具有较好的灵敏度,对光纤表面修饰、样品处理和杂交过程的优化可望使之应用于实际标本的检测。  相似文献   
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