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   1971篇
  免费   294篇
  国内免费   220篇
化学   1513篇
晶体学   19篇
力学   81篇
综合类   9篇
数学   209篇
物理学   654篇
  2024年   2篇
  2023年   46篇
  2022年   59篇
  2021年   75篇
  2020年   105篇
  2019年   89篇
  2018年   65篇
  2017年   70篇
  2016年   102篇
  2015年   113篇
  2014年   128篇
  2013年   138篇
  2012年   193篇
  2011年   210篇
  2010年   132篇
  2009年   114篇
  2008年   134篇
  2007年   109篇
  2006年   105篇
  2005年   74篇
  2004年   70篇
  2003年   49篇
  2002年   42篇
  2001年   12篇
  2000年   26篇
  1999年   33篇
  1998年   37篇
  1997年   23篇
  1996年   28篇
  1995年   18篇
  1994年   16篇
  1993年   9篇
  1992年   9篇
  1991年   9篇
  1990年   14篇
  1989年   2篇
  1988年   2篇
  1987年   6篇
  1986年   10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2485条查询结果,搜索用时 15 毫秒
121.
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   
122.
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   
123.
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   
124.
偶氮苯衍生物因其具有特殊的共轭体系常用作光开关特性的三阶非线性光学(NLO)开关材料,但有部分带有特殊基团的偶氮类分子在一般条件下无法显示其性能.然而,这类分子在被调节之后能展示出优异的光控的NLO开关性能.以无光控的NLO开关性能的5-(N-4-偶氮苯基)氨甲基间苯二甲酸为研究对象,并对其潜在的光控NLO开关性能进行调控.经过调节后的这类分子在光照条件下能顺利地经历可逆的顺反异构化反应,且产生三阶非线性性能的转换.其Z-扫描实验结果显示处于反式构型的材料展示出反饱和吸收和自散焦特性;在光照之后,这类材料转化为顺式构型并展现出饱和吸收和自聚焦行为.三阶NLO性能的转换是由于材料的结构发生转变其内部电子产生重排,使得它们在激光刺激下产生不同的响应机制.  相似文献   
125.
Superwetting membranes with responsive properties have attracted heightened attention because of their fine‐tunable surface wettability. However, their functional diversity is severely limited by the “black‐or‐white” wettability transition. Herein, we describe a coating strategy to fabricate multifunctional responsive superwetting membranes with SiO2/octadecylamine patterns. The adjustable patterns in the responsive region are the key factor for functional diversity. Specifically, the coated part of the membrane displayed a superhydrophobicity/superhydrophilicity transition at different pH values, whereas the uncoated part exhibited invariant superhydrophilicity. On the basis of this anisotropy/isotropy transition, the membranes can serve as either responsive permeable membranes or signal‐expression membranes, thus enabling the responsive separation and permeation of liquids with satisfactory separation efficiency (>99.90 %) and flux (ca. 60 L m?2 h), as well as real‐time liquid signal expression with alterable signals.  相似文献   
126.
An ambient aerosol concentration enrichment system coupled with ICP-MS for real-time monitoring of airborne radioactive particles is now under development. ICP-MS is very sensitive to sample introduction conditions, so it is necessary to develop an easy-use calibration method for on-line quantitative analysis in field application. In this paper, a calibration method using standard solution instead of monodisperse particles was established and validated preliminarily. First of all, four parameters for the method were determined experimentally, including: uptake flow rate and nebulisation efficiency of the Microconcentric nebuliser, nebulisation/transport efficiency of Aridus Desolvating Sample Introduction System, and Relative Sensitivity Factor between 159?Tb and 174?Yb. Then, monodisperse terbium nitrate particles were generated by a commercial Vibrating Orifice Aerosol Generator. Continuous aerosols of ytterbium nitrate droplets were nebulised from standard solution. They were mixed together, desolvated through the membrane dryer and introduced into ICP-MS for on-line analysis of terbium nitrate particles. The air sampled from nuclear environment was also introduced into ICP-MS to investigate the effect of flow rate on instrument responses. Finally, atom numbers of 159?Tb in discrete terbium nitrate particles were determined using the calibration method and compared to the calculated value. Results show that when air flow rate increase from 10?mL?min?1 to 100?mL?min?1, the ratio of 159?Tb ion count to 174?Yb ion intensity keeps constant although instrument sensitivity decreases by a factor of 25. The relative standard deviation of 159?Tb atom number measured is better than 18%. The discrepancy with the calculated value could be attributed to the over-estimation of atom number in the particles generated by VOAG because there was some liquid leakage in the VOAG.  相似文献   
127.
Chinese herbal medicines(CHMs) play an increasingly important role in the field of medicine and affects public health in the world.Although more and more strict has been employed to ensure the quality and safety of CHMs,pesticide residues in CHMs remain a serious issue and are the bottleneck for the global development of CHMs.In this work,we applied molecularly imprinted membrane electrospray mass spectrometry(MIM-ESI MS) for rapid detecting 4 classes of pesticide residues in CHMs,including organophosphorus(OPP),carbamates,pyrethroids and neonicotinoids in CHMs.Compared with our previous ambient ionization method MESI,MIM-ESI is capable of achieving a ~50-fold increase in the detection limit of conventional analytical methods owing to the specificity recognition and unique enrichment of MIM.The optimal experimental conditions were determined,and the method was further validated for its sensitivity and specificity.Our data showed that MIM-ESI MS is applicable for the direct quantitation of pesticide residues in CHMs.This detection technology may help to ensure the quality of CHMs in the future.  相似文献   
128.
One-pot synthesis of benzylacetamide from oxime can be carried out in 80–95% yield at 35–40 °C under ultrasound irradiation. This method provided several advantages such as simple work-up procedure, shorter reaction time and higher yield.  相似文献   
129.
Structure and magnetic properties of Nb-doped (FeZrB)100−xNbx alloy are investigated by X-ray diffraction (XRD), differential scanning calorimetry and vibrating sample magnetometer. The fully amorphous structure of the as-quenched ribbons is confirmed by the XRD pattern. With increasing Nb, the glass transition temperature and the onset crystallization temperature are increased, indicating increased stability of the amorphous structure. For x=1, the saturation magnetization of the ribbons is 125.7 emu/g and the optimized annealing temperature increases from 550 to 630 °C. The morphology of the crystallized phases is observed by scanning electron microscopy. The results show that nanocrystalline α-Fe grains are dispersed in the amorphous matrix.  相似文献   
130.
Excimer laser emitting at 248 nm is applied to produce microstructures on the surface of aluminum alloy. The surface morphology shows that hotspots and thermal fluidic structures both come to light. Two possible mechanisms of hotspots formation are proposed: near-field diffraction and interference, and extremely fast rapid thermal annealing. And for the formation of thermal fluidic pattern structure, a thin film model is applied.  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