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   951篇
  免费   233篇
  国内免费   137篇
化学   760篇
晶体学   8篇
力学   64篇
综合类   22篇
数学   106篇
物理学   361篇
  2024年   7篇
  2023年   28篇
  2022年   58篇
  2021年   44篇
  2020年   45篇
  2019年   37篇
  2018年   41篇
  2017年   29篇
  2016年   45篇
  2015年   55篇
  2014年   43篇
  2013年   68篇
  2012年   76篇
  2011年   87篇
  2010年   58篇
  2009年   64篇
  2008年   49篇
  2007年   45篇
  2006年   41篇
  2005年   35篇
  2004年   18篇
  2003年   111篇
  2002年   31篇
  2001年   21篇
  2000年   47篇
  1999年   22篇
  1998年   17篇
  1997年   15篇
  1996年   9篇
  1995年   15篇
  1994年   23篇
  1993年   5篇
  1992年   9篇
  1991年   4篇
  1990年   2篇
  1989年   4篇
  1988年   2篇
  1986年   1篇
  1985年   2篇
  1983年   1篇
  1982年   7篇
排序方式: 共有1321条查询结果,搜索用时 15 毫秒
991.
Zhuang Z  Su X  Yuan H  Sun Q  Xiao D  Choi MM 《The Analyst》2008,133(1):126-132
CuO nanowires have been prepared and applied for the fabrication of glucose sensors with highly enhanced sensitivity. Cu(OH)(2) nanowires were initially synthesised by a simple and fast procedure, CuO nanowires were then formed simply by removing the water through heat treatment. The structures and morphologies of Cu(OH)(2) and CuO nanowires were characterised by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy. The direct electrocatalytic oxidation of glucose in alkaline medium at CuO nanowire modified electrodes has been investigated in detail. Compared to a bare Cu electrode, a substantial decrease in the overvoltage of the glucose oxidation was observed at the CuO nanowire electrodes with oxidation starting at ca. 0.10 V vs. Ag/AgCl (saturated KCl). At an applied potential of 0.33 V, CuO nanowire electrodes produce high and reproducible sensitivity to glucose with 0.49 microA/micromol dm(-3). Linear responses were obtained over a concentration range from 0.40 micromol dm(-3) to 2.0 mmol dm(-3) with a detection limit of 49 nmol dm(-3) (S/N = 3). The CuO nanowire modified electrode allows highly sensitive, low working potential, stable, and fast amperometric sensing of glucose, thus is promising for the future development of non-enzymatic glucose sensors.  相似文献   
992.
以森田-贝里斯-希尔曼(MBH)碳酸酯和活泼亚甲基类化合物为原料,在叔胺的催化下,经历两次亲核取代反应得到关键叠氮中间体,再与三苯基膦作用经连续的Staudinger反应、分子内aza-Wittig反应及异构化等,在温和的反应条件下合成了17个新的多取代1,4-二氢喹啉类衍生物.中间体及目标化合物均为新化合物,其结构均经红外光谱、高分辨质谱、核磁共振氢谱和核磁共振碳谱确证.  相似文献   
993.
Pinus koraiensis nut-coated film is a kind of by-product of nut processing, which has been shown to contain flavonoids, polyphenols, and other substances that can be used to produce natural antioxidant extracts. In this study, response surface methodology (RSM) was used to optimize the extraction process of flavonoids of P. koraiensis nut-coated film (PNF), and macroporous resin HPD600 was used to purify PNF (P-PNF). Its antioxidant activity was examined by DPPH (1,1-diphenyl-2-picrylhydrazyl) radical scavenging capacity, oxygen free radical absorption capacity (ORAC), total oxygen radical capture (TRAP), and iron ion reduction capacity. Under the ideal extraction conditions comprising a cellulase dosage of 90 U/g, a material/liquid ratio of 1:20 (g/mL), and an extraction time of 2 h, the PNF yield was 3.37%. Purification conditions were sample concentration of 2.0 mg/mL, pH of 5, water washing volume of 3 bed volume (BV), eluent ethanol concentration of 50%, and volume of 2 BV. The P-PNF recovery was 84.32%, and purity increased from 33.80% to 61.70%. Additionally, P-PNF showed increased antioxidant activity compared to PNF. Cumulatively, this study obtained the optimal values for the process parameters in order to achieve the maximum rates of extraction of PNF for economically optimal production at an industrial scale.  相似文献   
994.
A highly stereoselective synthesis of chiral alpha-amino-beta-lactam through an ynamide-Kinugasa reaction is described. In addition, a mechanistic model is illustrated here to rationalize the observed diastereoselectivity, which depends on both the initial [3 + 2] cycloaddition step and the subsequent protonation for which both are highly selective.  相似文献   
995.
We have investigated the sensing performance of protein-based microcantilever biosensors prepared from multiple surface conjugation chemistries. The 11-mercaptoundecanoic acid monolayers were prepared according to both traditional and modified processes. In three protein-based biosensors, the modified process improved microcantilever sensing performance by increasing the bending amplitude, a critical step toward developing a cost-effective microcantilever-based sensor platform for medical diagnostics and environmental and drug screening applications. Scanning electron microscopy (SEM) images demonstrated that proteins immobilized on the microcantilever surface using the modified chemistry approach formed a compact layer.  相似文献   
996.
Eight kinds of density functionals named B3LYP, PBE1PBE, B1B95, BLYP, BP86, G96PW91, mPWPW91, and SVWN along with two different valence basis sets (LANL2DZ and CEP‐121g) are employed to study the transition‐metal dimers for the elements of group VIII. By comparing the equilibrium bond distances, vibrational frequencies, and dissociation energies of the ground state of these dimers with the available experimental values and theoretical data, we show that the “pure” DFT methods (G96PW91, BLYP, and BP86) with great‐gradient approximation always give better results relative to the hybrid HF/DFT schemes (B3LYP, PBE1PBE, and B1B95). The striking case found by us is that the G96PW91 functional, which is not tested in previous systemic studies, always predicts the dissociation energy to be well. The Ru2 and Os2 dimers are sensitive to not only the functionals employed but also the valence basis sets adopted. The natural bond orbital population is analyzed, and the molecular orbitals of the unpaired electrons are determined. Furthermore, our results indicate that the s and d orbitals of these dimers always hybridize with each other except for Rh2 and Pt2 molecules. And by analyzing the electron configuration of the bonding atom, the dissociation limit of the ground state is obtained. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008  相似文献   
997.
目前正交偶极子声波测井中广泛应用的各向异性反演方法为多参数联合反演的方法。该方法的目标函数由两部分构成:一是基于四分量旋转得到的快慢横波的波形匹配函数(简称主函数),二是主函数对方位求导后得到的辅助函数。该文深入研究了主函数与辅助函数以及二者的和(简称综合函数)随各向异性参数的变化特性与规律。数值模拟表明,主函数的最小值总是出现在各向异性大小为0、方位与快慢横波方位成45°的方位处,且在快横波方位上的地层各向异性大小附近存在极小值,该极值小于慢横波方位上的极小值;辅助函数在快慢横波方位上的值非常小,但在这两个方位上随各向异性大小变化不明显;综合函数可以反演出各向异性参数,但对方位的特性被弱化。  相似文献   
998.
A Mach–Zehnder interferometer (MZI) which is used as a wavelength-spacing tunable comb filter in a fiber ring laser is built by employing an optical variable delay line (OVDL). Stable multi-wavelength semiconductor optical amplifier (SOA)-fiber ring laser based on an SOA and the MZI comb filter is achieved. Wavelength spacing can be continuously tuned by adjusting the OVDL and, as an example, multi-wavelength lasing with the wavelength spacing of 0.4, 0.8, or 1.6 nm is demonstrated. The output of the proposed multi-wavelength SOA-fiber ring laser is quite stable at room temperature and the output spectrum can be adjusted by controlling the bias current of the SOA.  相似文献   
999.
王宏雁  委旭宁 《应用化学》2018,35(10):1184-1189
4-羟基香豆素类化合物与4-羟基喹啉酮类化合物是一类重要的有机杂环化合物,因为其良好的生理活性,被广泛应用于抗菌、抗炎、抗HIV、抗肿瘤等药物结构中。 本文用4-羟基香豆素类化合物或4-羟基喹啉酮类化合物作为底物、以硫磺粉(S)为硫源、以碘苯类衍生物作为芳基源,在氯化铜催化作用下合成了3-芳硫基-4-羟基香豆素类化合物和3-芳硫基-4-羟基喹啉酮类化合物。 该方法使用环境友好的硫磺粉为硫源替代有机硫,操作简单、无污染、成本低廉,为该类化合物的绿色合成提供了新的方案。  相似文献   
1000.
断续节理将对工程岩体的强度及变形等力学特性产生显著影响,损伤力学中视节理为岩体的一种宏观损伤,因而采用损伤张量来刻画其对岩体的影响。目前学术界提出了用节理的几何、强度及变形等3类参数来描述节理的物理力学性质,而目前的岩体损伤张量计算方法都只涉及前2类参数,均没有涉及其变形参数即法向及切向刚度。为此,在前人研究的基础上,基于断裂及损伤理论提出了考虑节理法向及切向刚度的单轴压缩下单条断续节理引起的损伤张量计算公式,进而通过考虑节理间相互作用给出了单组单排或多排节理岩体损伤张量计算公式。其次,以岩石细观动态损伤模型为基础,结合宏细观损伤耦合观点提出了一个能够同时考虑节理几何、强度及变形参数的断续节理岩体动态损伤本构模型。最后,利用该模型讨论了节理参数及载荷应变率等对岩体动态力学特性的影响,认为节理长度减小及摩擦角增大将导致岩体动态峰值强度及弹性模量增大;岩体动态峰值强度及弹性模量则随着节理法向及切向刚度的增大分别减小或增大;而当节理法向及切向刚度按照同一比例增大时,岩体动态峰值强度及弹性模量则是增大的。岩体动态峰值强度与载荷应变率呈正相关。  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