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   8350篇
  免费   1354篇
  国内免费   665篇
化学   5700篇
晶体学   88篇
力学   492篇
综合类   36篇
数学   999篇
物理学   3054篇
  2024年   11篇
  2023年   161篇
  2022年   243篇
  2021年   267篇
  2020年   364篇
  2019年   306篇
  2018年   267篇
  2017年   250篇
  2016年   413篇
  2015年   405篇
  2014年   459篇
  2013年   578篇
  2012年   775篇
  2011年   751篇
  2010年   529篇
  2009年   488篇
  2008年   551篇
  2007年   419篇
  2006年   456篇
  2005年   330篇
  2004年   263篇
  2003年   218篇
  2002年   172篇
  2001年   143篇
  2000年   148篇
  1999年   175篇
  1998年   155篇
  1997年   127篇
  1996年   131篇
  1995年   112篇
  1994年   97篇
  1993年   81篇
  1992年   79篇
  1991年   76篇
  1990年   45篇
  1989年   38篇
  1988年   39篇
  1987年   35篇
  1986年   28篇
  1985年   21篇
  1984年   20篇
  1983年   21篇
  1982年   9篇
  1981年   14篇
  1980年   9篇
  1977年   6篇
  1976年   10篇
  1975年   9篇
  1973年   8篇
  1972年   6篇
排序方式: 共有10000条查询结果,搜索用时 662 毫秒
361.
A new metal-organic coordination polymer [Zn(Pydc)(Dppz)] n (I) (H2Pydc = 2,6-pyridinedicarboxylic acid, Dppz = dipyrido[3,2-a:2′,3′-c]phenazine) was hydrothermally synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. The X-ray diffraction analysis reveals that I crystallizes in the monoclinic system, space group P21/c. The Pydc2? ligands adopt O,N,O′-tridentate chelating and monodentate bridging coordination mode to link two adjacent Zn2+ ions to form a one-dimensional (1D) zigzag chain. The adjacent chains are further linked through hydrogen bonds and π-π stacking interactions, forming a three-dimensional (3D) supramolecular framework. The unit cell parameters for I: a = 7.332(3) Å, b = 36.023(9) Å, c = 7.8838(13) Å, β = 105.65(3), V = 2005.1(10) Å3, Z = 4.  相似文献   
362.
The title cobalt(II) coordination polymer, [Co(Atibdc)(Dpa)] n (I) (H2Atibdc = 5-amino-2,4,6-triiodoisophthalic acid, Dpa = 2,2′-dipyridylanine), has been synthesized under solvothermal conditions and characterized by elemental analysis, IR, and X-ray crystallography structural analysis. Complex I exhibits a one-dimensional chain structure in which 5-amino-2,4,6-triiodoisophthalate as a bridging ligand interconnects adjacent two Co(II) centers to form a helical chain structure. The asymmetric unit includes one Co(II) center, one atibdc ligand, and one Dpa ligand. Each Co(II) center is five-coordinated and surrounded by two nitrogen atoms and three oxygen atoms from one Dpa ligand and two individual Atibdc ligands, leading to distorted trigonal bipyramid geometry. Adjacent chains are further linked through hydrogen bonds, C-H-π and π-π stacking interactions to form a three-dimensional supramolecular framework.  相似文献   
363.
The results of calorimetric study and thermal analysis of binary Al–Sn system are presented in this paper. The Oelsen calorimetry was used in thermodynamic analysis. Following thermodynamic properties were determined at 727 °C: activities, activity coefficients, partial/integral molar Gibbs excess, and mixing energies. The energetics of mixing in liquid Al–Sn alloys has been analyzed through the study of concentration fluctuation in the long-wavelength limit. Thermal analysis of selected alloys in Al–Sn system was done using differential thermal analysis. Defined characteristic phase transition temperatures were used for comparison with calculated phase diagram of investigated system. Good agreement with available literature data was obtained. Structural analysis of selected alloys was done using optic microscopy.  相似文献   
364.
5-Aminoindole and 3,4-ethylenedioxythiophene (EDOT) were copolymerized electrochemically on a carbon cloth (CC) electrode in an aqueous sulfuric acid solution. The as-prepared copolymer was characterized by cyclic voltammogram, SEM, and UV-vis and FT-IR spectra through which the electrochemical properties, structure, and composition of the as-obtained copolymer were determined. The electrochemical activity and stability of the as-formed copolymer are significantly improved in comparison with poly(5-aminoindole) due to the incorporation of EDOT units into the conjugated chain. The copolymer film-modified CC electrode was used as substrate for Pt particle deposition (denoted as Pt/copolymer/CC), and then, its catalytic activity towards formic acid electrooxidation was studied. Experimental results indicate that the catalytic activity of Pt/copolymer/CC towards formic acid electrooxidation is enhanced in comparison with that of Pt/homopolymer/CC, which can be attributed to the homogeneous distribution of Pt nanoparticles on the copolymer/CC substrate and the improved electrochemical activity of the copolymer film.  相似文献   
365.
Li2FeSiO4/C cathode materials have been prepared using the conventional solid-state method by varying the sintering temperature (650 °C, 700 °C and 750 °C), and the structure and electrochemical performance of Li2FeSiO4/C materials are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge–discharge tests, respectively. The results show that Li2FeSiO4 nano-crystals with a diameter of about 6–8 nm are inbedded in the amorphous carbon, and the Li2FeSiO4/C material obtained at 700 °C exhibits an initial discharge capacity of 195 mA?h g?1 at 1/16 C in the potential range of 1.5–4.8 V. The excellent electrochemical performance of Li2FeSiO4/C attributes to the improvement of conductivity and reduction of impurity by the optimization of the sintering temperature.  相似文献   
366.
An approximate method has been established to calculate the depth of the potential acting on an electron in a molecule at the saddle point along a chemical bond, denoted by Dpb. It is a new indicator which can be used for predicting the strength of a chemical bond. In this work, as a practical application for demonstrating thismethod, we calculated the Dpb of deoxyribonucleosides and ribonucleosides along all C-H and N-H chemical bonds using the method. The results are in fair agreement with those results of previously reported experimental and theoretical observations.  相似文献   
367.
建立在硝酸介质中用氢化物发生-原子荧光光谱法同时测定水中砷和锑的方法。优化了仪器工作条件、酸度、硼氢化钾及还原剂浓度。砷、锑的线性范围为0~10.0μg/L;检出限分别为0.02,0.01μg/L;测定结果的相对标准偏差分别为1.77%~3.72%,2.95%~4.87%(n=6);加标回收率分别为98%106%,96%105%。该法操作简便,灵敏度高,快速,便于推广,适用于水中砷和锑的同时测定。  相似文献   
368.
In the present work, a sensitive, facile and disposable sensing platform for trace analysis of heavy metal ions was developed at the Bi modified graphene‐poly(sodium 4‐styrenesulfonate) composite film screen printed electrode (GR/PSS/Bi/SPE). The GR/PSS/Bi/SPE improved sensitivity and linearity due to the functionalization of graphene with negatively charged PSS providing more absorbing sites. The detection limit of the GR/PSS/Bi/SPE is found to be 0.042 µg L?1 for Cd2+ and 0.089 µg L?1 for Pb2+ with linear responses of Cd2+ and Pb2+ in the range of 0.5–120 µg L?1. Finally, the practical application was confirmed in real water with satisfactory results.  相似文献   
369.
Hollow multilayer microcapsules made of aliphatic poly(urethane‐amine) (PUA) and sodium poly(styrene sulfonate) (PSS), templated on PSS‐doped CaCO3 particles, are prepared for pH‐/thermally responsive drug delivery. The electrostatic interaction and hydrogen bonding under weak‐acid conditions between aliphatic PUA and PSS contribute to the formation of multilayer microcapsules. Scanning electron microscopy (SEM) results demonstrate an obvious variation of the hollow multilayer microcapsules in response to changes in temperature and pH value. Drug‐release behaviors using DOX as a model drug demonstrate that the drug release increases on decreasing the pH value because of the interaction weakness between aliphatic PUA and PSS in acidic conditions. Moreover, the drug release is higher at 55 °C than that at 37 °C for the sake of the shrinkage of aliphatic PUA above its lower critical solution temperature (LCST).

  相似文献   

370.
An ultrasound‐enhanced in situ solvent formation microextraction has been developed first time and compared with ultrasound‐enhanced ionic‐liquid‐assisted dispersive liquid–liquid microextraction for the HPLC analysis of acaricides in environmental water samples. A ionic liquid ([C8MIM][PF6]) was used as the green extraction solvent through two pathways. The experimental parameters, such as the type and volume of both of the extraction solvent disperser solvent, ultrasonication time, and salt addition, were investigated and optimized. The analytical performance using the optimized conditions proved the feasibility of the developed methods for the quantitation of trace levels of acaricides by obtaining limits of detection that range from 0.54 to 3.68 μg/L. The in situ solvent formation microextraction method possesses more positive characteristics than the ionic‐liquid‐assisted dispersive liquid–liquid microextraction method (except for spirodiclofen determination) when comparing the validation parameters. Both methods were successfully applied to determining acaricides in real water samples.  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