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   4176篇
  免费   132篇
  国内免费   10篇
化学   2253篇
晶体学   42篇
力学   127篇
数学   456篇
物理学   1440篇
  2022年   47篇
  2021年   64篇
  2020年   75篇
  2019年   75篇
  2018年   86篇
  2017年   59篇
  2016年   109篇
  2015年   80篇
  2014年   104篇
  2013年   253篇
  2012年   225篇
  2011年   263篇
  2010年   161篇
  2009年   149篇
  2008年   210篇
  2007年   206篇
  2006年   217篇
  2005年   183篇
  2004年   127篇
  2003年   115篇
  2002年   101篇
  2001年   75篇
  2000年   75篇
  1999年   53篇
  1998年   42篇
  1997年   40篇
  1996年   50篇
  1995年   49篇
  1994年   43篇
  1993年   57篇
  1992年   45篇
  1991年   34篇
  1990年   49篇
  1989年   40篇
  1988年   40篇
  1987年   39篇
  1986年   29篇
  1985年   45篇
  1984年   38篇
  1983年   40篇
  1982年   36篇
  1981年   37篇
  1980年   41篇
  1979年   33篇
  1978年   38篇
  1977年   33篇
  1976年   37篇
  1975年   31篇
  1974年   35篇
  1973年   37篇
排序方式: 共有4318条查询结果,搜索用时 31 毫秒
221.
A new Cu(II) coordination polymer, {[Cu(1,3-BIP)(TFBDC)]·DMF}n(1,1,3-BIP is a 1,3-bis(imidazole)propane, and H2TFBDC is 2,3,5,6-tetrafluoroterephthalic acid) was prepared under solvothermal conditions and characterized by single-crystal and powder X-ray diffraction, IR spectra, thermogravimetric analyses and elemental analyses. The single-crystal X-ray diffraction reveals that metal coordination polymer 1(MCP 1) shows a two-dimensional sheet layer structure, which is further reinforced through strong intermolecular hydrogen bonding to form a 3 D supramolecular framework. Furthermore, the photocatalytic experiment result indicates the degradation ratios of methyl orange(MO) reach 83.4% within 180 minutes when MCP 1 acts as catalyst.  相似文献   
222.
We report for the first time sinapic acid (SA) sensing based on nanocomposite comprising electrochemically tuned gold nanoparticles (EAuNPs) and solvothermally reduced graphene oxide (rGO). The synthesized EAuNPs, rGO, and EAuNPs‐rGO nanocomposite were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED), particle size analysis, and Raman spectroscopy. A proof‐of‐concept electrochemical sensor for SA was developed based on synthesized EAuNPs‐rGO nanocomposite, which was characterized by electrochemical techniques such as cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The developed sensor detected SA with a linear dynamic range (LDR) between 20 μM and 200 μM and detection limit (DL) of 33.43 (±0.21) nM (RSD<3.32 %). To show the useful purpose of the sensor probe in clinical applications, SA was detected in human urine samples, which showed the percentage recovery between 82.6 % and 92.8 %. Interferences due to various molecules such as L‐cystine, glycine, alanine, serum albumin, uric acid, citric acid, ascorbic acid, and urea were tested. Long‐term stability of the sensor probe was examined, which was found to be stable up to 6 weeks. The sensor fabricated using EAuNPs‐rGO nanocomposite has many attractive features such as; simplicity, rapidity, and label‐free detection; hence, it could be a method of choice for SA detection in various matrices.  相似文献   
223.
Bacterial trans‐acyltransferase polyketide synthases (trans‐AT PKSs) are multimodular megaenzymes that biosynthesize many bioactive natural products. They contain a remarkable range of domains and module types that introduce different substituents into growing polyketide chains. As one such modification, we recently reported Baeyer–Villiger‐type oxygen insertion into nascent polyketide backbones, thereby generating malonyl thioester intermediates. In this work, genome mining focusing on architecturally diverse oxidation modules in trans‐AT PKSs led us to the culturable plant symbiont Gynuella sunshinyii, which harbors two distinct modules in one orphan PKS. The PKS product was revealed to be lobatamide A, a potent cytotoxin previously only known from a marine tunicate. Biochemical studies show that one module generates glycolyl thioester intermediates, while the other is proposed to be involved in oxime formation. The data suggest varied roles of oxygenation modules in the biosynthesis of polyketide scaffolds and support the importance of trans‐AT PKSs in the specialized metabolism of symbiotic bacteria.  相似文献   
224.
Roy  A.  Mukherjee  R. 《Fluid Dynamics》2022,56(1):S1-S18

This paper identifies laminar separation bubbles at the root or span-wise midsection of a rectangular wing using direct surface pressure measurements in the wind tunnel and analyses their behavior at different Reynolds numbers and angles of attack. The separation, transition, and reattachment locations are determined as functions of the angles of attack and the Reynolds number. The transition structure and turbulence characteristics in the separated shear layer are studied using laser Doppler velocimetry. Surface pressure data and simultaneously acquired velocity signals are correlated to show the pattern of growing disturbances in the shear layer. Surface oil flow visualizations clarified the wingtip and separation bubble’s interactions near the leading edge of the wing at the higher angles of attack. Turbulence statistics are also calculated from the streamwise velocity distributions, and an apparent deviation is observed for the skewness and flatness values from the normal distributions in the near-wall region. The separation bubble effect on aerodynamic coefficients of a 3D rectangular wing root section is studied and reported.

  相似文献   
225.
226.
This paper presents a study of thermodynamic analysis of the solubility-temperature phase diagrams for solutions of calcium, strontium and barium tungstate in sodium tungstate melts in the temperature range 660 to 1200 °C. At temperatures 1000 °C and above, the solutions were ideal but below 1000 °C the solutions became non-ideal and the non-ideality increased with decreasing temperature. At any mole fraction concentration of the solute the excess free energies of mixing and the activity coefficients increased in the order CaWO4 > SrWO4 > BaWO4, whereas the excess chemical potentials decreased in the order CaWO4 < SrWO4 < BaWO4.  相似文献   
227.
228.
The preparation and spectroscopic (1H NMR, UV and IR) characterization of three R3Sn(O2CCH2N(H)C(O)NH2) [R=Ph, c-Hex (cyclohexyl) or n-Bu] compounds are reported. A different mode of coordination is indicated for the hydantoate ligand in the R=Ph compound compared with the R=c-Hex and R=n-Bu compounds, as confirmed by a crystallographic analysis. The structure of [Ph3Sn(O2CCH2N(H)C(O)NH2)] is polymeric owing to the presence of bridging hydantoate ligands such that each ligand coordinates one tin atom, via one of the carboxylate oxygen atoms, and a symmetry-related tin atom via the carbonyl group at the other end of the molecule. The structure features distorted trigonal-bipyramidal tin atom geometries with a trans -R3SnO2 motif. The structure of [c-Hex3Sn(O2CCH2N(H)- C(O)NH2)], by contrast, is monomeric, distorted tetrahedral, as the carboxylate group is monodentate and there are no additional tin–ligand interactions. The structures are each stabilized by a number of intermolecular hydrogen bonds. Fungitoxicity and phytotoxicity studies indicate that the R=n-Bu derivative is the more active compound.  相似文献   
229.
Sinha BC  Roy SK 《Talanta》1975,22(9):763-765
The conventional method for separation of lead from a combined lead and barium sulphate precipitate by extraction with ammonium acetate has been critically studied. The results show that quantitative separation of lead is possible only when the molar concentration ratio of barium to lead is 4.2 or above, but at ratios below 4.2 the method fails because of the formation of a solid solution of lead and barium sulphates which is maximal at initial mole-ratio 0.42. The lead in the solid solution, however, forms a strong soluble complex with EDTA and can be quantitatively separated. Based on this, a gravimetric method has been worked out for determination of lead and barium in glass.  相似文献   
230.
Herein, we report the controlled and direct fabrication of Cu2O/CuO thin film on the conductive nickel foam using electrodeposition route for the electrochemical reduction of carbon dioxide (CO2) to methanol. The electrocatalytic reduction was performed in CO2 saturated aqueous solution consisting of KHCO3, pyridine and HCl at room temperature. CO2 reduction was carried out at a constant potential of −1.3 V for 120 min to study the electrochemical performance of the prepared electrocatalysts. Cu2O/CuO shows better electrocatalytic activity with highest current density of 46 mA/cm2. The prepared catalyst can be an efficient and selective electrode for the production of methanol.  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