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   15156篇
  免费   605篇
  国内免费   158篇
化学   10274篇
晶体学   130篇
力学   472篇
综合类   10篇
数学   1504篇
物理学   3529篇
  2023年   86篇
  2022年   277篇
  2021年   333篇
  2020年   292篇
  2019年   264篇
  2018年   264篇
  2017年   240篇
  2016年   457篇
  2015年   414篇
  2014年   540篇
  2013年   938篇
  2012年   1127篇
  2011年   1238篇
  2010年   722篇
  2009年   594篇
  2008年   990篇
  2007年   916篇
  2006年   857篇
  2005年   795篇
  2004年   674篇
  2003年   540篇
  2002年   538篇
  2001年   342篇
  2000年   331篇
  1999年   205篇
  1998年   125篇
  1997年   129篇
  1996年   150篇
  1995年   144篇
  1994年   142篇
  1993年   124篇
  1992年   115篇
  1991年   84篇
  1990年   85篇
  1989年   62篇
  1988年   57篇
  1987年   48篇
  1986年   31篇
  1985年   58篇
  1984年   52篇
  1983年   35篇
  1982年   49篇
  1981年   46篇
  1980年   35篇
  1979年   52篇
  1978年   49篇
  1977年   43篇
  1976年   41篇
  1975年   33篇
  1974年   25篇
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A facile and green synthetic approach for fabrication of starch-stabilized magnetite nanoparticles was implemented at moderate temperature. This synthesis involved the use of iron salts, potato starch,sodium hydroxide and deionized water as iron precursors, stabilizer, reducing agent and solvent respectively. The nanoparticles(NPs) were characterized by UV-vis, PXRD, HR-TEM, FESEM, EDX, VSM and FT-IR spectroscopy. The ultrasonic assisted co-precipitation technique provides well formation of highly distributed starch/Fe_3O_4-NPs. Based on UV–vis analysis, the sample showed the characteristic of surface plasmon resonance in the presence of Fe_3O_4-NPs. The PXRD pattern depicted the characteristic of the cubic lattice structure of Fe_3O_4-NPs. HR-TEM analysis showed the good dispersion of NPs with a mean diameter and standard deviation of 10.68 4.207 nm. The d spacing measured from the lattice images were found to be around 0.30 nm and 0.52 nm attributed to the Fe3O4 and starch, respectively. FESEM analysis confirmed the formation of spherical starch/Fe_3O_4-NPs with the emission of elements of C, O and Fe by EDX analysis. The magnetic properties illustrated by VSM analysis indicated that the as synthesized sample has a saturation magnetization and coercivity of 5.30 emu/g and 22.898 G respectively.Additionally, the FTIR analysis confirmed the binding of starch with Fe_3O_4-NPs. This method was cost effective, facile and eco-friendly alternative for preparation of NPs.  相似文献   
992.
The use of liquid crystals (LCs) as anisotropic solvents is desired for various potential applications and usually for other organic and inorganic compounds. In this work, solvent polarity parameters are obtained using a spectroscopic method for four LCs with a range of high and low dielectric anisotropy (?ε). Solvatochromic polarity parameters for these LCs were defined via Kamlet–Abboud–Taft polarity functions characterizing different temperatures and phases, isotropic and anisotropic, and using the Reichardt’s dye and 2,6-diphenyl-4-(2,4,6-triphenyl-1-pyridinio) phenolate standard probe. The investigated polarity parameters reveal the effects of LC media on the photo-physical behaviour of solute molecules in isotropic and anisotropic media. Subsequently, a new LC polarity parameter (Zo) is introduced as an overall matrix anisotropy polarity parameter to characterize variation between isotropic and anisotropic phases. The values of Zo are sorted from higher to lower dielectric anisotropies (?ε).  相似文献   
993.
Acid–base and coordination properties of alkyl and aryl meso-substituted porphyrins are studied spectrophotometrically in nonaqueous solutions. It is found that the nature of the substituent greatly affects the basicity of ligands for porphyrins characterized by a flat structure of macrocycle. The electronic effects of substituents have a much weaker influence on the kinetics of complexing. These effects could be due to the opposite orientation of some factors: an increase in the basicity and stability of the N–H bonds of porphyrin reaction centers. Dissociation constants pK b of the cationic forms of meso-substituted derivatives of porphyrin are measured. The values of pK b are in good agreement with classic concepts of the nature of substituents, particularly those indirectly included in the macrocycle through phenyl buffer rings.  相似文献   
994.
The organization of polysaccharides in plant cell walls is important for the mechanics of plant cells. Spectral analysis of cell walls by polarized IR can reveal polysaccharide organization, but may be complicated by dipoles not aligned with the backbone. For instance, analysis of uniaxially-aligned cellulose Iβ film revealed that the dipole transition vector of the 1160 cm?1 band involving stretch vibrations of glycosidic C1–O–C4 linkages is approximately at 30° with respect to the backbone of the cellulose chain, because of coupling with C5–O–C1 bonds in the six-membered rings. In the case of homogalacturonan, the dipole transition vector of the ester carbonyl group vibration (νC=O, 1745 cm?1) is expected to be nearly normal to the homogalacturonan backbone. Using this information and the dichroism equation, the change in net orientation of cell wall polymers upon mechanical stretch was determined by polarized IR analysis. Never-dried abaxial outer epidermal cell walls of the second scale of onion bulb were mechanically stretched along longitudinal or transverse directions with respect to the long axis of the cells and then dried while under mechanical stretch. The average orientations of both 1160 and 1745 cm?1 vibration transition dipoles were rotated by ~5° and ~4°, respectively, along the stretch direction from their initial random distributions upon longitudinal strain by 14%; and by ~4° and ~3°, respectively, upon transverse strain by 12%. These results imply that both cellulose microfibrils and pectins in the cell wall are passively realigned along the stretch direction by external mechanical force. The analytical methodology developed here will be useful to study how cell wall polymers might reorganize during cell wall growth and development.  相似文献   
995.
磁性聚苯胺纳米微球的合成与表征   总被引:1,自引:0,他引:1  
报道了具有核壳结构的Fe3O4-聚苯胺磁性纳米微球的合成方法和表征结果.微球同时具有导电性和磁性能.在优化的实验条件下,可得到饱和磁化强度Ms为55.4 emu/g,矫顽力Hc为62 Oe的磁性微球.微球的导电性随着微球中Fe含量的增加而下降.微球的磁性能则随着Fe含量的增加而增大.Fe3O4磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级.纳米Fe3O4粒子能够提高复合物的热性能.实验表明,磁流体和聚苯胺之间可能存在着一定的相互作用,但这种相互作用较为复杂,难于研究  相似文献   
996.
997.
998.
The chiral phosphorus derivatizing agent (CDA) 1 was prepared from optically pure (S)‐1,1‐bis‐2‐naphthol. It was first used in the determination of the enantiomeric excess of chiral alcohols and amines by means of 31P NMR spectroscopy. It showed that, for the chiral aromatic alcohols, no apparent kinetic resolution was noted and good base‐line separation was observed. Furthermore, the chemical shift difference (Δδ) of 31P NMR spectroscopy was much larger than those determined by the use of other chiral phosphorus derivatizing agents reported previously. However, for aliphatic alcohols, it showed not only obvious kinetic resolutions but incomplete base‐line separation. Moreover, we also found that the use of CDA 1 was suitable for the determination of enantiomeric excess of chiral primary amines. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:93–95, 2002; DOI 10.1002/hc.10018  相似文献   
999.
The applicability of ATR-FTIR for the determination of the HDO content in heavy water (D2O) was investigated. Two groups of calibration standard solutions, of low contents (0–1 n% H2O in heavy water) and of higher contents (0–10 n% H2O in heavy water) were prepared by adding properly calculated amount of H2O to D2O by weight. The absorbances at 3400 cm−1 (ν, O–H) against the calibration standards were measured five times using two kinds of interchangeable IREs (1 bound and 9 bound reflections). And four calibration curves were obtained by linear least square fit of the measured absorbances for the four different measurement conditions, which are (1) for low contents group using 1 bound reflection, (2) for low contents group using 9 bound reflections, (3) for higher contents group using 1 bound reflection, (4) for higher contents group using 9 bound reflections. Determined contents (c 0) of each calibration standards for the four measurement conditions were obtained by the calibration curves and compared to the calculated contents (c cal). The uncertainty sources were considered when the HDO in heavy water is determined according to the procedure of this work. The uncertainties u(c 0) of the determined contents (c 0) for the four different measurement conditions were calculated.  相似文献   
1000.
Liang JL  Yuan SX  Chan PW  Che CM 《Organic letters》2002,4(25):4507-4510
[reaction: see text] Unsaturated sulfonamides underwent direct intramolecular aziridination catalyzed by Rh(2)(OAc)(4) with PhI(OAc)(2) and Al(2)O(3) to give the corresponding aziridine products in excellent yields (up to 98%) and with good to excellent conversions. High turnovers (up to 1375) were achieved. The intermolecular rhodium-catalyzed amidation of cholesteryl acetate with PhI=NTs or PhI(OAc)(2)/NH(2)R as the nitrogen source exhibited both excellent regio- and alpha-selectivity (alpha/beta ratio up to 9:1).  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