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   6312篇
  免费   1212篇
  国内免费   876篇
化学   3784篇
晶体学   88篇
力学   363篇
综合类   2篇
数学   247篇
物理学   3916篇
  2024年   5篇
  2023年   335篇
  2022年   257篇
  2021年   252篇
  2020年   397篇
  2019年   201篇
  2018年   266篇
  2017年   353篇
  2016年   394篇
  2015年   396篇
  2014年   469篇
  2013年   476篇
  2012年   560篇
  2011年   378篇
  2010年   435篇
  2009年   410篇
  2008年   318篇
  2007年   382篇
  2006年   435篇
  2005年   259篇
  2004年   201篇
  2003年   182篇
  2002年   180篇
  2001年   237篇
  2000年   117篇
  1999年   227篇
  1998年   119篇
  1997年   84篇
  1996年   55篇
  1995年   7篇
  1994年   1篇
  1993年   4篇
  1992年   3篇
  1991年   1篇
  1985年   3篇
  1971年   1篇
排序方式: 共有8400条查询结果,搜索用时 328 毫秒
111.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.  相似文献   
112.
A novel sulfonated poly(arylene ether) containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N'-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton's reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly (MEA) prepared with the asmade film (706 EW, 100 μm dry thickness) shows better cell performance than Nation 115-MEA in the whole current density range.  相似文献   
113.
郭明  孔亮  历欣  邹汉法 《色谱》2002,20(2):137-139
 用磺化四苯基卟啉 (TPPS4 )作柱前衍生试剂 ,在微波作用下进行衍生反应 ,研究了衍生和分离Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的最佳条件。在 75 0W的微波作用下衍生反应 3min ,在C18柱上采用乙腈 水 (体积比为 2 2 5∶77 5 )体系作流动相 ,四乙基溴化铵 (TEABr)作离子对试剂 ,在 415nm处检测 ,建立了微波衍生 离子对高效液相快速分离、光度检测Ni2 + ,Mn2 + ,Zn2 + 和Cu2 + 的新方法。络合物和反应试剂在 15min内出峰完毕。Zn2 + ,Cu2 + ,Ni2 + 和Mn2 + 的检测限分别为 0 0 5 μg/L ,0 0 1μg/L ,0 10 μg/L和 0 40 μg/L。  相似文献   
114.
Amphiphilic polypyridyl mthenium(Ⅱ) complex cis-di(isothiocyanato)(4,4'-di-tert-butyl-2,2'-bipyridyl)(4,4'- dicarboxy-2,2'-bipyridyl)ruthenium(Ⅱ)(K005) has been synthesized and characterized by cyclic voltammetry, ^1H NMR, UV-Vis, and FT-IR spectroscopies. The sensitizer sensitizes TiO2 over a notably broad spectral range due to its intense metal-to-ligand charge-transfer (MLCT) bands at 537 and 418 nm. The photophysical and photochemical studies of K005 were contrasted with those of cis-Ru(dcbpy)2(NCS)2, known as the N3 dye, and the amphiphilic ruthenium(Ⅱ) dye Z907. A reversible couple at E1/2=0.725 V vs. saturated calomel electrode (SCE) with a separation of 0.08 V between the anodic and cathodic peaks, was observed due to the Ru^Ⅱ/Ⅲ couple by cyclic voltammetry. Furthermore, this amphiphilic ruthenium complex was successfully used as sensitizers for dye-sensitized solar cells with the efficiency of 3.72% at the 100 mW·cm^-2 irradiance of air mass 1.5 simulated sunlight without optimization of TiO2 films and the electrolyte.  相似文献   
115.
Sorption of Th(IV) on Na-rectorite as a function of pH, ionic strength, soil humic acid (HA) and fulvic acid (FA) are studied under ambient conditions by using a batch technique. The results indicate that the sorption of Th(IV) on Na-rectorite is not only dependent on medium pH values, but also dependent on medium ionic strength and humic substances. Surface complexation and cation competition exchange account for Th(IV) sorption on Na-rectorite. The sorption of Th(IV) on Na-rectorite decreases with the increase on the concentration of NaNO3, Mg(NO3)2 and Ca(NO3)2, and increases with the increasing amount of HA/FA in the suspension/adsorbed on rectorite. Soil HA/FA enhances the sorption of Th(IV) on rectorite at medium pH<4 drastically, but the presence of FA reduces the sorption of Th(IV) at medium pH>6, and HA has no effect on Th(IV) sorption at medium pH>6. An interpretation for the results is attempted, considering the occurrence of different sorption mechanisms.  相似文献   
116.
This report presents a facile approach for the low‐temperature synthesis of crystalline inorganic‐oxide composite hollow spheres by employing the bulk controlled synthesis of inorganic‐oxide nanocrystals with polymer spheres as templates. The sulfonated polystyrene gel layer can adsorb the target precursor and induce inorganic nanocrystals to grow on the template in situ. The crystalline phase and morphology of the composite shell is tunable. By simply adjusting the acidity of the titania sol, crystalline titania composite hollow spheres with tunable crystalline phases of anatase, rutile, or a mixture of both were achieved. The approach is general and has been extended to synthesize the representative perovskite oxide (barium and strontium titanate) composite hollow spheres. The traditional thermal treatment for crystallite transformation is not required, thus intact shells can be guaranteed. The combination of oxide properties such as high refractive index, high dielectric constant, and catalytic ability with the cavity of the hollow spheres is promising for applications such as opacifiers, photonic crystals, high‐κ‐gate dielectrics, and photocatalysis.  相似文献   
117.
Performance of MEMS-based DMFC is low, because graphite-based porous electrodes show poor compatibility with MEMS technology. Nanoimprint technology was adopted in this paper to prepare fine pattern on proton exchange membrane (PEM) in MEMS-based DMFC as a promising alternative to the graphite-based porous electrodes. Micro-convex with the diameter of about 600 nm and the height of 50–70 nm was prepared on Nafion® 117 membrane by the nanoimprint at 130 °C using silicon mold. Thick Pt film (20 nm) was deposited as catalyst directly on the nanoimprinted Nafion® 117 membrane. Then the Pt-coated PEM was sandwiched with micro-channeled silicon plates to form a micro-DMFC. With passively feeding of 1 M methanol solution and air at room temperature, the as-prepared cell had the open circuit voltage (OCV) of 0.74 V and the maximum power density of 0.20 mW/cm2. The measured OCV was higher than those (0.1–0.3 V) of the state-of-the-art MEMS-based DMFC with planar electrode and pure Pt catalyst.  相似文献   
118.
A cytotoxic compound from the leaves of Juglans mandshurica   总被引:1,自引:0,他引:1  
From Juglans mandshurica leaves, a new quinone compound was isolated through bioassay-guided fractionation. The structure elucidation of the compound was established based on spectroscopic studies, notably of the 2D NMR spectra. The compound exhibited moderate cytotoxic activities against Hela, MCF-7, BGC823 and 3T3-Llcell lines with IC50 ranges from 7.5 to 26.8 μmol/L.  相似文献   
119.
Summary The removal of heavy metal ion Co(II) from aqueous solution was studied usingg-Al2O3 by batch technique. The experiments were performed at T=20±2 °C, in 0.01M NaNO3 solutions and under aerobic conditions. The effect of pH, ionic strength, fulvic acid (FA) and alumina amount on the sorption of Co(II) on alumina were also investigated. The pH affected the sorption of Co(II) significantly as compared with the effect of FA and ionic strength. The results indicated that strong chemical bonds are formed between Co(II) and functional groups of the bare or FA coated alumina, and a precipitation of Co(II) takes place on the alumina surface, induced by a transition from the adsorption to surface. The addition sequences of Co/FA on Co(II) sorption were also studied: the sorption of Co(II) in the ternary system was found independent of addition sequences.</p> </p>  相似文献   
120.
The triblock copolymers, poly(styrene-b-isoprene-b-ε-caprolactone)s (PS-b-PI-b-PCL) have been synthesized successfully by combination of anionic polymerization and ring-opening polymerization. Diblock copolymer capped with hydroxyl group, PS-b-PI-OH was synthesized by sequential anionic polymerization of styrene and isoprene and following end-capping reaction of EO, and then it was used as macro initiator in the ring-opening polymerization of CL. The results of DSC and WAXD show big effect of amorphous PS-b-PI on the thermal behaviors of PCL block in the triblock copolymers and the lower degree of crystalline in the triblock copolymer with higher molecular weight of PS-b-PI was observed. The real-time observation on the polarized optical microscopy shows the spherulite growth rates of PCL27, PCL328 and PS-b-PI-b-PCL344 are 0.71, 0.46 and 0.07 μm s−1, respectively. The atomic force microscopy (AFM) images of the PS90-b-PI66-b-PCL28 show the columns morphology formed by it’s self-assembling.  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