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   1306篇
  免费   132篇
  国内免费   108篇
化学   687篇
晶体学   11篇
力学   173篇
综合类   17篇
数学   215篇
物理学   443篇
  2023年   13篇
  2022年   26篇
  2021年   27篇
  2020年   23篇
  2019年   38篇
  2018年   34篇
  2017年   40篇
  2016年   55篇
  2015年   42篇
  2014年   51篇
  2013年   125篇
  2012年   91篇
  2011年   70篇
  2010年   46篇
  2009年   77篇
  2008年   69篇
  2007年   86篇
  2006年   67篇
  2005年   61篇
  2004年   69篇
  2003年   68篇
  2002年   41篇
  2001年   23篇
  2000年   38篇
  1999年   38篇
  1998年   28篇
  1997年   23篇
  1996年   18篇
  1995年   27篇
  1994年   24篇
  1993年   17篇
  1992年   20篇
  1991年   10篇
  1990年   6篇
  1989年   6篇
  1988年   3篇
  1987年   4篇
  1986年   3篇
  1985年   8篇
  1984年   4篇
  1983年   3篇
  1981年   5篇
  1979年   2篇
  1978年   4篇
  1977年   1篇
  1976年   1篇
  1974年   3篇
  1973年   3篇
  1972年   1篇
  1971年   1篇
排序方式: 共有1546条查询结果,搜索用时 17 毫秒
31.
表面活性剂混合物水溶液中的囊泡形成   总被引:1,自引:0,他引:1  
1:1烷基羧酸钠-溴化烷基三甲铵混合水溶液的浓度在cmc以上时, 能自发或超声分散形成一类新型混合表面活性剂囊泡(单层膜), 正负离子表面活性剂的突出囊泡形成能力以及不同表面活性剂结构组合变化所显现的多样特性, 皆预示出混合功能有序组合体研究的广阔前景。  相似文献   
32.
Triglycidyl isocyanurate [2451-62-9] as a trifunctional epoxy monomer is mostly used as curing agent. It exists in the form of two diastereomer racemates according to the configuration of the three chiral carbon atoms in the molecule, i.e. beta- or RRR/SSS and alpha- or RRS/SSR. The binary solid-liquid phase diagram of the two diastereomer racemates has been determined by differential scanning calorimetry (DSC). The two diastereomer racemates have different crystalline structures and are physical mixtures with an eutectic phase diagram. The eutectic mixture melts at 92.3 ± 1.0 °C and has alpha-TGIC content of 93.44% by mass or mole. With the help of the phase diagram the ratio of the two diastereomer racemates in TGIC may be determined. The binary phase diagram shows that beta-TGIC can be separated with efficiency from the mixture and may serve for enantiomer synthesis of high optical activity giving rise to the development of novel polymers.  相似文献   
33.
ABSTRACT

Here, we present the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared ferroelectric liquid crystal (FLC) mixture, namely W302. The FLC mixture, comprising of pyrimidine compounds, was characterised through dielectric spectroscopy, differential scanning calorimetry (DSC), polarising optical microscopy (POM) and other electro-optical methods. The material parameters such as spontaneous polarisation, rotational viscosity, response time and tilt angle of W302 were found to be 14 nC/cm2, 240 mPa.s, 150 µs and 28?, respectively. The phase transition temperatures of W302 were observed through DSC and further confirmed by the dependence of dielectric loss factor in homogeneously aligned FLC sample with temperature. We also demonstrate the observance of a low-frequency dielectric relaxation mode due to the unwinding of the helix, called as partially unwound helical mode (p-UHM) along with Goldstone mode. The behaviour of p-UHM has been systematically studied with temperature and applied bias field. Further, dispersion of nCuO into host W302 has shown a significant increase in dielectric permittivity. Also, the p-UHM relaxation peak in the dielectric regime has disappeared with the incorporation of nCuO. These studies would be useful to fabricate better electro-optical devices for display, switching and beam steering applications. The formulation and characterization of a ferroelectric liquid crystal (FLC) mixture W302 composed of pyrimidine compounds is presented. Then, we observed the effect of copper (II) oxide nanoparticles (nCuO) on dielectric and electro-optical parameters of a newly prepared and characterized FLC mixture.  相似文献   
34.
A capillary electrophoresis (CE) with UV absorption detection method is described for the simultaneous determination of glufosinate, glyphosate, and aminomethylphosphoric acid. The 9‐fluorenylmethyl chloroformate (FMOC‐Cl) was used for precolumn derivatization of the non‐absorbing herbicides. The three analytes were separated by CE in 9 min with 25 mM borate buffer at pH 9, followed by detection with a UV detector at 260 nm. We demonstrate how the detection limit can be enhanced by using acetonitrile‐salt mixtures. With acetonitrile‐salt mixtures, the limit of detection (LOD) was in the 10?7 M range. Linearity of more than two orders of magnitude was generally obtained. Precisions of migration times and peak areas were less than 0.9% and 7.5%, respectively. The applicabilities of the method for the analysis of ground water and lake water were examined.  相似文献   
35.
Excess molar volumes VmE of the binary mixtures of (trifluoroethanol + 1-propanol), (trifluoroethanol + 2-propanol), (acetone + water), (methanol + water), (ethanol + water), (1-propanol + water), (2-propanol + water), and the ternary mixtures of (trifluoroethanol + methanol + water), (trifluoroethanol + ethanol + water), (trifluoroethanol~+ 1-propanol + water), (trifluoroethanol + 2-propanol + water) and (trifluoroethanol + acetone + water) were measured with a vibrating tube densimeter at the temperature of 298.15 K and the pressure 101 kPa. The extrema in VmE of trifluoroethanol mixtures occur at –0.690 cm3-mol–1 for (trifluoroethanol + 1-propanol), at –0.990~cm3-mol–1 for (trifluoroethanol + 2-propanol); at 0.562 and –0.973 cm3-mol–1 for (trifluoroethanol + methanol + water), at 0.629 and –0.973 cm3-mol–1 for (trifluoroethanol + ethanol + water), at 1.082 and –0.659 cm3-mol–1 for (trifluoroethanol~+ 1-propanol + water), at 0.998 and –0.991 cm3-mol–1 for (trifluoroethanol~+ 2-propanol + water), and at 0.515 and –1.472 cm3-mol–1 for (trifluoroethanol + acetone + water). The experimental ternary VmE values were predicted by empirical expressions using binary solution data.  相似文献   
36.
倪良  卢洁 《物理化学学报》1996,12(2):146-151
讨论了沸点升高法测定混和溶剂化热和汽化熵的原理,并用拟静态法测定了乙醇-丙酮,并-四氯化碳和苯,甲苯三组混和溶剂在不同组成下的正常沸点,根据沸点数据求得了混和泶微分汽化热和汽化熵,实验结果表明,二元混和溶剂与理想溶液偏离不大时,其正常汽化熵符合Trouton规则。  相似文献   
37.
A recently characterized oviposition-deterring pheromone (ODP, structure 1) of the European cherry fruit fly was used as a test case for probing the potential of tandem mass spectrometry (MS/MS) in structure elucidation as a stand-alone technique. The glycolipid-taurinate 1 was subjected to MS/MS analyses under a variety of conditions with and without preceding chemical degradation. Acidic methanolysis of 1 and subsequent in-batch derivatization (trideuterioacetylation) yielded methyl 2,3,4,6-tetrakis-O-trideuterioacetyl-glucopyranoside (2), methyl 8,15-bis-trideuterioacetoxy-palmitate (3), and taurine (4) as suitable target compounds for direct mixture analysis.Low energy collision induced dissociation (CID) on selected precursor ions (MS/MS on [M + H – CH3OH]+ and [M + H]+ produced by fast atom bombardment (FAB)) allowed direct identification of 2 and 4, respectively, by comparison with appropriate reference ions. In the case of 3, low energy CID (desorption chemical ionization (DCI) instead of FAB, MS/MS on [M + H]+) permitted deduction of gross molecular structure, but failed to provide positional detail. In sharp contrast,high energy CID of trideuterioacetylated intact 1 (FAB-MS/MS on [M – H] ions of la) clearly revealed a linear 8,15-hydroxylated palmitic acid backbone. Less certain was assignment of 15-O-glucosylation by this approach.  相似文献   
38.
提出一种利用萃取法间接测定Lewis碱性萃取剂碱度的简便方法, 选择常用的Lewis碱性萃取剂TOA/正辛醇和TRPO/煤油, 测定了其碱度, 为今后络合萃取剂的选择及其机理的研究提供理论指导.  相似文献   
39.
The two thermodynamic dissociation constants of glycine at 11 temperatures from 5 to 55°C in 50 mass % methanol-water mixed solvent have been determined from precise emf measurements with hydrogen-silver bromide electrodes in cells without liquid junction. The first acidic dissociation constant (K 1)for the process HG+H++G± is expressed as a function ofT(oK) by the equation pK 1 = 2043.5/T – 9.6504 + 0.019308T. At 25°C, pK 1is 2.961 in the mixed solvent, as compared with 2.350 in water, with H°=1497 cal-mole–1, G°=4038 cal-mole–1, S°=–8.52 cal-°K–1-mole–1, and C p o =–53 cal-°K–1-mole–1. The second acidic dissociation constant (K 2)for the process G±H++G over the temperature range studied is given by the equation pK 2 = 3627.1/T – 7.2371 + 0.015587T. At 25°C, pK 2is 9.578 in MeOH–H2O as compared with 9.780 in water, whereas H° is 10,257 cal-mole–1, G° is 13,063 cal-mole–1, S° is –9.41 cal-°K–1-mole–1, and C p o is –43 cal-°K–1-mole–1. The protonated glycine becomes weaker in 50 mass % methanol-water, whereas the second dissociation process becomes stronger despite the lower dielectric constant of the mixed solvent (=56.3 at 25°C).  相似文献   
40.
南照东  谭志诚  邢军 《中国化学》2005,23(7):823-828
The molar heat capacity of the azeotropic mixture composed of ethanol and toluene was measured by a high precision adiabatic calorimeter from 80 to 320 K. The glass transition and phase transitions of the azeotropic mixture were determined based on the heat capacity measurements. A glass transition at 103.350 K was found. A solid-solid phase transition at 127.282 K, two solid-liquid phase transitions at 153.612 and 160.584 K were observed, which correspond to the transition of metastable crystal to stable crystal of ethanol and the melting of ethanol and toluene, respectively. The thermodynamic functions and the excess ones of the mixture relative to the standard temperature 298.15 K were derived based on the relationships of the thermodynamic functions and the function of the measured heat capacity with respect to temperature.  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