全文获取类型
收费全文 | 2581篇 |
免费 | 279篇 |
国内免费 | 185篇 |
专业分类
化学 | 2172篇 |
晶体学 | 6篇 |
力学 | 80篇 |
综合类 | 20篇 |
数学 | 543篇 |
物理学 | 224篇 |
出版年
2024年 | 3篇 |
2023年 | 28篇 |
2022年 | 26篇 |
2021年 | 33篇 |
2020年 | 87篇 |
2019年 | 66篇 |
2018年 | 82篇 |
2017年 | 70篇 |
2016年 | 114篇 |
2015年 | 103篇 |
2014年 | 133篇 |
2013年 | 250篇 |
2012年 | 131篇 |
2011年 | 145篇 |
2010年 | 134篇 |
2009年 | 119篇 |
2008年 | 139篇 |
2007年 | 141篇 |
2006年 | 126篇 |
2005年 | 126篇 |
2004年 | 118篇 |
2003年 | 147篇 |
2002年 | 196篇 |
2001年 | 74篇 |
2000年 | 62篇 |
1999年 | 56篇 |
1998年 | 52篇 |
1997年 | 41篇 |
1996年 | 53篇 |
1995年 | 25篇 |
1994年 | 28篇 |
1993年 | 22篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 9篇 |
1988年 | 13篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1973年 | 3篇 |
1936年 | 1篇 |
排序方式: 共有3045条查询结果,搜索用时 15 毫秒
71.
焙烧温度对合成低碳醇用Cu/Mn/Ni/ZrO2催化剂性能的影响 总被引:2,自引:0,他引:2
研究了焙烧温度对合成低碳醇用Cu/Mn/Ni/ZrO2催化剂结构及催化性能的影响.随着焙烧温度的升高,催化剂的催化活性和产物分布都发生较大的变化.催化剂在较低的温度下焙烧,低温下反应液相产物的分布符合S-F方程;反应温度升高时,液相产物中主要是甲醇和异丁醇;在高温下焙烧的催化剂,其催化活性较低,但即使在较低的反应温度下,异丁醇在液相高级醇(C2+OH)中也是主要的产物.结合其他的一些反应结果与XRD,BET,TPR及EXAFS等表征结果,认为焙烧温度使催化剂的结构发生了较大的变化,进而影响催化剂各组分之间的相互作用,从而使催化剂对合成低碳醇反应表现出不同的催化性能. 相似文献
72.
73.
Summary Capillary electrophoresis has been used for the chiral analysis of two -amino alcohol pharmaceutical compounds. Capillary zone electrophoresis conditions were used with -cyclodextrin as a chiral mobile phase additive. The effects of variation of -cyclodextrin concentration, temperature, pH, background electrolyte composition and concentration have been investigated. Optimum separations were achieved for clenbuterol using -cyclodextrin at its solubility limit (16mM), the lowest practicable temperature (19°C), pH 4.0 and an electrolyte solution with a high ionic strength prepared from 0.1 M citric acid and 0.3 M Na2HPO4. For the development compound picumeterol and its (S)-enationmer, the optimum pH 4.0 buffer was prepared from 0.1 M citric acid and 0.2 M sodium acetate. Baseline separation with resolution greater than 2 was achieved for both compounds.This work was presented in part at the 2nd International Symposium on Chiral Discrimination, Rome, May 27–31, 1991. 相似文献
74.
T.E. Vittal Prasad N. Malleswara Reddy 《The Journal of chemical thermodynamics》2006,38(12):1696-1700
Bubble point temperatures at 95.5 kPa, over the entire composition range, are measured for the binary mixtures formed by m-cresol with: methanol, ethanol, 1-propanol, 2-propanol, and n-, iso-, sec-, and tert-butanols - using a Swietoslawski-type ebulliometer. The liquid phase composition - bubble point temperature measurements are well represented by the Wilson model. (Vapor + liquid) equilibria predicted from the model are presented. 相似文献
75.
Valiollah Mirkhani Shahram TangestaninejadBahram Yadollahi Ladan Alipanah 《Tetrahedron》2003,59(41):8213-8218
Epoxides can be cleaved in a regio- and stereoselective manner under neutral conditions with alcohols and acetic acid in the presence of catalytic amounts of decatungstocerate(IV) ion, ([CeW10O36]8−), affording the corresponding β-alkoxy and β-acetoxy alcohols in high yields. In water, ring opening of epoxides occurs with this catalyst to produce the corresponding diols in good yields. 相似文献
76.
Epoxides react smoothly with tetraallyltin in the presence of 2 mol% of Bi(OTf)3 under mild reaction conditions to afford the corresponding homoallylic alcohols in excellent yields with high regioselectivity while aryl aziridines produce exclusively allyl amines in good yields under similar conditions. 相似文献
77.
Satoshi Takamizawa Dr. Chihiro Kachi‐Terajima Dr. Masa‐aki Kohbara Takamasa Akatsuka Tetsuro Jin Dr. 《化学:亚洲杂志》2007,2(7):837-848
The vapor absorbency of the series of alcohols methanol, ethanol, 1‐propanol, 1‐butanol, and 1‐pentanol was characterized on the single‐crystal adsorbents [MII2(bza)4(pyz)]n (bza=benzoate, pyz=pyrazine, M=Rh ( 1 ), Cu ( 2 )). The crystal structures of all the alcohol inclusions were determined by single‐crystal X‐ray crystallography at 90 K. The crystal‐phase transition induced by guest adsorption occurred in the inclusion crystals except for 1‐propanol. A hydrogen‐bonded dimer of adsorbed alcohol was found in the methanol‐ and ethanol‐inclusion crystals, which is similar to a previous observation in 2 ?2EtOH (S. Takamizawa, T. Saito, T. Akatsuka, E. Nakata, Inorg. Chem. 2005 , 44, 1421–1424). In contrast, an isolated monomer was present in the channel for 1‐propanol, 1‐butanol, and 1‐pentanol inclusions. All adsorbed alcohols were stabilized by hydrophilic and/or hydrophobic interactions between host and guest. From the combined results of microscopic determination (crystal structure) and macroscopic observation (gas‐adsorption property), the observed transition induced by gas adsorption is explained by stepwise inclusion into the individual cavities, which is called the “step‐loading effect.” Alcohol/water separation was attempted by a pervaporation technique with microcrystals of 2 dispersed in a poly(dimethylsiloxane) membrane. In the alcohol/water separation, the membrane showed effective separation ability and gave separation factors (alcohol/water) of 5.6 and 4.7 for methanol and ethanol at room temperature, respectively. 相似文献
78.
高效阴离子交换色谱分离-脉冲安培检测法测定烟草料液中的糖、糖醇和醇类化合物 总被引:6,自引:0,他引:6
建立了高效阴离子交换色谱分离-脉冲安培检测法测定烟草料液中的糖、糖醇以及醇类化合物的方法。以NaOH为淋洗液,在CarboPac MA1阴离子交换柱上等度分离了肌醇、甘油、丙二醇、半乳糖醇、木糖醇、山梨醇、甘露醇、葡萄糖、果糖、蔗糖、甘露糖和半乳糖等12种化合物。对影响分离和检测的条件进行了优化,并在此优化条件下分析了烟草料液中的糖、糖醇以及醇类化合物。12种化合物的检出限为2.0~216μg/L(25.0μL进样,以3倍信噪比计算检出限)。12种化合物浓度为1~5mg/L的标准溶液连续7次进样的RSD为0.7%~4.3%。方法对烟草料液中12种化合物的加标回收率为80%~108%。方法灵敏、高效、简便、快捷。 相似文献
79.
Marta Catellani Sara Deledda Françoise Hénin Jacques Muzart 《Journal of organometallic chemistry》2003,687(2):473-482
A novel reaction sequence leading to the synthesis of substituted biphenyls containing a carbonyl group in an aliphatic chain has been achieved in one-pot reaction starting from iodoarenes and allylic alcohols under the catalytic action of palladium and norbornene. The latter is temporarily incorporated into a palladacycle, which directs the reaction towards the selective formation of an arylaryl bond. Norbornene spontaneously deinserts to allow the biphenylylpalladium bond thus formed to react in its turn with the allylic alcohol. 相似文献
80.
In ternary aqueous solutions, hydrophobic solutes such as alcohols tend to aggregate with surfactants to form mixed micelles. These systems can be studied by meas of the functions of transfer of hydrophobic solutes from water to aqueous solutions of surfactant. These thermodynamic functions often go through extrema in the critical micellar concentration (CMC) region of the surfactant. A simple model based on interactions between surfactant and hydrophobic solute monomers, on the distribution of the hydrophobic solute between water and the micelles and on the shift in the CMC induced by the hydrophobic solute, can simulate the magnitude and trends of the transfer functions using parameters which are mostly derived from the binary systems. In order to check the model more quantitatively, volumes and heat capacities of transfer of alcohols from water to aqueous solutions of a nonionic surfactant, octyldimethylamine oxide, were measured. A quantitative agreement was achieved with three adjustable parameters. Good fits are also obtained for the transfers to the ionic surfactants, octylamine hydrobromide and sodium dodecylsulfate. When the equilibrium displacement contribution is small, the distribution constants and the partial molar properties of the alcohols in the micellar phase agree well with the parameters obtained with similar models. 相似文献