全文获取类型
收费全文 | 164549篇 |
免费 | 32019篇 |
国内免费 | 9517篇 |
专业分类
化学 | 126624篇 |
晶体学 | 1208篇 |
力学 | 9388篇 |
综合类 | 525篇 |
数学 | 22070篇 |
物理学 | 46270篇 |
出版年
2024年 | 691篇 |
2023年 | 5748篇 |
2022年 | 4721篇 |
2021年 | 6067篇 |
2020年 | 8356篇 |
2019年 | 5852篇 |
2018年 | 6515篇 |
2017年 | 4823篇 |
2016年 | 10693篇 |
2015年 | 10407篇 |
2014年 | 10770篇 |
2013年 | 12601篇 |
2012年 | 14437篇 |
2011年 | 11681篇 |
2010年 | 10805篇 |
2009年 | 10398篇 |
2008年 | 7387篇 |
2007年 | 6402篇 |
2006年 | 5436篇 |
2005年 | 8173篇 |
2004年 | 6804篇 |
2003年 | 4551篇 |
2002年 | 2595篇 |
2001年 | 2140篇 |
2000年 | 1719篇 |
1999年 | 2037篇 |
1998年 | 1726篇 |
1997年 | 1737篇 |
1996年 | 1711篇 |
1995年 | 1546篇 |
1994年 | 1303篇 |
1993年 | 1264篇 |
1992年 | 1150篇 |
1991年 | 1028篇 |
1990年 | 843篇 |
1989年 | 690篇 |
1988年 | 605篇 |
1987年 | 475篇 |
1986年 | 452篇 |
1985年 | 405篇 |
1977年 | 352篇 |
1976年 | 474篇 |
1975年 | 515篇 |
1974年 | 542篇 |
1973年 | 371篇 |
1972年 | 494篇 |
1971年 | 441篇 |
1970年 | 659篇 |
1969年 | 496篇 |
1968年 | 537篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
991.
Luis A.?León Rafael?Notario Jairo?QuijanoEmail author Ederley?Vélez Claudia?Sánchez J. Camilo?Quijano Nouria?Al-Awadi 《Theoretical chemistry accounts》2003,110(6):387-394
Theoretical studies on the thermolysis in the gas phase of 4-arylideneimino-1,2,4-triazol-3(2H)-ones and 4-arylideneimino-1,2,4-triazol-3(2H)-thiones were carried out using density functional theory methods, at the B3LYP/6-31G(d) and B3LYP/6-311+G(2d,p) levels of theory. The proposed reaction mechanism occurs in one step, leading to the formation of 3-hydroxy-(2H)-1,2,4-triazole or 3-mercapto-(2H)-1,2,4-triazole and a 4-substituted benzonitrile, via a six-membered cyclic transition state. The progress of the reactions was followed by means of the Wiberg bond indices. The results indicate that the transition states have character intermediate between reactants and products, and the calculated synchronicities show that the reactions are slightly asynchronous, in the case of triazolones, and show a higher asynchronicity in the case of triazolthiones. The bond-breaking processes are slightly more advanced than the bond-forming ones, indicating a small bond deficiency in the transition states. Kinetic and activation parameters for the reactions studied have been calculated and compared with available experimental data.From the Proceedings of the 28th Congreso deQuímicos Teóricos de Expresión Latina (QUITEL 2002) 相似文献
992.
993.
Ion Association and Hydration in Aqueous Solutions of Nickel(II) and Cobalt(II) Sulfate 总被引:1,自引:0,他引:1
Ting?Chen Glenn?HefterEmail author Richard?Buchner 《Journal of solution chemistry》2005,34(9):1045-1066
Aqueous solutions of nickel(II) and cobalt(II) sulfate have been investigated at 25 ∘C by dielectric relaxation spectroscopy (DRS) over a wide range of frequencies (0.2 ≤ ν (GHz) ≤ 89) and salt concentrations
(0.025 ≤ c(mol-L−1) ≤ 1.4). The spectra indicate, as for MgSO4(aq) studied previously, the simultaneous presence of double solvent-separated, solvent-shared and contact ion pairs in both
NiSO4(aq) and CoSO4(aq). The stepwise formation constants for each ion-pair type and the overall association constant, obtained from the data
are in good agreement with ultrasonic relaxation and other estimates. The DR spectra at higher concentrations (c ≥ 0.5 mol-L−1) suggest the existence of a nonlinear triple ion M2SO42+(aq). Consistent with the very strong hydration of the salts, which have ‘effective’ hydration numbers approaching 27 at infinite
dilution, there are no significant differences in any of the relaxation or thermodynamic parameters for NiSO4(aq) and CoSO4(aq), except that the triple ion appears to be somewhat more stable for the latter. 相似文献
994.
Hitoshi?MatsukiEmail author Michio?Yamanaka Hiroshi?Kamaya Shoji?Kaneshina Issaku?Ueda 《Colloid and polymer science》2005,283(5):512-520
The dissociation equilibrium between uncharged local anesthetic lidocaine (LC) and charged local anesthetic LC (LCH+) in a surface-adsorbed film was investigated by measuring the surface tension and pH of aqueous solutions of a mixture of hydrochloric acid and LC. The surface tension values decreased slightly with increasing total molality mt at 0X20.5, where X2 is the mole fraction of LC in the mixture, while they decreased rapidly with increasing mt at 0.5<X21. It was shown from the pH measurements that almost all LC molecules were changed into LCH+ ions by protonation at 0X20.5 and both forms coexisted only at 0.5<X21. The quantities of the respective LC and LCH+ transferred from the aqueous solution to the adsorbed film, i.e., their surface densities, were calculated by applying the thermodynamic equations derived to the surface tension and pH data. A greater quantity of LC than LCH+ existed in the adsorbed film at the coexisting composition. The partitioning behavior of LC and LCH+ in the adsorbed film was characterized by three composition regions: (1) slight partitioning of low surface-active LCH+ in the region at 0X20.5, (2) preferential partitioning of LC at 0.5<X2<around 0.7, and (3) negative partitioning of LCH+ at around 0.7X21. The present results clearly indicate that uncharged local anesthetics transfer into hydrophobic environments such as cell membranes more than charged ones. 相似文献
995.
压力流驱动电色谱分析方法及其若干色谱行为 总被引:1,自引:0,他引:1
压力流驱动电色谱分析方法是一种新型色谱技术。它组合了HPLC和电泳两种技术,为分离提供了更多可控制的因素。介绍了压力流驱动电色谱的装置和毛细管电色谱柱的装置方法,从理论上讨论了影响电色谱分离的因素并用实验数据加以证明。最后尝试性地将电色谱法用于测定香蕉样品中萨索啉(Salsolinol)等的含量。 相似文献
996.
Doz. Dr. P. Bukovec B. Orel J. Šiftar 《Monatshefte für Chemie / Chemical Monthly》1974,105(6):1299-1305
The IR- and Raman Spectra of several compounds of the stoichiometryM 2 I M IIIF5H2O and their deuterated analogs have been interpreted on the basis of their crystal structures. The compounds studied were divided into two classes regarding the bonding of water molecules. The main spectroscopic difference between the two classes was found in the region of H2O vibrations in good agreement with theoretical predictions. The metal—fluorine and metal—oxygene vibrations gave no direct information concerning the two types of water. 相似文献
997.
Erik J. Faber Dr. Wouter Sparreboom Wilrike Groeneveld Louis C. P. M. de Smet Dr. Johan Bomer Wouter Olthuis Dr. Han Zuilhof Dr. Ernst J. R. Sudhölter Prof. Piet Bergveld Prof. Albert van den Berg Prof. 《Chemphyschem》2007,8(1):101-112
The electrochemical behavior of Si--C linked organic monolayers is studied in electrolyte-insulator-Si devices, under conditions normally encountered in potentiometric biosensors, to gain fundamental knowledge on the behavior of such Si electrodes under practical conditions. This is done via titration experiments, Mott-Schottky data analysis, and data fitting using a site-binding model. The results are compared with those of native SiO(2) layers and native SiO(2) layers modified with hexamethyldisilazane. All samples display pH sensitivity. The number of Si--OH groups on the alkylated samples is calculated to be less than 0.7 % of that of a pure SiO(2) insulator, which still causes a pH sensitivity of approximately 25 mV per pH unit in the pH range: 4-7. The alkylated samples hardly suffer from response changes during up- and down-going titrations, which indicates that very little oxide is additionally formed during the measurements. The pK(a) values of all samples with monolayers (4.0-4.4) are lower than that of native SiO(2) (6.0). The long-term drift (of approximately 1 mV h(-1)) is moderate. The results indicate that biosensors composed of alkylated Si substrates are feasible if a cross-sensitivity towards pH in the sensor signal is taken into account. 相似文献
998.
999.
镀金层识别及其厚度测定的X—荧光强度比值法 总被引:3,自引:0,他引:3
利用Au原子在X射线激发下所发射的Lβ线和M线的强度比值识别样品是镀金还是K金,同时利用这个比值测定镀金层的厚度,镀金层厚度的测定范围为0~4μm,测定值与标定值的相对误差小于15%。 相似文献
1000.
双质谱测定地卟啉取代基组成的解析方法及其应用 总被引:2,自引:0,他引:2
根据卟啉标样的双质谱特征,建立一种计算卟啉环上取代基组成的方法。卟啉的平均分子结构简式衡量其取代基的组成,尤其对地质体中相同碳数的卟啉“混合物”大环外取代基的构成十分有效。 相似文献