全文获取类型
收费全文 | 78267篇 |
免费 | 7184篇 |
国内免费 | 6185篇 |
专业分类
化学 | 11174篇 |
晶体学 | 967篇 |
力学 | 9892篇 |
综合类 | 668篇 |
数学 | 15037篇 |
物理学 | 14724篇 |
综合类 | 39174篇 |
出版年
2024年 | 230篇 |
2023年 | 764篇 |
2022年 | 1343篇 |
2021年 | 1476篇 |
2020年 | 1764篇 |
2019年 | 1566篇 |
2018年 | 1586篇 |
2017年 | 2151篇 |
2016年 | 2359篇 |
2015年 | 2352篇 |
2014年 | 3895篇 |
2013年 | 4345篇 |
2012年 | 4728篇 |
2011年 | 5144篇 |
2010年 | 4135篇 |
2009年 | 4685篇 |
2008年 | 4440篇 |
2007年 | 5220篇 |
2006年 | 4545篇 |
2005年 | 4268篇 |
2004年 | 3799篇 |
2003年 | 3425篇 |
2002年 | 3033篇 |
2001年 | 2555篇 |
2000年 | 2288篇 |
1999年 | 2101篇 |
1998年 | 1844篇 |
1997年 | 1682篇 |
1996年 | 1479篇 |
1995年 | 1258篇 |
1994年 | 1155篇 |
1993年 | 1019篇 |
1992年 | 957篇 |
1991年 | 810篇 |
1990年 | 759篇 |
1989年 | 637篇 |
1988年 | 564篇 |
1987年 | 396篇 |
1986年 | 216篇 |
1985年 | 150篇 |
1984年 | 120篇 |
1983年 | 58篇 |
1982年 | 74篇 |
1981年 | 50篇 |
1980年 | 27篇 |
1979年 | 44篇 |
1978年 | 31篇 |
1977年 | 38篇 |
1976年 | 13篇 |
1957年 | 12篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
J. A. Navio M. Macias A. Justo C. Real 《Journal of Thermal Analysis and Calorimetry》1992,38(4):673-682
The thermal decomposition of sodium nitrite or nitrate pre-adsorbed upon TiO2 surfaces has been investigated by employing several techniques as infrared spectroscopy (IR) and temperature programmed desorption in conjunction with mass spectrometry analysis (TPD-MS) to study the features observed during these thermal decompositions. Differential thermal analysis (DTA) in combination with X-ray diffraction analysis (XRD) were used to investigate the possibility of a solid state chemical reaction between the solid products originated from the thermal decomposition of the pre-adsorbed species and the TiO2. On the basis of our results, various characteristic features of these thermal decomposition reactions will be discussed.This work was supported by JUNTA DE ANDALUCIA (financial support for research groups/1990). 相似文献
992.
Richard R. Schmidt 《Angewandte Chemie (International ed. in English)》1986,25(3):212-235
Glycoproteins, glycolipids, and glycophospholipids (glycoconjugates) are components of membranes. The oligosaccharide residue is responsible for intercellular recognition and interaction; it acts as a receptor for proteins, hormones, and viruses and governs immune reactions. These significant activities have stimulated interest in oligosaccharides and glycoconjugates. With their help it should be possible to clarify the molecular basis of these phenomena and to derive new principles of physiological activity. Major advances in the synthesis of oligosaccharides have been made by the use of the Koenigs-Knorr method, in which glycosyl halides in the presence of heavy-metal salts are employed to transfer the glycosyl group to nucleophiles. The disadvantages of this procedure have led to an intensive search for new methods. Such methods will be discussed in this article. Emphasis is placed on glycoside and saccharide formation by 1-O-alkylation, on the trichloroacetimidate method, and on activation through the formation of glycosylsulfonium salts and glycosyl fluorides. 相似文献
993.
CuAl2O4 powder synthesis by sol-gel method and its photodegradation property under visible light irradiation 总被引:1,自引:0,他引:1
Jiang Yanyan Li Jinggang Sui Xiaotao Ning Guiling Wang Chengyu Gu Xiumei 《Journal of Sol-Gel Science and Technology》2007,42(1):41-45
Nanocrystalline spinel CuAl2O4 powders were prepared by sol-gel method from nitrate Cu(NO3)2·3H2O, Al(NO3)3·9H2O and complex C6H8O7·H2O. Sintering was carried out at 400, 500, 600, 700, 800°C respectively for 2 h in air. The XRD patterns started to appear
CuAl2O4 peaks after sintering of 500°C and consist of only CuAl2O4 peaks as spinel crystal after sintering of 700°C. The powders were analyzed by TEM and UV-vis diffuse reflectance spectrum
to be round, about 10–30 nm in size and Eg=1.77 eV. Photodegradation property of nanocrystalline CuAl2O4 powders was investigated by using methyl orange as model pollutant and mercury lamp (λ>400 nm) as energy source. The results
indicated that CuAl2O4 powders sintered at 700°C had the excellent visible photocatalytic property. Under the irradiation of visible light, methyl
orange could be degraded 97% in 120 min. 相似文献
994.
The homotopic method has been used to analyze the kinetic models of CO oxidation on two surface patches conjugated by COads spillover. On each patch reaction proceeds via a three-stage mechanism but with different constants. The stability of steady-states solution has been studied. COads spillover from one patch to another changes substantially the bifurcation picture of steady states and produces islands. 相似文献
995.
I. S. Kislina M. Yu. Kulikova S. G. Sysoeva O. N. Temkin 《Russian Chemical Bulletin》1994,43(10):1626-1629
The acidity functionsH
0
s of HCl solutions in EtOH-H2O solvents containing 1.09, 3.0, and 5.0% water have been measured at 25 and 40 °C by the indicator method. The concentration of HCl changes from 10–2 to 36m. Nitroanilines, for which a protonation mechanism is realized in the studied systems, were used as indicators.For each solvent,H
0
s is temperature independent atm
HCl < 4, and acidity atm
HCl > 4 mol L–1 increases more rapidly at 25 °C than at 40 °C. The acidity functions of aqueous and water-ethanol solutions of HCl were compared, and the concentrations of proton solvates of different compositions and their relative protonating ability were evaluated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1722–1725, October, 1994.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18356). 相似文献
996.
使用了不同密度泛函方法计算X-H (X = C, N, O, Si, P, S) 键离解能,并分析不同密度泛函方法的计算精度。研究发现大多数密度泛函方法包括B3LYP, B3P86, B3PW91, G96LYP, PBE1PBE,和BH&HLYP都明显低估键离解能13-25 kJ/mol。该现象与是否使用无限基组无关,因为即使使用无限基组键离解能仍然被低估。因此密度泛函方法不适合用于键离解能的估算。其中B3P86方法的偏差最小。进一步分析表明,使用限制性开壳层计算并无任何优势,在大多数情况下非限制性开壳层计算实际上比限制性开壳层计算要好。最后,我们发现了密度泛函方法对键离解能的低估是系统的,因此建议利用校准后的UDFT/6-311++G(d, p)方法计算化学键离解能。 相似文献
997.
《Electroanalysis》2005,17(17):1589-1594
Simultaneous determination of bismuth and copper by anodic stripping voltammetry using H‐point standard addition method (HPSAM) with simultaneous addition of analytes is described. The effect of various parameters including acid concentration, accumulation time, accumulation potential and concentration ratio of analytes in the standard solution on the sensitivity and accuracy of method were investigated. The results of applying the H‐point standard addition method showed that Cu2+ and Bi3+ could be determined simultaneously with the concentration ratios of Cu2+ to Bi3+ varying from 1 : 15 to 16 : 1 in the mixed sample. The method was successfully applied to the simultaneous determination of copper and bismuth in some synthetic mixtures. 相似文献
998.
An air-segmented continuous-flow method has been developed for the determination of molybdenum at ultra trace levels using
the catalytic effect of molybdate during the oxidation of L-ascorbic acid by hydrogen peroxide. Incorporation of an on-line
ion exchange column improved the tolerance limit for various ions. The detection limits with and without the column were 64 pmol L−1 and 17 pmol L−1, and the reproducibilities at 10 nmol L−1 were 2.1% and 0.2%, respectively. The proposed method was applied to the determination of molybdenum in seawater and lake
water as well as in rock and sediment samples. This method has the highest sensitivity among the available literature to our
knowledge, and is also convenient for routine analysis of molybdenum in various natural samples.
Author for correspondence. E-mail: masahito.sugiyama@ sojin0206.mbox.media.kyoto-u.ac.jp
Received October 23, 2002; accepted January 28, 2003
Published online May 19, 2003 相似文献
999.
用等压法研究了273.15 K下Li2B4O7-LiCl-H2O体系不同质量摩尔浓度分数的等压平衡浓度和水活度; 计算了LiCl和Li2B4O7混合盐溶液的渗透系数等热力学性质. 用273.15 K下的实验数据对Pitzer离子相互作用模型进行了参数化研究, 拟合求取了273.15 K下Pitzer离子相互作用参数, 用获得的参数计算了LiCl和Li2B4O7在Li2B4O7-LiCl-H2O体系中的活度系数. 273.15 K下由相应的Pitzer模型计算的渗透系数值与实验结果一致. 这对完善含锂、硼盐湖卤水体系的热力学模型具有重要意义. 相似文献
1000.
Liu JM Hu SR He XM Li XL Zhan FP Zeng LQ Li LD Zhu GH Huang XM 《Analytical and bioanalytical chemistry》2005,382(7):1507-1512
Silicon dioxide nano-particles, diameter 50 nm, containing morin (morin–SiO2) have been synthesized by the sol–gel method. They emit strong and stable room-temperature phosphorescence (SS-RTP) on filter paper as substrate, and bismuth can quench the intensity of the SS-RTP. On this basis a new morin–SiO2 solid-substrate room-temperature phosphorescence-quenching method has been established for determination of traces of bismuth. Reduction of phosphorescence intensity (Ip) is directly proportional to the concentration of bismuth in the working range 0.16–14.4 ag spot–1 (sample volume 0.40 L spot–1, corresponding to the concentration range 0.40–36.0 fg mL–1). The regression equation of the working curve is Ip=14.86+5.279×[Bi3+] (ag spot–1) (n=6, r=0.9982). The detection limit of this method is 0.026 ag spot–1 (corresponding to a concentration of 6.5×10–17 g mL–1).This sensitive, reproducible and accurate method has been used for successful analysis of real samples. 相似文献