全文获取类型
收费全文 | 856篇 |
免费 | 26篇 |
国内免费 | 4篇 |
专业分类
化学 | 648篇 |
晶体学 | 3篇 |
力学 | 18篇 |
数学 | 134篇 |
物理学 | 83篇 |
出版年
2023年 | 7篇 |
2022年 | 13篇 |
2021年 | 10篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2017年 | 6篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 24篇 |
2013年 | 41篇 |
2012年 | 40篇 |
2011年 | 66篇 |
2010年 | 28篇 |
2009年 | 22篇 |
2008年 | 58篇 |
2007年 | 51篇 |
2006年 | 69篇 |
2005年 | 44篇 |
2004年 | 43篇 |
2003年 | 39篇 |
2002年 | 40篇 |
2001年 | 5篇 |
2000年 | 10篇 |
1999年 | 8篇 |
1998年 | 10篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 8篇 |
1994年 | 9篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 9篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 9篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 3篇 |
1969年 | 2篇 |
排序方式: 共有886条查询结果,搜索用时 93 毫秒
41.
Dhanpat Rai Yuanxian Xia Linfeng Rao Nancy J. Hess Andrew R. Felmy Dean A. Moore David E. McCready 《Journal of solution chemistry》2005,34(4):469-498
The objectives of this study were to address uncertainties in the solubility product of (UO2)3(PO4)2⋅4H2O(c) and in the phosphate complexes of U(VI), and more importantly to develop needed thermodynamic data for the Pu(VI)-phosphate system in order to ascertain the extent to which U(VI) and Pu(VI) behave in an analogous fashion. Thus studies were conducted on (UO2)3(PO4)2⋅4H2O(c) and (PuO2)3(PO4)2⋅4H2O(am) solubilities for long-equilibration periods (up to 870 days) in a wide range of pH values (2.5 to 10.5) at fixed phosphate concentrations of 0.001 and 0.01 M, and in a range of phosphate concentrations (0.0001–1.0 M) at fixed pH values of about 3.5. A combination of techniques (XRD, DTA/TG, XAS, and thermodynamic analyses) was used to characterize the reaction products. The U(VI)-phosphate data for the most part agree closely with thermodynamic data presented in Guillaumont et al.,(1) although we cannot verify the existence of several U(VI) hydrolyses and phosphate species and we find the reported value for formation constant of UO2PO−4 is in error by more than two orders of magnitude. A comprehensive thermodynamic model for (PuO2)3(PO4)2⋅4H2O(am) solubility in the H+-Na+-OH−-Cl−-H2PO−4-HPO2−4-PO3−4-H2O system, previously unavailable, is presented and the data shows that the U(VI)-phosphate system is an excellent analog for the Pu(VI)-phosphate system. 相似文献
42.
Christopher M. Timperley Krystal E. Casey Stuart Notman David J. Sellers Nancy E. Williams Nichola H. Williams Gareth R. Williams 《Journal of fluorine chemistry》2006,127(12):1554-1563
Eighteen new fluorogenic analogues of organophosphorus nerve agents were synthesised and characterised. They included analogues of tabun, sarin, cyclosarin, soman, VX, and Russian VX, with the 7-oxy-4-methylcoumarin or 7-oxy-4-(trifluoromethyl)coumarin leaving group. These analogues inhibited acetylcholinesterase (AChE) effectively in vitro and therefore have potential as tools for the identification of novel organophosphatases in biological systems. Analogues of VX and Russian VX with the 7-amino-4-methylcoumarin group, although poor AChE inhibitors, may have utility for screening enzyme libraries for phosphoramidases capable of cleaving P-N bonds. 相似文献
43.
Nancy J. McMillan Russell S. Harmon Frank C. De Lucia Andrzej M. Miziolek 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007,62(12):1528-1536
Laser-induced breakdown spectroscopy (LIBS) provides an alternative chemical analytical technique that obviates the issues of sample preparation and sample destruction common to most laboratory-based analytical methods. This contribution explores the capability of LIBS analysis to identify carbonate and silicate minerals rapidly and accurately. Fifty-two mineral samples (18 carbonates, 9 pyroxenes and pyroxenoids, 6 amphiboles, 8 phyllosilicates, and 11 feldspars) were analyzed by LIBS. Two composite broadband spectra (averages of 10 shots each) were calculated for each sample to produce two databases each containing the composite LIBS spectra for the same 52 mineral samples. By using correlation coefficients resulting from the regression of the intensities of pairs of LIBS spectra, all 52 minerals were correctly identified in the database. If the LIBS spectra of each sample were compared to a database containing the other 51 minerals, 65% were identified as a mineral of similar composition from the same mineral family. The remaining minerals were misidentified for two reasons: 1) the mineral had high concentrations of an element not present in the database; and 2) the mineral was identified as a mineral with similar elemental composition from a different family. For instance, the Ca–Mg carbonate dolomite was misidentified as the Ca–Mg silicate diopside. This pilot study suggests that LIBS has promise in mineral identification and in situ analysis of minerals that record geological processes. 相似文献
44.
Bruce S. Dien Nick Nagle Kevin B. Hicks Vijay Singh Robert A. Moreau Melvin P. Tucker Nancy N. Nichols David B. Johnston Michael A. Cotta Quang Nguyen Rodney J. Bothast 《Applied biochemistry and biotechnology》2004,115(1-3):937-949
Approximately 9% of the 9.7 billion bushels of corn harvested in the United States was used for fuel ethanol production in 2002, half of which was prepared for fermentation by dry grinding. The University of Illinois has developed a modified dry grind process that allows recovery of the fiber fractions prior to fermentation. We report here on conversion of this fiber (Quick Fiber [QF]) to ethanol. QF was analyzed and found to contain 32%wt glucans and 65%wt total carbohydrates. QF was pretreated with dilute acid and converted into ethanol using either ethanologenic Escherichia coli strain FBR5 or Saccharomyces cerevisiae. For the bacterial fermentation the liquid fraction was fermented, and for the yeast fermentation both liquid and solids were fermented. For the bacterial fermentation, the final ethanol concentration was 30 g/L, a yield of 0.44 g ethanol/g of sugar(s) initially present in the hydrolysate, which is 85% of the theoretical yield. The ethanol yield with yeast was 0.096 gal/bu of processed corn assuming a QF yield of 3.04 lb/bu. The residuals from the fermentations were also evaluated as a source of corn fiber oil, which has value as a nutraceutical. Corn fiber oil yields were 8.28%wt for solids recovered following prtetreatment. 相似文献
45.
Narayani Ramakrishnan Marian E. Clay Liang-YAN Xue Helen H. Evans Antonio Rodriguez-Antunez Nancy L. Oleinick 《Photochemistry and photobiology》1988,48(3):297-303
Abstract— Chloroaluminum phthalocyanine (CAPC) is an efficient photosensitizer for the inactivation of Chinese hamster V79 cells. In order to investigate possible molecular mechanisms in the photo-dynamic action of CAPC and visible light, the induction and repair rate of two classes of DNA lesions have been determined, i.e. DNA single-strand breaks and DNA-protein cross-links. In cells pretreated with 1 μ.M CAPC, a fluence of 12 kJ/m2 of red light (>600 nm) kills approximately 50% of the cells and induces 3 to 3.5 Gy-equivalents of single-strand breaks. The repair of these breaks was slower than the repair of single-strand breaks induced by -irradiation. The photodynamic action of CAPC also induces a large number of DNA-protein cross-links which, in contrast to -radiation-induced DNA-protein cross-links, do not appear to be repaired during 4 h of post-treatment incubation in fresh medium. These studies suggest that DNA may be an important target for the cytotoxicity of CAPC + red light. 相似文献
46.
Eduardo Prez-Cordero Rosanna Buigas Nancy Brady Luis Echegoyen Claudia Arana Jean-Marie Lehn 《Helvetica chimica acta》1994,77(5):1222-1228
Reductive electrocrystallization at a constant current density (11.0–11.5 μA/cm2) of millimolar solutions of [M(bpy)3](PF6)2, where M = Fe, Ru, or Os, and bpy = 2,2′-bipyridine in acetonitrile containing 0.1M Bu4NPF6 results in the formation of dark crystals on the Pt cathode. The crystals grow as long, thin, and shiny needles having a hexagonal cross section of 0.1–0.5 mm in diameter. Combustion microanalyses results are consistent with the composition for [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3]. In addition, the chromophores are conserved, as confirmed by recording both the electronic and the 1H-NMR spectra after reoxidation of the electrocrystals in humid air. The spectra are identical to those for authentic samples of [Fe(bpy)3]2+, [Ru(bpy)3]2+, and [Os(bpy)3]2+. A ratio of 2.0 ± 0.1 e?/molecule is observed upon completion of the controlled potential electrolysis of a solution of [M(bpy)3]2+, which results in the precipitation of a dark solid and the almost complete fading of the color of the original solution. Unexpectedly, the crystals do not exhibit an ESR signal. These data indicate the formation of novel materials, crystalline [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3]. 相似文献
47.
Applied Biochemistry and Biotechnology - 相似文献
48.
The microwave spectrum of ethyl fluoroformate displays strong a-type R branch transitions from two rotameric forms. One species (extended form) has rotational constants A0 = 9191.3(9) MHz, B0 = 2112.61(1) MHz, C0 = 1756.73(1) MHz which are consistent with a syn-anti (τ1(OCOC) = 0°, r2(cocc) = 180°) planar heavy atom structure. The second species (compact form) has rotational constants A0 = 7760(3) MHz, B0 = 2388.38(4) MHz, C0 = 2102.47(3) MHz which are consistent with a syn-gauche (τ1(ococ) = 0°, τ2(cocc) ˜ 90°) structure. The two conformational forms have approximately equal energy (0 ± 40 cm−1). Four vibrational satellites of the extended species have been analyzed yielding a torsional frequency around the O-ethyl bond of 70(10) cm−1. Three vibrational satellites attributed to the O-ethyl torsion of the compact species have been analyzed yielding a vibrational frequency of 90(10) cm−1. Approximate Fourier coefficients of a three term potential function for internal rotation about the O-ethyl bond have been determined. Vibrational satellites attributed to the first excited states of the O-ester torsion have been analyzed for both conformers. The torsional vibrational frequency around the O-ester bond is 110(15) cm−1 for the extended conformers and 120(20) cm−1 for the compact. 相似文献
49.
50.