全文获取类型
收费全文 | 663篇 |
免费 | 27篇 |
国内免费 | 1篇 |
专业分类
化学 | 528篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 58篇 |
物理学 | 88篇 |
出版年
2022年 | 10篇 |
2021年 | 17篇 |
2020年 | 8篇 |
2019年 | 16篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 15篇 |
2015年 | 13篇 |
2014年 | 19篇 |
2013年 | 32篇 |
2012年 | 50篇 |
2011年 | 69篇 |
2010年 | 25篇 |
2009年 | 23篇 |
2008年 | 42篇 |
2007年 | 31篇 |
2006年 | 37篇 |
2005年 | 18篇 |
2004年 | 32篇 |
2003年 | 24篇 |
2002年 | 29篇 |
2001年 | 3篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 17篇 |
1995年 | 6篇 |
1994年 | 7篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1990年 | 4篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1932年 | 4篇 |
1930年 | 5篇 |
1925年 | 2篇 |
1913年 | 2篇 |
1902年 | 2篇 |
排序方式: 共有691条查询结果,搜索用时 15 毫秒
11.
12.
Diego Fontana de Andrade Louise Jank Vitor Breda Rego Roberto Minozzo Marcus Vinícius Burgel Sfoggia Álvaro Bavaresco Fabiano Barreto 《Biomedical chromatography : BMC》2020,34(9):e4873
Saponins from Quillaja saponaria have been commonly used as immunomodulatory adjuvants in foot-and-mouth disease vaccines (FMDVs). However, due to the lack of consensus over the possible exacerbation of local inflammatory responses in cattle and its economic impacts, their use has been discouraged by Brazilian authorities. A qualitative method intended to determine the presence of saponins from Q. saponaria bark extracts in FMDVs was developed and validated. Instrumental analysis was performed using an liquid chromatography (LC) coupled to a quadrupole–time-of-flight–mass spectrometry (TOF-MS) system. The method was validated according to the International Conference on Harmonization Harmonized Tripartite Guideline Q2 (R1) and Brazilian Ministry of Agriculture, Livestock and Food Supply Analytical Quality Assurance Guidelines. Validation parameters were determined and considered suitable to the established criteria. The validated method has been applied in routine analysis in the National Agricultural Laboratory at Rio Grande do Sul (LANAGRO-RS). All results obtained were in agreement with the vaccine's composition described by the manufacturer. The method is easy and adequate for analysis in routine laboratories. To the best of the authors' knowledge, this is the first report of a method which intends to investigate the presence of saponins from Q. saponaria bark extracts in veterinary vaccines. 相似文献
13.
14.
Luis F. Lafuerza Louise Dyson Bruce Edmonds Alan J. McKane 《The European Physical Journal B - Condensed Matter and Complex Systems》2016,89(7):159
A recently proposed model of social interaction in voting is investigated by simplifyingit down into a version that is more analytically tractable and which allows a mathematicalanalysis to be performed. This analysis clarifies the interplay of the different elementspresent in the system – social influence, heterogeneity and noise – and leads to a betterunderstanding of its properties. The origin of a regime of bistability is identified. Theinsight gained in this way gives further intuition into the behaviour of the originalmodel. 相似文献
15.
16.
Tandon SS Dul MC Lee JL Dawe LN Anwar MU Thompson LK 《Dalton transactions (Cambridge, England : 2003)》2011,40(14):3466-3475
Ligands based on carbo- and thio-carbohydrazone cores, modified with pyridine, carboxylate and oxime ends, have been examined. They display a tautomeric versatility based on the flexible nature of the hydrazone linkages, leading to varied coordination motifs. Examples of mononuclear (Co(II), Ni(II)), dinuclear (Co(III)), 1D chain (Cu(II)) and square [2 × 2] grid (Ni(II)) complexes are obtained. Ferromagnetic (Cu(II)) and antiferromagnetic (Ni(II)) exchange is observed, with spin coupling in the Ni(II)(4) square grids propagated through the μ-O and μ-S bridges. Weak antiferromagnetic exchange (J = -6.0 cm(-1)) is observed for the μ-O bridged grid, despite the large Ni-O-Ni angles (137-141°), while for the μ-S bridged grids much stronger exchange is observed (J = -148 cm(-1), -198 cm(-1)). This is much larger than expected based on the Ni-S-Ni bridge angles (151-169°), and is associated with the soft (less polarizing than oxygen) nature of the sulfur bridge, which would allow for much more efficient transmission of spin exchange than observed in the μ-O bridged case. Structures and variable temperature magnetic data are included, and spin exchange is analyzed using normal Heisenberg exchange models. No examples involving oxime (NO) bridging are reported, which reflects the positioning of the N,O and N,S donor combinations in each ligand, and the preferred coordination through these donor atoms. 相似文献
17.
Grainger RS Patel B Kariuki BM Male L Spencer N 《Journal of the American Chemical Society》2011,133(15):5843-5852
Three peri-substituted trisulfide-2-oxides are prepared by treatment of 1,8-naphthalene dithiols with thionyl chloride and pyridine. The 1,2,3-trithiane-2-oxide ring adopts a sofa conformation in the solid state, with a pseudoaxial oxygen and evidence of ring strain (peri-interaction). Heating the trisulfide-2-oxides in the presence of a diene results in formal sulfur monoxide (SO) transfer to form unsaturated cyclic sulfoxides, along with a recyclable 1,8-naphthalene disulfide. The presence of o-methoxy or o-tert-butyl substituents on the naphthalene ring lowers the temperature and increases the rate at which SO transfer occurs. Trapping experiments and kinetic studies are consistent with the generation of triplet SO, followed by in situ trapping by diene. Transfer of SO also occurs upon irradiation at room temperature, but yields of sulfoxide are lower. Dehydration of the sulfoxides under Pummerer conditions gives thiophenes, including the naturally occurring thioperillene. Two dienes form thiophenes directly under the SO transfer conditions. The methodology is applied in a formal synthesis of the antiplatelet medication Plavix. 相似文献
18.
Anderson BJ Guino-o MA Glueck DS Golen JA DiPasquale AG Liable-Sands LM Rheingold AL 《Organic letters》2008,10(20):4425-4428
Enantioselective tandem alkylation/arylation of primary phosphines with 1-bromo-8-chloromethylnaphthalene catalyzed by Pt(DuPhos) complexes gave P-stereogenic 1-phosphaacenaphthenes (AcePhos) in up to 74% ee. Diastereoselective formation of four P-C bonds in one pot with bis(primary) phosphines gave C2-symmetric diphosphines, including the o-phenylene derivative DuAcePhos, for which the rac isomer was formed with high enantioselectivity. These reactions, which appear to proceed via an unusual metal-mediated nucleophilic aromatic substitution pathway, yield a new class of heterocycles with potential applications in asymmetric catalysis. 相似文献
19.
Umar Hayat Philip N. Bartlett George H. Dodd Michael H. Lewis 《Journal of polymer science. Part A, Polymer chemistry》1988,26(1):201-206
The surface compositions of various polymeric films, grown electrochemically on platinum foils, have been investigated by energy-dispersive x-ray analysis in conjunction with scanning electron microscopy (SEM/EDS). Comparison of the relative area ratios of peaks for the C and N Kemission lines show that the EDS may be used to study the surface composition of polymers. The evidence presented strongly suggests that there is limited structural degradation and the elemental composition is not changed under the electron beam at relatively low accelerating voltages. This technique statistically samples the repeat units of the polymer. For samples grown in both aqueous and nonaqueous solutions. SEM/EDS provides evidence for extensive contamination with oxygen. 相似文献
20.
Kenneth P. Ghiggino Louise E. Bennett Robert W. Henderson 《Photochemistry and photobiology》1988,47(1):65-72
Abstract— The absorption and fluorescence properties of porphyrin c (P c ), the porphyrin chromophore present in cytochrome c , have been determined in several solvents and micellar environments. In aqueous buffer solutions at pH 7.5 Pc may exist in both a fluorescent monomeric form with quantum yield of fluorescence, (Φf ,) ∼ 0.03, and fluorescence lifetime, (τf ) ∼ 8 ns, and as a non-fluorescent aggregate. The proportion of monomeric form is higher in organic solvents and micelles but is reduced with increasing porphyrin concentrations in aqueous solutions. Porphyrin c readily complexes with Zn2+ to produce a fluorescent chelate (Zn-P c ) with Φf , ∼ 0.02 and τf , ∼ 2 ns at pH 7.5. The yields of singlet excited oxygen formation from Pc and the Zn-P c complex are higher than observed for hematoporphyrin derivative (HpD). Both P c and Zn-P c are effective agents in tumor phototherapy and do not induce the prolonged cutaneous photosensitivity observed with the use of HpD. 相似文献