全文获取类型
收费全文 | 1071篇 |
免费 | 31篇 |
专业分类
化学 | 781篇 |
晶体学 | 3篇 |
力学 | 34篇 |
数学 | 132篇 |
物理学 | 152篇 |
出版年
2023年 | 12篇 |
2022年 | 32篇 |
2021年 | 47篇 |
2020年 | 30篇 |
2019年 | 21篇 |
2018年 | 21篇 |
2017年 | 12篇 |
2016年 | 36篇 |
2015年 | 33篇 |
2014年 | 29篇 |
2013年 | 45篇 |
2012年 | 90篇 |
2011年 | 78篇 |
2010年 | 29篇 |
2009年 | 36篇 |
2008年 | 67篇 |
2007年 | 61篇 |
2006年 | 62篇 |
2005年 | 41篇 |
2004年 | 36篇 |
2003年 | 25篇 |
2002年 | 37篇 |
2001年 | 6篇 |
2000年 | 10篇 |
1999年 | 5篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 13篇 |
1995年 | 12篇 |
1994年 | 8篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 11篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 9篇 |
1979年 | 7篇 |
1978年 | 8篇 |
1977年 | 8篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1971年 | 4篇 |
1967年 | 3篇 |
1966年 | 3篇 |
排序方式: 共有1102条查询结果,搜索用时 15 毫秒
131.
P. Sreejith Shankar Serena Bigotti Paolo Lazzari Ilaria Manca Marco Spiga Monica Sani Matteo Zanda 《Tetrahedron letters》2013
Tubulysins are potent anti-mitotic natural compounds and a scalable and efficient synthetic route for generation of its analogues has been developed and extended to the synthesis of diastereoisomers and N-terminal analogues of tubulysin-U. Structure–activity-relationship studies on these synthetic analogues reaffirmed the significance of native stereochemistry of tubulysins for optimal biological activity and cytotoxicity. However, while modification of Tup stereochemistry has only minor effect on the tubulysins cytotoxicity, Tuv stereochemistry is critically important and modification of either Tuv stereocentre produced a dramatic drop in cytotoxicity. 相似文献
132.
11,11′-Dithiobis[1-(2-bromo-2-methylpropionyloxy)undecane], a conventional initiator for grafting polymers from gold surfaces, was synthesized in two steps from 11-mercapto-1-undecanol in 88–92% overall yield. Oxidative dimerization of 11-mercapto-1-undecanol with a catalytic amount of sodium iodide and 30% hydrogen peroxide in ethyl acetate proceeded in 96% yield. Esterification with 2-bromoisobutyryl bromide in dichloromethane was clean and almost quantitative (92% yield) with pyridine used as base, whereas triethylamine gave a messy reaction (64% yield). Alternatively, esterification with 2-bromo-2-methyl-propanoic acid in dichloromethane occurred readily under Steglich's conditions with N,N′-dicyclohexylcarbodiimide (DCC) and a catalytic amount of dimethylaminopyridine (DMAP; 88% yield). 相似文献
133.
Serena Fantasia Dr. Jonathan D. Egbert Václav Jurčík Dr. Catherine S. J. Cazin Dr. Heiko Jacobsen Dr. Luigi Cavallo Prof. Dr. D. Michael Heinekey Prof. Dr. Steven P. Nolan Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(28):5182-5186
An even split : In sharp contrast with the general behavior of Pd0 complexes, [Pd(IPr)(PCy3)] is able to activate the H? H bond. The resulting trans‐[Pd(H)2(IPr)(PCy3)] is the first isolated mononuclear dihydride palladium compound. Its formation is supported by multinuclear NMR spectroscopy, density functional calculations, and X‐ray diffraction studies. The stability and reactivity of this new species are examined.
134.
Serena Silvi Dr. Edwin C. Constable Prof. Catherine E. Housecroft Prof. Jonathon E. Beves Dr. Emma L. Dunphy Dr. Massimiliano Tomasulo Dr. Françisco M. Raymo Prof. Alberto Credi Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(1):178-185
Molecular logic gates process physical or chemical “inputs” to generate “outputs” based on a set of logical operators. We report the design and operation of a chemical ensemble in solution that behaves as integrated AND, OR, and XNOR gates with optical input and output signals. The ensemble is composed of a reversible merocyanine‐type photoacid and a ruthenium polypyridine complex that functions as a pH‐controlled three‐state luminescent switch. The light‐triggered release of protons from the photoacid is used to control the state of the transition‐metal complex. Therefore, the two molecular switching devices communicate with one another through the exchange of ionic signals. By means of such a double (optical–chemical–optical) signal‐transduction mechanism, inputs of violet light modulate a luminescence output in the red/far‐red region of the visible spectrum. Nondestructive reading is guaranteed because the green light used for excitation in the photoluminescence experiments does not affect the state of the gate. The reset is thermally driven and, thus, does not involve the addition of chemicals and accumulation of byproducts. Owing to its reversibility and stability, this molecular device can afford many cycles of digital operation. 相似文献
135.
Julia Schöffel Andrey Yu. Rogachev Dr. Serena DeBeer George Dr. Peter Burger Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(26):4734-4738
An N for Ir : The synthesis and X‐ray crystal structure of a late‐transition‐metal complex with a terminal nitrido ligand and its hydrogenation to the related amido complex are reported (see scheme).
136.
Gilbert Mercieca Sara Odoardi Serena Mestria Marisa Cassar Sabina Strano‐Rossi 《Journal of separation science》2020,43(14):2858-2868
The constant emergence of new psychoactive substances is a challenge to clinical and forensic toxicologists who need to constantly update analytical techniques to detect them. A large portion of these substances are synthetic cannabinoids. The aim of this study was to develop a rapid and simple method for the determination of synthetic cannabinoids and their metabolites in urine and blood using gas chromatography–mass spectrometry. The method involves an ultrasound‐assisted dispersive liquid–liquid microextraction that implies a rapid procedure, giving excellent extraction efficiencies with minimal use of toxic solvents. This is followed by silylation and analysis with gas chromatography–mass spectrometry. The chromatographic method allows for the separation and identification of 29 selected synthetic cannabinoids and some metabolites. The method was validated on urine and blood samples with the ability to detect and quantify all analytes with satisfactory limits of detection (from 1 to 5 ng/mL), limits of quantification (5 ng/mL), and selectivity and linearity (in the range of 5–200 ng/mL). The developed assay is highly applicable to laboratories with limited instrumental availability, due to the use of efficient and low‐cost sample preparation and instrumental equipment. The latter may contribute to enhance the detection of new psychoactive substances in clinical and forensic toxicology laboratories. 相似文献
137.
Takabayashi Y McDonald MT Papanikolaou D Margadonna S Wu G Liu RH Chen XH Prassides K 《Journal of the American Chemical Society》2008,130(29):9242-9243
The superconducting transition temperature of the high-Tc SmO1-xFxFeAs superconductors increases monotonically as the F-doping level x increases to 0.20. High-pressure magnetization experiments reveal a strong sensitivity of Tc to interatomic distances in the underdoped regime (x = 0.12) with the pressure coefficient of Tc, d(ln Tc)/dP being strongly positive. However, as the doping level increases further to x = 0.15, we find that this sensitivity is strongly suppressed and at the same time, d(ln Tc)/dP sharply switches over to assume negative values with Tc decreasing with increasing applied pressure. The abrupt change in the pressure response of the superconducting properties of the SmO1-xFxFeAs phases coincides with the putative existence of a quantum critical point (QCP) near x approximately 0.14, as proposed by resistivity and Hall effect measurements. 相似文献
138.
Margadonna S Takabayashi Y McDonald MT Kasperkiewicz K Mizuguchi Y Takano Y Fitch AN Suard E Prassides K 《Chemical communications (Cambridge, England)》2008,(43):5607-5609
The newly discovered superconductor FeSe(1-x) (x approximately 0.08, T(c)(onset) approximately 13.5 K at ambient pressure rising to 27 K at 1.48 GPa) exhibits a structural phase transition from tetragonal to orthorhombic below 70 K at ambient pressure-the crystal structure in the superconducting state shows remarkable similarities to that of the REFeAsO(1-x)F(x) (RE = rare earth) superconductors. 相似文献
139.
Kroly Vkey Duncan M. F. Edwards Luigi F. Zerilli Marianna Mk Jzsef Tams Vittorio Raverdino Antonio Selva 《Journal of mass spectrometry : JMS》1990,25(9):465-474
Results of 16 different mass spectrometric ionization and sample-introduction methods are compared for the case of a thermally very labile antibiotic, rifapentine. These suggest that extensive thermal decomposition occurs during evaporation when the sample can come into contact with hot metal parts, usually the source housing. The intensity of the molecular ion and the extent of fragmentation depend on various parameters, such as the ionization process, positive or negative-ion detection and the type of sample introduction. The most informative methods for rifapentine seem to be ‘in-beam’ electron impact, negative ionization with particle beam and direct liquid introduction interfaces and positive- and negative-ion fast atom bombardment. 相似文献
140.
Valentina Rittscher Serena Kuch Matthias Rehahn 《Macromolecular rapid communications》2016,37(10):814-819
For the first time, the successful Gilch synthesis of poly(ortho‐phenylene vinylenes) (ortho‐PPVs) is reported. The molar mass of the constitutionally homogeneous ortho‐PPVs reaches values as high as Mw ≈ 300 000 Da. The ortho‐connectivity of the repeating units forces the chains to assume closely packed conformations even in good solvents. Significant perturbation of the π–electron systems and considerable shortening of the conjugation lengths are the consequences. UV–vis absorption and photoluminescence maxima consequently are shifted clearly toward shorter wavelengths compared to, e.g., classic para‐PPVs.