全文获取类型
收费全文 | 1100篇 |
免费 | 34篇 |
国内免费 | 10篇 |
专业分类
化学 | 671篇 |
晶体学 | 6篇 |
力学 | 25篇 |
数学 | 246篇 |
物理学 | 196篇 |
出版年
2023年 | 6篇 |
2022年 | 5篇 |
2021年 | 11篇 |
2020年 | 17篇 |
2019年 | 20篇 |
2018年 | 17篇 |
2017年 | 17篇 |
2016年 | 24篇 |
2015年 | 31篇 |
2014年 | 16篇 |
2013年 | 57篇 |
2012年 | 62篇 |
2011年 | 71篇 |
2010年 | 47篇 |
2009年 | 50篇 |
2008年 | 67篇 |
2007年 | 58篇 |
2006年 | 75篇 |
2005年 | 58篇 |
2004年 | 62篇 |
2003年 | 55篇 |
2002年 | 46篇 |
2001年 | 15篇 |
2000年 | 18篇 |
1999年 | 9篇 |
1998年 | 27篇 |
1997年 | 20篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 7篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 10篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1984年 | 8篇 |
1983年 | 5篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 6篇 |
1978年 | 4篇 |
1974年 | 3篇 |
1934年 | 3篇 |
1933年 | 5篇 |
1919年 | 2篇 |
1905年 | 2篇 |
排序方式: 共有1144条查询结果,搜索用时 375 毫秒
11.
12.
M. Jonathan Fray Paul Allen Paul R. Bradley Clare E. Challenger Michael Closier Tim J. Evans Mark L. Lewis John P. Mathias Carly L. Nichols Yvonne M. Po-Ba Hayley Snow Mark H. Stefaniak Hannah V. Vuong 《Tetrahedron》2006,62(29):6869-6875
The synthesis of ten substituted aminomethylene tetrahydro-isoquinolines is described, proceeding in eight steps from 5-hydroxyisoquinoline via reductive amination of N-Boc tetrahydro-isoquinoline 5-carboxaldehyde. Likewise, reductive amination was used to prepare four substituted dihydro-isoindoles from the corresponding aldehyde. The dihydro-isoindole ring system was conveniently accessed via a 2+2+2 cycloaddition reaction. 相似文献
13.
14.
Tuo Jiang Samuele Bordi Angus E. McMillan Kuang-Yen Chen Fumito Saito Paula L. Nichols Benedikt M. Wanner Jeffrey W. Bode 《Chemical science》2021,12(20):6977
The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement. 相似文献
15.
The influence of moisture in the presence and absence of air on the solid state degradation of l-ascorbic acid has been investigated previously [1]. Reaction kinetics were studied using tristimulus colorimetry and a quantitative high performance liquid chromatographic assay for both total l-ascorbic acid and dehydroascorbic acid. The degradation gave rise to a discolouration of the samples, the most severely degraded samples were almost black in appearance although over 68% w/w of the l-ascorbic acid remained. The samples were analyzed for the presence of carbonyl compounds, furan related compounds, compounds responsible for the discolouration and evolution of carbon dioxide. No 2,4-dinitrophenylhydrazine (2,4-DNP) derivatives of carbonyl compounds or furan related compounds were detected by HPLC. An HPLC screening procedure was developed which was used to monitor for compounds responsible for the discolouration, at least eight unknown compounds were resolved and a relative response factor of 5.47 was assigned to them with respect to l-ascorbic acid at 280 nm. One mole of carbon dioxide was evolved per mole of l-ascorbic acid. This paper describes the investigation into the identity of the degradation products. 相似文献
16.
One of the major techniques used for the method development of ternary and quaternary high performance liquid chromatography (HPLC) systems has been to use mixture designs, often referred to as "Glajch's Triangle". This technique does not allow for the systematic and simultaneous optimization of other factors such as gradient time, pH and temperature that affect the quality of separations. An alternative approach is to use experimental designs. The condition, however, that the composition of all components of the mobile phase must total 100% presents a problem when trying to mathematically represent ranges of each mobile phase constituent of a ternary or quaternary system. A method is described here, based on spherical coordinate representations, that adheres to the constraints of the mobile phase composition and allows experimental designs, such as central composite and factorial designs, to be applied to the simultaneous optimization of the mobile phase composition. Other factors, in particular temperature and gradient time, can then be included in the design. As a result of applying these designs to the HPLC separation of phenols and corticosteroids, it was found necessary to include three-way interactions between experimental factors in the model. The significance of these interactions shows that they need to be considered in HPLC method development. 相似文献
17.
Explicit expressions are presented for calculating vibration-to-translation (VT) energy conversion probabilities, essential in molecular laser isotope separation. VT conversions in molecular collisions occur by two mechanisms: (1) high-energy impact transfers prevailing at higher temperatures, and (2) Van der Waals-bonding encounters followed by (pre-)dissociations at lower temperatures. While mechanism (1) has been studied for over fifty years culminating in the Schwartz–Slawsky–Herzberg relation, a useful analytic expression for (2) has so far been lacking. An improved dimer formation theory developed by the author together with molecular pre-dissociation physics now provides a VT conversion relation for mechanism (2), which correctly predicts observations. 相似文献
18.
Paul F. Reigler Jeff Larson Lyle Bowman 《Journal of polymer science. Part A, Polymer chemistry》1981,19(12):3247-3255
The thermal and/or catalytic degradation of chloride-containing polymers causes dehydrohalogenation which produces hydrochloric acid. A nonaqueous method has been developed for the termination of hydrochloric acid. The sample is dissolved in tetrahydrofuran and titrated potentiometrically with a standard tetrabutylammonium hydroxide solution in a 7.5% (V/V) aqueous tetrahydrofuran solution with a combination glass-calomel electrode. The method has a relative precision of ±3.7% at the 95% confidence limit and a sensitivity of 25 ppm HCI. 相似文献
19.
Periodic, self-consistent, density functional theory calculations have been performed to demonstrate that subsurface oxygen (O(sb)) dramatically increases the reactivity of the Ag(111) surface. O(sb) greatly facilitates the dissociation of H2, O2, and NO and enhances the binding of H, C, N, O, O2, CO, NO, C2H2, and C2H4 on the Ag(111) surface. This effect originates from an O(sb)-induced upshift of the d-band center of the Ag surface and becomes more pronounced at higher O(sb) coverage. Our findings point to the important role that near-surface impurities, such as O(sb), can play in determining the thermochemistry and kinetics of elementary steps catalyzed by transition metal surfaces. 相似文献
20.
A template-directed strategy to forming a bis(diimide) macrocycle through an intermediate asymmetric [2]catenane is reported. Saponification of the ester linkages within the crown ether component is much slower in the mechanically interlocked structure when compared to the free crown. The predominance of a single translational isomer leads to a dimeric structure, resulting in the generation of infinite channels within the crystal lattice. [structure: see text] 相似文献