全文获取类型
收费全文 | 2007篇 |
免费 | 83篇 |
国内免费 | 6篇 |
专业分类
化学 | 1448篇 |
晶体学 | 22篇 |
力学 | 49篇 |
数学 | 355篇 |
物理学 | 222篇 |
出版年
2023年 | 20篇 |
2022年 | 36篇 |
2021年 | 47篇 |
2020年 | 56篇 |
2019年 | 41篇 |
2018年 | 28篇 |
2017年 | 32篇 |
2016年 | 61篇 |
2015年 | 48篇 |
2014年 | 61篇 |
2013年 | 139篇 |
2012年 | 110篇 |
2011年 | 125篇 |
2010年 | 67篇 |
2009年 | 69篇 |
2008年 | 113篇 |
2007年 | 78篇 |
2006年 | 81篇 |
2005年 | 90篇 |
2004年 | 64篇 |
2003年 | 59篇 |
2002年 | 52篇 |
2001年 | 39篇 |
2000年 | 23篇 |
1999年 | 19篇 |
1998年 | 26篇 |
1997年 | 31篇 |
1996年 | 13篇 |
1995年 | 15篇 |
1994年 | 13篇 |
1993年 | 18篇 |
1992年 | 22篇 |
1991年 | 18篇 |
1990年 | 17篇 |
1989年 | 8篇 |
1988年 | 9篇 |
1985年 | 15篇 |
1984年 | 15篇 |
1983年 | 18篇 |
1982年 | 16篇 |
1981年 | 27篇 |
1980年 | 31篇 |
1979年 | 15篇 |
1978年 | 17篇 |
1977年 | 13篇 |
1976年 | 17篇 |
1975年 | 21篇 |
1974年 | 17篇 |
1973年 | 20篇 |
1966年 | 7篇 |
排序方式: 共有2096条查询结果,搜索用时 30 毫秒
991.
Marcel Schulz Adrian Gehl Jakob Schlenkrich Hendrik A. Schulze Prof. Dr. Stefan Zimmermann Dr. Andreas Schaate 《Angewandte Chemie (International ed. in English)》2018,57(39):12961-12965
A calixarene‐based metal–organic framework (Zr‐cal, [Zr6O4(OH)4(FA)6]2(cal)3], FA=formate, cal=1,3‐alt‐25,26,27,28‐tetrakis[(carboxy)methoxy]calixarene) was synthesized and characterized by single‐crystal X‐ray diffraction. The three‐dimensional framework is a 4,6‐connected network of gar topology and exhibits two equal but nonintersecting three‐dimensional pore systems. It has a specific BET surface area of 670 m2 g?1, and the calixarene cavities are accessible through the pore systems. The exposed calixarenes can be used for the visual detection and encapsulation of NO2 through the formation of deeply colored charge–transfer complexes inside the MOF. The highly selective complexation was analyzed by UV/Vis and IR spectroscopy, and the stability of the material was confirmed by powder X‐ray diffraction and 1H NMR spectroscopy. Finally, the MOF was used as a sensor material in a home‐made sensor cell and showed high sensitivity for NO2. 相似文献
992.
The author presents a generalization of THORPE'S method for the analysis of complex mixtures and describes an application of it to the determination of the γ-isomer in technical hexachlorcyclohexane. This method has the advantage of not requiring expensive apparatus.Portions of the materials under examination are treated with CH3OH at 20° C in such a way as to obtain, on the one hand, a solution saturated with regard to the (α + β ) isomers and, on the other hand, a solution saturated with regard to the (α + β + γ) isomers. Having determined tlie amounts of the products dissolved inthese solutions, the solubilities in CH3OH enable the contents of the (α + β) and the γ-isomers to be calculated. 相似文献
993.
Marcel Wild 《Order》1990,7(4):387-400
If two subspaces V and V of a sesquilinear space E are congruent (i.e., there is an isometry : E E with (V)=V) then their corresponding quadratic lattices V(V, E) and V(V, E) are isomorphic. It is shown that the converse holds for important types of sesquilinear spaces E, provided that dim(E) 3. However, the converse generally fails if dim(E) 3. 相似文献
994.
Numerical investigation of a multiserver retrial model 总被引:5,自引:0,他引:5
We consider a queueing model in which customers arrive in a Poisson stream to be served by one ofc servers. Each arriving customer enters a pool of active customers and starts generating requests for service at exponentially distributed time intervals at rate until he finds a free server and begins service. An analytical solution of this model is difficult and does not lend itself to numerical implementation. In this paper, we make a simplifying approximation, based on understanding of the physical behavior of the system, which yields an infinitesimal generator with a modified matrix-geometric equilibrium probability vector. That vector can be very efficiently computed even for high congestion levels. Illustrative numerical examples demonstrate the effectiveness of the approximation as well as the effect of the retrial rate on the system behavior for various levels of congestion. This study shows how numerical results for analytically intractable systems can be obtained by combining intuition with efficient algorithmic methods.This author's research was supported in part by Grants Nos. ECS-88-03061 from the National Science Foundation and AFOSR-88-0076 from the Air Force Office of Scientific Research. 相似文献
995.
Amorphous ribbons of Fe73.5Nb3Cu1Si13.5B9 have been annealed above the crystallization temperature. Annealed samples consisted of crystalline and amorphous phases in a wide temperature range. Two samples of different thicknesses of 33 µm and 27 µm were isothermally annealed at a temperature of 545°C from 0.5 to 5 h in a vacuum furnace. The amount of crystalline phase increases rapidly in the ticker sample. The crystalline part of the Mössbauer spectrum consists of four sharp sextets which can be assigned to a DO3-structure FeSi alloy. After 700°C annealing the amorphous phase was not observed and the crystalline phase consisted of the DO3-structure FeSi alloy, paramagnetic FeNbB and presumably Fe23B6 and Fe3SiB2. 相似文献
996.
Michael Schmitt Marcel B?hm Christian Ratzer Daniel Krügler Karl Kleinermanns Ivo Kalkman Giel Berden W Leo Meerts 《Chemphyschem》2006,7(6):1241-1249
The rotationally resolved UV spectra of the electronic origins of five isotopomers of the phenol dimer have been measured. The complex spectra are analyzed using a fitting strategy based on a genetic algorithm. The intermolecular geometry parameters have been determined from the inertial parameters for both electronic states and compared to the results of ab initio calculations. In the electronic ground state, a larger hydrogen-bond length than in the ab initio calculations is found together with a smaller tilt angle of the aromatic rings, which shows a more pronounced dispersion interaction. In the electronically excited state, the hydrogen-bond length decreases, as has been found for other hydrogen-bonded clusters of phenol, and the two aromatic rings are tilted less toward each other. 相似文献
997.
Thermolysis of several trans-1-isopropenyl-4-methylene-spiro[2.x]- alkanes (x = 4,5) in xylene solution at 130° causes quantitative rearrangement to 1-methylene-2-(3′-methylbut-2′-enyl)cycloalkanes ( – ). 相似文献
998.
Azadeh Golshan Hamid Abdollahi Samira Beyramysoltan Marcel Maeder Klaus Neymeyr Robert Rajkó Mathias Sawall Romá Tauler 《Analytica chimica acta》2016
Soft modelling or multivariate curve resolution (MCR) are well-known methodologies for the analysis of multivariate data in many different application fields. Results obtained by soft modelling methods are very likely impaired by rotational and scaling ambiguities, i.e. a full range of feasible solutions can describe the data equally well while fulfilling the constraints of the system. These issues are severely limiting the applicability of these methods and therefore, they can be considered as the most challenging ones. The purpose of the current review is to describe and critically compare the available methods that attempt at determining the range of ambiguity for the case of 3-component systems. Theoretical and practical aspects are discussed, based on a collection of simulated examples containing noise-free and noisy data sets as well as an experimental example. 相似文献
999.
Florin Marcel Musteata Manuel Sandoval Juan C. Ruiz-Macedo Kathleen Harrison Dennis McKenna William Millington 《Analytica chimica acta》2016
Introduction
Although solid phase microextraction (SPME) has been used extensively for fingerprinting volatile compounds emitted by plants, there are very few such reports for direct insertion SPME. In this research, direct contact of SPME probes with the interstitial fluid of plants was investigated as a method for phytochemical analysis.Objective
Medicinal plants from the Amazon have been the source of numerous drugs used in western medicine. However, a large number of species used in traditional medicine have not been characterized chemically, partly due to the difficulty of field work. In this project, the phytochemical composition of plants from several genera was fingerprinted by combining convenient field sampling by solid phase microextraction (SPME) with laboratory analysis by LC-MS. The new method was compared with classical sampling followed by liquid extraction (LE).Methodology
SPME probes were prepared by coating stainless steel wires with a mixture of polyacrylonitrile and either RP-amide or HS-F5 silica particles. Sampling was performed by inserting the microextraction probes into various tissues of living plants in their natural environment. After in vivo extraction, the probes were sealed under vacuum and refrigerated until analyzed. The probes were desorbed in mobile phase and analyzed on a Waters Acquity UPLC with triple quadrupole mass spectrometer in positive ion mode.Results
Twenty Amazonian plant species were sampled and unique metabolomic fingerprints were obtained. In addition, quantitative analysis was performed for previously identified compounds in three species. Comparison of the fingerprints obtained by in vivo SPME with those obtained by LE showed that 27% of the chromatographic features were unique to SPME, 57% were unique to LE, and 16% were common to both methods.Conclusion
In vivo SPME caused minimal damage to the plants, was much faster than traditional liquid extraction, and provided unique fingerprints for all investigated plants. SPME revealed unique chromatographic features, undetected by traditional extraction, although it produced only half as many peaks as ethanol extraction. 相似文献1000.
Inside Cover: Homo‐ and Heterodinuclear Ir and Rh Imine‐functionalized Protic NHC Complexes: Synthetic,Structural Studies,and Tautomerization/Metallotropism Insights (Chem. Eur. J. 8/2016)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)