全文获取类型
收费全文 | 202篇 |
免费 | 3篇 |
专业分类
化学 | 148篇 |
数学 | 19篇 |
物理学 | 38篇 |
出版年
2022年 | 3篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2019年 | 1篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 3篇 |
2015年 | 1篇 |
2014年 | 6篇 |
2013年 | 10篇 |
2012年 | 12篇 |
2011年 | 15篇 |
2010年 | 17篇 |
2009年 | 9篇 |
2008年 | 18篇 |
2007年 | 13篇 |
2006年 | 15篇 |
2005年 | 12篇 |
2004年 | 5篇 |
2003年 | 7篇 |
2002年 | 9篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 4篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有205条查询结果,搜索用时 15 毫秒
11.
Most branch-and-bound algorithms in global optimization depend on convex underestimators to calculate lower bounds of a minimization objective function. The $\alpha $ BB methodology produces such underestimators for sufficiently smooth functions by analyzing interval Hessian approximations. Several methods to rigorously determine the $\alpha $ BB parameters have been proposed, varying in tightness and computational complexity. We present new polynomial-time methods and compare their properties to existing approaches. The new methods are based on classical eigenvalue bounds from linear algebra and a more recent result on interval matrices. We show how parameters can be optimized with respect to the average underestimation error, in addition to the maximum error commonly used in $\alpha $ BB methods. Numerical comparisons are made, based on test functions and a set of randomly generated interval Hessians. The paper shows the relative strengths of the methods, and proves exact results where one method dominates another. 相似文献
12.
Saario SM Palomäki V Lehtonen M Nevalainen T Järvinen T Laitinen JT 《Chemistry & biology》2006,13(8):811-814
Previous studies indicate that in brain tissue the endocannabinoid 2-AG is inactivated by monoglyceride lipase (MGL)-catalyzed hydrolysis, and a recent report has indicated that MGL activity could be specifically inhibited by URB754 . In the present study, URB754 failed to inhibit 2-AG hydrolysis in rat brain preparations. In addition, brain cryosections were employed to assess whether URB754 could facilitate the detection of 2-AG-stimulated G protein activity. Nevertheless, whereas pretreatment with PMSF readily allowed detection of 2-AG-stimulated G protein activity, URB754 was ineffective. In contrast to previous claims, brain FAAH activity was also resistant to URB754. Thus, in our hands URB754 was not able to block the endocannabinoid-hydrolyzing enzymes and cannot serve as a lead structure for future development of MGL-specific inhibitors. 相似文献
13.
Comparison of different methods for the determination of volatile organic compounds in water samples
The aim of this work was to compare the characteristics of three methods, membrane inlet mass spectrometry (MIMS), purge-and-trap gas chromatography-mass spectrometry (P&T) and static headspace gas chromatography (HSGC), for the determination of volatile organic compounds in water samples as used in routine analysis. The characteristics examined included linear dynamic ranges, detection limits of selected environmentally hazardous volatile organic compounds (e.g. toluene, benzene and trichloroethene) in water, required analysis time and reproducibility of the analytical methods. The MIMS and P&T methods had the lowest detection limits for all the tested compounds, ranging from 0.1 to 5 mug 1(-1). Linear dynamic ranges using the MIMS method were about four orders of magnitude and using the P&T method about two orders of magnitude. Detection limits of the HSGC method were 10-100 times higher than those of the other two methods, but the linear dynamic ranges were larger, even up to six orders of magnitude. The analysis time per sample was shortest for the MIMS method, from 5 to 10 min, and ranged around from 35 to 45 min for the HSGC and P&T methods. The reproducibilities of the methods were of the same order of magnitude, in the range of 1-13%. Agreement between the analytical results obtained for spiked samples and for environmental water samples by the three different methods was very good. 相似文献
14.
Chemical studies on antioxidant mechanisms and free radical scavenging properties of lignans 总被引:1,自引:0,他引:1
Eklund PC Långvik OK Wärnå JP Salmi TO Willför SM Sjöholm RE 《Organic & biomolecular chemistry》2005,3(18):3336-3347
The antioxidant activity, in terms of radical scavenging capacity, of altogether 15 different lignans was measured by monitoring the scavenging of the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH). The effect of differences in skeletal arrangement or the degree of oxidation of the lignans was investigated in a structure-activity relationship study. A large variety in the radical scavenging capacities of the different lignans was observed and related to some structural features. Lignans with catechol (3,4-dihydroxyphenyl) moieties exhibited the highest radical scavenging capacity, while the corresponding guaiacyl (3-methoxy-4-hydroxyphenyl) lignans showed a slightly weaker scavenging capacity. In addition, the butanediol structure was found to enhance the activity, whereas a higher degree of oxidation at the benzylic positions decreased the activity. Additionally, the readily available lignans (-)-secoisolariciresinol, a mixture of hydroxymatairesinol epimers and (-)-matairesinol were studied in more detail, including kinetic measurements and identification of oxidation products in the reactions with DPPH and ABAP (2,2-azobis(2-methylpropionamidine) dihydrochloride. The identification of reaction products, by GC-MS, HPLC-MS and NMR spectroscopy, showed that dimerisation of the two aromatic moieties was the major radical termination reaction. Also, the formation of adducts was a predominant reaction in the experiments with ABAP. The kinetic data obtained from the reactions between the lignans and DPPH indicated a complex reaction mechanism. 相似文献
15.
Viktorova OS Kogan VT Manninen SA Kotiaho T Ketola RA Dubenskii BM Parinov SP Smirnov OV 《Journal of the American Society for Mass Spectrometry》2004,15(6):823-831
Sudden sampling introduction into a membrane inlet mass spectrometer (MIMS) considerably improves the selectivity of the membrane inlet and is therefore applicable even for compounds with low permeabilities through a silicone membrane. In this study the basics of cyclic non-steady-state sudden increase sample injection were studied using a three-membrane inlet and a portable sector double-focusing mass spectrometer. The operational parameters of the inlet system providing the most efficient enrichment of volatile organic compounds (VOCs) in air were defined. Simulation of the diffusion process following sudden sample introduction into the three-membrane inlet was also carried out. Experimental testing of the three-membrane inlet system with the cyclic sudden sample injection mode for benzene, toluene, styrene, and xylene in air was performed. The simulation and the experimental results demonstrated that, when this mode is used, the VOCs/nitrogen relative enrichment factor of samples introduced into the mass spectrometer equipped with a three-membrane inlet is increased by a factor of approximately 10(5) compared with a direct introduction method. This effect may be used to decrease detection limits of compounds obtained with mass spectrometry to decrease matrix flow through the inlet at the same detection limits. 相似文献
16.
Bernas A Kumar N Mäki-Arvela P Laine E Holmbom B Salmi T Murzin DY 《Chemical communications (Cambridge, England)》2002,(10):1142-1143
Development of a new heterogeneous catalytic pathway for isomerization of linoleic acid to conjugated linoleic acids at mild reaction conditions over Ni/H-MCM-41 in a soluted system. 相似文献
17.
18.
Andreas Bernas Birgitta Peltopakka Päivi Mäki-Arvela Kari Eränen Tapio Salmi Dmitry Yu. Murzin 《Research on Chemical Intermediates》2007,33(7):645-654
Dimethoxyborane was prepared by the reaction of trimethoxyboroxine, sodium borohydride and trimethyl borate in diethylene
glycol dimethyl ether solvent at 70°C under atmospheric pressure followed by distillation to increase the purity and analyzed
in liquid phase by FT-IR. The concentration of dimethoxyborane was identified by hydrolysis with water, which yields boric
acid, methanol and hydrogen, whereas the generated hydrogen was analyzed by the mass detector of a volumetric flow apparatus.
The FT-IR absorbance peak area showed a linear dependence on dimethoxyborane concentration in the wavenumber range 873 to
950 cm−1 for samples with dimethoxyborane concentrations 0 to 6.2 wt% in trimethyl borate. Data fitting using the least square method
gave an R
2 value of 97%. 相似文献
19.
Z-configured 1,4-diene or β,γ-unsaturated carbonyl systems are readily available by the Wittig reaction. Isomerization required for access into the E-series can easily be accomplished by irradiation using an ordinary tungsten lamp and diphenyl disulphide sensitizer. There is very little formation of conjugated isomers (less than 1%). 相似文献
20.
Andreas Lundell Joakim Westerlund Tapio Westerlund 《Journal of Global Optimization》2009,43(2-3):391-405
In this paper some transformation techniques, based on power transformations, are discussed. The techniques can be applied to solve optimization problems including signomial functions to global optimality. Signomial terms can always be convexified and underestimated using power transformations on the individual variables in the terms. However, often not all variables need to be transformed. A method for minimizing the number of original variables involved in the transformations is, therefore, presented. In order to illustrate how the given method can be integrated into the transformation framework, some mixed integer optimization problems including signomial functions are finally solved to global optimality using the given techniques. 相似文献