全文获取类型
收费全文 | 1133篇 |
免费 | 39篇 |
国内免费 | 6篇 |
专业分类
化学 | 806篇 |
晶体学 | 14篇 |
力学 | 19篇 |
数学 | 127篇 |
物理学 | 212篇 |
出版年
2023年 | 7篇 |
2022年 | 18篇 |
2021年 | 10篇 |
2020年 | 14篇 |
2019年 | 23篇 |
2018年 | 8篇 |
2017年 | 16篇 |
2016年 | 37篇 |
2015年 | 29篇 |
2014年 | 19篇 |
2013年 | 46篇 |
2012年 | 62篇 |
2011年 | 70篇 |
2010年 | 42篇 |
2009年 | 36篇 |
2008年 | 93篇 |
2007年 | 83篇 |
2006年 | 85篇 |
2005年 | 62篇 |
2004年 | 42篇 |
2003年 | 39篇 |
2002年 | 48篇 |
2001年 | 32篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 11篇 |
1997年 | 12篇 |
1996年 | 11篇 |
1995年 | 12篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1992年 | 19篇 |
1991年 | 11篇 |
1990年 | 12篇 |
1989年 | 14篇 |
1988年 | 10篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 15篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 10篇 |
1979年 | 3篇 |
1978年 | 9篇 |
1977年 | 3篇 |
1975年 | 4篇 |
1974年 | 3篇 |
1930年 | 2篇 |
排序方式: 共有1178条查询结果,搜索用时 0 毫秒
1.
Experimental and Theoretical Studies on the Rearrangement of 2‐Oxoazepane α,α‐Amino Acids into 2′‐Oxopiperidine β2,3,3‐Amino Acids: An Example of Intramolecular Catalysis 下载免费PDF全文
Dr. Diego Núñez‐Villanueva Dr. M. Ángeles Bonache Laura Lozano Dr. Lourdes Infantes Prof. José Elguero Prof. Ibon Alkorta Prof. M. Teresa García‐López Dr. Rosario González‐Muñiz Dr. Mercedes Martín‐Martínez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(6):2489-2500
Enantiopure β‐amino acids represent interesting scaffolds for peptidomimetics, foldamers and bioactive compounds. However, the synthesis of highly substituted analogues is still a major challenge. Herein, we describe the spontaneous rearrangement of 4‐carboxy‐2‐oxoazepane α,α‐amino acids to lead to 2′‐oxopiperidine‐containing β2,3,3‐amino acids, upon basic or acid hydrolysis of the 2‐oxoazepane α,α‐amino acid ester. Under acidic conditions, a totally stereoselective synthetic route has been developed. The reordering process involved the spontaneous breakdown of an amide bond, which typically requires strong conditions, and the formation of a new bond leading to the six‐membered heterocycle. A quantum mechanical study was carried out to obtain insight into the remarkable ease of this rearrangement, which occurs at room temperature, either in solution or upon storage of the 4‐carboxylic acid substituted 2‐oxoazepane derivatives. This theoretical study suggests that the rearrangement process occurs through a concerted mechanism, in which the energy of the transition states can be lowered by the participation of a catalytic water molecule. Interestingly, it also suggested a role for the carboxylic acid at position 4 of the 2‐oxoazepane ring, which facilitates this rearrangement, participating directly in the intramolecular catalysis. 相似文献
2.
When an organization solves a portfolio problem with public projects evaluated by multiple criteria, in which the economic dimension is not essential or not well characterized, the classical methods are not useful. We propose a non-linear preference model developed from normative Value Theory and using fuzzy sets to model some sources of imprecision. This model can be considered as a generalization of the classical approaches. However, the optimization problem is very complex in order to be solved with non-linear programming techniques. Therefore, the model is exploited by an evolutionary algorithm, able to achieve a strong improvement of the quality of solution. 相似文献
3.
E. Casarejos P. Armbruster L. Audouin J. Benlliure M. Bernas A. Boudard R. Legrain S. Leray B. Mustapha S. Czajkowski T. Enqvist B. Fernandez J. Pereira M. Pravikoff F. Rejmund K. -H. Schmidt C. Stephan J. Taieb L. Tassan-Got C. Villagrasa C. Volant W. Wlazlo 《Physics of Atomic Nuclei》2003,66(8):1413-1420
The isotopic production cross sections of heavy residues in relativistic heavy-ion collisions have been investigated in inverse kinematics. The primary reaction products were fully identified in mass and atomic number prior to beta decay using the fragment separator FRS. The huge collection of data obtained helps in the understanding of the two main reaction mechanisms involved: fragmentation and fission. These data provide basic information for future radioactive ion beam facilities and for technical applications like intense neutron sources by means of spallation targets. 相似文献
4.
Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature. 相似文献
5.
Lourdes Callau Marta Giamberini Jos Antonio Reina Ana Mantecn 《Journal of polymer science. Part A, Polymer chemistry》2006,44(6):1877-1889
The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P4 and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and 1H and 13C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C2 mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006 相似文献
6.
Weir AJ Klein SR Abrams G Adolphsen CE Akerlof C Alexander JP Alvarez M Amidei D Baden AR Ballam J Barish BC Barklow T Barnett BA Bartelt J Blockus D Bonvicini G Boyarski A Boyer J Brabson B Breakstone A Brom JM Bulos F Burchat PR Burke DL Butler F Calvino F Cence RJ Chapman J Cords D Coupal DP DeStaebler HC Dorfan DE Dorfan JM Drell PS Feldman GJ Fernandez E Field RC Ford WT Fordham C Frey R Fujino D Gan KK Gidal G Gladney L Glanzman T Gold MS Goldhaber G Green A Grosse-Wiesmann P Haggerty J 《Physical review D: Particles and fields》1990,41(5):1384-1388
7.
N. S. Nesterenko F. Thibault-Starzyk V. Montouilliout V. V. Yushchenko C. Fernandez J.-P. Gilson F. Fajula I. I. Ivanova 《Kinetics and Catalysis》2006,47(1):40-48
A new approach to the evaluation of the accessibility of acid sites in microporous/mesoporous materials is developed and tested
using a series of dealuminated mordenites. This approach is based on an IR-spectroscopic study of the consecutive adsorption
of substituted alkylpyridines (pyridine, 2,4,6-trimethylpyridine, and 2,4,6-triethylpyridine) and carbon monoxide. This method
allowed us to determine the strength and number of acid sites with various degrees of accessibility. The adsorption of 2,4,6-triethylpyridine
on various types of materials is studied. The extinction coefficients of alkylpyridines are determined using a McBain balance
placed in a cell for IR-spectroscopic measurements.
Original Russian Text N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.-P. Gilson,
F. Fajula, I.I. Ivanova, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 45–53. 相似文献
8.
Joan Albaigés Josep M. Bayona Pilar Fernandez Joan Grimalt Antoni Rosell Rafel Simó 《Mikrochimica acta》1991,104(1-6):13-27
An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon. 相似文献
9.
Alves Lourdes A. Felipe Maria G. A. Silva JoÃo B. Almeida E. Silva Silvio S. Prata Arnaldo M. R. 《Applied biochemistry and biotechnology》1998,70(1):89-98
Applied Biochemistry and Biotechnology - In order to remove or reduce the concentrations of toxic substances present in the sugarcane bagasse hemicellulose hydrolysate for xyloseto-xylitol... 相似文献
10.
A. Caubet A. Labarta R. Rodríguez A. Fernandez E. Molins V. Moreno J. Tejada 《Hyperfine Interactions》1986,28(1-4):773-776
By means of57Co Mössbauer emission spectroscopy and magnetic susceptibility measurements, the local symmetries and electronic structure of the Co(II) ions in the Co-5IMO and Co-5GMP complexes in the hydrated and dehydrated forms have been determined. 相似文献