全文获取类型
收费全文 | 802篇 |
免费 | 25篇 |
国内免费 | 13篇 |
专业分类
化学 | 415篇 |
力学 | 14篇 |
数学 | 205篇 |
物理学 | 206篇 |
出版年
2020年 | 6篇 |
2019年 | 7篇 |
2017年 | 8篇 |
2016年 | 20篇 |
2015年 | 9篇 |
2014年 | 25篇 |
2013年 | 27篇 |
2012年 | 21篇 |
2011年 | 32篇 |
2010年 | 16篇 |
2009年 | 19篇 |
2008年 | 36篇 |
2007年 | 46篇 |
2006年 | 39篇 |
2005年 | 40篇 |
2004年 | 30篇 |
2003年 | 24篇 |
2002年 | 17篇 |
2001年 | 19篇 |
2000年 | 13篇 |
1999年 | 11篇 |
1998年 | 9篇 |
1997年 | 12篇 |
1996年 | 12篇 |
1995年 | 12篇 |
1994年 | 18篇 |
1993年 | 11篇 |
1992年 | 10篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1983年 | 9篇 |
1982年 | 5篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 8篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 10篇 |
1975年 | 15篇 |
1974年 | 6篇 |
1973年 | 13篇 |
1972年 | 7篇 |
1968年 | 5篇 |
1967年 | 7篇 |
1958年 | 6篇 |
1956年 | 9篇 |
1927年 | 8篇 |
排序方式: 共有840条查询结果,搜索用时 312 毫秒
51.
H.-D. Bauer Reinhold Rennekamp Jürgen Thomas 《Analytical and bioanalytical chemistry》1998,361(6-7):515-521
Concerning the conventional TEM-imaging as well as the analytical procedures the capabilities are pointed out: electron diffraction,
energy dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS). The possibilities of investigation
of both nanocrystalline materials and multilayers are discussed, accompanied by examples of current investigations: At alloys,
produced by intense milling, at single nanocrystals the imaging by diffraction contrast was successful, the analysis has failed
because of the sample thickness. By means of energy spectroscopic imaging multilayers from Fe-SiB/NbCu and Fe/Cr as well as
Al2O3/TiN have been characterized.
Received: 15 July 1997 / Revised: 16 February 1998 / Accepted: 21 February 1998 相似文献
52.
53.
C. Kelbch R. Koch S. Hagmann K. Ullmann H. Schmidt-Böcking C. O. Reinhold D. R. Schultz R. E. Olson G. Kraft 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,22(4):713-721
Double differential cross sections for the emission of Delta-electrons have been measured in fast uranium-rare gas collisions. The well-known Binary Encounter peak reveals unexpected structures for certain observation angles and its intensity increases towards smaller angles, which is in contradiction to results and scaling laws obtained by experiments with light ion impact. The observed dependencies are fairly well described by recent calculations in the framework of IA and CTMC. From systematic experimental as well as theoretical studies we can derive that the potential of the partially stripped projectile ion gives rise to rainbow and glory scattering of the target electron in the field of the projectile. The rainbow scattering is observed in the laboratory frame as pronounced interference structures, whereas the glory scattering is responsible for the steep increase of the cross sections for binary-encounter electrons towards small laboratory ejection angles. The observed effects have a dramatic influence on the commonq 2 scaling laws derived from experiments with light ions. Furthermore, since the binary-encounter electrons ejected at forward angles have approximately twice the projectile velocity, these new phenomena have an important influence on the electronic stopping power of heavy ions and therefore have to be taken into account for the investigation of radiation damage by these ions e.g. in biological matter. 相似文献
54.
Hartung R 《Analytical and bioanalytical chemistry》1996,356(3-4):228-232
The potentiometric analysis of CO2, H2 and CO, H2O-mixtures using oxide ion-conducting solid electrolytes requires the adjustment of the water-gas equilibrium without side reactions in the high-temperature galvanic cell. Conventional cell designs suitable for the analysis of H2, H2O and CO, CO2-mixtures are not applicable due to the insufficient gas residence times in the cells and the insufficient catalytical activity of the platinum electrodes. Solid electrolyte cells have to be modified by integrating of suitable catalysts. Under optimized conditions of gas velocity and cell temperature both gas systems can be analyzed only by measuring the cell tension U (=–emf) and temperature in the favorized temperature range around 813°C. Here systematical errors of the component ratio or the mole fraction were smaller than 6%. Several fundamental requirements for the application of catalysts in solid electrolyte cells for the analysis of reactive water-gas mixtures are pointed out. 相似文献
55.
Kazimiera J. L. Paciorek James H. Nakahara Reinhold H. Rratzer 《Journal of mass spectrometry : JMS》1976,11(11):1217-1219
Electron impact fragmentation patterns were obtained for perfluoroalkylether nitriles, C,F,O[CF(CF3)CFIO]ICF(CF3)CN (x = 1 and 2), perfluoroalkylether acyl halides, CSF,OCF(CF,)-CF2OCF(CF3)COX (X = F and Cl), n-perfluorooctanonitrile and n-perfiuorooctanoyl chloride. The perfluoroalkyl and perfluoroalkylether nitriles afforded ions characteristic of the nitrile function. The major fragment from the acyl chlorides was the [COClJ]+ ion; the presence of chlorine was evidenced also by rearrangement ions of the general form [RfCl] t. The perfluoroalkylether compounds appeared to undergo a typical fragmentation governed by the cleavage of the carbon-oxygen bond. 相似文献
56.
Activation of CO2 at Transition Metal Centres: The Route of the CO2 Reduction at Nikel(0) Moieties A competing reaction in the catalytic cyclooligomerization of hex-3-yne and CO2 at the (TMED)Ni(0)-fragment (TMED = N,N,N′,N′-tetramethylethylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO3). So it is possible to explain the generation of II (TMED)Ni(diethylmalicacidanhydride) and III (a nickel trimer with two (TMED)Ni(CO3) units). Both complexes are characterized by X-ray analysis. The reduction of CO2 to CO most likely proceeds via an intermediate in which two molecules of carbon dioxide are coupled head-to-tail to form a metallacycle. An ab initio scf geometry optimization supports the existence of such an intermediate. 相似文献
57.
Kleiner RE Brudno Y Birnbaum ME Liu DR 《Journal of the American Chemical Society》2008,130(14):4646-4659
The DNA-templated polymerization of synthetic building blocks provides a potential route to the laboratory evolution of sequence-defined polymers with structures and properties not necessarily limited to those of natural biopolymers. We previously reported the efficient and sequence-specific DNA-templated polymerization of peptide nucleic acid (PNA) aldehydes. Here, we report the enzyme-free, DNA-templated polymerization of side-chain-functionalized PNA tetramer and pentamer aldehydes. We observed that polymerization of tetramer and pentamer PNA building blocks with a single lysine-based side chain at various positions in the building block could proceed efficiently and sequence specifically. In addition, DNA-templated polymerization also proceeded efficiently and in a sequence-specific manner with pentamer PNA aldehydes containing two or three lysine side chains in a single building block to generate more densely functionalized polymers. To further our understanding of side-chain compatibility and expand the capabilities of this system, we also examined the polymerization efficiencies of 20 pentamer building blocks each containing one of five different side-chain groups and four different side-chain regio- and stereochemistries. Polymerization reactions were efficient for all five different side-chain groups and for three of the four combinations of side-chain regio- and stereochemistries. Differences in the efficiency and initial rate of polymerization correlate with the apparent melting temperature of each building block, which is dependent on side-chain regio- and stereochemistry but relatively insensitive to side-chain structure among the substrates tested. Our findings represent a significant step toward the evolution of sequence-defined synthetic polymers and also demonstrate that enzyme-free nucleic acid-templated polymerization can occur efficiently using substrates with a wide range of side-chain structures, functionalization positions within each building block, and functionalization densities. 相似文献
58.
59.
Schütz K Persike M Carle R Schieber A 《Analytical and bioanalytical chemistry》2006,384(7-8):1511-1517
The anthocyanin pattern of artichoke heads (Cynara scolymus L.) has been investigated by high-performance liquid chromatography–electrospray ionization mass spectrometry. For this purpose a suitable extraction and liquid chromatographic method was developed. Besides the main anthocyanins—cyanidin 3,5-diglucoside, cyanidin 3-glucoside, cyanidin 3,5-malonyldiglucoside, cyanidin 3-(3′′-malonyl)glucoside, and cyanidin 3-(6′′-malonyl)glucoside—several minor compounds were identified. Among these, two peonidin derivatives and one delphinidin derivative were characterized on the basis of their fragmentation patterns. To the best of our knowledge this is the first report on anthocyanins in artichoke heads consisting of aglycones other than those of cyanidin. Quantification of individual compounds was performed by external calibration. Cyanidin 3-(6′′-malonyl)glucoside was found to be the major anthocyanin in all the samples analyzed. Total anthocyanin content ranged from 8.4 to 1,705.4 mg kg−1 dry mass.
相似文献
60.
Beat Ernst Reinhold Oehrlein Daniel Bellu Jozef Gonda Rainer Jeschke Udo Nubbemeyer 《Helvetica chimica acta》1997,80(3):876-891
A novel type of ketene-Claisen rearrangement in which the precursor of the rearrangement is generated in situ by reaction of optically active allyl thioethers with dichloroketene is described. A characteristic feature of this rearrangement is the excellent chemoselectivity in favor of allyl thioethers vs. allyl ethers, i.e., exclusive chirality transfer of the allylic sulfur moiety is observed with 12, 13 , and 25--27 . The cyclic, optically active allyl thioethers (+)-(R)- 4 and (?)-(S)- 4 and the open-chain allyl thioethers 11--13 rearrange with in situ generated dichloroketene to the optically active thioesters (?)-(S)- 28 , (+)-(R)- 28 , and 31-33 , respectively. A chirality-transfer of > 99% in the cyclic cases (+)-(R)- 4 and (?)-(S)- 4 , and 96--98 % in the open-chain cases 11--13 is observed. Furthermore, the dichloroketene-Claisen rearrangement is characterized by a high asymmetric 1,2-induction. The chiral allylic sulfides 25--27 give the optically active thioesters 36--38 with a 1,2-induction > 99% as determined by NMR-shift experiments. 相似文献