全文获取类型
收费全文 | 823篇 |
免费 | 58篇 |
国内免费 | 1篇 |
专业分类
化学 | 622篇 |
晶体学 | 4篇 |
力学 | 4篇 |
数学 | 114篇 |
物理学 | 83篇 |
无线电 | 55篇 |
出版年
2023年 | 9篇 |
2022年 | 9篇 |
2021年 | 17篇 |
2020年 | 36篇 |
2019年 | 32篇 |
2018年 | 16篇 |
2017年 | 14篇 |
2016年 | 26篇 |
2015年 | 25篇 |
2014年 | 48篇 |
2013年 | 33篇 |
2012年 | 58篇 |
2011年 | 45篇 |
2010年 | 43篇 |
2009年 | 34篇 |
2008年 | 42篇 |
2007年 | 32篇 |
2006年 | 31篇 |
2005年 | 36篇 |
2004年 | 26篇 |
2003年 | 21篇 |
2002年 | 23篇 |
2001年 | 20篇 |
2000年 | 15篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 9篇 |
1996年 | 7篇 |
1995年 | 7篇 |
1994年 | 7篇 |
1993年 | 9篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 6篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1986年 | 3篇 |
1983年 | 4篇 |
1982年 | 4篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1970年 | 3篇 |
1967年 | 3篇 |
排序方式: 共有882条查询结果,搜索用时 234 毫秒
1.
Iodine(III)‐Catalyzed Rearrangements of Imides: A Versatile Route to α,α‐Dialkylated α‐Hydroxy Carboxylamides 下载免费PDF全文
Anna Ulmer Dr. Maciej Stodulski Stefanie V. Kohlhepp Christoph Patzelt Dr. Alexander Pöthig Dr. Wolfgang Bettray Dr. Tanja Gulder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(4):1444-1448
A tertiary hydroxy group α to a carboxyl moiety comprises a key structural motif in many bioactive substances. With the herein presented metal‐free rearrangement of imides triggered by hypervalent λ3‐iodane, an easy and selective way to gain access to such a compound class, namely α,α‐disubstituted‐α‐hydroxy carboxylamides, was established. Their additional methylene bromide side chain constitutes a useful handle for rapid diversification, as demonstrated by a series of further functionalizations. Moreover, the in situ formation of an iodine(III) species under the reaction conditions was proven. Our findings clearly corroborate that hypervalent λ3‐benziodoxolones are involved in these organocatalytic reactions. 相似文献
2.
Tanja Vidaković-Koch Tamara Miličić Luka A. Živković Hoon Seng Chan Ulrike Krewer Menka Petkovska 《Current Opinion in Electrochemistry》2021
The nonlinear frequency response analysis (NFRA) can be seen as an extension of electrochemical impedance spectroscopy. NFRA gives a full and detailed representation of the system response and can establish a connection between model parameters and the experimentally observed phenomena. In this article, different theoretical NFRA approaches and the most recent application examples are discussed. A simple electrochemical example is used to showcase the benefits and disadvantages of analyzing the system response by using different approaches. In addition, it was shown how to extract experimental harmonic values and analyze them. 相似文献
3.
4.
F. Seiffert R. Schwengner G. Winter L. Funke W. Lieberz R. Reinhardt K. P. Schmittgen D. Weil R. Wrzal K. O. Zell P. von Brentano 《Zeitschrift für Physik A Hadrons and Nuclei》1991,340(2):141-153
Excited states of73Se have been investigated up to spin, 21/2 using techniques of in-beamγ-ray spectroscopy in connection with the70Ge(α, n) reaction. Mean lifetimes of 12 levels have been determined applying Doppler-shift andγ-RF-methods. Five different bands have been identified that reflect a variety of different excitation modes. The decoupled 9/2+ band is likely to correspond to an oblate deformation while the 5/2+ band is interpreted as a strongly coupled prolate band built on the Nilsson configuration [422] 5/2+. The 3/2? band is a strongly coupled band built on the [301] 3/2} configuration.Nuclear reactions:70Ge(α,n),E=14, 16, 18, 19, 20MeV; measuredE γ,I γ,σ(E γ,θ),γγ-coin, linear polarization, DSA,γ(t).75Se deduced levels,I, π, τ, δ(E2/M1), B(σλ). Enriched targets, Ge detectors. 相似文献
5.
Friedrich Weil 《Fresenius' Journal of Analytical Chemistry》1872,11(1):284
Ohne Zusammenfassung 相似文献
6.
Slootweg JC Vlaar MJ Vugts DJ Eichelsheim T Merhai W de Kanter FJ Schakel M Ehlers AW Lutz M Spek AL Lammertsma K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(16):4808-4818
Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents. 相似文献
7.
Baran EJ Weil M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):707-710
The infrared and Raman spectra of the crystalline hexaoxotellurates Hg3TeO6 and Hg2TeO5 were recorded and discussed on the basis of a site symmetry analysis derived from known structural data. Approximate values for the Te-O bond force constants are reported and some comparisons with related species are made. 相似文献
8.
Weil Joseph Brewer Mark Hendrickson Richard Sarikaya Ayda Ladisch Michael R. 《Applied biochemistry and biotechnology》1998,(1):99-111
Yellow poplar wood sawdust consists of 41% cellulose and 19% hemicellulose. The goal of pressure cooking this material in
water is to hydrate the more chemically resistive regions of cellulose in order to enhance enzymatic conversion to glucose.
Pretreatment can generate organic acids through acid-catalyzed degradation of monosaccharides formed because of acids released
from the biomass material or the inherent acidity of the water at temperatures above 160°C. The resulting acids will further
promote the acid-catalyzed degradation of monomers that cause both a reduction in the yield and the formation of fermentation
inhibitors such as hydroxymethyl furfural and furfural. A continuous pH-monitoring system was developed to help characterize
the trends in pH during pretreatment and to assist in the development of a base (2.0 M KOH) addition profile to help keep
the pH within a specified range in order to reduce any catalytic degradation and the formation of any monosac-charide degradation
products during pretreatment. The results of this work are discussed. 相似文献
9.
Conformational stability of G-quartets found in telomeric DNA quadruplex structures requires the coordination of monovalent ions. Here, an extensive Hartree-Fock and density functional theory analysis of the energetically favored position of Li+, Na+, and K+ ions is presented. The calculations show that at quartet-quartet distances observed in DNA quadruplex structures (3.3 A), the Li+ and Na+ ions favor positions of 0.55 and 0.95 A outside the plane of the G-quartet, respectively. The larger K+ ion prefers a central position between successive G-quartets. The energy barrier separating the minima in the quartet-ion-quartet model are much smaller for the Li+ and Na+ ions compared with the K+ ion; this suggests that K+ ions will not move as freely through the central channel of the DNA quadruplex. Spin-spin coupling constants and isotropic chemical shifts in G-quartets extracted from crystal structures of K+- and Na+-coordinated DNA quadruplexes were calculated with B3LYP/6-311G(d). The results show that the sizes of the trans-hydrogen-bond couplings are influenced primarily by the hydrogen bond geometry and only slightly by the presence of the ion. The calculations show that the R(N2N7) distance of the N2-H2...N7 hydrogen bond is characterized by strong correlations to both the chemical shifts of the donor group atoms and the (h2)J(N2N7) couplings. In contrast, weaker correlations between the (h3)J(N1C6') couplings and single geometric factors related to the N1-H1...O6=C6 hydrogen bond are observed. As such, deriving geometric information on the hydrogen bond through the use of trans-hydrogen-bond couplings and chemical shifts is more complex for the N1-H1...O6=C6 hydrogen bond than for the N2-H2...N7 moiety. The computed trans-hydrogen-bond couplings are shown to correlate with the experimentally determined couplings. However, the experimental values do not show such strong geometric dependencies. 相似文献
10.
The biochemical transport and binding of nicotine depends on the hydrogen bonding between water and binding site residues to the pyridine ring and the protonated pyrrolidinium ring. To test the independence of these two moderately separated hydrogen-bonding sites, we have calculated the structures of clusters of protonated nicotine with water and a bicarbonate anion, benzene, indole, or a second water molecule. Unprotonated nicotine-water clusters have also been studied for contrast. The potential energy surfaces are first explored with an intermolecular anisotropic atom-atom model potential. Full geometry optimizations are then carried out using density functional theory to include nonadditive terms in the interaction energies. The presence of the charge on the pyrrolidine nitrogen removes the conventional hydrogen-bonding site on the pyridine ring. The hydrogen-bond ability of this site is nearly recovered when the protonated pyrrolidinium ring is bound to a bicarbonate anion, whereas its interaction with benzene shows a much smaller effect. Indole appears to partially restore the hydrogen-bond ability of the pyridine nitrogen, although indole and benzene both pi-bond to the pyrrolidinium ring. A second hydrogen-bonding water produces a significant conformational distortion of the nicotine. This demonstrates the limitations of the conventional qualitative predictions of hydrogen bonding based on the independence of molecular fragments. It also provides benchmarks for the development of atomistic modeling of biochemical systems. 相似文献