全文获取类型
收费全文 | 1060篇 |
免费 | 32篇 |
国内免费 | 7篇 |
专业分类
化学 | 762篇 |
晶体学 | 8篇 |
力学 | 13篇 |
数学 | 203篇 |
物理学 | 113篇 |
出版年
2023年 | 6篇 |
2022年 | 7篇 |
2021年 | 10篇 |
2020年 | 14篇 |
2019年 | 11篇 |
2018年 | 11篇 |
2017年 | 15篇 |
2016年 | 24篇 |
2015年 | 33篇 |
2014年 | 21篇 |
2013年 | 44篇 |
2012年 | 67篇 |
2011年 | 74篇 |
2010年 | 41篇 |
2009年 | 37篇 |
2008年 | 54篇 |
2007年 | 65篇 |
2006年 | 59篇 |
2005年 | 65篇 |
2004年 | 68篇 |
2003年 | 49篇 |
2002年 | 40篇 |
2001年 | 19篇 |
2000年 | 11篇 |
1999年 | 10篇 |
1998年 | 14篇 |
1997年 | 12篇 |
1996年 | 18篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 10篇 |
1992年 | 4篇 |
1991年 | 6篇 |
1990年 | 10篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 10篇 |
1985年 | 16篇 |
1984年 | 22篇 |
1983年 | 8篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1978年 | 4篇 |
1976年 | 9篇 |
1973年 | 3篇 |
1970年 | 3篇 |
1969年 | 6篇 |
1938年 | 2篇 |
排序方式: 共有1099条查询结果,搜索用时 15 毫秒
81.
Ferrando-Soria J Pardo E Ruiz-García R Cano J Lloret F Julve M Journaux Y Pasán J Ruiz-Pérez C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(7):2176-2188
A series of neutral oxamato‐bridged heterobimetallic chains of general formula [MCu(Lx)2(S)2] ? p S ? q H2O [p=0–1, q=0–2.5; L1=N‐2,6‐dimethylphenyloxamate, S=DMF with M=Mn ( 1 a ) and Co ( 1 b ); L2=N‐2,6‐diethylphenyloxamate, S=DMF with M=Mn ( 2 a ) and Co ( 2 b ) or S=DMSO with M=Mn ( 2 c ) and Co ( 2 d ); L3=N‐2,6‐diisopropylphenyloxamate, S=DMF with M=Mn ( 3 a ) and Co ( 3 b ) or S=DMSO with M=Mn ( 3 c ) and Co ( 3 d )] were prepared by treating the corresponding anionic oxamatocopper(II) complexes [Cu(Lx)2]2? (x=1–3) with M2+ cations (M=Mn and Co) in DMF or DMSO as the solvent. The single‐crystal X‐ray structures of 2 a and 3 a reveal the occurrence of well‐isolated, zigzag, oxamato‐bridged manganese(II)–copper(II) chains. The intrachain Cu ??? Mn distances across the oxamato bridge are 5.3761(7) and 5.4002(17) Å for 2 a and 3 a , respectively, whereas the shortest interchain Mn ??? Mn distances are 9.4475(16) and 8.1649(14) Å for 2 a and 3 a , respectively. All of these MIICuII chains (M=Mn and Co) exhibit 1D ferrimagnetic behaviour with moderately strong intrachain antiferromagnetic coupling between the square‐planar CuII and octahedral high‐spin MII ions across the oxamato bridge [?J=31.4–35.2 and 33.4–44.8 cm?1, respectively; H =∑i?J S M,i( S Cu,i+ S Cu,i?1)]. Only the CoIICuII chains show slow magnetic relaxation effects characteristic of single‐chain magnets (SCMs). Analysis of the magnetic relaxation dynamics of 3 d shows a thermally activated mechanism (Arrhenius law dependence) with values of the pre‐exponential factor (τ0=2.6×10?9 s) and activation energy (Ea=7.7 cm?1) that are typical of SCMs. In contrast, two relaxation regimes are observed for 2 d in different temperature regions (τ0=3.2×10?10 s and Ea=24.7 cm?1 for T<4.5 K and τ0=3.2×10?14 s and Ea=37.5 cm?1 for T>4.5 K). 相似文献
82.
Eva Borràs Joan Ferré Ricard Boqué Montserrat Mestres Laura Aceña Olga Busto 《Analytica chimica acta》2015
The ever increasing interest of consumers for safety, authenticity and quality of food commodities has driven the attention towards the analytical techniques used for analyzing these commodities. In recent years, rapid and reliable sensor, spectroscopic and chromatographic techniques have emerged that, together with multivariate and multiway chemometrics, have improved the whole control process by reducing the time of analysis and providing more informative results. In this progression of more and better information, the combination (fusion) of outputs of different instrumental techniques has emerged as a means for increasing the reliability of classification or prediction of foodstuff specifications as compared to using a single analytical technique. Although promising results have been obtained in food and beverage authentication and quality assessment, the combination of data from several techniques is not straightforward and represents an important challenge for chemometricians. This review provides a general overview of data fusion strategies that have been used in the field of food and beverage authentication and quality assessment. 相似文献
83.
Ernest Giralt Miguel Feliz Mario Rubiralta Joan Bosch 《Journal of heterocyclic chemistry》1984,21(3):715-720
Carbon-carbon sp3-sp2 rotational barriers of 3,3-dimethyl-2-(3,4,5-trimethoxyphenyl)-4-piperidones and their ethylene ketals have been evaluated using nmr techniques. The conformation of 1 hydrochloride has been studied by NOE determinations. Values found for the hydrochlorides of the title compounds are discussed in terms of equilibria with free bases and nitrogen inversion. 相似文献
84.
Spore photoproduct (SP) lyase, which catalyzes the direct reversal of SP (5-thyminyl-5,6-dihydrothymine) to thymine monomers, is the only identified nonphotoactivatable pyrimidine dimer lyase. Unlike DNA photolyase, SP lyase does not contain a flavin cofactor and does not require light for activation. Instead, preliminary studies point to the presence of an iron-sulfur cluster in SP lyase and the requirement for S-adenosylmethionine (AdoMet) for catalytic activity, suggesting that SP lyase belongs to the growing group of iron-sulfur cluster and AdoMet-dependent radical enzymes. Here we provide evidence for the role of AdoMet as a reversible deoxyadenosyl radical generator, which initiates repair by hydrogen atom abstraction from C-6 of SP. Reaction of 6-(3)H-SP, but not methyl-(3)H-SP, with SP lyase and AdoMet results in transfer of (3)H to AdoMet, while no tritiated 5'-deoxyadenosine is observed. When 5'-tritiated AdoMet is used in the reaction with unlabeled SP, transfer of (3)H into the repaired thymine monomers is observed. These results point to the reversible generation of a 5'-deoxyadenosyl radical intermediate, which reacts directly with the DNA lesion to initiate a radical-mediated beta-scission. We also demonstrate that AdoMet is a catalytic cofactor that is not consumed during turnover. Together, these results support a novel radical-based mechanism for the repair of UV-induced DNA damage. 相似文献
85.
Joan Llorens Marc Pera-Titus 《Colloids and surfaces. A, Physicochemical and engineering aspects》2009,350(1-3):63-72
This study presents an experimental and theoretical analysis of the effect of surface heterogeneity on the capacity of 20 commercial activated carbons to adsorb hydrogen at 77 and 258 K and for maximum pressures of 20 bar. Some of the samples have been subjected to surface modification by impregnation or by surface oxidation prior to the hydrogen adsorption measurements. All the activated carbons have been analyzed by N2 adsorption at 77 K using the thermodynamic isotherm presented in a previous study. The hydrogen adsorption capacity of the activated carbons has been well correlated to the micropore volume and the characteristic m2 parameter of the thermodynamic isotherm accounting for the energy heterogeneity of the material. On the basis of the model presented here, we discuss how surface heterogeneity, in addition to the adsorption strength, might affect the ability of activated carbons and related materials to adsorb hydrogen. 相似文献
86.
A method for the identification of double bond locations in polyunsaturated long chain alkenones adapted to nanogram amounts
as currently analyzed by gas chromatography coupled to mass spectrometry (GC-MS) has been developed. The method is based on
interpretation of the electron impact mass spectra of the imino derivatives of the carbonyl groups using either cyclopentyl
or phenyl substitutents. Other complementary derivatization methods such as elaidization and hydrogenation have also been
used for structural characterization of these compounds. This application has led to the identification of a novel homologous
series of di-, tri-, and tetraunsaturated ketones with carbon number chain lengths between 37 and 40 in coastal hypersaline
sediments. The novel series identified shows a distribution in which the double bond position between different homologs is
established by reference to the distance from the carbonyl group whereas the previously known alkenones were constituted by
unsaturated homologs with double bonds located at defined distances of the terminal methyl. This difference points out to
a dissimilar, but still unknown, biogenic precursor of these novel alkenones. 相似文献
87.
Mrinal Kanti Paira Tapan Kumar Mondal Elena López-Torres Joan Ribas Chittaranjan Sinha 《Polyhedron》2010
Copper(II) complexes of 3-((2-(alkylthio)phenylazo)-2,4-pentanedione, tridentate O, N, S donor ligands, are described in this work. Chloride bridged copper(II) polymers (1) and thiocyanato bridged copper(II) dimmers (2) are characterized by a single crystal X-ray diffraction study. The complexes show antiferromagnetic interactions, with J = −0.5 ± 0.1 cm−1 (1a) and −25.8 ± 0.5 cm−1 (2b), which implies stronger coupling in the –SCN-bridging compound. The spectra, redox and magnetism are explained by DFT studies. 相似文献
88.
Giménez-Romero D Agrisuelas J García-Jareño JJ Gregori J Gabrielli C Perrot H Vicente F 《Journal of the American Chemical Society》2007,129(22):7121-7126
This paper demonstrates the importance of the structural changeover in controlling the physical-chemical properties of hexacyanometalate-like materials (Prussian Blue). A meticulous in situ study of compositional variations using electroacoustic impedance techniques associated to electrogravimetric techniques in hexacyanoferrates containing K+ alkali metals reveals the existence of a nanostructural changeover coupled to a change of the magnetic properties of these electromagnetic materials. In the same way, the electroacoustic impedance techniques can be useful both in the understanding and in the in situ monitoring of the structural changeovers and the magnetic behavior of all kinds of materials. 相似文献
89.
Two coordination polymers, [Cu(bpp)(H2O)2(ClO4)2]n (1) and {[Cu(bpds)2(ClO4)2] · 1.5(H2O)}n (2) [bpp, 1,3-bis(4-pyridyl)propane and bpds, 4,4′-bipyridyl disulfide] have been synthesized and characterized by X-ray single crystal diffraction study and magnetic measurement. Both the coordination polymers display 1D chains with perchlorate anions acting as pendant ligands. In 1 undulated polymers are built by Cu(H2O)2(ClO4)2 units connected by single bpp and in complex 2 Cu(ClO4)2 fragments are linked by pairs of bpds ligands to form a double-stranded chain. The crystal packing evidences polymers of 1 involved in weak H-bonding interactions leading to a 3D supramolecular network. Magnetic study reveals weak antiferromagnetic interactions in both complexes. 相似文献
90.
Adam J. McShane Yuanyuan Shen Mary Joan Castillo Xudong Yao 《Journal of the American Society for Mass Spectrometry》2014,25(10):1694-1704
Direct reductive methylation of peptides is a common method for quantitative proteomics. It is an active derivatization technique; with participation of the dimethylamino group, the derivatized peptides preferentially release intense a1 ions. The advantageous generation of a1 ions for quantitative proteomic profiling, however, is not desirable for targeted proteomic quantitation using multiple reaction monitoring mass spectrometry; this mass spectrometric method prefers the derivatizing group to stay with the intact peptide ions and multiple fragments as passive mass tags. This work investigated collisional fragmentation of peptides whose amine groups were derivatized with five linear ω-dimethylamino acids, from 2-(dimethylamino)-acetic acid to 6-(dimethylamino)-hexanoic acid. Tandem mass spectra of the derivatized tryptic peptides revealed different preferential breakdown pathways. Together with energy resolved mass spectrometry, it was found that shutting down the active participation of the terminal dimethylamino group in fragmentation of derivatized peptides is possible. However, it took a separation of five methylene groups between the terminal dimethylamino group and the amide formed upon peptide derivatization. For the first time, the gas-phase fragmentation of peptides derivatized with linear ω-dimethylamino acids of systematically increasing alkyl chain lengths is reported. Figure
? 相似文献