全文获取类型
收费全文 | 211篇 |
免费 | 4篇 |
学科分类
数理化 | 215篇 |
出版年
2023年 | 2篇 |
2022年 | 10篇 |
2021年 | 15篇 |
2020年 | 1篇 |
2019年 | 8篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 4篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 16篇 |
2011年 | 14篇 |
2010年 | 14篇 |
2009年 | 8篇 |
2008年 | 12篇 |
2007年 | 14篇 |
2006年 | 15篇 |
2005年 | 14篇 |
2004年 | 1篇 |
2003年 | 6篇 |
2002年 | 6篇 |
2001年 | 1篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1983年 | 3篇 |
1981年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1967年 | 2篇 |
排序方式: 共有215条查询结果,搜索用时 0 毫秒
41.
Aliakbar Dehno Khalaji Gholamhossein GrivaniMorteza Rezaei Karla FejfarovaMichal Dusek 《Polyhedron》2011,30(17):2790-2794
Three mercury(II) complexes, [Hg((23-MeO-ba)2en)X2] (X = I (1), Br (2) and Cl(3)), and the ligand (23-MeO-ba)2en ((23-MeO-ba)2en = N,N′-bis(2,3-dimethoxybenzylidene)-1,2-diaminoethane) have been synthesized and characterized by elemental analyses, FT-IR and 1H NMR spectroscopy. The crystal and molecular structures of 1 and 2 were determined by X-ray crystallography from single-crystal data. The metal-to-ligand ratio was found to be 1:1. The mercury(II) center in 1 and 2 has a distorted tetrahedral geometry with HgN2I2 and HgN2Br2 chromophores, respectively. The Schiff base ligand (23-MeO-ba)2en acts as a chelating ligand, coordinating via the two nitrogen atoms to the mercury(II) center, and it adopts an E,E conformation. The coordination sphere of the mercury(II) center in 1 and 2 is completed by the two I and Br atoms, respectively. In complex 1 an inter-molecular non-classical hydrogen bond of the type C-H?O was found, while in complex 2 inter- and intra-molecular non-classical hydrogen bonds of the type C-H?X (X = O and Br) were found. The 1H NMR spectra of the complexes exhibit downfield as well as upfield shifts of the free ligand resonances, reflecting changes in the ligand’s geometry during its coordination. 相似文献
42.
A novel catalytic allylation of H-phosphinic acids is described. Using Pd/xantphos (2 mol %), H-phosphinic acids react directly with allylic alcohols to produce P-allylated disubstituted phosphinic acids. 相似文献
43.
Cotí KK Wang Y Lin WY Chen CC Tak For Yu Z Liu K Shen CK Selke M Yeh A Lu W Tseng HR 《Chemical communications (Cambridge, England)》2008,(29):3426-3428
A new type of dynamic micromixer combining the concepts of parallel multi-lamination and hydrodynamic focusing was developed for arbitrary control of disguised chemical selectivity. 相似文献
44.
Luis Cabrales Karla Calderon Irvin Hinojosa Felipe Valencia Noureddine Abidi 《International Journal of Polymer Analysis and Characterization》2016,21(8):718-727
Oils and fats derived from animals and plants provide a good renewable source for polymer precursors. In this investigation, fatty acids derived from plant oils and diols were used as monomers to produce polyesters by melt polycondensation. Sebacic acid, hexanediol, and hydroquinone were used as precursors in the polymer synthesis. The polymers were characterized by gel permeation chromatography, Fourier transform infrared spectroscopy, three-bending point flexural test, X-ray diffraction, tensile testing, and contact angle. The resulting polyesters were blended with epoxies to create materials with an increased elongation at break without affecting other mechanical properties. 相似文献
45.
SNPs are one of the main sources of DNA variation among humans. Their unique properties make them useful polymorphic markers for a wide range of fields, such as medicine, forensics, and population genetics. Although several high-throughput techniques have been (and are being) developed for the vast typing of SNPs in the medical context, population genetic studies involve the typing of few and select SNPs for targeted research. This results in SNPs having to be typed in multiple reactions, consuming large amounts of time and of DNA. In order to improve the current situation in the area of human Y-chromosome diversity studies, we decided to employ a system based on a multiplex oligo ligation assay/PCR (OLA/PCR) followed by CE to create a Y multiplex capable of distinguishing, in a single reaction, all the major haplogroups and as many subhaplogroups on the Y-chromosome phylogeny as possible. Our efforts resulted in the creation of a robust and accurate 35plex (35 SNPs in a single reaction) that when tested on 165 human DNA samples from different geographic areas, proved capable of assigning samples to their corresponding haplogroup. 相似文献
46.
Yang XL Kapoor M Otero FJ Slike BM Tsuruta H Frausto R Bates A Ewalt KL Cheresh DA Schimmel P 《Chemistry & biology》2007,14(12):1323-1333
Disease-causing mutations occur in genes for aminoacyl tRNA synthetases. That some mutations are dominant suggests a gain of function. Native tRNA synthetases, such as tyrosyl-tRNA synthetase (TyrRS) and tryptophanyl-tRNA synthetase, catalyze aminoacylation and are also procytokines that are activated by natural fragmentation. In principle, however, gain-of-function phenotypes could arise from mutational activation of synthetase procytokines. From crystal structure analysis, we hypothesized that a steric block of a critical Glu-Leu-Arg (ELR) motif in full-length TyrRS suppresses the cytokine activity of a natural fragment. To test this hypothesis, we attempted to uncover ELR in the procytokine by mutating a conserved tyrosine (Y341) that tethers ELR. Site-specific proteolytic cleavage and small-angle X-ray scattering established subtle opening of the structure by the mutation. Strikingly, four different assays demonstrated mutational activation of cytokine functions. The results prove the possibilities for constitutive gain-of-function mutations in tRNA synthetases. 相似文献
47.
Karla M. Robotti Hongfeng Yin Reid Brennen Lukas Trojer Kevin Killeen 《Journal of separation science》2009,32(20):3379-3387
Polyimide HPLC‐Chip devices containing poly(methylstyrene‐bis‐p‐vinylphenyl)ethane (MS/BVPE) stationary phase within the device channels and with wall attachment were prepared by thermally initiated free radical polymerization. The microfluidic devices were coupled to both UV and MS detectors. The potential of the MS/BVPE monolith as an alternative separation media within chip devices was investigated by side‐by‐side comparisons to particulate media within commercial devices. The chromatographic behavior of this stationary phase was comparable to particulate media for separations of proteins as the average peak width at half‐height was equal (6.2 s) for a separation within 8 min under gradient elution conditions. The ability to control the porosity characteristics of the MS/BVPE monolith with changes in polymerization time also extended its utility into small analyte (< 500 Da) applications, although more optimization is needed to match conventional RP media for these applications. The good mechanical stability of the MS/BVPE monolith within the microdevices enabled excellent run‐to‐run repeatability (%RSD retention time (? 0.16) and chip‐to‐chip reproducibility (%RSD retention time (1.4). The use of this material within enrichment channels also shows its potential value in more complex work flows. 相似文献
48.
Aliakbar Dehno Khalaji Sepideh Maghsodlou Rad Gholamhossein Grivani Karla Fejfarova Michal Dusek Debasis Das 《Journal of chemical crystallography》2011,41(8):1145-1149
Abstract
Schiff-base compound (E)-4-dimethamino[(1-phenylethyl)iminomethyl]benzyne was synthesized and characterized by elemental analyses (CHN), FT-IR and 1H-NMR spectroscopic techniques and thermogravimetric analyses (TG). Crystal structure of the title compound was obtained by single crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group P21 with unit cell parameters: a = 8.5283(2), b = 6.0699(2), c = 13.6997(4) Ǻ, β = 91.471(2)°, V = 708.94(4) Ǻ3 and Z = 2. 相似文献49.
Caramori GF Kunitz AG Andriani KF Doro FG Frenking G Tfouni E 《Dalton transactions (Cambridge, England : 2003)》2012,41(24):7327-7339
Ruthenium complexes including nitrosyl or nitrite complexes are particularly interesting because they can not only scavenge but also release nitric oxide in a controlled manner, regulating the NO-level in vivo. The judicious choice of ligands attached to the [RuNO] core has been shown to be a suitable strategy to modulate NO reactivity in these complexes. In order to understand the influence of different equatorial ligands on the electronic structure of the Ru-NO chemical bonding, and thus on the reactivity of the coordinated NO, we propose an investigation of the nature of the Ru-NO chemical bond by means of energy decomposition analysis (EDA), considering tetraamine and tetraazamacrocycles as equatorial ligands, prior to and after the reduction of the {RuNO}(6) moiety by one electron. This investigation provides a deep insight into the Ru-NO bonding situation, which is fundamental in designing new ruthenium nitrosyl complexes with potential biological applications. 相似文献
50.
Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ~57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs. 相似文献