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121.
Gor'kov PL Chekmenev EY Li C Cotten M Buffy JJ Traaseth NJ Veglia G Brey WW 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,185(1):77-93
RF heating of solid-state biological samples is known to be a destabilizing factor in high-field NMR experiments that shortens the sample lifetime by continuous dehydration during the high-power cross-polarization and decoupling pulses. In this work, we describe specially designed, large volume, low-E 15N-1H solid-state NMR probes developed for 600 and 900 MHz PISEMA studies of dilute membrane proteins oriented in hydrated and dielectrically lossy lipid bilayers. The probes use an orthogonal coil design in which separate resonators pursue their own aims at the respective frequencies, resulting in a simplified and more efficient matching network. Sample heating at the 1H frequency is minimized by a loop-gap resonator which produces a homogeneous magnetic field B1 with low electric field E. Within the loop-gap resonator, a multi-turn solenoid closely matching the shape of the sample serves as an efficient observe coil. We compare power dissipation in a typical lossy bilayer sample in the new low-E probe and in a previously reported 15N-1H probe which uses a double-tuned 4-turn solenoid. RF loss in the sample is measured in each probe by observing changes in the 1H 360 degrees pulse lengths. For the same values of 1H B1 field, sample heating in the new probe was found to be smaller by an order of magnitude. Applications of the low-E design to the PISEMA study of membrane proteins in their native hydrated bilayer environment are demonstrated at 600 and 900 MHz. 相似文献
122.
Quantitative Structural Constraints for Organic Powders at Natural Isotopic Abundance Using Dynamic Nuclear Polarization Solid‐State NMR Spectroscopy 下载免费PDF全文
Dr. Giulia Mollica Myriam Dekhil Dr. Fabio Ziarelli Dr. Pierre Thureau Prof. Stéphane Viel 《Angewandte Chemie (International ed. in English)》2015,54(20):6028-6031
A straightforward method is reported to quantitatively relate structural constraints based on 13C–13C double‐quantum build‐up curves obtained by dynamic nuclear polarization (DNP) solid‐state NMR to the crystal structure of organic powders at natural isotopic abundance. This method relies on the significant gain in NMR sensitivity provided by DNP (approximately 50‐fold, lowering the experimental time from a few years to a few days), and is sensitive to the molecular conformation and crystal packing of the studied powder sample (in this case theophylline). This method allows trial crystal structures to be rapidly and effectively discriminated, and paves the way to three‐dimensional structure elucidation of powders through combination with powder X‐ray diffraction, crystal‐structure prediction, and density functional theory computation of NMR chemical shifts. 相似文献
123.
Turner AD Hatfield RG Rapkova M Higman W Algoet M Suarez-Isla BA Cordova M Caceres C van de Riet J Gibbs R Thomas K Quilliam M Lees DN 《Analytical and bioanalytical chemistry》2011,399(3):1257-1270
A refined version of the pre-column oxidation liquid chromatography with fluorescence detection (ox-LC-FLD) official method AOAC 2005.06 was developed in the UK and validated for the determination of paralytic shellfish poisoning toxins in UK shellfish. Analysis was undertaken here for the comparison of PSP toxicities determined using the LC method for a range of UK bivalve shellfish species against the official European reference method, the PSP mouse bioassay (MBA, AOAC 959.08). Comparative results indicated a good correlation in results for some species (mussels, cockles and clams) but a poor correlation for two species of oysters (Pacific oysters and native oysters), where the LC results in terms of total saxitoxin equivalents were found to be on average more than double the values determined by MBA. With the potential for either LC over-estimation or MBA under-estimation, additional oyster and mussel samples were analysed using MBA and ox-LC-FLD together with further analytical and functional methodologies: a post-column oxidation LC method (LC-ox-FLD), an electrophysiological assay and hydrophilic interaction liquid chromatography with tandem mass spectrometric detection. Results highlighted a good correlation among non-bioassay results, indicating a likely cause of difference was the under-estimation in the MBA, rather than an over-estimation in the LC results. 相似文献
124.
Nowik W Bonose-Crosnier de Bellaistre M Tchapla A Héron S 《Journal of chromatography. A》2011,1218(23):3636-3647
A series of reversed phases bonded with several functional groups was investigated for separation of anthraquinone derivatives, following the previous work, dedicated to the selectivity of octadecyl silica bonded phases. Considering wide diversity of substitutions in hydrophobic anthraquinone skeleton, interactions like dipole-dipole, π-π or H-bond acceptor/donor, as well as inclusion complexes formation can be employed to improve separation. In this study, several phases with grafts like cyano, nitro, aromatic, PEG, diol, calixarene and cyclodextrin were used with water-acetonitrile gradient for separation of thirty anthraquinoids' standards. The evaluation of performances was measured using the symmetry parameter and the number of critical pairs of peaks formed. The results point out the aromatic and calixarene bonded silica as the most interesting in terms of symmetry and critical pairs number. Finally we tested the performance of Caltrex Resorcinaren, Pursuit XRs DP and Luna Phenyl-Hexyl on real samples of anthraquinone natural dye extracted from a red thread taken from a 15th C. tapestry. We observed and compared the retention behaviour of some new anthraquinoids additional to our standards set and showing behaviour particular to substituted anthraquinone carboxylic acids. 相似文献
125.
Ouberai M Brannstrom K Vestling M Olofsson A Dumy P Chierici S Garcia J 《Organic & biomolecular chemistry》2011,9(4):1140-1147
The multifaceted nature of Alzheimer's disease (AD) has led to the development of multi-targeted compounds based on the classical AD drug, tacrine, first known to inhibit the acetylcholine-degrading enzyme acetylcholinesterase (AChE). In the present work, we explore the potentiality of multimers of tacrine in this field. The synthesis using the so-called "click chemistry" and the in vitro study of the conjugates are described. Two or four copies of the tacrine molecule are "clicked" on a constrained cyclopeptide template proven to be a convenient tool for multimeric presentation. The multimers significantly inhibit self-induced amyloid fibril formation from Aβ(40) at low inhibitor to Aβ molar ratios at which the tacrine monomer is fully inactive (Thioflavin T assays and AFM observation). Moreover, they have the capacity to bind to Aβ(40) fibrils (SPR assays) while retaining the AChE inhibitory activity of the parent tacrine. 相似文献
126.
Consider an irreducible polynomial of the form f(X) = X p ? aX ? b ∈ 𝔽[X] and α a root of f(X), where 𝔽 is a field of characteristic p. In 1975, F.J. Sullivan stated a lemma that provides the trace, taken with respect to the extension 𝔽(α)/𝔽, of elements of the form α n , where 0 ≤ n ≤ p 2 ? 1. We present a generalization of Sullivan's Lemma and provide another proof of the original lemma. We explain how computing Tr(α n ) for n < p r can be reduced to computing the traces Tr(α m ) for all m ≤ r(p ? 1). 相似文献
127.
When a totally unpolarized light is scattered by a medium that spatially totally depolarizes incident polarized light, the scattered field presents an increase of the order described by the temporal degree of polarization. We analyze the behavior of some polarization and coherence properties in such a physical situation. 相似文献
128.
129.
A soft computing-based approach to spatio-temporal prediction 总被引:1,自引:0,他引:1
Rúbia E.O. Schultz Tania M. Centeno Gilles Selleron Myriam R. Delgado 《International Journal of Approximate Reasoning》2009,50(1):3-20
This paper aims to incorporate intelligent mechanisms based on Soft Computing in Geographical Information Systems (GIS). The proposal here is to present a spatio-temporal prediction method of forestry evolution for a sequence of binary images by means of fuzzy inference systems (FIS), genetic algorithm (GA) and genetic programming (GP). The main inference is based on a fuzzy system which processes a set of crisp/fuzzy relations and infers a crisp relation representing the predicted image at a predefined date. The fuzzy system is formed by a fixed fuzzy rule base and a partition set that may be defined by an expert or optimized by means of a GA. Genetic programming may also be adopted to generate the size of predicted area used in the final stage of the inference process. The developed methodology is applied in regions of Venezuela, France and Guatemala to identify their forestry evolution trends. The proposed approaches are compared with other techniques to validate the system. 相似文献
130.
Rolf A. Kramer Roman Flehr Myriam Lay Michael U. Kumke Willi Bannwarth 《Helvetica chimica acta》2009,92(10):1933-1943
We describe the preparation as well as a detailed photophysical study of Fmoc‐amino acid building blocks carrying different carbostyril (=quinolin‐2(1H)‐one) heterocycles as donors in a FRET (fluorescence‐resonance‐energy transfer) system in combination with a [RuII(bathophenanthroline)] complex (bathophenanthroline=4,7‐diphenyl‐1,10‐phenanthroline). The efforts resulted in a clear preference for building block 16 due to its ease of synthesis (Scheme 2), its chemical robustness, and the FRET efficiency when incorporated into peptides. 相似文献