全文获取类型
收费全文 | 668篇 |
免费 | 13篇 |
国内免费 | 3篇 |
专业分类
化学 | 382篇 |
晶体学 | 1篇 |
力学 | 9篇 |
数学 | 89篇 |
物理学 | 203篇 |
出版年
2023年 | 4篇 |
2022年 | 4篇 |
2020年 | 3篇 |
2019年 | 10篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 11篇 |
2015年 | 7篇 |
2014年 | 11篇 |
2013年 | 58篇 |
2012年 | 22篇 |
2011年 | 39篇 |
2010年 | 14篇 |
2009年 | 12篇 |
2008年 | 26篇 |
2007年 | 33篇 |
2006年 | 31篇 |
2005年 | 25篇 |
2004年 | 26篇 |
2003年 | 22篇 |
2002年 | 36篇 |
2001年 | 35篇 |
2000年 | 25篇 |
1999年 | 9篇 |
1998年 | 10篇 |
1997年 | 6篇 |
1996年 | 20篇 |
1995年 | 14篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 14篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 5篇 |
1986年 | 10篇 |
1985年 | 5篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 12篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1975年 | 3篇 |
1973年 | 7篇 |
1972年 | 3篇 |
1971年 | 3篇 |
1968年 | 3篇 |
排序方式: 共有684条查询结果,搜索用时 15 毫秒
71.
72.
Fu Y Ye F Sanders WG Collinson MM Higgins DA 《The journal of physical chemistry. B》2006,110(18):9164-9170
Single molecule spectroscopy is applied in studies of diffusion and surface adsorption in sol-gel-derived mesoporous silica thin films. Mesoporous films are obtained by spin casting surfactant-templated sols onto glass substrates. Small-angle X-ray diffraction results are consistent with hexagonally ordered mesophases in as-synthesized (i.e., surfactant-containing) films. Upon calcination, a 30% contraction and disordering of these structures occurs. Nile Red is used as a fluorescent probe of both the as-synthesized and calcined films. It is loaded into the samples at subnanomolar levels either prior to spin casting or after calcination. Fluorescence imaging and single-point fluorescence time transients show the dye molecules to be relatively mobile in the as-synthesized samples. In contrast, the molecules appear entrapped at fixed locations in dry calcined films. In calcined films rehydrated under high humidity conditions, the Nile Red molecules again become mobile. Time transients obtained from the as-synthesized and rehydrated samples provide clear evidence for frequent reversible adsorption of the dye to the silica surfaces. Autocorrelations of the time transients provide quantitative data on the mean diffusion coefficients (D = 2.4 x 10(-10) and 2.6 x 10(-10) cm2/s) and mean desorption times (1/k = 25 and 40 s) for the as-synthesized and rehydrated films, respectively. The results prove both water and surfactant play important roles in governing matrix interactions and mass transport. 相似文献
73.
74.
Sorption of carbon dioxide, ethylene, and nitrous oxide in poly(methyl methacrylate) (PMMA) at 35°C has been characterized for each gas as a pure component and for mixtures of carbon dioxide/ethylene and carbon dioxide/nitrous oxide. Pressures up to 20 atm were examined. Pure-component sorption isotherms are concave to the pressure axis for each of the gases. This behavior is accurately described by the dual-mode sorption model. Using only the purecomponent dual-mode parameters and the generalization of the model for gas mixtures, one can predict the total concentration of gas sorbed in the polymer to within an average deviation of ±2.01% for the CO2/C2H4/PMMA system and ±0.98% for the CO2/N2O/PMMA system. In both systems, for each component of the mixture, sorption levels were lower than corresponding pure-component sorption levels at pressures equal to the partial pressure of the respective components in the mixture. Depression of the sorbed concentration in mixture situations appears to be a general feature of the above systems and can be substantial in some situations. For the CO2/C2H4/PMMA system, use of pure-component sorption data to estimate the total sorbed concentration in the mixture would be in error by as much as 40% if one failed to account for competition phenomena responsible for depression in mixed-gas situations. Mixture pressures as high as 20 atm were studied for both systems and in the CO2/N2O/PMMA system sorbed concentrations reach 33.90 [cm3(STP)/cm3 polymer] without any significant deviation from model predictions. 相似文献
75.
It is hypothesized that different parts of the thyroarytenoid muscle (TA) are functionally specialized. Specifically, the TA is divided into a lateral muscularis compartment and a medial vocalis compartment. This study examined the distribution of muscle spindles throughout the human TA as an indicator of these functional differences. Histological cross-sections from the anterior, middle, and posterior regions of five human membranous vocal folds were examined for the number and location of muscle spindles. There was an average of 6.1 muscle spindles in sections from each region with no significant variation between the different regions (p < .05). However, in sections from all three regions, the muscle spindles were always found to be concentrated in the superior medial quadrant of the TA (mean 85.9%, p < .01). The inferior medial, superior lateral, and inferior lateral quadrants of the TA contained 11.96%, 2.17%, and 0%, respectively, of the total muscle spindles. Within the superior medial quadrant, most of the muscle spindles were localized in the most superficial part of the muscle.The results of this study demonstrate that the majority of TA muscle spindlesare concentrated in its superior medial quadrant, an area we have termed the superior vocalis subcompartment (SC. This finding suggests that the superior vocalis SC is functionally distinct from the remainder of the TA. It is hypothesized that tension in the superior vocalis SC can be controlled independently from the remainder of the TA, and this capability is used to effect the biomechanics of vocal fold vibration during phonation. 相似文献
76.
77.
We comment on the paper “ISLAND – Inverse-Square-Law Acceleration Measurement using Inertial Drift,” by Lockerbie, N.A.: Gen.
Rel. Grav. 36, 593–600 (2004). 相似文献
78.
Sanders MP Verhoeven S de Graaf C Roumen L Vroling B Nabuurs SB de Vlieg J Klomp JP 《Journal of chemical information and modeling》2011,51(9):2277-2292
G-protein coupled receptors (GPCRs) are important drug targets for various diseases and of major interest to pharmaceutical companies. The function of individual members of this protein family can be modulated by the binding of small molecules at the extracellular side of the structurally conserved transmembrane (TM) domain. Here, we present Snooker, a structure-based approach to generate pharmacophore hypotheses for compounds binding to this extracellular side of the TM domain. Snooker does not require knowledge of ligands, is therefore suitable for apo-proteins, and can be applied to all receptors of the GPCR protein family. The method comprises the construction of a homology model of the TM domains and prioritization of residues on the probability of being ligand binding. Subsequently, protein properties are converted to ligand space, and pharmacophore features are generated at positions where protein ligand interactions are likely. Using this semiautomated knowledge-driven bioinformatics approach we have created pharmacophore hypotheses for 15 different GPCRs from several different subfamilies. For the beta-2-adrenergic receptor we show that ligand poses predicted by Snooker pharmacophore hypotheses reproduce literature supported binding modes for ~75% of compounds fulfilling pharmacophore constraints. All 15 pharmacophore hypotheses represent interactions with essential residues for ligand binding as observed in mutagenesis experiments and compound selections based on these hypotheses are shown to be target specific. For 8 out of 15 targets enrichment factors above 10-fold are observed in the top 0.5% ranked compounds in a virtual screen. Additionally, prospectively predicted ligand binding poses in the human dopamine D3 receptor based on Snooker pharmacophores were ranked among the best models in the community wide GPCR dock 2010. 相似文献
79.
Kellenbach E Sanders K Michiels PJ Girard FC 《Analytical and bioanalytical chemistry》2011,399(2):621-628
The recently revised European Pharmacopeia and US Pharmacopeia heparin sodium monographs include nuclear magnetic resonance
(NMR) tests on both identity and purity. In KMnO4-bleached heparin, an unidentified NMR signal is present at 2.10 ppm at a level of 15–20% of the mean of signal height of
the major glucosamine (GlcNAc/GlcNS,6S) anomeric proton signal at 5.42 ppm and of the major iduronic acid (IdoA2S) anomeric
proton signal at 5.21 ppm. According to the new monographs, no unidentified signals greater than 4% should be detected at
that position. Thus, the material did not meet the acceptance criterion. The signal at 2.10 ppm has been present at the same
level in all released MSD KMnO4-bleached heparin sodium batches analyzed over the past 10 years. The signal is a result of the KMnO4 bleaching. No (oversulfated) chondroitin sulfate or dermatan sulfate was detected in this material. A comprehensive NMR study
using long-range heteronuclear 2D techniques identifies this signal at 2.10 ppm as originating from the acetyl methyl group
of (6-sulfated) 2-N-acetyl-2-deoxy-glucono-1,5-lactone. This modified monosaccharide is formed by the KMnO4 oxidation of the reducing end of a terminal N-acetylglucosamine. 相似文献
80.
Denis A. Brosnan John P. Sanders Stephanie A. Hart 《Journal of Thermal Analysis and Calorimetry》2011,106(1):109-115
Thermal analysis techniques have been used in characterizing building materials from significant historic properties in the
Charleston, South Carolina area. Determining the chemical and physical effects of deterioration resulting from long periods
of exposure is a first step in formulating preservation strategies. In this regard, simultaneous thermal analysis coupled
with evolved gas analysis has been used to study reactions between air, seawater, and masonry materials. Further, the traditional
petrographic identification of mortar composition is greatly facilitated through use of thermal analysis. Simultaneous thermal
analysis allows for an exact determination of the calcium carbonate content in mortars as an alternative to the use of an
inferred value based on chemical analysis data. The partial dissolution of calcium carbonate in the presence of sea salt is
a major deterioration process. Further, natural cements manufactured in the United States are identified, in part, based on
their thermogravimetric (TG) traces and their evolved gases. The data indicates that natural cements form some carbonate phases
in addition to the major hydrate phases. Clay bricks are found to exhibit interaction with sea water, with uptake of bicarbonate
suggested. Additionally, there is evidence of re-hydroxylation in the 160 year old bricks. The bricks made in coastal zones
contain a considerable free silica fraction that is composed of a small percentage of cristobalite. The silica content of
the clay bricks is seen to result in very high thermal expansion coefficients in the area of 10 × 10−6 to 12 × 10−6 K−1. These studies provide guidance in restoration efforts where authenticity of cements is important. In the event that replacement
bricks are required, matching the thermal expansion coefficient of the original bricks is a requirement for preservation of
the masonry structure. 相似文献