全文获取类型
收费全文 | 748篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 563篇 |
晶体学 | 7篇 |
力学 | 14篇 |
数学 | 96篇 |
物理学 | 93篇 |
出版年
2023年 | 4篇 |
2022年 | 7篇 |
2021年 | 11篇 |
2020年 | 11篇 |
2019年 | 9篇 |
2018年 | 12篇 |
2017年 | 7篇 |
2016年 | 15篇 |
2015年 | 20篇 |
2014年 | 20篇 |
2013年 | 31篇 |
2012年 | 49篇 |
2011年 | 43篇 |
2010年 | 28篇 |
2009年 | 38篇 |
2008年 | 42篇 |
2007年 | 38篇 |
2006年 | 47篇 |
2005年 | 55篇 |
2004年 | 44篇 |
2003年 | 40篇 |
2002年 | 24篇 |
2001年 | 9篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 9篇 |
1994年 | 6篇 |
1993年 | 9篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 6篇 |
1989年 | 8篇 |
1987年 | 3篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 4篇 |
1972年 | 4篇 |
1971年 | 3篇 |
1941年 | 2篇 |
排序方式: 共有773条查询结果,搜索用时 600 毫秒
1.
Kristin Fischer Silvio Prause Stefan Spange Frank Cichos Christian Von Borczyskowski 《Journal of Polymer Science.Polymer Physics》2003,41(11):1210-1218
Solvent‐dependent ultraviolet–visible (UV–vis) absorption and Stokes shifts including strong hydrogen‐bond‐donating (HBD) solvents such as 2,2,2‐trifluoroethanol and 1,1,1,3,3,3‐hexafluoro‐2‐propanol of two coumarine dyes (Co 151 and Co 153) were analyzed with multiple‐square analyses of linear solvation energy relationships and the Kamlet–Taft solvent parameter set to α (HBD capacity), β (hydrogen‐bond‐accepting capacity), and π* (dipolarity/polarizability). The UV–vis absorption and emission spectra of Co 151 and Co 153 were measured when adsorbed on various polysaccharides such as different cellulose batches, carboxymethylcelluloses with different degrees of substitution, and chitine. As a result of this evaluation, Co 153 is recommended as an alternative UV–vis probe for evaluating the dipolarity/polarizability of cellulose and cellulose derivates. Multiple adsorption of Co 153 on Linters cellulose took place indicating a wide‐surface polarity distribution, which makes the determination of a rigid polarity parameter questionable. Thus, fluorescence measurements of adsorbed Co 153 are suitable to detect inhomogenities on a surface but not for the determination of empirical polarity parameters. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1210–1218, 2003 相似文献
2.
3.
Thomas J. Cloonan Gaylord W. Richards Anthony L. Lentine Frederick B. McCormick John R. Erickson 《Optical and Quantum Electronics》1992,24(4):S415-S442
Free-space optical implementations of switching networks have been proposed to circumvent many of the system-level problems that may be encountered in systems that require many high-density, high-bandwidth connections. The details of a new class of switching network (the EGS network), that is well-suited to free-space implementations, is described. The common control injection problem that plagues most free-space photonic networks, i.e. how can control information from an electronic source be injected into the network for applications that require relatively high network reconfiguration rates, is examined. A new technique for control injection, called embedded control, which permits network operation even with relatively high network reconfiguration rates is also proposed. 相似文献
4.
5.
Frost R. L. Weier M. L. Erickson Kristy L. 《Journal of Thermal Analysis and Calorimetry》2004,76(3):1025-1033
Struvite (NH4MgPO4·6H2O) is a mineral often found in urinary tracts and kidneys. Thermal decomposition using slow low heating shows that the 'kidney'
stone can be decomposed at temperatures below 40°C. At this temperature both ammonia and water are evolved. If more rapid
heating is employed the decomposition occurs at around 80°C. The implication of this work rests with the use of low slow heat
for the decomposition of the kidney stones.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
6.
Thermodynamics of the dissociation of 2-aminopyridinium ion in synthetic seawater and a standard for pH in marine systems 总被引:1,自引:0,他引:1
Buffer solutions composed of 2-aminopyridinium chloride and 2-aminopyridine in synthetic seawater are useful as a supplement to buffers of Tris (pH 8.2) and Bis (pH 8.8) in standardizing measurements of hydrogen ion concentration (pm
H
or pH(SWS)) in oceanography. The dissociation constant of 2-amino-pyridinium ion over the range of salinities (S) from 30 to 40 has now been determined from the emf of cells without liquid junction at eight temperatures (T) from 278.15 to 313.15 K. The results fit the equation pK=2498.31/T–15.3274+2.4050 lnT+S(0.012928–2.9417×10–5T) with a standard deviation of 0.0023. Thermodynamic constants for the dissociation process and standard reference values of pm
H
and pH(SWS) were derived from the data. The pm
H
of the buffer consisting of 2-aminopyridinium chloride and 2-aminopyridine (each 0.04 molal) in synthetic seawater of salinity 35 varies from 7.356 at 278.15 K to 6.601 at 313.15 K. 相似文献
7.
Using reaction rate data collected in aprotic solvents, we have determined that the Baylis-Hillman rate-determining step is second order in aldehyde and first order in DABCO and acrylate. On the basis of these data, we have proposed a new mechanism involving a hemiacetal intermediate. The proposed mechanism was then supported using two different kinetic isotope experiments. 相似文献
8.
Pandey S Redden RA Hendricks AE Fletcher KA Palmer CP 《Journal of colloid and interface science》2003,262(2):579-587
Solubilization environment afforded by several of the novel allyl glycidyl ether-modified methylhydrosiloxane polymers are investigated using a common polycyclic aromatic hydrocarbon fluorescence probe, pyrene. The backbone of the polymer has been modified by the addition of an alkyl chain of varying length (either C8, C12, or C18) and to differing degrees of substitution. The nomenclature adopted for the purposes of these studies is as follows: "AGENT" represents the backbone polymer with no alkyl substitution, and "OAGENT", "DAGENT", and "SAGENT" are substituted with n-octyl, n-dodecyl, and n-octadecyl, respectively. The percentage of alkyl substitution is designated as 10, 15, and 20%. The pyrene polarity scale (defined as the ratio of the intensity of peak I to peak III) was used to determine the relative dipolarity of the cybotactic region provided by approximately 1 w/w% aqueous polymer solutions compared to 10 mM sodium dodecylsulfate (SDS) micellar solution. Results indicate that 10-15% DAGENT afforded the most hydrophobic solubilization site, followed by 15% OAGENT and 15% SAGENT. In addition, as the degree of alkyl substitution of DAGENT increased from 10 to 20%, the cybotactic region appeared to become more hydrophobic. Furthermore, a deeper investigation into the relative size of the solubilization site revealed that all alkyl-substituted polymers promoted excimer formation at relatively low pyrene concentrations, indicating the possibility of localized concentration enhancement within the solvation pockets and/or compartmentalization of the solute molecules. The pyrene fluorescence excitation data strongly indicates ground-state heterogeneity that is most prominent in AGENT and decreases as the alkyl chain length is increased. This provides a relative sense of the size and shape of the solvation pockets afforded by each polymer solution. An overall analysis of the collected data indicated that these alkyl-substituted polymers may provide a more selective and efficient pseudostationary phase in electrokinetic chromatography with better solvation capacity for hydrophobic compounds compared to SDS. 相似文献
9.
Mingjian Wen Samuel M. Blau Evan Walter Clark Spotte-Smith Shyam Dwaraknath Kristin A. Persson 《Chemical science》2021,12(5):1858
A broad collection of technologies, including e.g. drug metabolism, biofuel combustion, photochemical decontamination of water, and interfacial passivation in energy production/storage systems rely on chemical processes that involve bond-breaking molecular reactions. In this context, a fundamental thermodynamic property of interest is the bond dissociation energy (BDE) which measures the strength of a chemical bond. Fast and accurate prediction of BDEs for arbitrary molecules would lay the groundwork for data-driven projections of complex reaction cascades and hence a deeper understanding of these critical chemical processes and, ultimately, how to reverse design them. In this paper, we propose a chemically inspired graph neural network machine learning model, BonDNet, for the rapid and accurate prediction of BDEs. BonDNet maps the difference between the molecular representations of the reactants and products to the reaction BDE. Because of the use of this difference representation and the introduction of global features, including molecular charge, it is the first machine learning model capable of predicting both homolytic and heterolytic BDEs for molecules of any charge. To test the model, we have constructed a dataset of both homolytic and heterolytic BDEs for neutral and charged (−1 and +1) molecules. BonDNet achieves a mean absolute error (MAE) of 0.022 eV for unseen test data, significantly below chemical accuracy (0.043 eV). Besides the ability to handle complex bond dissociation reactions that no previous model could consider, BonDNet distinguishes itself even in only predicting homolytic BDEs for neutral molecules; it achieves an MAE of 0.020 eV on the PubChem BDE dataset, a 20% improvement over the previous best performing model. We gain additional insight into the model''s predictions by analyzing the patterns in the features representing the molecules and the bond dissociation reactions, which are qualitatively consistent with chemical rules and intuition. BonDNet is just one application of our general approach to representing and learning chemical reactivity, and it could be easily extended to the prediction of other reaction properties in the future.Prediction of bond dissociation energies for charged molecules with a graph neural network enabled by global molecular features and reaction difference features between products and reactants. 相似文献
10.
Accurate data on transport properties such as viscosity are essential in plant and process design involving ionic liquids. In this study, we determined the absolute viscosity of the ionic liquid + water system at water mole fractions from 0 to 0.25 for three 1-alkyl-3-methylimidazolium ionic liquids: 1-butyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide and 1-ethyl-3-methylimidazolium bis(trifluoromethane sulfonyl)imide. In each case, the excimer to monomer ratio for 1,m-bis(1-pyrenyl)alkanes (m= 3 or 10) was found to increase linearly with the mole fraction of water. Of the probes studied only PRODAN and rhodamine 6G, both of which have the ability to participate in hydrogen bonding, exhibited Perrin hydrodynamic behavior in the lower viscosity bis(trifluoromethane sulfonyl)imides. As a result, these probes allow for the extrapolation of the absolute viscosity of the ionic liquid mixture from the experimental fluorescence steady-state polarization values. 相似文献