全文获取类型
收费全文 | 398篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 254篇 |
晶体学 | 4篇 |
力学 | 16篇 |
数学 | 47篇 |
物理学 | 89篇 |
出版年
2024年 | 2篇 |
2023年 | 2篇 |
2022年 | 7篇 |
2021年 | 13篇 |
2020年 | 14篇 |
2019年 | 19篇 |
2018年 | 9篇 |
2017年 | 4篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 16篇 |
2013年 | 30篇 |
2012年 | 18篇 |
2011年 | 15篇 |
2010年 | 9篇 |
2009年 | 13篇 |
2008年 | 14篇 |
2007年 | 14篇 |
2006年 | 12篇 |
2005年 | 6篇 |
2004年 | 6篇 |
2003年 | 11篇 |
2002年 | 8篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1993年 | 2篇 |
1992年 | 4篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 8篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 11篇 |
1977年 | 7篇 |
1975年 | 6篇 |
1974年 | 4篇 |
1972年 | 2篇 |
1971年 | 2篇 |
1945年 | 1篇 |
排序方式: 共有410条查询结果,搜索用时 15 毫秒
1.
In quasi-steady operation, convection currents in a Bridgmandevice, used for producing a semi-conductor crystal, createinhomogeneities that may make the crystal unusable. It has oftenbeen suggested that additional forces due to rotation or magnetismmight be efficacious in reducing the segregation of the elementsof the alloy. It has been found that, over a wide range of rotationrates, there is no improvement in performance due to rotationabout the vertical axis. However, numerical results that havebeen obtained previously (Lee & Pearlstein, J. Crys. Growth240, 2002) indicate that, when effects of centrifugal buoyancyare introduced, a substantial reduction in segregation is achieved.In the work reported here, by contrast, in which we extend previouslarge-Rayleigh-number asymptotic analysis to include centrifugalbuoyancy, we find no improvement in radial segregation, butrather increasing segregation with increasing rotation rate. 相似文献
2.
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
3.
W.E. Falconer G.R. Jones W.A. Sunder M.J. Vasile Annabel A. Muenter T.R. Dyke W. Klemperer 《Journal of fluorine chemistry》1974,4(2):213-234
Most known non-radioactive pentafluorides have been examined by molecular-beam mass spectrometry and by the deflection of molecular beams in inhomogeneous electric fields. Extensive association of the vapors occurs for all but the lighter pentafluorides and the interhalogens. The interhalogen pentafluorides are strongly polar, consistent with the accepted C4v symmetry. The transition-metal and Group V pentafluorides are all non-polar, except VF5 and CrF5 for which temperature-dependent polarity is observed. However, uncertainty exists as to whether these observations are applicable to monomeric pentafluorides in all cases. Mass-spectral cracking patterns are presented for all species. 相似文献
4.
The preparation of 6,6′-[(2-hydroxy-1,3-propanediyl)]bis(oxy)]bis(3-hydroxy)]-2-benzofurancarboxylic acid) diethyl ester trisodium salt trihydrate ( 6 ), a compound structurally related to disodium cromoglycate (DSCG), is described. 相似文献
5.
A new and efficient synthesis of benzof'uro[3,2-b]quinolin-6(11H) one ( 3 ) is reported, by treatment of 2- {[(phenoxy)acetyl]amino} benzoic acid ( 6a ) with polyphosphoric acid. An intermediate in the conversion of 3 to 6a , namely, 2-(3-benzofuranylamino)benzoic acid ( 7 ), was defined. An improved method for the synthesis of 6a is also described, which was used to prepare analogs ( 6b-n ) of 6a . In addition, an 11-alkoxy derivative ( 8 ) and 11-dialkylamino derivatives ( 10 and 11 ) of benzofuro [3,2-b]quinoline were prepared from 3 . 相似文献
6.
The intramolecular aza-Wacker reaction has unparalleled potential for the site-selective amination of olefins, but it is perhaps underappreciated relative to other alkene oxidations. The first part of this review makes the distinction between classical and tethered aza-Wacker cyclization reactions and summarizes examples of the latter. The second portion focuses on developments in asymmetric aza-Wacker cyclization technology. The final part of the review summarizes applications of all classes of aza-Wacker cyclization reactions to natural product assembly.The aza-Wacker cyclization reaction is a powerful strategy for alkene amination. 相似文献
7.
8.
Bikshandarkoil R. Srinivasan Christian N?ther Sunder N. Dhuri Wolfgang Bensch 《Monatshefte für Chemie / Chemical Monthly》2006,121(2):397-411
Four new organic ammonium tetrathiotungstates (N–Me–enH2)[WS4] (1), (N,N′-dm-1,3-pnH2)[WS4] (2), (1,4-bnH2)[WS4] (3), and (mipaH)2[WS4] (4), (N–Me–enH2 = N-methylethylenediammonium, N,N′-dm-1,3-pnH2 = N,N′-dimethyl-1,3-propanediammonium, 1,4-bnH2 = 1,4-butanediammonium, and mipaH = monoisopropylammonium) were synthesized by the base promoted cation exchange reaction and characterized by elemental analysis,
infrared, Raman, UV-Vis and 1H NMR spectroscopy as well as single crystal X-ray crystallography. The structures of 1–4 consist of [WS4]2− tetrahedra which are linked to the organic ammonium cations via N–H⋯S hydrogen bonding. The strength and number of the S⋯H
interactions affect the W–S bond lengths as evidenced by distinct short and long W–S bonds. The IR spectra exhibit splitting
of the W–S vibrations, which can be attributed to the distortion of the [WS4]2− tetrahedron. From a comparative study of several known tetrathiotungstates it is observed that a difference of more than
0.033 ? between the longest and shortest W–S bonds in a tetrathiotungstate will result in the splitting of the asymmetric
stretching vibration of the W–S bond. 相似文献
9.
Spring DR Krishnan S Blackwell HE Schreiber SL 《Journal of the American Chemical Society》2002,124(7):1354-1363
Diversity-oriented synthesis of structurally complex and diverse small molecules can be used as the first step in a process to explore cellular and organismal pathways. The success of this process is likely going to be dependent on advances in the synthesis of small molecules having natural product-like structures in an efficient and stereoselective manner. The development, scope, and mechanism of the oxidation of organocuprates was investigated and exploited in the atropdiastereoselective synthesis of biaryl-containing medium rings (9-, 10-, and 11-membered rings). The methodology was performed on high-capacity, large polystyrene beads by metalating aryl bromides with i-PrBu(2)MgLi, followed by transmetalating with CuCN x 2LiBr and then oxidizing with 1,3-dinitrobenzene, and was used in a diversity-oriented synthesis of biaryl-containing medium rings (library total theoretical maximum 1412 members). The high capacity beads were arrayed into 384-well plates and, using a process optimized during the development of a one bead/one stock solution technology platform, converted into arrays of stock solutions, with each stock solution containing largely one compound. These stock solutions were used in numerous phenotypic and protein-binding assays. The process described outlines a pathway that we feel will contribute to a comprehensive and systematic chemical approach to exploring biology (chemical genetics). 相似文献
10.
Functional nanofibrous membranes fabricated by electrospinning technology have attracted much attention in the removal of heavy metal ions from contaminated wastewater. The high specific surface area, high porosity and ease of functionality create an enhanced throughput and high adsorption capacity of the nanofibrous membrane. However, the relatively poor mechanical properties of the membrane with a non-woven nanofibrous structure are one of the major concerns, which can limit the applications in wastewater treatment. Different strategies and methodologies were explored to address the problems and were reviewed in this work, highlighting the possibilities of overcoming the poor mechanical properties of the nanofibrous membrane and to ensure the recyclability and reusability of the membrane during the adsorption process. 相似文献