全文获取类型
收费全文 | 130篇 |
免费 | 7篇 |
国内免费 | 3篇 |
专业分类
化学 | 113篇 |
数学 | 17篇 |
物理学 | 10篇 |
出版年
2023年 | 1篇 |
2022年 | 3篇 |
2021年 | 6篇 |
2020年 | 6篇 |
2019年 | 4篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 12篇 |
2015年 | 6篇 |
2013年 | 12篇 |
2012年 | 9篇 |
2011年 | 6篇 |
2010年 | 7篇 |
2009年 | 10篇 |
2008年 | 6篇 |
2007年 | 9篇 |
2006年 | 6篇 |
2005年 | 10篇 |
2004年 | 1篇 |
2003年 | 1篇 |
2002年 | 6篇 |
2000年 | 3篇 |
1995年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1983年 | 1篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有140条查询结果,搜索用时 15 毫秒
31.
In manufacturing systems, batch building processes are very common, as goods are often transported or processed in batches and must therefore be collected before these transport or processing steps can occur. In this paper, we present a method for the performance analysis of general batch building processes in material flow systems under the timeout and capacity rules. The proposed model allows for stochastic collecting times and incorporates no restrictions with respect to the number of arriving units and their interarrival times. The accuracy of the discrete-time approach is demonstrated by comparing this approach with a discrete-event simulation model in continuous-time. Subsequently, the model is applied to two cases: a transportation case from the health care industry and the process of building a batch for a batch processor. 相似文献
32.
The formation processes of α-Keggin-type [H2W12O40]6− and [H3W12O40]5− complexes were investigated in aqueous WVI (0.05–0.50 M) solutions. The formation of [H2W12O40]6− was ascertained by the appearance of a 183W NMR line at −117 ppm, but no evidence was found for the existence of [H3W12O40]5− in the solution at the accessible pH range. The addition of (CH3)4N+ (Me4N+) to the WVI solution directly precipitated the (Me4N)6[H2W12O40] salt. On the other hand, the addition of the larger Bu4N+ cation precipitates the (Bu4N)4.5H0.5[H3W12O40] salt, because a naked proton formed during the crystallization process or in the solid state may enter into the Keggin shell to produce [H3W12O40]5−. This explanation is based on the fact that [H2W12O40]6− is not spontaneously converted into [H3W12O40]5− in acidified aqueous solution. On the basis of their voltammetric properties, a simple diagnostic criterion was developed to distinguish between [H2W12O40]6− and [H3W12O40]5−. 相似文献
33.
Polymeric technetium tetrachloride reacts with monodentate donor ligands such as THF, acetonitrile, DMSO, thioxane (1-oxa-4-thiacyclohexane), PMe2Ph, PPh3, OPPh3, or OH2 via cleavage of the polymeric network and the formation of [TcCl4(L)2] complexes. The configuration of the products is dependent on the donor atoms such that trans coordination is established with "soft" donor atoms such as sulfur or phosphorus, while cis-[TcCl4(L)2] complexes are formed with the "harder" donors oxygen or nitrogen. The ambivalent thioxane binds to technetium via the sulfur atom. The trans products are air stable and resistant to hydrolysis. The cis complexes, however, undergo stepwise hydrolysis, during which complexes of the composition [Cl3(L)2TcOTc(L)2Cl3] (L = CH3CN, DMSO, or OH2) are formed. They are the first representatives of a new class of technetium(IV) complexes with a bridging oxo ligand. The Tc-O bond lengths in these bridges are between 1.803(1) and 1.823(2) A. 相似文献
34.
[Structure: see text] The asymmetric synthesis of N-propargylamides through Michael addition of the alkynylborane 1 to N-acylimines is reported. The N-acetylimines provide the best substrates for the process exhibiting high selectivity (56-95% ee) with predictable stereochemistry. In several cases, 5 crystallizes in essentially pure form (97-99% ee) and a single-crystal X-ray structure was also obtained for 5g (R1=R2=Me, R3=o-Cl-C6C4). The process regenerates 4 for its direct conversion back to 1 and facilitates the efficient recovery of the pseudoephedrine. 相似文献
35.
Let G be a 2-dimensional connected, compact Abelian group and s be a positive integer. We prove that a classification of s-sheeted covering maps over G is reduced to a classification of s-index torsionfree supergroups of the Pontrjagin dual . Using group theoretic results from earlier paper we demonstrate its consequences. We also prove that for a connected compact group Y:
- (1)
- Every finite-sheeted covering map from a connected space over Y is equivalent to a covering homomorphism from a compact, connected group.
- (2)
- If two finite-sheeted covering homomorphisms over Y are equivalent, then they are equivalent as topological homomorphisms.
36.
Burgos CH Canales E Matos K Soderquist JA 《Journal of the American Chemical Society》2005,127(22):8044-8049
The remarkable versatility and selectivity of the 10-(trimethylsilyl)-9-borabicyclo[3.3.2]decanes (10-TMS-9-BBDs) in the allyl- and crotylboration of representative aldehydes are reported. The new reagents are prepared through air-stable crystalline pseudoephedrine borinic ester complexes of the 10-TMS-9-BBDs (4), which are available in 63% overall yield from B-MeO-9-BBN through a simple two-step procedure. These complexes 4 are directly converted to the corresponding B-allyl-10-TMS-9-BBDs (1) with allylmagnesium bromide, which either can be isolated (98%) or used in situ for the allylations. The remarkable enantioselectivity (96 to > or =99% ee) of these reagents in the rapid (<3 h), asymmetric allylboration process at -78 degrees C is only slightly diminished when it is conducted at 25 degrees C, a phenomenon attributable to its rigid bicyclic structure. In addition to providing the homoallylic alcohols 6 efficiently (68-80%), the procedure also permits the efficient recovery of 4 (68-84%) for the direct regeneration of 1. Alternatively, an oxidative workup procedure can be used for the preparation of 6. The reagent gives predictable stereochemistry and exhibits an extremely high level of reagent control in the allylboration of d-glyceraldehyde acetonide. A simple and efficient procedure has been developed for the preparation of all four geometric and enantiomeric isomers of the B-crotyl-10-TMS-9-BBDs (10) from optically pure enantiomers of B-MeO-10-TMS-9-BBD (3). These reagents 10 also add rapidly (<3 h) and efficiently to representative aldehydes at -78 degrees C, providing ready access to all four of the possible stereoisomers of the beta-methyl homoallylic alcohols 12-15 (69-92%) in high dr (> or =98:2) and ee (94-99%). 相似文献
37.
Karadas F Ertas G Ozkaraoglu E Suzer S 《Langmuir : the ACS journal of surfaces and colloids》2005,21(1):437-442
Prolonged exposure to X-rays of HAuCl(4) deposited from an aqueous solution onto a SiO(2)/Si substrate or into a poly(methyl methacrylate) (PMMA) matrix induces reduction of the Au(3+) ions to Au(0) and subsequent nucleation to gold nanoclusters as recorded by X-ray photoelectron spectroscopy. The corresponding major oxidation product is determined as chlorine {HAuCl(4)(ads) + X-rays --> Au(ads) + (3/2)Cl(2)(ads) + HCl(ads)}, which is initially adsorbed onto the surface but eventually diffuses out of the system into the vacuum. The reduced gold atoms aggregate (three-dimensionally) into gold nanoclusters as evidenced by the variation in the binding energy during X-ray exposure, which starts as 1.3 eV but approaches a value that is 0.5 eV higher than that of the bulk gold. The disappearance of the oxidation product (Cl2p signal) and the growth of the nanoclusters (related to the measured binding energy difference between the Si2p of the oxide and Au4f of the reduced gold) exhibit first-order kinetics which is approximately 3 times slower than the reduction of Au(3+), indicating that both of the former processes are diffusion controlled. Similarly, gold ions incorporated into PMMA can also be reduced and aggregated to gold nanoclusters using 254 nm deep UV irradiation in air evidenced by UV-vis-NIR absorption spectrocopy. 相似文献
38.
Nora Graf Eda Yegen Thomas Gross Andreas Lippitz Wilfried Weigel Simone Krakert Andreas Terfort Wolfgang E.S. Unger 《Surface science》2009,603(18):2849-2860
The chemical constitution of functionalized supports is an important parameter that determines their performance in a broad range of applications, e.g. for immobilization of biomolecules. Supports with amino functionalized surfaces are also often used for DNA microarray experiments. However, spectral data which have been reported for surfaces with amino functionalities suffer from some inconsistencies. In this article a detailed XPS (X-ray photoelectron spectroscopy) and NEXAFS (Near edge X-ray absorption fine structure) database for amino functionalized surfaces is presented. Amino-terminated surfaces prepared from aliphatic and aromatic aminosilanes or aminothiols and a field sample are considered. Effects of aging in air and damage by radiation are addressed as well. 相似文献
39.
Eda Gungor Gurkan Hizal Umit Tunca 《Journal of polymer science. Part A, Polymer chemistry》2009,47(13):3409-3418
We employed for the first time double click reactions: Cu(I) catalyzed azide‐alkyne 1,3‐dipolar cycloaddition and Diels–Alder (4 + 2) reactions for the preparation of H‐shaped polymer possessing pentablocks with different chemical nature (H‐shaped quintopolymer) using one‐pot technique. H‐shaped quintopolymer consists of poly(ethylene glycol) (PEG)‐poly(methylmethacrylate) (PMMA) and poly(ε‐caprolactone) (PCL)‐polystyrene (PS) blocks as side chains and poly (tert‐butylacrylate) (PtBA) as a main chain. For the preparation of H‐shaped quintopolymer, PEG‐b‐PMMA and PCL‐b‐PS copolymers with maleimide and alkyne functional groups at their centers, respectively, were synthesized and simply reacted in one‐pot with PtBA with α‐anthracene‐ω‐azide end functionalities in N,N‐dimethylformamide (DMF) using CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as catalyst at 120 °C for 48 h. The precursors and the target H‐shaped quintopolymer were characterized comprehensively by 1H NMR, UV, FTIR, GPC, and triple detection GPC. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3409–3418, 2009 相似文献
40.
The singular homology groups of compact CW-complexes are finitelygenerated, but the groups of compact metric spaces in generalare very easy to generate infinitely and our understanding ofthese groups is far from complete even for the following compactsubset of the plane, called the Hawaiian earring:
Griffiths [11] gave a presentation of the fundamental groupof H and the proof was completed by Morgan and Morrison [15].The same group is presented as the free -product of integers Z in [4, Appendix]. Hence the firstintegral singular homology group H1(H) is the abelianizationof the group . These results have been generalized to non-metrizable counterparts HI of H(see Section 3). In Section 2 we prove that H1(X) is torsion-free and Hi(X) =0 for each one-dimensional normal space X and for each i 2.The result for i 2 is a slight generalization of [2, Theorem5]. In Section 3 we provide an explicit presentation of H1(H)and also H1(HI) by using results of [4]. Throughout this paper, a continuum means a compact connectedmetric space and all maps are assumed to be continuous. Allhomology groups have the integers Z as the coefficients. Thebouquet with n circles is denoted by Bn. The base point (0, 0) of Bn is denoted by o forsimplicity. 相似文献