全文获取类型
收费全文 | 386篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 326篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 39篇 |
物理学 | 52篇 |
出版年
2023年 | 9篇 |
2022年 | 3篇 |
2021年 | 12篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 17篇 |
2014年 | 16篇 |
2013年 | 31篇 |
2012年 | 19篇 |
2011年 | 27篇 |
2010年 | 16篇 |
2009年 | 19篇 |
2008年 | 20篇 |
2007年 | 26篇 |
2006年 | 31篇 |
2005年 | 25篇 |
2004年 | 21篇 |
2003年 | 17篇 |
2002年 | 9篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 3篇 |
1981年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有420条查询结果,搜索用时 62 毫秒
121.
13C NMR spectra of ms-tetraphenylchlorins, new aminoalkyl- and hydroxy-pyrroline substituted ms-tetra-phenylchlorins, and ms-tetraphenylisobacteriochlorins are presented and discussed. Significant changes in the chemical shifts of the α-pyrrole, α-pyrroline and meso skeletal carbons are found in chlorins and isobacteriochlorins in comparison to porphyrins. In contrast, the chemical shifts of the β-pyrrole carbons are almost unaffected by the structural modifications in chlorin and isobacteriochlorin. The chemical shifts of the α-pyrrole carbons in the various chlorins and isobacteriochlorins are strongly affected by the substitutents of the pyrroline ring, or by the introduction of an additional pyrroline ring in isobacteriochlorins. The results show that most of the electron density is concentrated in the unreduced part of the molecule, i.e. in the pyrrole rings and, especially, on the α-pyrrole carbons and is transferred or removed through the aromatic pathway by substituents on the pyrroline ring. These observations are supporting evidence that the α-pyrrole, α-pyrroline and meso-carbons are in the aromatic pathway and favour the proposal of a 16 atom dianion as the preferred delocalization pathway in chlorins and isobacteriochlorins. 相似文献
122.
Joost Manassen Robert Rein 《Journal of polymer science. Part A, Polymer chemistry》1970,8(6):1403-1417
The charge delocalization in the conjugated vinyl intermediates, which are assumed to be the reactive intermediates in acetylene polymerization, is calculated, taking into account σ as well as π electrons. Delocalization is shown to exist, but it is of a different kind for cations and anions. In the anion, the σ charge is localized at the reactive center and the π change is displaced into the system. In the cations, the σ charge flows towards the reactive center and the π charge is more or less unaffected. π-overlap charges between the carbon atoms are much less affected than in the case of the corresponding allyl type anion and cation. The calculated charge delocalizations are compared with the little experimental evidence there is, and possible implications of σ and π delocalizations on reactivity and specificity of reaction are discussed. 相似文献
123.
Joost R. W. Woittiez 《Fresenius' Journal of Analytical Chemistry》1990,338(4):575-579
Summary This paper describes the use of certified reference materials to monitor the long-term quality of radiochemical separations. The practical limitations which determine the actual design of the quality control are discussed. The hypothesis that the high yield of the radiochemical separation will be constant with time has been checked and validated for the elements Zn, Fe, Co, Cd, Mo and to a lesser extent for W and Th using NBS SRM 1577A, BCR CRM 274 and IAEA RM A-11. This validation could not be made for the elements Cr, Au and Ag. Especially for Cr there is a serious lack of appropriate certified reference materials. 相似文献
124.
Abstract— The photoreduction of free base porphyrins by tertiary amines in the visible spectral range leads to the formation of chlorin. The increase of the apparent first order rates to yield chlorin is correlated with the inductive effect on the nitrogen of the amine used. A mechanism involving a charge transfer interaction between the photoexcited singlet of the prophyrin and the amine is proposed. The porphyrin radicals formed recombine to form a light sensitive dimer which disproportionates in the dark to yield chlorin and porphyrin. The mechanism is elucidated by the use of EPR, laser and flash photolysis. 相似文献
125.
Dinuclear Palladium Complexes with Two Ligand‐Centered Radicals and a Single Bridging Ligand: Subtle Tuning of Magnetic Properties
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
M. Sc. Daniël L. J. Broere Dr. Serhiy Demeshko Prof. Dr. Bas de Bruin Dr. Evgeny A. Pidko Prof. Dr. Joost N. H. Reek Dr. Maxime A. Siegler Dr. Martin Lutz Dr. Jarl Ivar van der Vlugt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5879-5886
The facile and tunable preparation of unique dinuclear [(L?)Pd?X?Pd(L?)] complexes (X=Cl or N3), bearing a ligand radical on each Pd, is disclosed, as well as their magnetochemistry in solution and solid state is reported. Chloride abstraction from [PdCl( NNOISQ )] ( NNOISQ =iminosemiquinonato) with TlPF6 results in an unusual monochlorido‐bridged dinuclear open‐shell diradical species, [{Pd( NNO ISQ)}2(μ‐Cl)]+, with an unusually small Pd‐Cl‐Pd angle (ca. 93°, determined by X‐ray). This suggests an intramolecular d8–d8 interaction, which is supported by DFT calculations. SQUID measurements indicate moderate antiferromagnetic spin exchange between the two ligand radicals and an overall singlet ground state in the solid state. VT EPR spectroscopy shows a transient signal corresponding to a triplet state between 20 and 60 K. Complex 2 reacts with PPh3 to generate [Pd(NNOISQ)(PPh3)]+ and one equivalent of [PdCl( NNOISQ )]. Reacting an 1:1 mixture of [PdCl( NNOISQ )] and [Pd(N3)( NNOI SQ)] furnishes the 1,1‐azido‐bridged dinuclear diradical [{Pd( NNO ISQ)}2(κ1‐N;μ‐N3]+, with a Pd‐N‐Pd angle close to 127° (X‐ray). Magnetic and EPR measurements indicate two independent S=1/2 spin carriers and no magnetic interaction in the solid state. The two diradical species both show no spin exchange in solution, likely because of unhindered rotation around the Pd?X?Pd core. This work demonstrates that a single bridging atom can induce subtle and tunable changes in structural and magnetic properties of novel dinuclear Pd complexes featuring two ligand‐based radicals. 相似文献
126.
127.
Dr. Matthias Otte Petrus F. Kuijpers Dipl.‐Chem. Oliver Troeppner Prof. Dr. Ivana Ivanović‐Burmazović Prof. Dr. Joost N. H. Reek Prof. Dr. Bas de Bruin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10170-10178
The synthesis of a new, cubic M8L6 cage is described. This new assembly was characterised by using NMR spectroscopy, DOSY, TGA, MS, and molecular modelling techniques. Interestingly, the enlarged cavity size of this new supramolecular assembly allows the selective encapsulation of tetra(4‐pyridyl)metalloporphyrins (MII(TPyP), M=Zn, Co). The obtained encapsulated cobalt–porphyrin embedded in the cubic zinc–porphyrin assembly is the first example of a catalytically active encapsulated transition‐metal complex in a cubic M8L6 cage. The substrate accessibility of this system was demonstrated through radical‐trapping experiments, and its catalytic activity was demonstrated in two different radical‐type transformations. The reactivity of the encapsulated CoII(TPyP) complex is significantly increased compared to free CoII(TPyP) and other cobalt–porphyrin complexes. The reactions catalysed by this system are the first examples of cobalt–porphyrin‐catalysed radical‐type transformations involving diazo compounds which occur inside a supramolecular cage. 相似文献
128.
We present a new numerical scheme to study systems of nonconvex, irregular, and punctured particles in an efficient manner. We employ this method to analyze regular packings of odd-shaped bodies, both from a nanoparticle and from a computational geometry perspective. Besides determining close-packed structures for 17 irregular shapes, we confirm several conjectures for the packings of a large set of 142 convex polyhedra and extend upon these. We also prove that we have obtained the densest packing for both rhombicuboctahedra and rhombic enneacontrahedra and we have improved upon the packing of enneagons and truncated tetrahedra. 相似文献
129.
Marino Gran Florence Sterck Joost Vercruysse 《Journal of Pure and Applied Algebra》2019,223(10):4171-4190
We prove that the category of cocommutative Hopf algebras over a field is a semi-abelian category. This result extends a previous special case of it, based on the Milnor–Moore theorem, where the field was assumed to have zero characteristic. Takeuchi's theorem asserting that the category of commutative and cocommutative Hopf algebras over a field is abelian immediately follows from this new observation. We also prove that the category of cocommutative Hopf algebras over a field is action representable. We make some new observations concerning the categorical commutator of normal Hopf subalgebras, and this leads to the proof that two definitions of crossed modules of cocommutative Hopf algebras are equivalent in this context. 相似文献
130.
M. Jayakannan X. Lou Joost L. J. van Dongen Ren A. J. Janssen 《Journal of polymer science. Part A, Polymer chemistry》2005,43(7):1454-1462
Regioregular poly(3‐octylthiophene)s were synthesized through a palladium‐catalyzed Suzuki polycondensation of 2‐(5‐iodo‐4‐octyl‐2‐thienyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane. The effects of the palladium catalyst {tetrakis(triphenylphosphine)palladium(0) [Pd(PPh3)4], palladium(II) acetate [Pd(OAc)2], [1, 1′‐bis(diphenylphosphino)ferrocene]dichloropalladium(II) [Pd(dppf)Cl2], tris(dibenzylideneacetone)dipalladium(0), or bis(triphenylphosphine)palladium(II) dichloride [Pd(PPh3)2Cl2]} and the reaction conditions (bases and solvents) were investigated. NMR spectroscopy revealed that poly(3‐octylthiophene)s prepared via this route were essentially regioregular. According to size exclusion chromatography, the highest molecular weights were obtained with in situ generated Pd(PPh3)4 and tetrakis(tri‐o‐tolylphosphine]palladium(0) {Pd[P(o‐Tol)3]4} catalysts or more reactive, phosphine‐free Pd(OAc)2. Matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry was used to analyze end groups and allowed the determination of some mechanistic aspects of the Suzuki polycondensation. The polymers were commonly terminated with hydrogen or iodine as a result of deboronation and some deiodination. Pd(PPh3)4, Pd(PPh3)2Cl2, and Pd[P(o‐Tol)3]4 induced aryl–aryl exchange reactions with the palladium center and resulted in some chains having phenyl‐ and o‐tolyl‐capped chain ends. Pd(dppf)Cl2 yielded only one type of chain, and it had hydrogen end groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1454–1462, 2005 相似文献