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1.
Crystal Structures of the Fluorochloroplatinates(IV) cis-[(C5H5N)2CH2][PtF4Cl2], trans-[(C5H5N)2CH2][PtF4Cl2] · H2O, and [(C5H5N)2CH2][PtF5Cl] The complex ions cis-[PtF4Cl2]2?, trans-[PtF4Cl2]2? and [PtF5Cl]2? have been synthesized by stereoselective ligand exchange reactions utilizing the trans effect and are separated by ion exchange chromatography on diethylaminoethyl cellulose. These anions form stable AB-type salts with the doubly charged cation dipyridiniomethane, [(C5H5N)2CH2]2+. X-ray structure determinations on single crystals of cis-[(C5H5N)2CH2][PtF4Cl2] ( 1 ) (monoclinic, space group P21/n with a = 10.379(10), b = 9.635(2), c = 13.738(2) Å, β = 99.142(10)°, Z = 4), trans-[(C5H5N)2CH2][PtF4Cl2] · H2O ( 2 ) (triclinic, space group P1 with a = 7.757(4), b = 10.059(7), c = 10.408(6) Å, α = 82.49(5), β = 68.92(4), γ = 75.46(4)°, Z = 2) and [(C5H5N)2CH2][PtF5Cl] ( 3 ) (orthorhombic, space group Pnma with a = 10.394(3), b = 13.320(2), c = 9.2694(10) Å, Z = 4), reveal the perfect ordering of the anion sublattice. The stronger trans influence of Cl compared with F is observed in asymmetric axes $ {\rm F}^ \bullet $? Pt? Cl′. The bond lengths Pt? $ {\rm F}^ \bullet $ are 0.026 Å (1.4%) longer and the Pt? Cl′ distances are 0.078 Å (3,3%) shorter in comparison with those of symmetrically coordinated axes. The weakening of the Pt? $ {\rm F}^ \bullet $ bond and the strengthening of the Pt? Cl′ bond is better recognizable from shifts of the stretching vibrations by 8% to lower and by 13% to higher frequencies, respectively. Correspondingly, the valence force constants are found to be 15% lower and 22% higher. The trans influence is observed most distinctly in the 19F-nmr spectra exhibiting the coupling constant 1J($ {\rm F}^ \bullet $Pt) to be 29% smaller than 1J(FPt). 相似文献
2.
Dissoziation Behaviour of Dimerie Metal Halides and the Formation of MnAl2Cl8 The thermal dissoziation was measured of the gaseous dimeric metal halides Al2Cl6, Ga2Cl6, In2Cl6, and Mn2I4 and the formation of the gaseous chloride complex MnAl2Cl8 by MnCl2,f and Al2Cl6,g in a membrane manometer. The enthalpy and the entropy of these reactions were derived. 相似文献
3.
Reaction of trimethylsilyl-protected cytosine with methyl iodide afforded N1-methylated product. Subsequent treatment with ethanol resulted in cleavage of the protection group forming [(MeCyt)2H]I (4). Identity of was confirmed by microanalysis, mass spectrometry, 1H and 13C NMR spectroscopy and by single-crystal X-ray diffraction analysis. Crystals of consist of dimeric [(MeCyt)2H]+ cations and I- anions. These ions are arranged in the crystal such that there is a strong base stacking (mean stacking distance 3,467 angstroms) and, furthermore, pi interactions between I- and cytosine rings (mean distance 3,737 angstroms). The dimeric [(MeCyt)2H]+ cations are centrosymmetric having three strong hydrogen bonds, namely two terminal N4-H...O' ones (N4...O' 2.815(4) angstroms) and a central N3-H...N3' (N3...N3' 2.813(4) angstroms) one. Quantum chemical calculations on the DFT level of theory show that the gas phase structure of the dimeric cation exhibits two different terminal N-HO hydrogen bonds, a stronger (N4...O' 2.722 angstroms) and a weaker one (N4'...O 2.960 angstroms). The central N3-HN3[prime or minute] hydrogen bond (N3...N3' 2.852 angstroms) was characterized to have an unsymmetrically located proton and a typical double minimum potential with a very low activation barrier. The interaction energy between [(MeCyt)H]+ and MeCyt yielding [(MeCyt)2H]+ was calculated to be -42.4 kcal mol(-1)(ZPE and BSSE corrected). Comparison with the interaction energy (calculated on the same level of the theory) between cytosine and guanine yielding the triply hydrogen-bonded Watson-Crick dimer (-24.2 kcal mol(-1)) revealed a much higher stability of the hydrogen bonds in [(MeCyt)2H]+. 相似文献
4.
Dirk Steinborn Olaf Gravenhorst Clemens Bruhn Dusan Miklo Michal Dunaj-Jur
o Alfred Kolbe 《无机化学与普通化学杂志》1997,623(12):1954-1958
Synthesis and Characterization of Aquapentachloroplatinates(IV) – Structure of [K(18-crown-6)][PtCl5(H2O)] The crown ether complex of the aquapentachloroplatinic acid of the composition [H13O6][PtCl5(H4O2)] · 2(18-cr-6) ( 2 ) reacts with K2CO3 and [NnBu4]OH in aqueous solution to give [K(18-cr-6)][PtCl5(H2O)] ( 5 a ) and [NnBu4][PtCl5(H2O)] · 1/2 (18-cr-6) · H2O ( 5 b ), respectively. Both compounds were characterized by microanalysis, vibrational (IR, Raman) and NMR (1H, 13C, 195Pt) spectroscopy. The X-ray structure analysis of 5 a (orthorhombic, pnma; a = 16,550(4), b = 18,044(3), c = 7,415(1) Å; Z = 4; R1 = 0,0183; wR2 = 0,0414) reveals that the crystal is threaded by chains built up of [PtCl5(H2O)]? and [K(18-cr-6)]+ units. There are tight K …? Cl contacts (d(K? Cl1)) = 3,0881(9) Å and OW? H? Ocr hydrogen bridges (d(O1 …? O2) = 2,806(3) Å) between these units. The coordination polyhedron [PtCl5O] has approximately C4v symmetry. 相似文献
5.
G. Lehmann und T. Bruhn 《Fresenius' Journal of Analytical Chemistry》1968,243(1):300-314
Zusammenfassung Ein Verfahren zur quantitativen Bestimmung der Ascorbinsäure und Dehydroascorbinsäure nach der Hydroxamatmethode wird beschrieben. Das Verfahren gestattet die Erfassung von Ascorbinsäure und Dehydroascorbinsäure in einer Reaktion, wobei in saurer Lösung beständige Eisen(III)-hydroxamatkomplexe bei 500 nm photometrisch ausgewertet werden können. Die Methode ist leicht durchführbar und nicht so störanfällig wie andere Nachweise; sie kann auch zur qualitativen Probe z. B. auf der Dünnschichtplatte herangezogen werden, wenn Ascorbinsäure neben anderen Carbonsäuren nachzuweisen ist.Es wird ferner die dünnschicht-chromatographische Trennung auf Celluloseschichten der Hydroxamsäuren, die aus der Ascorbinsäure und Dehydroascorbinsäure entstehen, beschrieben.
Unserem verehrten Lehrer, Herrn Prof. Dr. O. Neunhoeffer, danken wir für sein stetiges Interesse an der Arbeit und seine anregenden Diskussionen, Herrn Prof. Dr. B. Eistert für wertvolle Hinweise und Unterstützung durch Institutsmittel.
Herrn Prof. Dr. B. Eistert zum 65. Geburtstag gewidmet.
Auszug aus der Diplomarbeit von T. Bruhn: Bestimmung der Ascorbinsäure mit Hilfe ihrer Hydroxylaminoderivate, Saarbrücken 1968. 相似文献
On the behaviour of Ascorbic acid towards hydroxylamine, a contribution to the analysis of vitamin C
A spectrometric method is presented for the quantitative determination of 0.5–5 mg/100 ml of ascorbic and dehydroascorbic acids. It is based on the formation of hydroxamates by reaction with hydroxylamine. The conditions and the application of this method are discussed. Colouring matter and phenolic compounds, which can present difficulty in the photometric measurement, are eliminated by treatment with polyamide powder. Furthermore, the separation of the hydroxamic acid derivatives of ascorbic and dehydroascorbic acids by thinlayer chromatography on cellulose is described.
Unserem verehrten Lehrer, Herrn Prof. Dr. O. Neunhoeffer, danken wir für sein stetiges Interesse an der Arbeit und seine anregenden Diskussionen, Herrn Prof. Dr. B. Eistert für wertvolle Hinweise und Unterstützung durch Institutsmittel.
Herrn Prof. Dr. B. Eistert zum 65. Geburtstag gewidmet.
Auszug aus der Diplomarbeit von T. Bruhn: Bestimmung der Ascorbinsäure mit Hilfe ihrer Hydroxylaminoderivate, Saarbrücken 1968. 相似文献
6.
Siemeling U Bausch K Fink H Bruhn C Baldus M Angerstein B Plessow R Brockhinke A 《Dalton transactions (Cambridge, England : 2003)》2005,(14):2365-2374
The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state. 相似文献
7.
Inside Back Cover: Circularly Polarized Luminescence from Axially Chiral BODIPY DYEmers: An Experimental and Computational Study (Chem. Eur. J. 45/2016) 下载免费PDF全文
8.
9.
We demonstrate a proof for the existence of a maximal potential for the higher nonlinear evolution equation (see part I). This maximum potential depends upon the plasma parameters and therefore upon the mechanism of instability too. The problems of the stability and of the asymptotic soliton solution are discussed. Finally we present different numerical results. 相似文献
10.
Henning Bruhn 《Discrete Mathematics》2008,308(16):3694-3698
Owari is an old African game that consists of cyclically ordered pits that are filled with pebbles. In a sowing move all the pebbles are taken out of one pit and distributed one by one in subsequent pits. Repeated sowing will give rise to recurrent states of the owari. Bouchet studied such periodical states in an idealised setup, where there are infinitely many pits. We characterise periodical states in owaris with finitely many pits. Our result implies Bouchet's result. 相似文献