全文获取类型
收费全文 | 837篇 |
免费 | 13篇 |
国内免费 | 5篇 |
专业分类
化学 | 605篇 |
晶体学 | 5篇 |
力学 | 17篇 |
数学 | 74篇 |
物理学 | 154篇 |
出版年
2020年 | 8篇 |
2019年 | 8篇 |
2017年 | 9篇 |
2016年 | 10篇 |
2015年 | 9篇 |
2014年 | 8篇 |
2013年 | 23篇 |
2012年 | 26篇 |
2011年 | 28篇 |
2010年 | 23篇 |
2009年 | 13篇 |
2008年 | 30篇 |
2007年 | 24篇 |
2006年 | 21篇 |
2005年 | 28篇 |
2004年 | 22篇 |
2003年 | 23篇 |
2002年 | 19篇 |
2001年 | 13篇 |
2000年 | 21篇 |
1999年 | 17篇 |
1998年 | 15篇 |
1997年 | 20篇 |
1996年 | 22篇 |
1995年 | 28篇 |
1994年 | 19篇 |
1993年 | 19篇 |
1992年 | 20篇 |
1991年 | 10篇 |
1990年 | 14篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 14篇 |
1986年 | 13篇 |
1985年 | 21篇 |
1984年 | 23篇 |
1983年 | 13篇 |
1982年 | 8篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 9篇 |
1978年 | 13篇 |
1977年 | 9篇 |
1976年 | 8篇 |
1975年 | 15篇 |
1974年 | 13篇 |
1971年 | 7篇 |
1969年 | 13篇 |
1968年 | 12篇 |
1967年 | 9篇 |
排序方式: 共有855条查询结果,搜索用时 15 毫秒
41.
C. Etzlstorfer H. Falk E. Mayr S. Schwarzinger 《Monatshefte für Chemie / Chemical Monthly》1996,127(12):1229-1237
Summary The strongly enhanced acidity of the bay hydroxyl group as compared to the respectiveperi hydroxyl groups of fringelite D, hypericin, and stentorin could be rationalized on the basis of a vinylogous carboxylic acid and was nicely corroborated by semiempirical calculations of the AM1 type. Experimental data obtained from several independent experimental methods, like polarized absorption spectroscopy, hole burning, and isotope effects, as well as from semiempirical AM1 and 6–31G levelab initio calculations conclusively pointed to dissymmetrical hydrogen bonding systems in both theperi andbay regions of the correspondingbay phenolate ions.
Zu Acidität und Wasserstoffbrückenbindung von Hydroxyphenanthroperylenchinonen wie Fringelit D, Hypericin und Stentorin
Zusammenfassung Die stark erhöhte Acidität der bay-Hydroxylgruppen gegenüber jener derperi-Hydroxylgruppen von Fringelit D, Hypericin und Stentorin läßt sich auf der Basis einer vinylogen Carbonsäure verstehen und wurde auch durch semiempirische Rechnungen vom AM1-Typ erhärtet. Daten aus unabhängigen Experimenten wie Polarisationsspektroskopie, Lochbrennen und Isotopeneffekte sowie semiempirische AM1- undab initio-Rechnungen auf 6–31G Niveau belegen ein unsymmetrisches Wasserstoffbrückenbindungssystem sowohl für denperi-als auch denbay-Bereich der entsprechendenbay-Phenolationen.相似文献
42.
Helmut Marko Norbert Müller Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》1989,120(2):163-168
Summary The intermolecular complex formation of bilirubin and biliverdin with two proteins (basic pancreatic trypsin inhibitor and lysozyme) were studied by optical and chiroptical methods. Evidence for specific intermolecular interactions of biliverdin with both proteins was found. Bilirubin forms a soluble complex only with lysozyme.
UV-VIS und CD-spektroskopische Untersuchungen intermolekularer Wechselwirkungen von Gallenpigmenten mit kleinen Proteinen
Zusammenfassung Die intermolekulare Komplexbildung von Bilirubin und Biliverdin mit zwei Proteinen (basischer pankreatischer Trypsininhibitor und Lysozym) wurden mittels optischer und chiroptischer Spektroskopie untersucht. Für Biliverdin konnten intermolekulare Wechselwirkungen mit beiden Proteinen nachgewiesen werden. Bilirubin bildet nur mit Lysozym einen löslichen Komplex.相似文献
43.
Heinz Falk Karl Grubmayr Martha Marko 《Monatshefte für Chemie / Chemical Monthly》1989,120(8-9):771-779
Summary A violinoid and a 2,3-dihydrobilindione chromophore is attachedvia an appendix anchored at rings A of the pigments by means of reacting them with the polyacryl-N-acryloxysuccinimid copolymer to yield water-soluble chromopolymers. They are characterized by a molecular mass of about 4000 to 6000 and a relation of one chromophoric unit per 6 to 22 monomers. Their absorption spectra and circular dichroism recorded in water and dimethylsulfoxide as solvents are discussed with respect to structural aspects, and in comparison with monomeric chromophore derivatives.
Herrn Prof. Dr. K. Schlögl mit den besten Wünschen zum 65. Geburtstag gewidmet 相似文献
44.
The carrier mediated transport of cations using model compounds of the verdinoid and rubinoid bile pigment structural type as ionophores is studied. Verdinoid bile pigments turn out to be very effective carriers for cations exhibiting a pronounced selectivity for certain transition metal ions like Cr+-+, Fe++, Cu++ and Zn++. The scope of this behaviour of verdinoid bile pigments is compared to [18]-crown-6 and meso-tetraphenylporphin and is discussed with regard to structural, biological, analytical and technical implications. 相似文献
45.
Roland A. Obermüller Christoph Etzlstorfer Heinz Falk 《Monatshefte für Chemie / Chemical Monthly》2002,133(1):89-96
Summary. A hypericin derivative was synthesized in which instead of the methyl groups two benzene rings were condensed to the chromophoric
system in order to extend its conjugation. This derivative showed lowered fluorescence and concomitantly enhanced sensitized
production of active oxygen species as compared to hypericin. However, in contrast to intuition its long wavelength band remained
unshifted in comparison to its parent compound hypericin. Geometry and absorption properties were also investigated by means
of semiempirical calculations.
Received July 27, 2001. Accepted August 9, 2001 相似文献
46.
Christoph Kratky Heinz Falk Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1985,116(5):607-623
The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet. 相似文献
47.
Heinz Falk Franz Lehner Marianne Rothböck 《Monatshefte für Chemie / Chemical Monthly》1985,116(11):1359-1361
Donors are added regioselectively to position 10 of 2,3-dihydrobilatrienes-abc in a reversible reaction, which is complicated in case of strongly basic donors due to the easy deprotonation of the partially saturated ring. Compared to the bilatrienes-abc the addition equilibrium is retarded by about two orders of magnitude. 相似文献
48.
Optical resolution by counter-current distribution has been demonstrated on a preparative scale for two chiral ferrocene derivatives, e.g. 1.2-(α-oxotetramethylene)ferrocene (1), and 1.2-(α-butenylene)ferrocene (2), resp., in the system cyclohexane—(+)-diethyltartrate. The optical yields were 12 and 1%, resp., and are in good agreement with the values calculated from the partition coefficients of the enantiomers. The optical purity of1 could be increased to 40% by crystallization from cyclohexane. A resolution of1 with an optical yield of 14% was also possible by thin layer partition chromatography on silica gel using the same solvents. 相似文献
49.
Ingo Hartenbach Falk Lissner Tanja Nikelski Steffen F. Meier Helge Müller‐Bunz Thomas Schleid 《无机化学与普通化学杂志》2005,631(12):2377-2382
About Lanthanide Oxotantalates with the Formula MTaO4 (M = La – Nd, Sm – Lu) Besides being a by‐product of solid state syntheses in tantalum ampoules the lanthanide(III) oxotantalates of the formula MTaO4 can be easily prepared by sintering lanthanide sesquioxide M2O3 and tantalum(V) oxide Ta2O5 with sodium chloride as flux. Under these conditions two structure types emerge depending upon the M3+ cationic radius. For M = La – Pr the MTaO4‐type tantalates crystallize in the space group P21/c with lattice constants of a = 762(±1), b = 553(±4), c = 777(±4) pm, β = 101(±1)° and four formula units per unit cell. With M = Nd, Sm – Lu, the monoclinic cell dimensions (space group P2/c) shrink to the lattice constants like a = 516(±9), b = 551(±9), c = 534(±9) pm, β = 96.5(±0.3)° and there are only two formula units present. Both structures show a coordination sphere of eight oxygen atoms for the lanthanide trications shaped as distorted square antiprism for the structure with the larger lanthanides (in the following referred to as A‐type) and as trigonal dodecahedron for the structure with the smaller ones (called as B‐type in the following). The coordination environment about the Ta5+ cations can be described as a slightly distorted octahedron (CN = 6) for the A‐type structure of MTaO4 and a heavily distorted one (CN = 6) for the B‐type. The difference between the two types results from the interconnection of these [TaO6]7? octahedra. Whereas they are connected via four vertices to form corrugated layers according to parallel the bc‐plane in the A‐type, the octahedra of the B‐type MTaO4 structure share edges to built up zig‐zag chains along the c axis. 相似文献
50.
Summary A strategy was developed which uses the adduct of ozone and triphenyl phosphite as a substitute for photochemically generated singlet oxygen in ene reactions of olefins. The resulting allylic hydroperoxide can be conveniently reduced by a second mole of phosphite to yield the corresponding allylic alcohol. The aryl phosphate produced as the by-product can either be recycled by reduction or used itself as a commodity. As an example, the two key steps of the rose oxide synthesis involving singlet oxygen can thus be reduced to a one pot procedure. With respect to the reaction mechanism, additional arguments for the direct reaction of the olefin with the phosphite ozonide were gathered. A simple decomposition of the ozonide to produce singlet oxygen was made rather unlikely.
Ozon als Sauerstoffquelle für En-Reaktionen von Olefinen
Zusammenfassung Es wurde eine Strategie zum Ersatz von photochemisch erzeugtem Singlett-Sauerstoff durch das Addukt aus Ozon und Triphenylphosphit zum Einsatz in En-Reaktionen von Olefinen entwickelt. Das entstehende allylische Hydroperoxid kann durch ein zweites Molekül Phosphit einfach zum entsprechenden allylischen Alkolhol reduziert werden. Das als Nebenprodukt entstehende Arylphosphat kann entweder durch Reduktion recycliert oder direkt als Handelsware weiterverwendet werden. Auf diese Weise können zum Beispiel die beiden Stufen der Rosenoxidsynthese, an denen Singlett-Sauerstoff beteiligt ist, zu einer Eintopfreaktion vereinfacht werden. Bezüglich des Reaktionsmechanismus wurden zusätzliche Hinweise auf die direkte Reaktion des Phosphitozonids mit dem Olefin gefunden. Eine Zersetzung des Ozonids unter Bildung von Singlettsauerstoff ist nicht wahrscheinlich.相似文献