全文获取类型
收费全文 | 1113篇 |
免费 | 94篇 |
国内免费 | 6篇 |
专业分类
化学 | 844篇 |
晶体学 | 15篇 |
力学 | 18篇 |
数学 | 136篇 |
物理学 | 200篇 |
出版年
2023年 | 29篇 |
2022年 | 21篇 |
2021年 | 45篇 |
2020年 | 63篇 |
2019年 | 54篇 |
2018年 | 22篇 |
2017年 | 30篇 |
2016年 | 52篇 |
2015年 | 61篇 |
2014年 | 45篇 |
2013年 | 58篇 |
2012年 | 67篇 |
2011年 | 84篇 |
2010年 | 42篇 |
2009年 | 46篇 |
2008年 | 47篇 |
2007年 | 44篇 |
2006年 | 48篇 |
2005年 | 26篇 |
2004年 | 18篇 |
2003年 | 21篇 |
2002年 | 21篇 |
2001年 | 15篇 |
2000年 | 12篇 |
1999年 | 11篇 |
1998年 | 13篇 |
1996年 | 5篇 |
1995年 | 9篇 |
1994年 | 4篇 |
1993年 | 10篇 |
1992年 | 6篇 |
1991年 | 10篇 |
1990年 | 9篇 |
1989年 | 12篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 6篇 |
1985年 | 11篇 |
1984年 | 6篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 9篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1977年 | 16篇 |
1976年 | 7篇 |
1975年 | 10篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1937年 | 5篇 |
排序方式: 共有1213条查询结果,搜索用时 218 毫秒
11.
Idealized polymethines are defined as conjugated chain molecules with complete bond equilization and charge alternation. A constant π-bond order along the chain with N atoms has been derived for three types of polymethines which differ by the nature of the heteroatomic end groups. Corresponding to the number of π-electrons they are termined (N + 1)π-, Nπ- or (N ? 1)π-polymethines. This classification embraces closed shell as well as open shell systems. The relations for the energy eigenvalues, coefficients and derived quantities have been obtained in closed form. The results for the different classes of polymethines are strongly related. Their molecular properties should be similar. 相似文献
12.
Zusammenfassung 42 Heterocyclen, die sich formal von alternierenden und nichtalternierenden Kohlenwasserstoffen durch Ersatz einer Doppelbindung durch die Heteroatome Sauerstoff, Stickstoff, Schwefel und Selen ableiten, werden nach dem Pariser-Parr-Pople-Verfahren berechnet und ihre Spektren im nahen Ultraviolett und Sichtbaren beschrieben. Schwefel und Selen werden dabei im LCAO-MO-Verfahren nach dem p-Modell behandelt. In den meisten Fällen können die Berechnungen nicht nur die spektralen Charakteristika gut wiedergeben, sondern auch Beziehungen in den Spektren iso--elektronischer Verbindungen gleicher Struktur verständlich machen. Berechnungen an kationischen Stickstoffheterocyclen führten dann zu falschen Ergebnissen, wenn die Stickstoffparameter vom Pyrroltyp übernommen werden.
Anmerkung: Die Arbeit wurde in dem von Prof. Dr. R. Mayer geleiteten Schwefelarbeitskreis der TU Dresden durchgeführt. 相似文献
PPP-calculations and comparison of electronic spectra of iso--electronic oxygen, nitrogen, sulfur, and selenium heterocycles
42 heterocyclic compounds, formally derived from alternant or nonalternant hydrocarbons by replacing a C=C group by an oxygen, nitrogen, sulfur or selenium atom, are studied by the Pariser-Parr-Pople-type of calculation. By means of these results the near ultraviolet and visible spectra are described. The sulfur and the selenium atoms are treated in the LCAO-MO-method using the p-model. In most cases spectral features are not only well reproduced, but interrelations of the spectra of iso--electronic compounds, possessing analogous structures are interpreted, too. On calculating cationic nitrogen heterocycles using parameters of pyrrol type nitrogen results are unsatisfactory.
Résumé 42 composés hétérocycliques, formellement dérivés d'hydrocarbures alternants ou non alternants par remplacement d'un groupement C=C par un atome d'oxygène, d'azote, de soufre ou de sélénium, sont étudiés par la méthode de Pariser-Parr-Pople. Les résultats obtenus permettent de décrire le spectre U.V. proche et visible. Soufre et sélénium sont traités en utilisant le modèle p. Dans la plupart des cas les caractères spectraux sont non seulement correctement reproduits, mais les relations entre les spectres des composés iso--électroniques à structures analogues peuvent être interprétées. Les calculs concernant les heterocycles à azote cationique sont insatisfaisants lorsqu'ils sont effectués avec des paramètres de l'azote du type pyrrole.
Anmerkung: Die Arbeit wurde in dem von Prof. Dr. R. Mayer geleiteten Schwefelarbeitskreis der TU Dresden durchgeführt. 相似文献
13.
Gerald Koitz Walter Fabian Hans-Werner Schmidt Hans Junek 《Monatshefte für Chemie / Chemical Monthly》1981,112(8-9):973-985
The synthesis of several 2-aminopyridines is described. The reaction of tetracyanoethylene with 3-imino-propane-carbonitrile gives 2-amino-3,4,5-tricyano-pyridines with alkyl and aryl-substituents, resp., in position 6. Nucleophilic substitution of 2-amino-6-chloro-3,5-dicyanopyridines and 2-amino-6-chloro-3,4,5-tricyano-pyridines with phenolates leads to a variety of pyridines. Spectroscopical data of absorption and fluorescence are presented and the influence of the cyano groups is discussed. The results are in good agreement with quantum chemical calculations (PPP).
Herrn Univ-Prof. Dr.A. Holasek zum 60. Geburtstag gewidmet. 相似文献
14.
Fabian Mohr 《Journal of organometallic chemistry》2004,689(2):374-379
The polyether bis(alkynes) α,ω-bis(O-propargyl)triethylene glycol and α,ω-bis(O-4-propargyloxyphenoxy)triethylene glycol reacted with [AuCl(SMe2)] in the presence of base to form the corresponding oligomeric gold(I) acetylide complexes (AuCCCH2O(CH2CH2O)3CH2CCAu)n and (AuCCCH2OC6H4O(CH2CH2O)3C6H4OCH2CCAu)n. These digold(I) diacetylide complexes reacted with diphosphine ligands to give macrocyclic digold(I) complexes of the type [Au2(μ-CC)(μ-PP)], where CC is the diacetylide and PP is a diphosphine ligand. These digold(I) complexes bind the cations Li+, Na+, K+ and Cs+, as studied by electrospray mass spectrometry. 相似文献
15.
In order to elucidate certain controversies in interpreting the π-electronic structure of some simple quinone and indigo dyes the Pariser–Parr–Pople SC β,γ-wave-functions have been subjected to configuration analyses. Whereas 2,5-diamino-quinone (1) can be excellently represented by coupling of two trimethine-merocyanine chains, the analogous consideration is less appropriate with bispyrrolindigo (2). In this case the results of the configuration analyses indicate clearly the limited applicability of the Longuet/Higgins–Murrell–method. 相似文献
16.
17.
Méndez LA Jiménez J Cerrada E Mohr F Laguna M 《Journal of the American Chemical Society》2005,127(3):852-853
The symmetric digold(II)dichloride bis(ylide) complex [Au2Cl2(mu-{CH2}2PPh2)2] reacts with acetylides to form the asymmetric heterovalent gold(I)/gold(III) complexes [AuI(mu-{CH2}2PPh2)2AuIII(CCR)2] [R = Ph, tBu, and SiMe3], the phenyl analogue of which was characterized by X-ray crystallography. These compounds represent the first examples of gold(III) complexes containing two acetylide ligands. [AuI(mu-{CH2}2PPh2)2AuIII(CCPh)2] undergoes a reversible comproportionation reaction upon treatment with [Ag(ClO4)tht] to give the symmetric digold(II) cationic complex [Au2(tht)2(mu-{CH2}2PPh2)2](ClO4)2. If this complex is treated with phenylacetylene in the presence of base, the heterovalent gold(I)/gold(III) complex is re-formed. This reversible interconversion between binuclear gold(I)/gold(III) and digold(II) bis(ylide) complexes is unprecedented. 相似文献
18.
V. A. Bakulev Yu. O. Subbotina V. M. F. Fabian 《Chemistry of Heterocyclic Compounds》2003,39(11):1504-1515
The cyclization of 1,3,5-hexatrien-1-one, 1, and the Z- and E-isomers of 1-aza-1,3-butadienylketene 3 were studied using the semiempirical AM1 and PM3 methods. Cyclizations of compounds 1 and Z-3 are shown to occur via a mono-rotation mechanism with barriers of 15.49 and 32.85 kcal/mol respectively. The reactions proceed via non-planar transition states which result from rotation of the methylene group for compound 1 and the imino group for compound Z-3. Cyclization of E-3 proceeds via a non-rotatory mechanism through a planar transition state. The activation barrier is 4.83 kcal/mol (AM1). The electronic structures of the initial and final states, and of some intermediate structures, including the transition states for the cyclization of compounds 1 and 3, were analyzed by the natural orbital method using HF/6-31G*//AM1 calculations. Energetic, structural, and orbital criteria indicate the heteroelectric mechanism for the cyclization of compound E-3 and the pericyclic mechanism for the cyclization of compounds 1 and Z-3. 相似文献
19.
Michael A. Luzuriaga Candace E. Benjamin Michael W. Gaertner Hamilton Lee Fabian C. Herbert Snipta Mallick 《Supramolecular chemistry》2019,31(8):485-490
ABSTRACTDrug delivery using metal-organic frameworks (MOF) has elicited interest in their biocompatibility; however, few studies have been conducted on their stability in common buffers, cell media, and blood proteins. In particular, the use of ZIF-8, a MOF interconnected by Zn and methylimidazole, has been frequently employed. In this study, we tested single crystals of ZIF-8 with common laboratory buffers, cell media, and serum, and noted several issues. Buffers containing phosphate and bicarbonate alter the appearance and composition of ZIF-8; however, these buffers do not appear to cause cargo to leak out even when the ZIF-8 itself is displaced by phosphates. On the other hand, serum dissolves ZIF-8, causing premature cargo release. Our results show that ZIF-8 undergoes surface chemistry changes that may affect the interpretation of cellular uptake and cargo release data. On the other hand, it provides a rational explanation as to how ZIF-8 neatly dissolves in vivo. 相似文献
20.
Journal of Theoretical Probability - We investigate the space-time regularity of the local time associated with Volterra–Lévy processes, including Volterra processes driven by $$\alpha... 相似文献