全文获取类型
收费全文 | 1614篇 |
免费 | 99篇 |
国内免费 | 2篇 |
专业分类
化学 | 1283篇 |
晶体学 | 3篇 |
力学 | 36篇 |
综合类 | 1篇 |
数学 | 194篇 |
物理学 | 198篇 |
出版年
2024年 | 4篇 |
2023年 | 28篇 |
2022年 | 30篇 |
2021年 | 31篇 |
2020年 | 59篇 |
2019年 | 36篇 |
2018年 | 23篇 |
2017年 | 17篇 |
2016年 | 83篇 |
2015年 | 76篇 |
2014年 | 69篇 |
2013年 | 77篇 |
2012年 | 102篇 |
2011年 | 104篇 |
2010年 | 75篇 |
2009年 | 59篇 |
2008年 | 100篇 |
2007年 | 105篇 |
2006年 | 103篇 |
2005年 | 91篇 |
2004年 | 79篇 |
2003年 | 58篇 |
2002年 | 34篇 |
2001年 | 27篇 |
2000年 | 18篇 |
1999年 | 21篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 11篇 |
1991年 | 10篇 |
1990年 | 6篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1986年 | 7篇 |
1985年 | 5篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 7篇 |
1980年 | 8篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1977年 | 10篇 |
1976年 | 9篇 |
1975年 | 6篇 |
1916年 | 3篇 |
排序方式: 共有1715条查询结果,搜索用时 15 毫秒
101.
The synthesis of imidazolinium salts from the reaction of formamidines and (2-bromoethyl)diphenylsulfonium triflate is described. A variety of symmetrical and unsymmetrical imidazolinium triflate salts were synthesized in high yield in short reaction times under mild conditions. Aromatic and aliphatic N-substituents work well. The reaction is proposed to proceed via generation of a vinyl sulfonium salt intermediate from the bromoethylsulfonium triflate. 相似文献
102.
A property of a system is called actual, if the observation of the outcome of the test that pertains to that property yields
an affirmation with certainty. We formalize the act of observation by assuming the outcome itself is an actual property of
the state of the observer after the act of observation and correlates with the state of the system. For an actual property
this correlation needs to be perfect. A property is called classical if either the property or its negation is actual. We
show by a diagonal argument that there exist classical properties of an observer that he cannot observe perfectly. Because
states are identified with the collection of properties that are actual for that state, it follows no observer can perfectly
observe his own state. Implications for the quantum measurement problem are briefly discussed.
PACS: 02.10-v, 03.65.Ta 相似文献
103.
Jannik Brückmann Dr. Carolin Müller Tamar Maisuradze Dr. Alexander K. Mengele Dr. Djawed Nauroozi Sven Fauth Andreas Gruber Prof. Dr. Stefanie Gräfe Prof. Dr. Kerstin Leopold Dr. Stephan Kupfer Prof. Dr. Benjamin Dietzek-Ivanšić Prof. Dr. Sven Rau 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(51):e202200766
The synthesis and detailed characterization of a new Ru polypyridine complex containing a heteroditopic bridging ligand with previously unexplored metal-metal distances is presented. Due to the twisted geometry of the novel ligand, the resultant division of the ligand in two distinct subunits leads to steady state as well as excited state properties of the corresponding mononuclear Ru(II) polypyridine complex resembling those of prototype [Ru(bpy)3]2+ (bpy=2,2'-bipyridine). The localization of the initially optically excited and the nature of the long-lived excited states on the Ru-facing ligand spheres is evaluated by resonance Raman and fs-TA spectroscopy, respectively, and supported by DFT and TDDFT calculations. Coordination of a second metal (Zn or Rh) to the available bis-pyrimidyl-like coordination sphere strongly influences the frontier orbitals, apparent by, for example, luminescence quenching. Thus, the new bridging ligand motif offers electronic properties, which can be adjusted by the nature of the second metal center. Using the heterodinuclear Ru−Rh complex, visible light-driven reduction of NAD+ to NADH was achieved, highlighting the potential of this system for photocatalytic applications. 相似文献
104.
105.
Sven Walter 《Acta Analytica》2005,20(3):32-47
Frank Jackson and Philip Pettit have defended a non-reductive account of causal relevance known as the ‘program explanation
account’. Allegedly, irreducible mental properties can be causally relevant in virtue of figuring in non-redundant program explanations which convey information not conveyed by explanations in terms of the physical properties that actually do the ‘causal work’.
I argue that none of the possible ways to spell out the intuitively plausible idea of a program explanation serves its purpose,
viz., defends non-reductive physicalism against Jaegwon Kim’s Causal Exclusion Argument according to which non-reductive physicalism is committed to epiphenomenalism because irreducible mental properties are ‘screened
off’ from causal relevance by their physical realizers. Jackson and Pettit’s most promising explication of a program explanation
appeals to the idea of invariance of effect under variation of realization, but I show that invariance of effect under variation of realization is neither necessary nor sufficient for causal relevance. 相似文献
106.
Jonas
rtegren Philippe Busson Ulf W. Gedde Anders Hult Anders Eriksson Mikael Lindgren Per-Otto Arntzn David S. Hermann Per Rudquist Sven T. Lagerwall 《Macromolecular Symposia》1999,148(1):179-195
Highly oriented pyroelectric liquid-crystalline polymers were prepared by photopolymerization under the influence of a static electric field from binary mixtures of two acrylate monomers exhibiting chiral smectic C mesomorphism. Both monomers contained nitro groups to yield second order nonlinear optical properties (second harmonic generation) and one of the monomers had two functional groups to yield a crosslinked polymer. The room temperature second order nonlinear susceptibility of the polymers showed during the first two hours a 10 % decrease after which it remained constant during the next 48 days. At elevated temperatures there was a significant difference in the nonlinear optical properties over time between crosslinked and uncrosslinked polymers. The uncrosslinked polymer showed a pronounced loss of second order nonlinear optical activity with time at ≥38°C. The crosslinked polymer showed a much smaller and basically a temperature independent decrease rate in the second order nonlinear optical properties at all the ageing temperatures (23-130°C). Both the loss in mesogen order parameter, very evident for the uncrosslinked polymer, and conformational changes occurring within the mesogens (β mechanism), may account for the observations made. 相似文献
107.
Sven J. Cyvin Bjørg N. Cyvin Jon Brunvoll Rong-Si Chen 《Monatshefte für Chemie / Chemical Monthly》1989,120(10):833-847
Summary Classes of coronoids (or degenerate coronoids), r and q are obtained by providing the rectangle-shaped benzenoids Rj (m, 3) with a naphthalenic or pyrenic hole, respectively. The numbers of Kekulé structures (K) are studied. It was found for theK numbers of the classes in question:r=4/5R andq=1/5R. The classes r and q are similar to r and q, respectively, but the naphthalenic or pyrenic hole is oriented in a different way. For these classes it was found:r=3/5R,q=2/5R.
Die Anzahl von Kekulé-Strukturen für hochkondensierte Benzenoide mit rechteckigem Umriß, 8. Mitt.: Einige perforierte benzenoide Rechteck-Strukturen
Zusammenfassung Es werden Klassen r und q von Coronoiden (oder degenerierten Coronoiden) erhalten, wobei Benzenoide mit rechteckigem Umriß, Rj(m, 3), mit einem Naphthalin- oder Pyren-Loch versehen werden. Die Anzahl von Kekulé-Strukturen (K) wird untersucht; dabei wurde für die untersuchten Klassenr=4/5R undq=1/5R gefunden. Die Klassen r und q verhalten sich ähnlich, das Naphthalin- oder Pyren-Loch ist jedoch anders orientiert; dafür wurder=3/5R undq=2/5R gefunden.相似文献
108.
109.
Mang C Jakupovic S Schunk S Ambrosi HD Schwarz O Jakupovic J 《Journal of combinatorial chemistry》2006,8(2):268-274
The generation of a natural-product-based library starting from andrographolide is described. Utilizing andrographolide itself in parallel solution-phase synthesis leads to a 360-membered library. The initial transformation of the starting material via ozonolysis is followed by the conversion into a suitable template by introduction of a thiazole moiety. Subsequent decoration at two points of diversity yields the desired natural product derivatives. The selection of actually synthesized compounds is based on a virtually generated library and the assessment of its members with respect to physicochemical parameters, thus ensuring pharmacological relevance of the compounds. 相似文献
110.
Michael Karnahl Christian Kuhnt Frank W. HeinemannMichael Schmitt Sven Rau Jürgen Popp Benjamin Dietzek 《Chemical physics》2012,393(1):65-73
Molecular photocatalysts allow for selectively tuning their function on a molecular level based on an in-depth understanding of their chemical and photophysical properties. This contribution reports the synthesis and photophysical characterization of the novel molecular photocatalyst [(tbbpy)2Ru(tpac)PdCl2]2+RutpacPd (with tpac = tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]acridine) and its mononuclear building block. Furthermore, detailed photocatalytic activity measurements of RutpacPd are presented. The introduction of the tpac-ligand into the molecular framework offers a potential route to reduce the impact of water as compared to the well-studied class of RutpphzPd (with tpphz = tetrapyrido[3,2-a:2′,3′-c:3″,2″-h:2?,3?-j]phenazine) complexes. The distinct impact of water on the electron-transfer processes in tpphz-ligands stems from the possibility of water to form hydrogen bonds to the phenazine nitrogen atoms and will potentially reduced when replacing the phenazine by the acridine unit. The effect of this structural variation on the catalytic properties and the underlying ultrafast intramolecular charge transfer behavior will be discussed in detail. 相似文献