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排序方式: 共有498条查询结果,搜索用时 20 毫秒
1.
Dr. Xiaoming Jie Dr. Qiu Sun Dr. Constantin G. Daniliuc Robert Knitsch Prof. Dr. Michael Ryan Hansen Prof. Dr. Hellmut Eckert Dr. Gerald Kehr Prof. Dr. Gerhard Erker 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(6):1269-1273
The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)4 . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO2 molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions. 相似文献
2.
Philip Eckert Prof. Dr. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(69):15751-15754
The impact of LiBr and ZnBr2 salts on the Negishi coupling of alkylZnBr and dialkylzinc nucleophiles with both electron-rich and -poor aryl electrophiles has been examined. Focusing only on the more difficult coupling of deactivated (electron-rich) oxidative addition partners, LiBr promotes coupling with BuZnBr, but does not have such an effect with Bu2Zn. The presence of exogenous ZnBr2 shuts down the coupling of both BuZnBr and Bu2Zn, which has been shown before with alkyl electrophiles. Strikingly, the addition of LiBr to Bu2Zn reactions containing exogenous ZnBr2 now fully restores coupling to levels seen without any salt present. This suggests that there is a very important interaction between LiBr and ZnBr2. It is proposed that Lewis acid adducts are forming between ZnBr2 and the electron-rich Pd0 centre and the bromide from LiBr forms inorganic zincates that prevent the catalyst from binding to ZnBr2. This idea has been supported by catalyst design as chlorinating the backbone of the NHC ring of Pd-PEPPSI-IPent to produce Pd-PEPPSI-IPentCl catalyst now gives quantitative conversion, up from a ceiling of only 50 % with the former catalyst. 相似文献
3.
Philip Eckert Prof. Michael G. Organ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(35):e202200665
Bulky Pd−N-heterocyclic carbene (NHC) catalysts (e. g., N-(di-2,6-(3-pentyl)phenyl), IPent) have been shown to have significantly higher reactivity in a wide variety of cross-coupling applications (i. e., C−C, C−S, C−N) than less hindered variants (e. g., N-(di-2,6-(isopropyl)phenyl), IPr). Further, chlorinating the backbone of the NHC ring sees an even greater increase in reactivity. In the cross-coupling of (hetero)aryl electrophiles to secondary alkyl nucleophiles, making the N-aryl groups larger reduces the amount of β-hydride elimination leading to alkene byproducts and chlorinating the NHC core had an even greater effect, all but eliminating alkene formation. In the present study involving the cross-coupling of primary alkyl electrophiles and nucleophiles, a sharp and surprising reversal of all of the above trends was observed. Bulkier catalysts had generally slower rate of reaction and β-hydride elimination worsened leading to extensive amounts of alkene byproducts. 相似文献
4.
Christian Schlereth Christine Eckert René Schaaf Bernd Skiera 《European Journal of Operational Research》2014
Self-explicated approaches are popular preference measurement approaches for products with many attributes. This article classifies previous self-explicated approaches according to their evaluation types, i.e. trade-off- versus non-trade-off-based, and outlines their advantages and disadvantages. In addition, it proposes a new method, the presorted adaptive self-explicated approach that is based on Netzer and Srinivasan’s (2011) adaptive self-explicated approach and that combines trade-off- and non-trade-off-based evaluation types. Two empirical studies compare this new method with the most popular existing self-explicated approaches, including the adaptive self-explicated approach and paired comparison preference measurement. The new method overcomes the insufficient discrimination between importance weights, as usually found in non-trade-off-based evaluation types; discourages respondents’ simplification strategies, as are frequently encountered in trade-off evaluation types; is easy to implement; and yields high predictive validity compared with other popular self-explicated approaches. 相似文献
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6.
Poor aqueous solubility of active compounds is a major issue in today’s drug delivery. In this study the smartFilm-technology was exploited to improve the dermal penetration efficacy of a poorly soluble active compound (curcumin). Results were compared to the dermal penetration efficacy of curcumin from curcumin bulk suspensions and nanocrystals, respectively. The smartFilms enabled an effective dermal and transdermal penetration of curcumin, whereas curcumin bulk- and nanosuspensions were less efficient when the curcumin content was similar to the curcumin content in the smartFilms. Interestingly, it was found that increasing numbers of curcumin particles within the suspensions increased the passive dermal penetration of curcumin. The effect is caused by an aqueous meniscus that is created between particle and skin if the dispersion medium evaporates. The connecting liquid meniscus causes a local swelling of the stratum corneum and maintains a high local concentration gradient between drug particles and skin. Thus, leading to a high local passive dermal penetration of curcumin. The findings suggest a new dermal penetration mechanism for active compounds from nano-particulate drug delivery systems, which can be the base for the development of topical drug products with improved penetration efficacy in the future. 相似文献
7.
Controlled Light‐Mediated Preparation of Gold Nanoparticles by a Norrish Type I Reaction of Photoactive Polymers 下载免费PDF全文
Florian Mäsing Dr. Artur Mardyukov Carsten Doerenkamp Prof. Dr. Hellmut Eckert Ursula Malkus Harald Nüsse Prof. Dr. Jürgen Klingauf Prof. Dr. Armido Studer 《Angewandte Chemie (International ed. in English)》2015,54(43):12612-12617
Gold nanoparticles (AuNPs) are subjects of broad interest in scientific community due to their promising physicochemical properties. Herein we report the facile and controlled light‐mediated preparation of gold nanoparticles through a Norrish type I reaction of photoactive polymers. These carefully designed polymers act as reagents for the photochemical reduction of gold ions, as well as stabilizers for the in situ generated AuNPs. Manipulating the length and composition of the photoactive polymers allows for control of AuNP size. Nanoparticle diameter can be controlled from 1.5 nm to 9.6 nm. 相似文献
8.
9.
Jennifer Malberg Michael Bodensteiner Daniel Paul Thomas Wiegand Hellmut Eckert Robert Wolf 《Angewandte Chemie (International ed. in English)》2014,53(10):2771-2775
Molecular squares are among the most common supramolecular architectures, but phospha‐organometallic complexes have not been used as building blocks for this type of structure. Herein we describe the formation of the molecular square [Au{Co(P2C2tBu2)2}]4 ( 1 ) by the self‐assembly of anionic 1,3‐diphosphacyclobutadiene cobalt complexes and gold(I) cations. The X‐ray crystallographic determination of the molecular structure of 1 is complemented by solid‐state 31P and 13C NMR investigations. High‐level DFT calculations confirm the assignment of the 31P and 13C NMR resonances. 相似文献
10.
In this paper, we generalize earlier work dealing with maxima of discrete random variables. We show that row-wise stationary block maxima of a triangular array of integer valued random variables converge to a Gumbel extreme value distribution if row-wise variances grow sufficiently fast as the row-size increases. As a by-product, we derive analytical expressions of normalising constants for most classical unbounded discrete distributions. A brief simulation illustrates our theoretical result. Also, we highlight its usefulness in practice with a real risk assessment problem, namely the evaluation of extreme avalanche occurrence numbers in the French Alps. 相似文献