全文获取类型
收费全文 | 230篇 |
免费 | 4篇 |
专业分类
化学 | 157篇 |
晶体学 | 4篇 |
数学 | 25篇 |
物理学 | 48篇 |
出版年
2023年 | 3篇 |
2022年 | 1篇 |
2020年 | 3篇 |
2019年 | 1篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 4篇 |
2015年 | 2篇 |
2014年 | 1篇 |
2013年 | 10篇 |
2012年 | 6篇 |
2011年 | 3篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 10篇 |
2007年 | 17篇 |
2006年 | 13篇 |
2005年 | 14篇 |
2004年 | 17篇 |
2003年 | 7篇 |
2002年 | 14篇 |
2001年 | 7篇 |
2000年 | 11篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 8篇 |
1996年 | 14篇 |
1995年 | 2篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 2篇 |
1971年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有234条查询结果,搜索用时 15 毫秒
1.
Laurens Kooijman Dr. Matthias Schuster Christian Baumann Simon Jurt Dr. Frank Löhr Dr. Boris Fürtig Prof. Dr. Peter Güntert Prof. Dr. Oliver Zerbe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21151-21158
To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR. 相似文献
2.
Laurens D. B. Mandemaker Miguel Rivera-Torrente Guusje Delen Dr. Jan P. Hofmann Dr. Matthias Lorenz Dr. Alex Belianinov Prof. Dr. Bert M. Weckhuysen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):691-698
Metal–organic frameworks (MOFs) are a promising class of materials for many applications, due to their high chemical tunability and superb porosity. By growing MOFs as (thin-)films, additional properties and potential applications become available. Here, copper (II) 1,3,5-benzenetricarboxylate (Cu-BTC) metal–organic framework (MOF) thin-films are reported, which were synthesized by spin-coating, resulting in “nanowebs”, that is, fiber-like structures. These surface-mounted MOFs (SURMOFs) were studied by using photoinduced force microscopy (PiFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The optimal concentration of precursors (10 mm ) was determined that resulted in chemically homogeneous, pure nanowebs. Furthermore, the morphology and (un)coordinated Cu sites in the web were tuned by varying the rotation speed of the spin-coating process. X-ray diffraction (XRD) analysis showed that rotation speeds ≥2000 rpm (with precursors in a water/ethanol solution) generate the catena-triaqua-μ-(1,3,5-benzenetricarboxylate)-copper(II), or Cu(BTC)(H2O)3 coordination polymer. X-ray photoelectron spectroscopy (XPS) highlighted the strong decrease in number of (defective) Cu+ sites, as the nanowebs mainly consist of coordinated Cu2+ Lewis acid sites (LAS) and organic linker–linker, for example, hydrogen-bonding, interactions. Finally, the Lewis-acidic character of the Cu sites is illustrated by testing the films as catalysts in the isomerization of α-pinene oxide. The higher number of LAS (≥3000 rpm), result in higher campholenic aldehyde selectivity reaching up to 87.7 %. Furthermore, the strength of a combined micro- and spectroscopic approach in understanding the nature of MOF thin-films in a spatially resolved manner is highlighted. 相似文献
3.
Laurens van Gelderen Gadi Rothenberg V. Roberto Calderone Karen Wilson N. Raveendran Shiju 《应用有机金属化学》2013,27(1):23-27
Copper immobilized on a functionalized silica support is a good catalyst for the homocoupling of terminal alkynes. The so‐called Glaser–Hay coupling reaction can be run in air with catalytic amounts of base. The copper catalyst is active for multiple substituted alkynes, in both polar and non‐polar solvents, with good to excellent yields (75–95%). Depending on the alkyne, full conversion can be achieved within 3–24 h. The catalyst was characterized by TGA, inductively coupled plasma and X‐ray photoelectron spectroscopy. Leaching tests confirm that the catalyst is and remains heterogeneous. Importantly, the overall reaction requires only alkyne and oxygen (in this case, air) as reagents, making this a clean catalytic oxidative coupling reaction. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
4.
5.
In an Internet auction, the expected payoff acts as a benchmark of the reasonableness of the price that is paid for the purchased
item. Since the number of potential bidders is not observable, the expected payoff is difficult to estimate accurately. We
approach this problem by considering the bids as a record and 2-record sequence of the potential bidder’s valuation and using
the Extreme Value Theory models to model the tail distribution of the bidder’s valuation and study the expected payoff. Along
the discussions for three different cases regarding the extreme value index γ, we show that the observed payoff does not act as an accurate estimation of the expected payoff in all the cases except a
subclass of the case γ = 0. Within this subclass and under a second order condition, the observed payoff consistently converges to the expected
payoff and the corresponding asymptotic normality holds.
相似文献
6.
7.
8.
Laurens Cherchye Kristof De Witte Erwin Ooghe Ides Nicaise 《European Journal of Operational Research》2010
We present a nonparametric approach for (1) efficiency and (2) equity evaluation in education. Firstly, we use a nonparametric (Data Envelopment Analysis) model that is specially tailored to assess educational efficiency at the pupil level. The model accounts for the fact that typically minimal prior structure is available for the behavior (objectives and feasibility set) under evaluation. It allows for uncertainty in the data, while it corrects for exogenous ‘environmental’ characteristics that are specific to each pupil. Secondly, we propose two multidimensional stochastic dominance criteria as naturally complementary aggregation criteria for comparing the performance of different school types (private and public schools). While the first criterion only accounts for efficiency, the second criterion also takes equity into consideration. The model is applied for comparing private (but publicly funded) and public primary schools in Flanders. Our application finds that no school type robustly dominates another type when controlling for the school environment and taking equity into account. More generally, it demonstrates the usefulness of our nonparametric approach, which includes environmental and equity considerations, for obtaining ‘fair’ performance comparisons in the public sector context. 相似文献
9.
10.
Huub Kooijman Anthony L. Spek Gerard A. van Albada Patrick Gamez Jan Reedijk 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(2):m51-m54
In the crystal structure of [Cu(CF3SO3)(C2N3)(C8H7N5)2]·0.5C2H6O, the CuII atom adopts a distorted octahedral geometry, with the basal plane formed by two N atoms of one dipyrimidinylamine ligand, one N atom of the second pyrimidine ligand and a nitrile N atom of the dicyanamide anion [Cu—N = 1.972 (2)–2.021 (2) Å]. The apical positions are occupied by an N atom of the second ligand [Cu—N = 2.208 (2) Å], and an O atom of the trifluoromethanesulfonate anion [Cu—O = 2.747 (2) Å] at a semi‐coordination distance. Pairs of inversion‐related N—H⋯N hydrogen bonds of the so‐called Watson–Crick type, augmented by two C—H⋯N contacts, link adjacent complexes into an infinite one‐dimensional chain running in the [101] direction. 相似文献