全文获取类型
收费全文 | 386篇 |
免费 | 31篇 |
国内免费 | 3篇 |
专业分类
化学 | 326篇 |
晶体学 | 1篇 |
力学 | 2篇 |
数学 | 39篇 |
物理学 | 52篇 |
出版年
2023年 | 9篇 |
2022年 | 3篇 |
2021年 | 12篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 17篇 |
2014年 | 16篇 |
2013年 | 31篇 |
2012年 | 19篇 |
2011年 | 27篇 |
2010年 | 16篇 |
2009年 | 19篇 |
2008年 | 20篇 |
2007年 | 26篇 |
2006年 | 31篇 |
2005年 | 25篇 |
2004年 | 21篇 |
2003年 | 17篇 |
2002年 | 9篇 |
2001年 | 11篇 |
2000年 | 5篇 |
1999年 | 1篇 |
1998年 | 2篇 |
1997年 | 4篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1992年 | 1篇 |
1990年 | 2篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 3篇 |
1981年 | 3篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 2篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有420条查询结果,搜索用时 31 毫秒
81.
Supramolecular encapsulation of small guest molecules inside well-defined cavities of molecular capsules has witnessed broad attention because of the unusual behaviour of these systems. The molecular capsules generally consist of rigid complementary building blocks that are held together by multiple, complementary non-covalent interactions. Interestingly, it has been shown that chemical transformations can take place inside these capsules and in some examples the reaction is accelerated, while in other cases otherwise instable intermediates could be isolated in the capsulated form. Many reactions of interest require a transition-metal (TM) catalyst, and the creation of new capsules in which such catalysts are implemented within the structure is thus required for the development of resourceful type of catalyst systems for these processes. In this concept article we will discuss new strategies to arrive at such systems, with a focus on a ligand-templated approach. In this approach, multifunctional ligands are used as templates for the encapsulation process by supramolecular building blocks and concomitantly for the formation of TM complexes that are active in catalytic processes. The obtained encapsulated transition-metal catalysts show unusual reactivity and selectivity behaviour that will be discussed in detail. 相似文献
82.
Green's function retrieval by crosscorrelation may suffer from irregularities in the source distribution, asymmetric illumination, intrinsic losses, etc. Multidimensional deconvolution (MDD) may overcome these limitations. A unified representation for Green's function retrieval by MDD is proposed. From this representation, it follows that the traditional crosscorrelation method gives a Green's function of which the source is smeared in space and time. This smearing is quantified by a space-time point-spread function (PSF), which can be retrieved from measurements at an array of receivers. MDD removes this PSF and thus deblurs and deghosts the source of the Green's function obtained by correlation. 相似文献
83.
van Pul C Roos FG Derksen OS Buijs J Vlaardingerbroek MT Kopinga K Wijn PF 《Magnetic resonance imaging》2004,22(9):1169-1180
In the neonatal brain, it is important to use a fast imaging technique to acquire all diffusion weighted images (DWI) for apparent diffusion coefficient (ADC) calculation. Taking into account the occurrence of typical echo planar imaging (EPI) artifacts, we have investigated whether single-shot (SSh) or multishot (MSh) DWI-EPI should be preferred. In 14 neonates, 17 adult patients and 5 adult volunteers, DWIs are obtained both with SSh and MSh EPI. The occurrence of artifacts and their influence on the ADC are explored and further quantified using simulations and phantom studies. Two radiologists scored overall image quality and diagnosability of all images. Single-shot and MSh DWI-EPI scored equally well in neonates with respect to overall image quality and diagnosability. In newborns, more motion artifacts in MSh can be noticed while N/2-ghost artifacts in SSh occur less frequently than in adults. Both N/2-ghost and motion artifacts result in significant ADC abnormalities. There is a serious risk that these artifacts will be mistaken for genuine diffusion abnormalities. N/2-ghost artifacts are hardly noticed in the neonatal brain, which might be due to smaller cerebrospinal fluid (CSF) velocity than in adults. Apparent diffusion coefficient values in MSh are unreliable if motion occurs. We conclude that for ADC calculations in neonates SSh DWI-EPI is more reliable than MSh. 相似文献
84.
Balmes O Resta A Wermeille D Felici R Messing ME Deppert K Liu Z Grass ME Bluhm H van Rijn R Frenken JW Westerström R Blomberg S Gustafson J Andersen JN Lundgren E 《Physical chemistry chemical physics : PCCP》2012,14(14):4796-4801
The structure and chemical composition of Pd nanoparticles exposed to pure CO and mixtures of CO and O(2) at elevated temperatures have been studied in situ by a combination of X-ray Diffraction and X-ray Photoelectron Spectroscopy in pressures ranging from ultra high vacuum to 10 mbar and from room temperature to a few hundred degrees celsius. Our investigation shows that under CO exposure, above a certain temperature, carbon dissolves into the Pd particles forming a carbide phase. Upon exposure to CO and O(2) mixtures, the carbide phase forms and disappears reversibly, switching at the stoichiometric ratio for CO oxidation. This finding opens new scenarios for the understanding of catalytic oxidation of C-based molecules. 相似文献
85.
Gadzikwa T Bellini R Dekker HL Reek JN 《Journal of the American Chemical Society》2012,134(6):2860-2863
A chiral supramolecular ligand has been assembled and applied to the rhodium-catalyzed asymmetric hydroformylation of unfunctionalized internal alkenes. Spatial confinement of the metal center within a chiral pocket results in reversed regioselectivity and remarkable enantioselectivities. 相似文献
86.
Dr. Martin Wolffs Juliën L. J. van Velthoven Dr. Xianwen Lou Ralf A. A. Bovee Maarten Pouderoijen Joost L. J. van Dongen Dr. Albertus P. H. J. Schenning Prof. Dr. E. W. Meijer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(47):15057-15064
The self‐assembly of two enantiomerically pure hexa(oligo (p‐phenylene vinylene))‐substituted benzenes having 24 stereocenters was studied in pure methylcyclohexane (MCH) and in a mixture of MCH/toluene (4:1). Irrespective of the solvent a cooperative supramolecular polymerization mechanism was determined for these star‐shaped molecules by using temperature‐dependent CD and UV/Vis spectroscopy. Quite remarkably, a transition from one helical supramolecular state (A) to a second more thermodynamically stable supramolecular helical assembly (B) was observed. The rate of the A→B transition was strongly dependent on the nature of the solvent; being faster in the solvent mixture than in pure MCH. By using size exclusion chromatography we could relate the increased rate to a decreased stability of the supramolecular A state in the solvent mixture. Next, we mixed the two enantiomerically pure hexa‐substituted benzene derivatives in a so‐called majority‐rules experiment, which lead to the anitcipated chiral amplification in the A state. More importantly it appeared that the A→B transition was significantly hampered in these mixed systems. Furthermore, the absence of chiral amplification in the B state revealed the formation of separated enantiomerically pure assemblies. Therefore, by using a wide variety of spectroscopic and chromatographic techniques we determined the influence of solvent and enantiomeric purity on the transition between different supramolecular states. 相似文献
87.
Videokymographic images of deviant or irregular vocal fold vibration, including diplophonia, the transition from falsetto to modal voice, irregular vibration onset and offset, and phonation following partial laryngectomy were compared with the synchronously recorded acoustic speech signals. A clear relation was shown between videokymographic image sequences and acoustic speech signals, and the effect of irregular or incomplete vocal fold vibration patterns was recognized in the amount of perceived breathiness and roughness and by the harmonics-to-noise ratio in the speech signal. Mechanisms causing roughness are the presence of mucus, phase differences between the left and right vocal fold, and short-term frequency and amplitude modulation. It can be concluded that the use of simultaneously recorded videokymographic image sequences and speech signals contributes to the understanding of the effect of irregular vocal fold vibration on voice quality. 相似文献
88.
In this paper it is proved that for any ℚ-algebraR any locally nilpotentR-derivationD onR[X,Y] having divergence zero and 1 ∈ (D(X),D(Y)) (i) has a slice, and (ii)A
D
=R[P] for someP. Furthermore, it is shown that any surjectiveR-derivation onR[X,Y] having divergence zero is locally nilpotent. Connections with the Jacobian Conjecture are made. 相似文献
89.
Berkhout Joost Heidergott Bernd Sommer Jennifer Daduna Hans 《Computational Management Science》2019,16(4):697-714
Computational Management Science - Queuing networks are a well-established approach to modeling and analysis of complex systems. This paper develops an approach to risk-analysis of queuing network... 相似文献
90.
Cui-Lian Liu Eduard O. Bobylev Yang Fu David A. Poole III Dr. Koen Robeyns Prof. Dr. Charles-André Fustin Prof. Dr. Yann Garcia Prof. Dr. Joost N. H. Reek Prof. Dr. Michael L. Singleton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(52):11960-11965
Non-covalent interactions are important for directing protein folding across multiple intermediates and can even provide access to multiple stable structures with different properties and functions. Herein, we describe an approach for mimicking this behavior in the self-assembly of metal–organic cages. Two ligands, the bend angles of which are controlled by non-covalent interactions and one ligand lacking the above-mentioned interactions, were synthesized and used for self-assembly with Pd2+. As these weak interactions are easily broken, the bend angles have a controlled flexibility giving access to M2( L1 )4, M6( L2 )12, and M12( L2 )24 cages. By controlling the self-assembly conditions this process can be directed in a stepwise fashion. Additionally, the multiple endohedral hydrogen-bonding sites on the ligand were found to play a role in the binding and discrimination of neutral guests. 相似文献