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1.
Ya-Shan Huang Yuan Xue Prof. Alvaro Muñoz-Castro Prof. Dr. Ivan A. Popov Prof. Dr. Zhong-Ming Sun 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(62):e202202192
During the past two decades, single-atom-centered medium-sized germanium clusters [M@Gen] (M=transition metals, n>12) have been extensively explored, both from theoretical perspectives and experimental gas-phase syntheses. However, the actual structural arrangements of the Ge13 and Ge14 endohedral cages are still ambiguous and have long remained an unresolved problem for experimental implementation. In this work, we successfully synthesize 13-/14-vertex Ge clusters [Nb@Ge13]3− ( 1 ) and [Nb@Ge14]3− ( 2 ), which are structurally characterized and exhibit unprecedented topologies, neither classical deltahedra nor 3-connected polyhedral structures. Theoretical analysis indicates that the major stabilization of the Ge backbones arises due to the substantial interaction of Ge 4p-AOs with the endohedral Nb 4d-AOs through three/four-center two-electron bonds with an enhanced electron density accumulated over the shortest Nb−Ge13 contact in 1 . Low occupancies of the direct two-center two-electron (2c–2e) Nb−Ge and Ge−Ge σ bonds point to a considerable degree of electron delocalization over the Ge cages revealing their electron deficiency. 相似文献
2.
Gustavo D. Mendes Thais da Silva Pereira Júlio César Rodrigues Elaine Marcílio Santos Mariani Rafaela Souza Rodrigo Alvaro Brandão Lopes-Martins Natalícia de Jesus Antunes Ronilson Agnaldo Moreno Gilberto De Nucci 《Biomedical chromatography : BMC》2020,34(4):e4731
To assess the bioequivalence of two zolpidem hemitartrate formulations in 30 healthy volunteers. Plasma samples were obtained over a 24 h period. Plasma concentrations of zolpidem were analyzed by liquid chromatography coupled to tandem mass spectrometry with positive ion electrospray ionization using multiple reaction monitoring. Values of peak concentration (Cmax), area under curve (AUC), half-life, elimination constant, volume of distribution and clearance showed statistically significant differences when comparing women (604.34 ng h/ml, 127.36 ng/ml, 4.4 h, 0.18 1/h, 50.56 L and 8.55 L/h, respectively) and men (276.1 ng h/ml, 70.9 ng/ml, 3.3 h, 0.26 1/h, 91.42 L and 24.34 L/h, respectively), receiving the same dose (5 mg), respectively. The geometric means with corresponding 90% confidence interval for Test/Reference percentage ratios were 99.73% (CI 93.69–106.16) for Cmax, 97.44% (90% CI = 91.85–103.37%) for area under curve of plasma concentration until the last concentration observed (AUClast) and 98.30% (90% CI = 92.48–104.49) for the area under curve between the first sample (pre-dosage) and infinity (AUC0–inf). Since the 90% CI for AUClast, AUC0–inf and Cmax ratios were within the 80–125% interval proposed by the US Food and Drug Administration, it was concluded that zolpidem hemitartrate formulation (5 mg orodispersible tablet) is bioequivalent to the zolpidem hemitartrate formulation (Patz SL 5 mg sublingual tablet) with regard to both the rate and the extent of absorption. A new formulation of zolpidem 2.5 mg may be useful in women for the same clinical benefits as the 5 mg formulation in men. 相似文献
3.
4.
This work discusses the performance impact from the tetrahedralization of non‐conforming meshes generated by a parallel octree method capable of handling arbitrary immersed geometries. First, we review conforming techniques for meshes created from octrees. Then we implement a tetrahedralization scheme based on templates in a parallel meshing algorithm that uses a linear octree with 2:1 balancing constraint. Besides, we also propose a change on the partitioning strategy for the same meshing algorithm to improve the octree refinement load balancing. Scalability analyses show that the chosen tetrahedralization technique preserves algorithm performance. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
5.
Dr. Desmond MacLeod Carey Dr. Tatiana Gomez Dr. Cesar Morales-Verdejo Dr. Alvaro Muñoz-Castro 《ChemistryOpen》2015,4(5):651-655
The complexation of metal cations into a host–guest situation is particularly well exemplified by [2.2.2]paracyclophane and AgI, which leads to a strong cation–π interaction with a specific face of the host molecule. Through this study we sought a deeper understanding of the effects the metal center has on the NMR spectroscopic properties of the prototypical organic host, generating theoretical reasons for the observed experimental results with an aim to determine the role of the cation–π interaction in a host–guest scenario. From an analysis of certain components of the induced magnetic field and the 13C NMR shielding tensor under its own principal axis system (PAS), the local and overall magnetic behavior can be clearly described. Interestingly, the magnetic response of such a complex exhibits a large axis-dependent behavior, which leads to an overall shielding effect for the coordinating carbon atoms and a deshielding effect for the respective uncoordinated counterparts, evidence that complements previous experimental results. This proposed approach can be useful to gain further insight into the local and overall variation of NMR shifts for host–guest pairs involving both inorganic and organic hosts. 相似文献
6.
Dr. Arianna Melillo Dr. Antonio Franconetti Prof. Dr. Mercedes Alvaro Prof. Dr. Belen Ferrer Prof. Hermenegildo Garcia 《Chemistry (Weinheim an der Bergstrasse, Germany)》2023,29(1):e202202625
Hydrogenation of multiple bonds are among the most general and important organic reactions. Typical heterogeneous catalysts are based on transition metal nanoparticles, including noble metals. Data are presented here showing that metal nodes of MIL-101(Cr) and UiO-66 in the absence of occluded metal nanoparticles can promote hydrogenation of polarized X=Y double bonds of nitro and carbonyl groups. The catalytic activity is a function of the composition of the metal node and the organic linker. It is proposed that the reaction mechanism is based on the operation of frustrated Lewis acid/base pairs. 相似文献
7.
Dications of cycloparaphenyles ([n]CPPs) are known to exhibit in-plane global aromaticity, contained in a nanobelt structure. Recently synthesized ortho and meta isomers of [n]CPPs break the radial symmetry of π structure incorporating perpendicular oriented π orbitals. Herein we set to explore the aromaticity of neutral and dicationic ortho and meta isomers of [8]CPP by dissecting the induced magnetic field to contributions of the twofold radial/perpendicular π system using delocalized canonical molecular orbitals (CMO), and introducing the natural localized molecular orbitals (NLMO) analysis with DFT methods. The dications sustain a reduced global aromatic character of the radial π system under a perpendicular orientation of the external field which declines from ortho to meta isomer and reinforces local aromaticity of ortho ring while it destroys aromaticity of meta ring. Aromaticity variations are determined by symmetry governed rotational excitations of frontier π orbitals. The parallel orientation reveals a substantial reduction of local aromaticity verified with NICSπ analysis and electron delocalization indices. 相似文献
8.
A numerical investigation was conducted to analyze the unsteady laminar flow field and heat transfer characteristics in a
plane channel with two square bars mounted side by side to the approaching flow. A finite volume technique is applied with
a fine grid and time resolution. The transverse separation distance between the bars (G/d) is varied from 0 to 5, whereas
the bar height to channel height is d/H=1/8, and the channel length is L=5H. Different flow regimes develop in the channel
due the interaction between the two mounted square bars, steady flow, flow with vortex shedding synchronization either in
phase or in anti-phase, or biased flow with low frequency modulation of vortex shedding are found. Results show that the pressure
drop increase and heat transfer enhancement are strongly dependent of the transverse separation distance of the bars and the
channel Reynolds number. 相似文献
9.
Passive Optical Networks(PONs)are considered as the preferred solution for broadband fibre-based access networks.This is because PONs present low cost deployment,low energy consumption and also meet high bandwidth demands from end users.In addition,end users expect a high availability for access networks,while operators are more concerned about reducing the failure impact(number of clients affected by failures).Moreover,operators are also interested in reducing the cost of the access network.This paper provides a deep insight into the consequences that the physical topology and design decisions cause on the availability,the failure impact and the cost of a PON.In order to do that,the physical layout of the PON deployment area is approximated by a network geometric model.A PON deployed according to the geometric model is then assessed in terms of failure impact,availability and cost.This way,the effects of different design decisions and the physical layout on these three parameters are evaluated.In addition,the tradeoffs between availability,failure impact and cost caused by planning decisions and the physical topology are identified and pinpointed. 相似文献
10.
José Alvaro Rodrigues-Neto 《International Journal of Game Theory》2014,43(2):403-413
A partitional model of knowledge is monotonic if there exists a linear order on the state space such that, for every player, each element of her partition contains only a sequence of consecutive states. In monotonic models, the absence of alternating cycles is equivalent to the property that, for every pair of players, the join of their partitions contains only singletons. Under these equivalent conditions any set of posteriors for the players is consistent (i.e., there is a common prior). When checking for consistency in a monotonic model, it is not necessary to evaluate all cycle equations; if the cycle equations corresponding to cycles of length two hold, then there is a common prior. 相似文献