全文获取类型
收费全文 | 811篇 |
免费 | 37篇 |
国内免费 | 2篇 |
专业分类
化学 | 597篇 |
晶体学 | 8篇 |
力学 | 14篇 |
数学 | 124篇 |
物理学 | 107篇 |
出版年
2023年 | 8篇 |
2022年 | 7篇 |
2021年 | 21篇 |
2020年 | 17篇 |
2019年 | 15篇 |
2018年 | 15篇 |
2017年 | 19篇 |
2016年 | 35篇 |
2015年 | 30篇 |
2014年 | 29篇 |
2013年 | 48篇 |
2012年 | 60篇 |
2011年 | 54篇 |
2010年 | 42篇 |
2009年 | 24篇 |
2008年 | 50篇 |
2007年 | 49篇 |
2006年 | 58篇 |
2005年 | 44篇 |
2004年 | 22篇 |
2003年 | 27篇 |
2002年 | 16篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 3篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 10篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1986年 | 7篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1973年 | 3篇 |
1971年 | 2篇 |
排序方式: 共有850条查询结果,搜索用时 31 毫秒
41.
Luis M. Mateo Qiang Sun Shi‐Xia Liu Jesse J. Bergkamp Kristjan Eimre Carlo A. Pignedoli Pascal Ruffieux Silvio Decurtins Giovanni Bottari Roman Fasel Tomas Torres 《Angewandte Chemie (International ed. in English)》2020,59(3):1334-1339
On‐surface synthesis offers a versatile approach to prepare novel carbon‐based nanostructures that cannot be obtained by conventional solution chemistry. Graphene nanoribbons (GNRs) have potential for a variety of applications. A key issue for their application in molecular electronics is in the fine‐tuning of their electronic properties through structural modifications, such as heteroatom doping or the incorporation of non‐benzenoid rings. In this context, the covalent fusion of GNRs and porphyrins (Pors) is a highly appealing strategy. Herein we present the selective on‐surface synthesis of a Por–GNR hybrid, which consists of two Pors connected by a short GNR segment. The atomically precise structure of the Por–GNR hybrid has been characterized by bond‐resolved scanning tunneling microscopy (STM) and noncontact atomic force microscopy (nc‐AFM). The electronic properties have been investigated by scanning tunneling spectroscopy (STS), in combination with DFT calculations, which reveals a low electronic gap of 0.4 eV. 相似文献
42.
Lauren M. Reid Ileana Guzzetti Tor Svensson Anna-Carin Carlsson Wu Su Tomas Leek Lena von Sydow Werngard Czechtizky Marija Miljak Chandra Verma Leonardo De Maria Jonathan W. Essex 《Chemical science》2022,13(7):1957
Understanding the conformational ensembles of intrinsically disordered proteins and peptides (IDPs) in their various biological environments is essential for understanding their mechanisms and functional roles in the proteome, leading to a greater knowledge of, and potential treatments for, a broad range of diseases. To determine whether molecular simulation is able to generate accurate conformational ensembles of IDPs, we explore the structural landscape of the PLP peptide (an intrinsically disordered region of the proteolipid membrane protein) in aqueous and membrane-mimicking solvents, using replica exchange with solute scaling (REST2), and examine the ability of four force fields (ff14SB, ff14IDPSFF, CHARMM36 and CHARMM36m) to reproduce literature circular dichroism (CD) data. Results from variable temperature (VT) 1H and Rotating frame Overhauser Effect SpectroscopY (ROESY) nuclear magnetic resonance (NMR) experiments are also presented and are consistent with the structural observations obtained from the simulations and CD. We also apply the optimum simulation protocol to TP2 and ONEG (a cell-penetrating peptide (CPP) and a negative control peptide, respectively) to gain insight into the structural differences that may account for the observed difference in their membrane-penetrating abilities. Of the tested force fields, we find that CHARMM36 and CHARMM36m are best suited to the study of IDPs, and accurately predict a disordered to helical conformational transition of the PLP peptide accompanying the change from aqueous to membrane-mimicking solvents. We also identify an α-helical structure of TP2 in the membrane-mimicking solvents and provide a discussion of the mechanistic implications of this observation with reference to the previous literature on the peptide. From these results, we recommend the use of CHARMM36m with the REST2 protocol for the study of environment-specific IDP conformations. We believe that the simulation protocol will allow the study of a broad range of IDPs that undergo conformational transitions in different biological environments.A protocol for simulating intrinsically disordered peptides in aqueous and hydrophobic solvents is proposed. Results from four force fields are compared with experiment. CHARMM36m performs the best for the simulated IDPs in all environments. 相似文献
43.
Marcela Dvorakova Marie Pribylova Radek Pohl Marie E. Migaud Tomas Vanek 《Tetrahedron》2012,68(33):6701-6711
A migration of methyloxycarbonyl group from secondary to primary hydroxyl was observed in furanosides (ribosides and xylosides) under usual desilylation conditions using tetrabutylammonium fluoride. The migration was studied further on several alkyloxycarbonyl furanosides under either basic or acidic conditions. As follows from 13C labelling experiments and product distribution, the migration in xylosides, proceeds intramolecularly via six-membered cyclic carbonate, whereas in ribosides, the migration is intermolecular. Acidic conditions prevented the migration in ribosides whereas the migration in xylosides was circumvented under neutral conditions. 相似文献
44.
For plus-operators in a Banach indefinite space, we consider a linear-fractional relation. The classes of operators with the
empty domain of definition for such a relation are described. The sufficient (and necessary, in some meaning) conditions for
the chain rule to be valid are given. 相似文献
45.
Aleksandar Donev Vasily V. Bulatov Tomas Oppelstrup George H. Gilmer Babak Sadigh Malvin H. Kalos 《Journal of computational physics》2010,229(9):3214-3236
We develop an asynchronous event-driven First-Passage Kinetic Monte Carlo (FPKMC) algorithm for continuous time and space systems involving multiple diffusing and reacting species of spherical particles in two and three dimensions. The FPKMC algorithm presented here is based on the method introduced in Oppelstrup et al. [10] and is implemented in a robust and flexible framework. Unlike standard KMC algorithms such as the n-fold algorithm, FPKMC is most efficient at low densities where it replaces the many small hops needed for reactants to find each other with large first-passage hops sampled from exact time-dependent Green’s functions, without sacrificing accuracy. We describe in detail the key components of the algorithm, including the event-loop and the sampling of first-passage probability distributions, and demonstrate the accuracy of the new method. We apply the FPKMC algorithm to the challenging problem of simulation of long-term irradiation of metals, relevant to the performance and aging of nuclear materials in current and future nuclear power plants. The problem of radiation damage spans many decades of time-scales, from picosecond spikes caused by primary cascades, to years of slow damage annealing and microstructure evolution. Our implementation of the FPKMC algorithm has been able to simulate the irradiation of a metal sample for durations that are orders of magnitude longer than any previous simulations using the standard Object KMC or more recent asynchronous algorithms. 相似文献
46.
Petr Munster Tomas Horvath Josef Vojtech Ondrej Havlis Martin Slapak Pavel Skoda 《Fiber and Integrated Optics》2017,36(3):144-156
Currently, individual optical fibers are mostly used for each non-data application, which is very inefficient and uneconomical. Sharing a single fiber for multiple applications is a promising solution. However, in the case of a non-data application, the situation is much more complicated compared to data because of special application´s requirements. In laboratory setup, we performed a measurement with a standard G.652D optical fiber for analyzing possible interaction of stable frequency/accurate time transmission, 1.25/10Gbps data transmission (typical bitrates for access point-to-point networks), and high-power sensor signal for different channel spacing and different pulse duration of sensor signal. 相似文献
47.
A series of para-substituted benzene derivatives were subjected to whole-cell fermentation with Escherichia coli JM109 (pDTG601), an organism expressing toluene dioxygenase (TDO). Several compounds proved to be excellent substrates for TDO, including 4-bromo-phenylacetylene, 4-bromobenzaldehyde, 4-bromobenzyl alcohol and 4-bromo-allylbenzene. Some of the first para-functionalized diene diols produced using TDO, are useful substrates for further synthetic manipulations, including their use in the potential synthesis of complex natural products. 相似文献
48.
We consider Schrödinger operators on radial metric trees and prove Lieb–Thirring and Cwikel–Lieb–Rozenblum inequalities for their negative eigenvalues. The validity of these inequalities depends on the volume growth of the tree. We show that the bounds are valid in the endpoint case and reflect the correct order in the weak or strong coupling limit. 相似文献
49.
Hunter CA Jones PS Tiger P Tomas S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(23):5435-5446
Chemical double-mutant cycles have been used to quantify intermolecular functional-group interactions in H-bonded zipper complexes in chloroform. If the same interaction is measured in zippers of different overall stability, the double-mutant cycles can be combined to produce a triple-mutant box. This construct quantifies cooperativity between the functional group interaction of interest and the other interactions that are used to change the overall stability of the complexes. The sum of two edge-to-face aromatic interactions (-2.9 +/- 0.5 kJ mol-1) is shown to be insensitive to changes of up to 13.7 +/- 0.2 kJ mol-1 in the overall stability of the complex. In principle, enthalpic cooperative effects caused by entropy-enthalpy compensation could perturb the measurement of intermolecular interactions when using the double-mutant cycle approach, but these experiments show that, for this system, the magnitude of the effect lies within the error of the measurements. 相似文献
50.
Evidence is presented for normal-spinel domain of homogeneity between the compositions InS1.50?ε and InS1.35. Structural study of a single crystal of composition InS1.44 indicates indium vacancies on the tetrahedral sites. The compound In2S3, regardless of conditions of formation, is a tetragonal superstructure of the spinel lattice (a0) with and c = 3a0. The spinel-type domain shows peritectic decomposition at 850°C for the composition InS1.40. 相似文献