全文获取类型
收费全文 | 1571篇 |
免费 | 51篇 |
国内免费 | 2篇 |
专业分类
化学 | 1055篇 |
晶体学 | 6篇 |
力学 | 19篇 |
数学 | 213篇 |
物理学 | 331篇 |
出版年
2024年 | 3篇 |
2023年 | 13篇 |
2022年 | 55篇 |
2021年 | 49篇 |
2020年 | 40篇 |
2019年 | 43篇 |
2018年 | 29篇 |
2017年 | 28篇 |
2016年 | 77篇 |
2015年 | 50篇 |
2014年 | 62篇 |
2013年 | 64篇 |
2012年 | 127篇 |
2011年 | 146篇 |
2010年 | 109篇 |
2009年 | 64篇 |
2008年 | 99篇 |
2007年 | 133篇 |
2006年 | 77篇 |
2005年 | 64篇 |
2004年 | 53篇 |
2003年 | 37篇 |
2002年 | 27篇 |
2001年 | 11篇 |
2000年 | 12篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 13篇 |
1995年 | 18篇 |
1994年 | 17篇 |
1993年 | 8篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 6篇 |
1987年 | 2篇 |
1985年 | 2篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1935年 | 1篇 |
1905年 | 3篇 |
1904年 | 2篇 |
排序方式: 共有1624条查询结果,搜索用时 15 毫秒
61.
We introduce a new method to simulate the physics of rare events. The method, an extension of the Temperature Accelerated Molecular Dynamics, comes in use when the collective variables introduced to characterize the rare events are either non-analytical or so complex that computing their derivative is not practical. We illustrate the functioning of the method by studying the homogeneous crystallization in a sample of Lennard-Jones particles. The process is studied by introducing a new collective variable that we call Effective Nucleus Size N. We have computed the free energy barriers and the size of critical nucleus, which result in agreement with data available in the literature. We have also performed simulations in the liquid domain of the phase diagram. We found a free energy curve monotonically growing with the nucleus size, consistent with the liquid domain. 相似文献
62.
63.
Marta Oliveira Subramanian Viswanathan Simone Morais Cristina Delerue-Matos 《Chemical Papers》2012,66(10):891-898
Disposable screen-printed electrodes (SPCE) were modified using a cosmetic product to partially block the electrode surface in order to obtain a microelectrode array. The microarrays formed were electropolymerized with aniline. Scanning electron microscopy was used to evaluate the modified and polymerized electrode surface. Electrochemical characteristics of the constructed sensor for cadmium analysis were evaluated by cyclic and square-wave voltammetry. Optimized stripping procedure in which the preconcentration of cadmium was achieved by depositing at ?1.20 V (vs. Ag/AgCl) resulted in a well defined anodic peak at approximately ?0.7 V at pH 4.6. The achieved limit of detection was 4 × 10?9 mol dm?3. Spray modified and polymerized microarray electrodes were successfully applied to quantify cadmium in fish sample digests. 相似文献
64.
Beckers H Esser S Metzroth T Behnke M Willner H Gauss J Hahn J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(3):832-844
Sulfenic acid (HSOH, 1 ) has been synthesized in the gas‐phase by low‐pressure high‐temperature (1150 °C) pyrolysis of di‐tert‐butyl sulfoxide (tBu2SO, 2 ) and characterized by means of matrix isolation and gas‐phase IR spectroscopy. High‐level coupled‐cluster (CC) calculations (CCSD(T)/cc‐pVTZ and CCSD(T)/cc‐pVQZ) support the first identification of the gas‐phase IR spectrum of 1 and enable its spectral characterization. Five of the six vibrational fundamentals of matrix‐isolated 1 have been assigned, and its rotational‐resolved gas‐phase IR spectrum provides additional information on the O–H and S–H stretching fundamentals. Investigations of the pyrolysis reaction by mass spectrometry, matrix isolation, and gas‐phase FT‐IR spectroscopy reveal that, up to 500 °C, 2 decomposes selectively into tert‐butylsulfenic acid, (tBuSOH, 3 ), and 2‐methylpropene. The formation of the isomeric sulfoxide (tBu(H)SO, 3 a ) has been excluded. Transient 3 has been characterized by a comprehensive matrix and gas‐phase vibrational IR study guided by the predicted vibrational spectrum calculated at the density functional theory (DFT) level (B3LYP/6‐311+G(2d,p)). At higher temperatures, the intramolecular decomposition of 3 , monitored by matrix IR spectroscopy, yields short‐lived 1 along with 2‐methylpropene, but also H2O, and most probably sulfur atoms. In addition, HSSOH ( 6 ), H2, and S2O are found among the final pyrolysis products observed at 1150 °C in the gas phase owing to competing intra‐ and intermolecular decomposition routes of 3 . The decomposition routes of the starting compound 2 and of the primary intermediate 3 are discussed on the basis of experimental results and a computational study performed at the B3LYP/6‐311G* and second‐order Møller–Plesset (MP2/6‐311G* and RI‐MP2/QZVPP) levels of theory. 相似文献
65.
We report on the structure and bonding in the title iron(III) complexes, containing the tris[(N'-tert-butylureayl)-N-ethyl]amine ligand, with density functional theory techniques. In agreement with the experimental data, a high-spin electronic state is favored for all of the systems we considered. H bonds between the terminal oxo and hydroxo ligands and NH groups present in the organic ligand coordinated to the metal have a remarkable effect on the overall coordination geometry. In fact, the structure of model complexes without H bonds shows shorter Fe-O bond lengths. This is a consequence of the ability of the H bonds to stabilize a remarkable amount of electron density localized on the terminal oxo and hydroxo ligands. Energy analysis indicates that each H bond stabilizes the nonheme complexes by roughly 35 kJ/mol. Molecular orbital analysis indicates a reduction of two Fe-O bonding electrons on going from a complex with a terminal oxo ligand to a complex with a terminal hydroxo ligand. This reduction in the number of bonding electrons is also supported by frequency analysis. 相似文献
66.
Dr. Luca Fornasari Dr. Anna Olejniczak Dr. Federica Rossi Dr. Simone d'Agostino Prof. Michele R. Chierotti Prof. Roberto Gobetto Prof. Andrzej Katrusiak Prof. Dario Braga 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(22):5061-5069
The structures and solid-state dynamics of the supramolecular salts of the general formula [(12-crown-4)2 ⋅ DABCOH2](X)2 (where DABCO=1,4-diazabicyclo[2.2.2]octane, X=BF4, ClO4) have been investigated as a function of temperature (from 100 to 360 K) and pressure (up to 3.4 GPa), through the combination of variable-temperature and variable-pressure XRD techniques and variable-temperature solid-state NMR spectroscopy. The two salts are isomorphous and crystallize in the enantiomeric space groups P3221 and P3121. All building blocks composing the supramolecular complex display dynamic processes at ambient temperature and pressure. It has been demonstrated that the motion of the crown ethers is maintained on lowering the temperature (down to 100 K) or on increasing the pressure (up to 1.5 GPa) thanks to the correlation between neighboring molecules, which mesh and rotate in a concerted manner similar to spiral gears. Above 1.55 GPa, a collapse-type transition to a lower-symmetry ordered structure, not attainable at a temperature of 100 K, takes place, proving, thus, that the pressure acts as the means to couple and decouple the gears. The relationship between temperature and pressure effects on molecular motion in the solid state has also been discussed. 相似文献
67.
Morra S Valetti F Sadeghi SJ King PW Meyer T Gilardi G 《Chemical communications (Cambridge, England)》2011,47(38):10566-10568
[FeFe]-hydrogenases are efficient natural catalysts that can be exploited for hydrogen production. Immobilization of the recombinant [FeFe]-hydrogenase CaHydA was achieved for the first time on an anatase TiO(2) electrode. The enzyme is able to interact and exchange electrons with the electrode and to catalyze hydrogen production with an efficiency of 70%. 相似文献
68.
Emanuele Miserazzi Mario Alessandro SpottiRoberto Profeta Simone SpadaArnaldo Nalin Elisa MoroDaniele Andreotti 《Tetrahedron letters》2011,52(3):448-452
An interesting and surprising rearrangement was observed during the reaction of 4-N-benzyl piperazinone derivatives with Lawesson’s reagent as a thionating agent. Investigation into the possible mechanism responsible for these results is reported herein. 相似文献
69.
Beatrice Adelizzi Andreas T. Rsch Daan J. vanRijen R. Simone Martire Serkan Esiner Martin Lutz Anja R. A. Palmans E. W. Meijer 《Helvetica chimica acta》2019,102(5)
Recent studies on water‐splitting photoelectrochemical cells (PECs) have demonstrated the intriguing possibility of controlling the spin state in this chemical reaction to form H2 and O2 by exploiting the chirality of organic π‐conjugated supramolecular polymers. Although this fascinating phenomenon has been disclosed, the chiral supramolecular materials reported thus far are not optimized for acting as efficient photosensitizer for dye‐sensitized PECs. In this work we report on the design, synthesis, and characterization of chiral supramolecular aggregates based on C3‐symmetric triphenylamine‐based dyes that are able to both absorb visible light and control the spin state of the process. Variable temperature‐dependent spectroscopic measurements reveal the assembly process of the dyes and confirm the formation of chiral aggregates, both in solution as well as on solid supports. Photoelectrochemical measurements on TiO2‐based anodes validate the advantage of using chiral supramolecular aggregates as photosensitizer displaying higher photocurrent compared to achiral analogues. Moreover, fluorimetric tests for the quantification of the hydrogen peroxide produced, confirm the possibility of controlling the spin of the reaction exerting spin‐selection with chiral supramolecular polymers. These results represent a further step towards the next‐generation of organic‐based water‐splitting solar cells. 相似文献
70.
Polyamide 12 (PA12) is used in a variety of applications when low moisture absorption, good dimensional stability, and toughness are required. Polyamide 12 is one of the polymers most frequently employed to fabricate angioplasty balloon catheters; however, its high hydrophobicity and chemical inertness require the application of coatings to make its surface more hydrophilic and biocompatible. In this work, an alternative method, based on the photochemical reaction of PA12 with a hydrophilic aromatic azide, was developed. Static and dynamic contact angle measurements evidenced that the surface modification process was able to improve PA12 wettability and that the effects were retained even after 12 months from surface treatment. Polyamide 12 modification resulted in an increase of its surface free energy, as evaluated by the van Oss, Good, and Chaudhury method. X‐ray photoelectron spectroscopy confirmed the presence of the aromatic azide on PA12 surface. Finally, compliance tests showed that the modification process did not reduce the mechanical performance of balloons. 相似文献