全文获取类型
收费全文 | 2525篇 |
免费 | 87篇 |
国内免费 | 11篇 |
专业分类
化学 | 1781篇 |
晶体学 | 9篇 |
力学 | 99篇 |
数学 | 277篇 |
物理学 | 457篇 |
出版年
2023年 | 13篇 |
2021年 | 18篇 |
2020年 | 35篇 |
2019年 | 30篇 |
2018年 | 17篇 |
2017年 | 13篇 |
2016年 | 40篇 |
2015年 | 45篇 |
2014年 | 56篇 |
2013年 | 112篇 |
2012年 | 126篇 |
2011年 | 181篇 |
2010年 | 64篇 |
2009年 | 64篇 |
2008年 | 180篇 |
2007年 | 177篇 |
2006年 | 143篇 |
2005年 | 149篇 |
2004年 | 127篇 |
2003年 | 110篇 |
2002年 | 93篇 |
2001年 | 39篇 |
2000年 | 24篇 |
1999年 | 29篇 |
1998年 | 31篇 |
1997年 | 29篇 |
1996年 | 40篇 |
1995年 | 26篇 |
1994年 | 24篇 |
1993年 | 13篇 |
1992年 | 16篇 |
1991年 | 27篇 |
1990年 | 26篇 |
1989年 | 25篇 |
1988年 | 16篇 |
1987年 | 19篇 |
1986年 | 26篇 |
1985年 | 36篇 |
1984年 | 28篇 |
1983年 | 31篇 |
1982年 | 32篇 |
1981年 | 38篇 |
1980年 | 25篇 |
1979年 | 19篇 |
1978年 | 27篇 |
1977年 | 23篇 |
1976年 | 15篇 |
1975年 | 12篇 |
1974年 | 22篇 |
1973年 | 16篇 |
排序方式: 共有2623条查询结果,搜索用时 15 毫秒
111.
Lana E. Greene J. Stuart Grossert Robert L. White 《Journal of mass spectrometry : JMS》2013,48(3):312-320
Under conditions of collision‐induced dissociation (CID), anions of α‐hydroxycarboxylic acids usually fragment to yield the distinctive hydroxycarbonyl anion (m/z 45) and/or the complementary product anion formed by neutral loss of formic acid (46 u). Further support for the known two‐step mechanism, involving an ion‐neutral complex for the formation of the hydroxycarbonyl anion from the carboxyl group, is herein provided by tandem mass spectrometric results and density functional theory computations on the glycolate, lactate and 3‐phenyllactate ions. A fourth, structurally related α‐hydroxycarboxylate ion, obtained by deprotonation of mandelic acid, showed only loss of carbon dioxide upon CID. Density functional theory computations on the mandelate ion indicated that similar energy inputs were required for a direct, phenyl‐assisted decarboxylation and a postulated novel rearrangement to a carbonate ester, which yielded the benzyl oxide ion upon loss of CO2. Rearrangement of the glycolate ion led to expulsion of carbon monoxide, whereas the 3‐phenyllactate ion showed the loss of water and formation of the benzyl anion and the benzyl radical as competing processes. The fragmentation pathways proposed for lactate and 3‐phenyllactate are supported by isotopic labeling. The relative computed energies of saddle points and product ions for all proposed fragmentation pathways are consistent with the energies supplied during CID experiments and the observed relative intensities of product ions. The diverse reaction pathways characterized for this set of four α‐hydroxycarboxylate ions demonstrate that it is crucial to understand the effects of structural variations when attempting to predict the gas‐phase reactivity and CID spectra of carboxylate ions. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
112.
113.
J. Sarah Caygill Stuart D. Collyer Joanne L. Holmes Frank Davis Séamus P. J. Higson 《Electroanalysis》2013,25(11):2445-2452
We describe the use of cobalt phthalocyanine as a mediator to improve the sensitivity for the electrochemical detection of TNT. Commercial screen‐printed electrodes containing cobalt phthalocyanine were employed for determination of TNT. Improved sensitivities compared to screen‐printed carbon electrodes without phthalocyanine were observed, current response for cyclic voltammetric measurements at modified electrodes being at least double that of unmodified electrodes. A synergistic effect between oxygen and TNT reduction was also observed. Correlation between TNT concentrations and sensor output was observed between 0–200 µM TNT. Initial proof‐of‐concept experiments combining electrochemical determinations, with the use of an air‐sampling cyclone, are also reported. 相似文献
114.
115.
116.
Manea S. AlKhalifah Chunhong Lei Steven A. Myers Stuart P. Kitney 《Liquid crystals》2013,40(3):402-417
The cross-linking of polymerisable liquid crystalline semiconductors is a promising approach to solution-processable, multilayer, organic photovoltaics. Here we demonstrate an organic bilayer photovoltaic with an insoluble electron-donating layer formed by cross-linking a nematic reactive mesogen. We investigate a range of perylene diimide (PDI) materials, some of which are liquid crystalline, as the overlying electron acceptor layer. We find that carrier mobility of the acceptor materials is enhanced by liquid crystallinity and that mobility limits the performance of photovoltaic devices. 相似文献
117.
Dr. Stuart Bogatko Dr. Emilie Cauët Dr. Eric Bylaska Dr. Gregory Schenter Dr. John Fulton Prof. John Weare 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):3047-3060
Herein, we report on the structure and dynamics of the aqueous Ca2+ system studied by using ab initio molecular dynamics (AIMD) simulations. Our detailed study revealed the formation of well‐formed hydration shells with characteristics that were significantly different to those of bulk water. To facilitate a robust comparison with state‐of‐the‐art X‐ray absorption fine structure (XAFS) data, we employ a 1st principles MD‐XAFS procedure and directly compare simulated and experimental XAFS spectra. A comparison of the data for the aqueous Ca2+ system with those of the recently reported Zn2+, Fe3+, and Al3+ species showed that many of their structural characteristics correlated well with charge density on the cation. Some very important exceptions were found, which indicated a strong sensitivity of the solvent structure towards the cation′s valence electronic structure. Average dipole moments for the 2nd shell of all cations were suppressed relative to bulk water. 相似文献
118.
Richard W. Hutchinson Kavita George Doug Johns Lee Craven Gary Zhang Pullen Shnoda 《Cellulose (London, England)》2013,20(1):537-545
Oxidized regenerated cellulose (ORC) has been used as an absorbable hemostat since World War II. In the present study, hemostasis time was determined in a spleen incision model in swine. The effect of mass on absorbable hemostat efficacy and hemostasis time was evaluated by standardizing the ORC materials on a mass basis. The median hemostasis time for a single layer of the new nonwoven ORC was as much as 51 % shorter than woven ORC (P < 0.001). The mean hemostasis time for nonwoven ORC was not affected by the mass of hemostat applied to the wound. The hemostatic efficacy of woven ORC increased with the mass (layers) of hemostat applied to the wound. Nonwoven ORC is significantly faster in achieving hemostasis than woven ORC, and its hemostatic efficacy is not influenced by the mass of material applied. Tissue reaction was minimal and the material was fully absorbed by 14 days. 相似文献
119.
Daniel J. Tate Mohamed Abdelbasit Colin A. KilnerHelena J. Shepherd Stuart L. WarrinerRichard J. Bushby 《Tetrahedron》2014
3,6,8,11-Tetramethoxybenzo[j]fluoranthene can be made from 1,6-dimethoxynaphthalene in a one-pot ferric chloride oxidation/methanol reduction procedure. The reaction is tolerant of the presence of substituents in the 7-position of the naphthalene nucleus and provides a quick and easy route to these particular benzo[j]fluoranthenes. The reactions presumably proceed through initial formation of a bond between the 4-positions of two naphthalene molecules followed by closure of the five-membered ring. Indeed in one case some 4,4′-binaphthyl was isolated from the reaction mixture and it was generally found that better yields of the benzo[j]fluoranthrenes were obtained starting from the 4,4′-binaphthyl rather than by using the naphthalene as the starting material. In an analogous manner to the ring-closure of the 4,4′-binaphthyls, starting from a hexakisalkoxyphenylnaphthalene, a hexakisalkoxyfluoranthene could be obtained. 相似文献
120.
Specific ion effects on the electrophoretic mobility of small,highly charged peptides: A modeling study
下载免费PDF全文
![点击此处可从《Journal of separation science》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Stuart A. Allison Hengfu Wu Tuyen M. Bui Lac Dang Giang H. Huynh Tam Nguyen Linda Soegiarto Bi C. Truong 《Journal of separation science》2014,37(17):2403-2410
In this work, we use coarse‐grained modeling to study the free solution electrophoretic mobility of small highly charged peptides (lysine, arginine, and short oligos thereof (up to nonapeptides)) in NaCl and Na2SO4 aqueous solutions at neutral pH and room temperature. The experimental data are taken from the literature. A bead modeling methodology that treats the electrostatics at the level of the nonlinear Poisson Boltzmann equation developed previously in our laboratory is able to account for the mobility of all peptides in NaCl, but not Na2SO4. The peptide mobilities in Na2SO4 can be accounted for by including sulfate binding in the model and this is proposed as one possible explanation for the discrepancy. Oligo arginine peptides bind more sulfate than oligo lysines and sulfate binding increases with the oligo length. 相似文献