全文获取类型
收费全文 | 485篇 |
免费 | 35篇 |
专业分类
化学 | 350篇 |
晶体学 | 5篇 |
力学 | 17篇 |
数学 | 71篇 |
物理学 | 77篇 |
出版年
2023年 | 4篇 |
2022年 | 1篇 |
2021年 | 7篇 |
2020年 | 11篇 |
2019年 | 15篇 |
2018年 | 9篇 |
2017年 | 8篇 |
2016年 | 28篇 |
2015年 | 29篇 |
2014年 | 13篇 |
2013年 | 31篇 |
2012年 | 32篇 |
2011年 | 42篇 |
2010年 | 33篇 |
2009年 | 26篇 |
2008年 | 47篇 |
2007年 | 27篇 |
2006年 | 28篇 |
2005年 | 30篇 |
2004年 | 21篇 |
2003年 | 9篇 |
2002年 | 12篇 |
2001年 | 11篇 |
2000年 | 1篇 |
1999年 | 3篇 |
1998年 | 4篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1986年 | 1篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1966年 | 2篇 |
1965年 | 2篇 |
1960年 | 1篇 |
1958年 | 1篇 |
1951年 | 1篇 |
1934年 | 3篇 |
1920年 | 1篇 |
1899年 | 2篇 |
排序方式: 共有520条查询结果,搜索用时 250 毫秒
81.
van der Heden van Noort GJ Verhagen CP van der Horst MG Overkleeft HS van der Marel GA Filippov DV 《Organic letters》2008,10(20):4461-4464
A one-pot procedure for the preparation of phosphoramidates, phosphorothioates, pyrophosphates, phosphodiesters, and phosphofluoridates has been devised using di(p-methoxybenzyl)-N,N-diisopropylphosphoramidite as the common phosphitylating reagent. 相似文献
82.
Maarten K. Sabbe Marie‐Françoise Reyniers Prof. Dr. Veronique Van Speybroeck Dr. Michel Waroquier Prof. Dr. Guy B. Marin Prof. Dr. 《Chemphyschem》2008,9(1):124-140
A consistent set of group additive values ΔGAV° for 46 groups is derived, allowing the calculation of rate coefficients for hydrocarbon radical additions and β-scission reactions. A database of 51 rate coefficients based on CBS-QB3 calculations with corrections for hindered internal rotation was used as training set. The results of this computational method agree well with experimentally observed rate coefficients with a mean factor of deviation of 3, as benchmarked on a set of nine reactions. The temperature dependence on the resulting ΔGAV°s in the broad range of 300–1300 K is limited to ±4.5 kJ mol−1 on activation energies and to ±0.4 on logA (A: pre-exponential factor) for 90 % of the groups. Validation of the ΔGAV°s was performed for a test set of 13 reactions. In the absence of severe steric hindrance and resonance effects in the transition state, the rate coefficients predicted by group additivity are within a factor of 3 of the CBS-QB3 ab initio rate coefficients for more than 90 % of the reactions in the test set. It can thus be expected that in most cases the GA method performs even better than standard DFT calculations for which a deviation factor of 10 is generally considered to be acceptable. 相似文献
83.
Dijkstra HP Sprong H Aerts BN Kruithof CA Egmond MR Klein Gebbink RJ 《Organic & biomolecular chemistry》2008,6(3):523-531
Reactive phosphonates are important probes to target the active site of serine hydrolases, one of the largest and most diverse family of enzymes. Developing such inhibitory probes is of special importance in activity based protein profiling, a strategy that is increasingly used to gain information about a certain class of enzymes in complex proteosomes. Therefore, gaining detailed information about these inhibition events on the individual protein level is important since it affords information that can be used to fine-tune the probe for a specific task. Here, we report a novel and versatile synthesis protocol to access a variety of functionalised p-nitrophenyl phosphonate (PNPP) inhibitors from a common azide functionalised precursor using click chemistry. The obtained PNPPs were successfully used to covalently label serine hydrolases in their active sites with molecular tags. Furthermore, a model study is described in which we developed straightforward protocols that can be used to study protein inhibition events. Kinetic studies using UV-Vis and fluorescence spectroscopy techniques revealed that these PNPPs possess different inhibition rates for various proteins and were shown to be suitable probes to discriminate between various lipases. Additionally, we demonstrate that PNPPs are highly selective for serine hydrolases, making these probes very interesting as diagnostic or affinity probes for studying proteins in complex proteosomes. 相似文献
84.
Imogen Foubert Eveline Fredrick Jeroen Vereecken Maarten Sichien Koen Dewettinck 《Thermochimica Acta》2008,471(1-2):7-13
Differential scanning calorimeters have frequently been used to study the isothermal crystallization kinetics of fats and oils. In some circumstances (e.g. start of crystallization during cooling to the crystallization temperature, crystallization in emulsion) this straightforward approach is not applicable. This paper describes an indirect DSC method for determination of the crystallization kinetics under these ‘difficult’ circumstances. The principle is to stop the crystallization at different moments during the isothermal crystallization and raise the sample temperature. The amount of heat released is then used as a measure for the amount of crystallization and plotted as function of time. Combination of the stop-and-return method with the direct method may sometimes be used to save on measurement time. Stop-and-return experiments can furthermore be used to gain more insight in the crystallization mechanism based on the fact that different polymorphic forms and fractions have different melting temperatures. 相似文献
85.
Eliton S. Medeiros Luiz H. C. Mattoso Rubens Bernardes-Filho Delilah F. Wood William J. Orts 《Colloid and polymer science》2008,286(11):1265-1272
Nanostructured films of poly(o-ethoxyaniline) (POEA) alternated with cellulose nanofibrils (CnF) were successfully produced
by self assembly (SA) at different pH values and investigated by atomic force microscopy and ultraviolet-visible spectroscopy.
Results show that it was possible to build up films by alternating POEA and CnF layers with relatively precise architectural
control by controlling the number of layers and pH. Film thickness had a dependence on pH which is a combination of the effects
of the deposited amount for each POEA layer and the pH at which the absorption of the cellulose nanofibrils was carried out.
Comparison of alternated layers of POEA and CnF with multi-immersions of POEA at different pH values, as measured by the ratio
between slopes of the straight lines of deposited amount of polymer versus the number of self-assembled layers, shows that
alternate deposition at pH 2 has a fourfold increase in the slope. Alternatively, at pH 5, there is no significant difference
whether the deposition is alternated (POEA–CnF) or not (POEA). 相似文献
86.
Hoeben FJ Zhang J Lee CC Pouderoijen MJ Wolffs M Würthner F Schenning AP Meijer EW De Feyter S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(28):8579-8589
A melamine derivative has been covalently equipped with two oligo(para-phenylenevinylene) (OPV) chromophores. This procedure yields a bifunctional molecule with two hydrogen-bonding arrays available for complementary binding to perylene bisimide derivatives. Depending on the solvent, hydrogen-bonded trimers, tetramers, and dimers on a graphite surface are observed for pure OPV-melamine by using scanning tunneling microscopy (STM). Upon the addition of perylene bisimide, linear tapes of perylene bisimide, 12-membered rosettes that consist of alternating hydrogen-bonded OPV-melamine and perylene bisimide moieties are visualized. These results provide direct evidence for the possible modes of hydrogen bonding within a supramolecular co-assembly in solution. Subsequently, the optical properties of pure OPV-melamine and co-assemblies with a perylene bisimide derivative were characterized in solution. In an apolar solvent, OPV-melamine self-assembles into chiral superstructures. Disassembly into molecularly dissolved species is reversibly controlled by concentration and temperature. Complementary hydrogen bonding to a perylene bisimide derivative in an apolar solvent yields multicomponent, pi-stacked dye assemblies of enhanced stability that are characterized by fluorescence quenching of the constituent chromophores. Titration experiments reveal that a mixture of hydrogen-bonded oligomers is present in solution, rather than a single discrete assembly. The solution experiments are consistent with the STM results, which revealed various supramolecular assemblies. Our system is likely not to be optimally programmed to obtain a discrete co-assembled structure in quantitative yield. 相似文献
87.
Dr. Ana M. Castilla Dr. Mark A. Miller Prof. Jonathan R. Nitschke Dr. Maarten M. J. Smulders 《Angewandte Chemie (International ed. in English)》2016,55(36):10616-10620
The derivation and application of a statistical mechanical model to quantify stereochemical communication in metal–organic assemblies is reported. The factors affecting the stereochemical communication within and between the metal stereocenters of the assemblies were experimentally studied by optical spectroscopy and analyzed in terms of a free energy penalty per “incorrect” amine enantiomer incorporated, and a free energy of coupling between stereocenters. These intra‐ and inter‐vertex coupling constants are used to track the degree of stereochemical communication across a range of metal–organic assemblies (employing different ligands, peripheral amines, and metals); temperature‐dependent equilibria between diastereomeric cages are also quantified. The model thus provides a unified understanding of the factors that shape the chirotopic void spaces enclosed by metal–organic container molecules. 相似文献
88.
Heart rate variability analysis by chaotic global techniques in children with attention deficit hyperactivity disorder
下载免费PDF全文
![点击此处可从《Complexity》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Rubens Wajnsztejn Tatiana Dias De Carvalho David M. Garner Luiz Carlos Marques Vanderlei Moacir Fernandes Godoy Rodrigo Daminello Raimundo Celso Ferreira Vitor E. Valenti Luiz Carlos De Abreu 《Complexity》2016,21(6):412-419
Attention deficit hyperactivity disorder (ADHD) is characterized by decreased attention span, impulsiveness, and hyperactivity. Autonomic nervous system imbalance was previously described in this population. We aim to compare the autonomic function of children with ADHD and controls by analyzing heart rate variability (HRV). Children with ADHD (22 boys, mean age 9.964 years) and 28 controls (15 boys, mean age 9.857 years) rested in supine position with spontaneous breathing for 20 min. Heart rate was recorded beat by beat. HRV analysis was performed by use of chaotic global techniques. ADHD promoted an increase in the chaotic forward parameter. The algorithm which applied all three chaotic global parameters was only the second optimum statistically measured by Kruskal–Wallis (P < 0.0001) and low standard deviations. It was also highly influential by principal component analysis with almost all variation covered by the first two components. The third algorithm which lacked the (high spectral Detrended Fluctuation Analysis) parameter performed best statistically. However, we chose the algorithm which applied all three chaotic globals due to previous studies mentioned in the text—forward and inverse problems. Comparison of the autonomic function by analyzing HRV with chaotic global techniques suggests an increase in chaotic activity in children with ADHD in relation to the control group. © 2015 Wiley Periodicals, Inc. Complexity 21: 412–419, 2016 相似文献
89.
We consider an inverse source problem for an inhomogeneous wave equation with discrete-in-time sources, modeling a seismic rupture. The inverse source problem, with an arbitrary source term on the right-hand side of the wave equation, is not uniquely solvable. Here we formulate conditions on the source term that allow us to show uniqueness and that provide a reasonable model for the application of interest. We assume that the source term is supported on a finite set of times and that the support in space moves with subsonic velocity. Moreover, we assume that the spatial part of the source is singular on a hypersurface, an application being a seismic rupture along a fault plane. Given data collected over time on a detection surface that encloses the spatial projection of the support of the source, we show how to recover the times and locations of sources microlocally and then reconstruct the smooth part of the source assuming that it is the same at each source location. 相似文献
90.
de Andrade RR Rivera EC Costa AC Atala DI Maugeri Filho F Maciel Filho R 《Applied biochemistry and biotechnology》2007,137(1-12):753-763
In this work, a procedure was established to develop a mathematical model considering the effect of temperature on reaction kinetics. Experiments were performed in batch mode in temperatures from 30 to 38 degrees C. The microorganism used was Saccharomyces cerevisiae and the culture media, sugarcane molasses. The objective is to assess the difficulty in updating the kinetic parameters when there are changes in fermentation conditions. We conclude that, although the re-estimation is a time-consuming task, it is possible to accurately describe the process when there are changes in raw material composition if a re-estimation of parameters is performed. 相似文献