全文获取类型
收费全文 | 961篇 |
免费 | 62篇 |
国内免费 | 61篇 |
专业分类
化学 | 523篇 |
晶体学 | 5篇 |
力学 | 19篇 |
综合类 | 10篇 |
数学 | 102篇 |
物理学 | 425篇 |
出版年
2024年 | 3篇 |
2023年 | 18篇 |
2022年 | 38篇 |
2021年 | 33篇 |
2020年 | 34篇 |
2019年 | 28篇 |
2018年 | 32篇 |
2017年 | 38篇 |
2016年 | 48篇 |
2015年 | 37篇 |
2014年 | 62篇 |
2013年 | 60篇 |
2012年 | 55篇 |
2011年 | 53篇 |
2010年 | 36篇 |
2009年 | 55篇 |
2008年 | 61篇 |
2007年 | 67篇 |
2006年 | 40篇 |
2005年 | 41篇 |
2004年 | 31篇 |
2003年 | 29篇 |
2002年 | 23篇 |
2001年 | 17篇 |
2000年 | 18篇 |
1999年 | 16篇 |
1998年 | 19篇 |
1997年 | 8篇 |
1996年 | 11篇 |
1995年 | 4篇 |
1994年 | 15篇 |
1993年 | 5篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有1084条查询结果,搜索用时 734 毫秒
21.
Monika Schuster Robert Inführ Claudia Turecek Jürgen Stampfl Franz Varga Robert Liska 《Monatshefte für Chemie / Chemical Monthly》2006,137(7):843-853
Summary. To substitute cross-linked photopolymers in rapid prototyping of mold materials and therefore extend the range of materials
which can be casted, organo-soluble photopolymers were developed. Branched bisalkylacrylamides were suitable as base component
for such formulations, due to their high reactivity, good mechanical properties, and excellent solubility of the formed polymers.
These molding materials were used to prepare cellular biocompatible materials which could be used as bone replacement materials.
Biocompatible crosslinkers based on methacrylates from hydrolyzed gelatine or lactic acid ethyleneglycol blockcopolymers and
commercially available reactive diluents are the base components of such a formulation. Biocompatibility was investigated
by osteoblast-like cells. Cellular biocompatible parts were obtained by thermal polymerization in soluble mould materials
prepared by 3D-photoshaping. 相似文献
22.
Résumé L'analyse de coupes lourdes (huile de distillation sous vide et huile issue du séparateur à chaud) provenant de l'hydroliquéfaction
catalytique du charbon a été réalisée par mise en ouvre de différentes techniques chromatographiques. L'identification des
principales structures résulte de l'application de la chromatographie par couplage de transfert de charge en mode HPLC et
des spectroscopies UV et de masse.
Donotor-acceptor complex chromatography —Application to analysis of coal liquefaction products by HPLC
Summary A Vacuum gas oil and the corresponding residue of a coal liquefaction product were investigated by means of HPLC and MS. Nearly a complete identification was performed by chromatographic, UV-spectroscopic methods and MS.
相似文献
23.
Summary The effect of perchlorate anion as mobile phase modifier on the separation factor, α, forN-(dansyl)-dl-norvaline andN-(dansyl)-dl-tryptophan on a human serum albumin (HSA) column was studied by varying the concentration,c, of the chaotropic agent and the column temperatureT. Gibbs-Helmholtz parameters Δ(ΔH) and Δ(ΔS) between thed andl enantiomers were determined from linear van't Hoff plots of lnα against 1/T. Thermodynamic results indicated that the enhancement of the separation factor observed asc was increased was enthalpically controlled owing to stereoselective H-bonding interactions. Such behavior was used to optimize
the chromatographic conditions for separation ofN-(dansyl)-amino acids on HSA. 相似文献
24.
I. M. Mutton 《Chromatographia》1998,47(5-6):291-298
Summary Rapid analyses were performed using reversed-phase liquid chromatography with short (20–100 mm) columns swept by fast yet
shallow gradients, and the results compared with those obtained with 150 mm columns and slow gradients. The resolution losses
incurred with shorter columns were minimised by employing elevated flow rates, to ensure that comparable mean retention factors
were experienced by individual analytes during gradients run on different columns. This conserves gradient steepness. High
quality performance was obtained with turn-around times of 5–10 minutes. An overall 5-fold enhancement in the rate of information
generation was obtained. The relevance of instrumental parameters and of column and packing dimensions, upon the potential
for improved performance is discussed. Some implications for the rapidly developing technique of capillary electrochromatography
are briefly indicated. 相似文献
25.
Michael J. Monteiro 《Journal of polymer science. Part A, Polymer chemistry》2005,43(15):3189-3204
Living radical polymerization has allowed complex polymer architectures to be synthesized in bulk, solution, and water. The most versatile of these techniques is reversible addition–fragmentation chain transfer (RAFT), which allows a wide range of functional and nonfunctional polymers to be made with predictable molecular weight distributions (MWDs), ranging from very narrow to quite broad. The great complexity of the RAFT mechanism and how the kinetic parameters affect the rate of polymerization and MWD are not obvious. Therefore, the aim of this article is to provide useful insights into the important kinetic parameters that control the rate of polymerization and the evolution of the MWD with conversion. We discuss how a change in the chain‐transfer constant can affect the evolution of the MWD. It is shown how we can, in principle, use only one RAFT agent to obtain a polymer with any MWD. Retardation and inhibition are discussed in terms of (1) the leaving R group reactivity and (2) the intermediate radical termination model versus the slow fragmentation model. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3189–3204, 2005 相似文献
26.
A simple detection method to observe the uniplanar orientation behavior of native cellulose microfibrils to the cell wall surface by using Fourier transform infrared (FTIR) spectroscopy in the transmission mode is reported. Four bands at 1372, 1355, 1337, and 1317 cm−1 (the latter two have been mentioned previously by Liang and Marchessault (1960, J. Polym. Sci. 43: 85–100)) were found to be sensitive to such orientation: the two middle bands at 1355 and 1337 cm−1 increase remarkably when the 0.60–61 nm lattice planes lie parallel to the cell wall surfaces. The reverse was true when the 0.53–54 nm lattice planes oriented preferentially. Polarization of the two bands at 1372 and 1355 cm−1 was parallel, while that of the other two bands at lower wavenumbers, i.e., at 1337 and 1317 cm−1, was perpendicular to the molecular axis of cellulose. These bands were assigned to OH-related motion, probably to in-plane OH bending, as reported by Maréchal and Chanzy (2000, J. Mol. Spectrosc. 523: 183–196). 相似文献
27.
Wenzel TJ Freeman BE Sek DC Zopf JJ Nakamura T Yongzhu J Hirose K Tobe Y 《Analytical and bioanalytical chemistry》2004,378(6):1536-1547
Chiral crown ethers 1 and 5 are useful enantiomeric discriminating agents in 1H NMR spectroscopy for neutral and protonated primary amines, amino acids, and amino alcohols. The presence of the carboxylic acid groups in 1 and 5 provide sites at which ytterbium(III) can bind. Adding ytterbium(III) nitrate to crown–substrate mixtures in methanol-d4 causes shifts in the spectra of substrates and often enhances the chiral discrimination in the 1H NMR spectrum. The enhancement in enantiomeric discrimination that occurs in the presence of ytterbium(III) allows lower concentrations of the crown ether to be used in chiral recognition studies. Several amide derivatives of 1 were prepared and evaluated as chiral NMR discriminating agents, although except for 1e, these were less effective than 1. 相似文献
28.
Fu-Ken Liu 《Analytica chimica acta》2005,528(2):249-254
This paper demonstrates that capillary electrophoresis (CE) can be employed for characterizing the sizes of nanometer-scale gold particles. We characterized the gold nanoparticles by effecting CE separation using a buffer of SDS (70 mM) and 3-cyclohexylamino-1-propanesulfonic acid (CAPS; 10 mM) at pH 11.0 and an applied voltage of 18 kV and obtained a linear relationship (R2 > 0.99) between electrophoretic mobilities and size for nanoparticles whose diameters fall in the regime from 5.0 ± 0.5 to 41.2 ± 3.3 nm; the relative standard deviations of these electrophoretic mobilities are <0.8%. We evaluated the feasibility of employing these separation conditions for the size characterization by of gold nanoparticle samples that were synthesized by a rapid microwave heating method. We confirmed that this CE method is a valid one for size characterization by comparing the results obtained by CE with those provided by scanning electron microscopy (SEM); a good correlation exists between these two techniques. Our results demonstrate that CE can be employed to accelerate the analysis of the sizes of nanomaterials. 相似文献
29.
Summary The imperfect mirror image relationship of the circular dichroism of (M) and (P) helical biliverdins bound to a homochiral entity (ICD) has been studied using the kinetically stable racemates (M+P)2 and (M+P)3. The phenomena associated with and eventual implications for the interpretation of ICD spectra of naturally occurring kinetically labile biliverdins in terms of chiral recognition are discussed.Dedicated to ProfessorKarl Schlögl on the occasion of his 70th birthday 相似文献
30.
Oliveira SC Paiva TC Visconti AE Giudici R 《Applied biochemistry and biotechnology》1998,74(3):161-172
Discrimination between different rival models for describing the inhibitory effect of ethanol both on yeast growth and on
fermentation was studied for a continuous process of alcoholic fermentation in a tower reactor with recycling of flocculating
cells. Models tested include linear, parabolic, hyperbolic, exponential, and generalized nonlinear power-law types. The best
expressions were identified under the criteria that all the kinetic parameters should assume acceptable values in a feasible
range and should result in the best fit of the experimental data. The kinetic parameters were estimated from steady-state
data of several sugar concentrations in feeding stream (S0 = 160, 170, 180, 190, 200 g/L), constant dilution rate (D = 0.2 h-1), recycle ratio (α = 13.6), and temperature (T = 30°C). The best model for the yeast growth was of power-law type, whereas
for the product formation the best model was of linear type. These models were able to reproduce the trends of the process
variables satisfactorily. 相似文献