全文获取类型
收费全文 | 1095篇 |
免费 | 39篇 |
专业分类
化学 | 787篇 |
晶体学 | 8篇 |
力学 | 34篇 |
数学 | 83篇 |
物理学 | 222篇 |
出版年
2023年 | 8篇 |
2022年 | 24篇 |
2021年 | 22篇 |
2020年 | 15篇 |
2019年 | 23篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 20篇 |
2015年 | 26篇 |
2014年 | 46篇 |
2013年 | 43篇 |
2012年 | 68篇 |
2011年 | 88篇 |
2010年 | 51篇 |
2009年 | 71篇 |
2008年 | 87篇 |
2007年 | 69篇 |
2006年 | 67篇 |
2005年 | 46篇 |
2004年 | 30篇 |
2003年 | 27篇 |
2002年 | 26篇 |
2001年 | 19篇 |
2000年 | 15篇 |
1999年 | 14篇 |
1998年 | 12篇 |
1997年 | 19篇 |
1996年 | 13篇 |
1995年 | 10篇 |
1994年 | 16篇 |
1993年 | 11篇 |
1992年 | 13篇 |
1991年 | 7篇 |
1990年 | 8篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 6篇 |
1980年 | 8篇 |
1978年 | 5篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 12篇 |
1973年 | 12篇 |
1964年 | 2篇 |
排序方式: 共有1134条查询结果,搜索用时 15 毫秒
51.
Controlled release properties of Chitosan encapsulated volatile Citronella Oil microcapsules by thermal treatments 总被引:9,自引:0,他引:9
This research uses modified orifice method to prepare the O/W type Chitosan encapsulated volatile Citronella Oil microcapsules. In this article, we investigated the forming condition of microcapsules and the influence to sustained release effect of volatile Citronella Oil by applying thermal pretreatment to microcapsules. The results suggest that the forming of microcapsules should be processed under the fundamental conditions of: (1) the concentration of Chitosan is at least 0.2 wt%, (2) NaOH is greater than 0.1 wt%, and (3) with the additive of coconut oil as natural surfactant, so that we could obtain final product of microcapsules with better formation and dispersion. The changes in concentration of Chitosan will affect the encapsulation efficiency of the volatile Citronella Oil. When the concentrations of Chitosan are 0.5%, 1.0% and 1.5%, the encapsulation efficiencies are 98.2%, 95.8% and 94.7%, respectively. The particle size of Chitosan microcapsules would decrease as the emulsification stirring speed increases. When the stirring speeds are 400 rpm, 800 rpm, and 1500 rpm, the average particle sizes of microcapsules produced are 225 ± 24 μm, 131 ± 20 μm, and 11 ± 3 μm, respectively. If the microcapsules were thermal pretreated at 80 °C, the structure of Chitosan wall membrane would shrink and thus achieve the effect of sustained release. The sustaining effect would increase along with treatment time increases. 相似文献
52.
Chen YH Chang FR Lu MC Hsieh PW Wu MJ Du YC Wu YC 《Molecules (Basel, Switzerland)》2008,13(2):255-266
Three new compounds: 2R,3R-pterosin L 3-O-beta-D-glucopyranoside (1), beta-D-xylopyranosyl(1-->2)-7-O-benzoyl-beta-D-glucopyranoside (2) and 4-O-benzoyl-beta-D-xylo-pyranosyl(1-->2)-7-O-benzoyl-beta-D-glucopyranoside (3), together with nine known compounds, were isolated from the ethyl acetate extract of Pteris ensiformis. 5-[2-Hydroxyethylidene]-2(5H)-furanone (4), which had been synthesized, was isolated from natural sources for the first time. The structures of all isolated compounds were determined on the basis of mass and spectroscopic evidence. Compound 1 and pterosin B (5) show cytotoxicity against HL 60 cells (human leukemia) with the IC(50) values of 3.7 and 8.7 microg/mL, respectively. 相似文献
53.
Kai‐Hsuan Hsieh Chih‐Ying Hsu I‐Ju Hung Chih‐Ling Yeh Yau‐Hung Chen Chien‐Chung Cheng 《中国化学会会志》2021,68(1):34-38
Liposomes composed of cell‐penetrating peptide derivatives increased transport across the cell membrane. Conjugating rhodamine to a cell‐penetrating peptide increased the toxicity of rhodamine in E. coli and zebrafish embryos. A similar total protein inhibition pattern with different intensities, indicating that the interaction pathways of the rho‐KTTKS‐CONH2 monomer and liposomes were the same. It suggests that the rho‐KTTKS‐CONH2 liposomes showed higher toxicity because better transport across the cell membrane increased the effective concentration inside cells. The staining of zebrafish embryos using rho‐KTTKS‐CONH2 liposomes showed a longer retention time, suggesting that it can penetrate deeper tissues or organs in zebrafish. 相似文献
54.
A very stiff finitely extensible nonlinear elastic (FENE)-Fraenkel spring is proposed to replace the rigid rod in the bead-rod model. This allows the adoption of a fast predictor-corrector method so that large time steps can be taken in Brownian dynamics (BD) simulations without over- or understretching the stiff springs. In contrast to the simple bead-rod model, BD simulations with beads and FENE-Fraenkel (FF) springs yield a random-walk configuration at equilibrium. We compare the simulation results of the free-draining bead-FF-spring model with those for the bead-rod model in relaxation, start-up of uniaxial extensional, and simple shear flows, and find that both methods generate nearly identical results. The computational cost per time step for a free-draining BD simulation with the proposed bead-FF-spring model is about twice as high as the traditional bead-rod model with the midpoint algorithm of Liu [J. Chem. Phys. 90, 5826 (1989)]. Nevertheless, computations with the bead-FF-spring model are as efficient as those with the bead-rod model in extensional flow because the former allows larger time steps. Moreover, the Brownian contribution to the stress for the bead-FF-spring model is isotropic and therefore simplifies the calculation of the polymer stresses. In addition, hydrodynamic interaction can more easily be incorporated into the bead-FF-spring model than into the bead-rod model since the metric force arising from the non-Cartesian coordinates used in bead-rod simulations is absent from bead-spring simulations. Finally, with our newly developed bead-FF-spring model, existing computer codes for the bead-spring models can trivially be converted to ones for effective bead-rod simulations merely by replacing the usual FENE or Cohen spring law with a FENE-Fraenkel law, and this convertibility provides a very convenient way to perform multiscale BD simulations. 相似文献
55.
In this study, on-line sample concentration methods, which coupled field-amplified sample injection and sweeping technology with MEEKC, were used to detect and analyze eight common penicillin antibiotics (nafcillin, dicloxacillin, ampicillin, oxacillin, penicillin V, cloxacillin, penicillin G, and amoxicillin). During the optimization of field-amplified sample injection-sweeping MEEKC, the composition of sample matrix and the length of acidic plug were found to be the predominant influences for penicillin stacking. Both zwitterionic ampicillin and amoxicillin could only be stacked through cation-selective-exhaustive-injection sweeping, whereas the other six penicillin compounds were found to be concentrated by anion-selective-exhaustive-injection sweeping. Hence, in order to simultaneously concentrate the eight penicillins in a single-run sweeping step, a combination of successive anion- and cation-selective injections was used. When compared with previous CE-UV methods, the proposed on-line concentration MEEKC method provided better detection sensitivity and faster separation for these penicillins either in single ion-selective injection or in successive anion-/cation-selective injection where the LODs were in the range of 0.2-2.8 microg/L and 0.5-5.8 microg/L, respectively. 相似文献
56.
Ya-Ting Hsieh Nai-Tzu Kuo Eamor M. Woo 《Journal of Thermal Analysis and Calorimetry》2012,107(2):745-756
Abstract
Thermal behavior, miscibility, and crystalline morphology in blends of low-molecular-weight poly(l-lactic acid) (LMw-PLLA) or high-molecular-weight PLLA (HMw-PLLA) with various polyesters such as poly(butylene adipate) (PBA), poly(ethylene adipate) (PEA), poly(trimethylene adipate) (PTA), or poly(ethylene succinate) (PESu), respectively, were explored using differential scanning calorimeter (DSC), and polarized-light optical microscopy (POM). Phase behavior in blends of PLLA with other polyesters has been intriguing and not straight forward. Using a low- and high molecular weight PLLA, this study aimed at mainly using thermal analyses for probing the phase behavior, phase diagrams, and temperature dependence of blends systems composed of PLLA of two different molecular weights (low and high) with a series of aliphatic polyesters of different structures varying in the (CH2/CO) ratio in main chains. The blends of LMw-PLLA/PEA and LMw-PLLA/PTA show miscibility in melt and amorphous glassy states. Meanwhile, the LMw-PLLA/PESu blend is immiscible with an asymmetry-shaped upper critical solution temperature (UCST) at 220–240 °C depending on the blend composition. In contrast to miscibility in LMw-PLLA/PTA and LMw-PLLA/PEA blends, HMw-PLLA with polyesters are mostly immiscible; and HMw-PLLA/PTA blend is the only one showing an asymmetry-shaped UCST phase diagram with clarity points at 195–235 °C (depending on composition). Reversibility of UCST behavior, with no chemical transreactions, in these blends was proven by solvent recasting, gel permeation chromatography, and Fourier transform infrared spectroscopy (FT-IR). Crystalline morphology behavior of the LMw-PLLA/PEA and LMw-PLLA/PTA blends furnishes addition evidence for miscibility in the amorphous phase between LMw-PLLA and PTA or PEA. 相似文献57.
DeGraw AJ Zhao Z Strickland CL Taban AH Hsieh J Jefferies M Xie W Shintani DK McMahan CM Cornish K Distefano MD 《The Journal of organic chemistry》2007,72(13):4587-4595
A number of biochemical processes rely on isoprenoids, including the post-translational modification of signaling proteins and the biosynthesis of a wide array of compounds. Photoactivatable analogues have been developed to study isoprenoid utilizing enzymes such as the isoprenoid synthases and prenyltransferases. While these initial analogues proved to be excellent structural analogues with good cross-linking capability, they lack the stability needed when the goals include isolation of cross-linked species, tryptic digestion, and subsequent peptide sequencing. Here, the synthesis of a benzophenone-based farnesyl diphosphate analogue containing a stable phosphonophosphate group is described. Inhibition kinetics, photolabeling experiments, as well as X-ray crystallographic analysis with a protein prenyltransferase are described, verifying this compound as a good isoprenoid mimetic. In addition, the utility of this new analogue was explored by using it to photoaffinity label crude protein extracts obtained from Hevea brasiliensis latex. Those experiments suggest that a small protein, rubber elongation factor, interacts directly with farnesyl diphosphate during rubber biosynthesis. These results indicate that this benzophenone-based isoprenoid analogue will be useful for identifying enzymes that utilize farnesyl diphosphate as a substrate. 相似文献
58.
Hsieh S Miller BJ Södergren AH Kjaergaard HG 《The journal of physical chemistry. A》2007,111(25):5415-5421
We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings. 相似文献
59.
60.
In this study, a sample stacking step coupled with microemulsion electrokinetic chromatography (MEEKC) was used to detect and analyze nine aromatic acids (benzoic acid (BA), isophthalic acid (IPA), terephthalic acid (TPA), p-toluic acid (p-TA), 4-carboxylbenzaldehyde (4-CBA), trimesic acid (TSA), trimellitic acid (TMA), o-phthalic acid (OPA), and hemimellitic acid (HMA)) which are common impurities produced during aromatic acid synthesis. First, the presence of both acid and water plugs at the front of the capillary improved the reproducibility in retention time and peak intensity of the tested analytes in the stacking method. Second, the pH and the electrolyte type of acidic plug and sample matrix were found to be the predominant influences on the aromatic acid stacking. The detection limits of these aromatic acids were reduced to the range of 0.00007-0.00032 μg mL−1 by this optimal sample stacking step. This proposed on-line concentration MEEKC method was able to detect trace levels of aromatic acid impurities in commercial aromatic acid products that were not previously possible by the normal MEEKC method. Furthermore, these results in comparison with our previous studies on sample stacking MEEKC method indicated that all acidic species were concentrated by this simple stacking procedure. The sensitivity enhancement, however, was highly dependent on the types of functional groups present in the structures of analytes, and the enhancement was in the order of first the compounds carrying both carboxy and hydroxy groups (e.g. phenolic acid), followed by carboxylic acid compounds (e.g. aromatic acid), and then phenol compounds (e.g. polyphenol). 相似文献