全文获取类型
收费全文 | 421篇 |
免费 | 53篇 |
国内免费 | 94篇 |
专业分类
化学 | 339篇 |
晶体学 | 19篇 |
力学 | 63篇 |
综合类 | 4篇 |
数学 | 44篇 |
物理学 | 99篇 |
出版年
2024年 | 1篇 |
2023年 | 10篇 |
2022年 | 12篇 |
2021年 | 12篇 |
2020年 | 18篇 |
2019年 | 17篇 |
2018年 | 19篇 |
2017年 | 35篇 |
2016年 | 40篇 |
2015年 | 14篇 |
2014年 | 31篇 |
2013年 | 46篇 |
2012年 | 34篇 |
2011年 | 30篇 |
2010年 | 27篇 |
2009年 | 15篇 |
2008年 | 21篇 |
2007年 | 25篇 |
2006年 | 27篇 |
2005年 | 30篇 |
2004年 | 7篇 |
2003年 | 12篇 |
2002年 | 4篇 |
2001年 | 13篇 |
2000年 | 12篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 10篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有568条查询结果,搜索用时 15 毫秒
1.
Azobenzene‐Functionalized Cage Silsesquioxanes as Inorganic–Organic Hybrid,Photoresponsive, Nanoscale,Building Blocks
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Hongzhi Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4731-4738
Mono‐ and octa‐azobenzene‐functionalized cage silsesquioxanes were easily synthesized by the reaction of 4‐bromoazobenzene with monovinyl‐substituted octasilsesquioxane and cubic octavinylsilsesquioxane through the Heck coupling reaction. Excited‐state energies obtained from time‐dependent density functional theory (TDDFT) and the CAM‐B3LYP functional correlate very well with experimental trans–cis photoisomerization results from UV/Vis spectroscopy. These azobenzene‐functionalized cages exhibit good thermal stability and are fluorescent with maximum emission at approximately 400 nm, making them potential materials for blue‐light emission. 相似文献
2.
Xiaoqing Liu Chuncheng Li Dong Zhang Yaonan Xiao 《Journal of Polymer Science.Polymer Physics》2006,44(6):900-913
This article investigated the melting behaviors, crystallization kinetics, and spherulitic morphologies of poly(butylene succinate) (PBS) and its copolyester (PBSR) modified with rosin maleopimaric acid anhydride, using wide‐angle X‐ray diffraction, differential scanning calorimeter (DSC), and polarized optical microscope. Subsequent DSC scans of isothermally crystallized PBS and PBSR exhibited two melting endotherms, respectively, which was due to the melt‐recrystallization process occurring during the DSC scans. The equilibrium melting point of PBSR (125.9 °C) was lower than that of PBS (139 °C). The commonly used Avrami equation was used to describe the isothermal crystallization kinetics. For nonisothermal crystallization studies, the model combining Avrami equation and Ozawa equation was employed. The result showed a consistent trend in the crystallization process. The crystallization rate was decreased, the perfection of crystals was decreased, the recrystallization was reduced, and the spherulitic morphologies were changed when the huge hydrogenated phenanthrene ring was added into the chain of PBS. The activation energy (ΔE) for the isothermal crystallization process determined by Arrhenius method was 255.9 kJ/mol for PBS and 345.7 kJ/mol for PBSR. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 900–913, 2006 相似文献
3.
A simple and novel method was developed to successfully synthesize N-succinyl-O-carboxymethylchitosan (NSOCMCS) using N-acylation of chitosan with succinic anhydride. The NSOCMCS structure was characterized by Fourier transform infrared and
1H nuclear magnetic resonance. The aggregation behaviors of NSOCMCS were studied using fluorescence spectroscopy, dynamic light
scattering, and atomic force microscopy techniques. The critical aggregation concentration of NSOCMCS in water was determined
to be 0.2–0.3 mg/ml. The apparent hydrodynamic radium of an NSOCMCS aggregate was dependent on the concentration. The aggregates
demonstrated a much swollen association conformation in aqueous solution. The possible aggregation mechanisms for the NSOCMCS
in water are discussed. Moreover, a driving force to form an open aggregation morphology was revealed in this study. Aggregation
behaviors are important physicochemical properties of NSOCMCS, which impact the potential application in the biomedical field. 相似文献
4.
Grader G.S. Shter G.E. Avnir D. Frenkel H. Sclar D. Dolev A. 《Journal of Sol-Gel Science and Technology》2001,21(3):157-165
The effect of wetting non-hydrolytic derived alumina xerogels with water and organic solvents in the 20–70°C range on the alumina's properties was investigated. Wetting with organic solvents does not affect the alumina. However, contact with water was found to change the sharp crystallization at 800°C to a continuous crystallization starting at 450°C. Water treatment for a day at room temperature (RT) followed by second calcination decreased the surface area by 10%. This decrease in surface area is less pronounced with increasing wetting periods. On the other hand water treatment at 50–70°C followed by a second calcination resulted in a surface area increase of up to 15%. Upon water treatment the total pore volume has decreased from 0.65 (cm3/gr) to 0.48 (cm3/gr) and the average pore size decreased from 6.8 nm to 4.1 nm. The Cl content was found to be uneffected by the water treatment, remaining at 2.5% wt. Wetting with water at elevated temperature (70°C) accelerated the morphological changes, eliminating the crystallization peak at 800°C in one hour. A dissolution-reprecipitation mechanism is suggested to explain the results. In addition, Mass-Spectroscopy of the effluent gas during heat treatment revealed the emission of CO2 and water upon phase transition into -Al2O3, at 1150–1300°C. 相似文献
5.
Aspects of the mechanism of the overall reaction between CaCO3/CaO and SO2/SO3 under oxidizing conditions are discussed. The limestone and lime sulphation processes were carried out in a thermobalance
under conditions relevant to atmospheric fluidized bed combustion. Sulphated samples, prepared in the form of cross-section
particles, were examined in a scanning electron microscope by energy-dispersive X-ray and back-scattered electron imaging.
Photomicrographs are presented. The reaction proceeded from the outer surface of the particles and along the pores. Surface
textural changes during the reaction were considered. The layer of products was identified as controlling both the rate and
extent of limestone/lime sulphation. In the products, two sulphur-bearing solids (CaSO4 and CaS) were identified. The presence of CaS, which may cause difficulties in practice, is attributed to CaSO3 disproportionation.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
6.
Diglycidyl ether of 4,4′-dihydroxybiphenol (BPDGE) is a liquid crystalline epoxy. The biphenyl epoxy (diglycidyl ether of 3,3′,5,5′-tetramethyl-4,4′-biphenyl, TMBPDGE) has found great applications in plastic encapsulated semiconductor packaging. Phenol novolac (PN) was used as curing agent. The reaction kinetics of BPDGE/PN and TMBPDGE/PN systems in the presence of triphenylphosphine (TPP) were characterized by an isoconversional method under dynamic conditions using differential scanning calorimetry (DSC) measurements. The results showed that the curing of epoxy resins involves different reaction stages and the values of activation energy are dependent on the degree of conversion. The effects of curing temperature on their phase structure have been investigated with polarized optical microscopy and Wide-angle X-ray diffraction. With proper curing process, BPDGE showed a nematic phase when cured with PN. 相似文献
7.
Ni^2—交换蒙脱石中的镍物种及焙烧温度影响研究 总被引:2,自引:0,他引:2
对一组自制Ni^2+交换蒙脱石样品中镍物种的存在在形及焙烧温度影响进行了TPR和XRD考察结果表明,样品中镍负载量等于或小于Ni^2+的交换量时,镍主要以难还原听可交换性阳离子Ni(OH)^q+x和易还原的自由态镍Ni(OH)2或NiO两种形式存在。 相似文献
8.
《Electroanalysis》2004,16(12):1051-1058
The voltammetric behavior of α‐ketoglutarate (α‐KG) at the hanging mercury drop electrode (HMDE) has been investigated in acetate buffer solution. Under the optimum experimental conditions (pH 4.5, 0.2 M NaAc‐HAc buffer solution), a sensitive reductive wave of α‐KG was obtained by linear scan voltammetry (LSV) and the peak potential was ?1.18 V (vs. SCE), which was an irreversible adsorption wave. The kinetic parameters of the electrode process were α=0.3 and ks=0.72 1/s. There was a linear relationship between peak current ip, α‐KG and α‐KG concentration in the range of 2×10?6–8×10?4 M α‐KG. The detection limit was 8×10?7 M and the relative standard deviation was 2.0% (Cα‐KG=8×10?4 M, n=10). Applications of the reductive wave of α‐KG for practical analysis were addressed as follows: (1) It can be used for the quantitative analysis of α‐KG in biological samples and the results agree well with those obtained from the established ultraviolet spectrophotometric method. (2) Utilizing the complexing effect between α‐KG and aluminum, a linear relationship holds between the decrease of peak current of α‐KG Δip and the added Al concentration Cequation/tex2gif-inf-5.gif in the range of 5.0×10?6–2.5×10?4 M. The detection limit was 2.2×10?6 M and the relative standard deviation was 3.1% (Cequation/tex2gif-inf-6.gif=4×10?5 M, n=10). It was successfully applied to the detection of aluminum in water and synthetic biological samples with satisfactory results, which were consistent with those of ICP‐AES. (3) It was also applied to study the effect of AlIII on the glutamate dehydrogenase (GDH) activity in the catalytically reaction of α‐KG+NH +NADH?L ‐glutamate+NAD++H2O by differential pulse polarography (DPP) technique. By monitoring DPP reductive currents of NAD+ and α‐KG, an elementary important result was found that Al could greatly affect the activity of GDH. This study could be attributed to intrinsic understanding of the aluminum's toxicity in enzyme reaction processes. 相似文献
9.
The effect of calcining conditions on the rehydration of dead burnt magnesium oxide using magnesium acetate as a hydrating agent 总被引:1,自引:0,他引:1
C. A. Strydom E. M. van der Merwe M. E. Aphane 《Journal of Thermal Analysis and Calorimetry》2005,80(3):659-662
Summary Magnesium oxide was produced through calcination of magnesite ore. A rehydration percentage of MgO to Mg(OH)2 of higher than 60% is obtained using calcination temperatures of 1000°C and below. At these temperatures medium reactive MgO was formed. The extend to which dead burnt MgO (obtained after calcination at 1200°C and higher) may be rehydrated is dependent on the calcination time, but even after 1 h and using magnesium acetate as a hydrating agent only 40% of the initial product has rehydrated to Mg(OH)2. After 4 and more hours of calcinations at 1200°C, a maximum of approximately 14% of the initial MgO is rehydrated back to Mg(OH)2. Thermogravimetric analysis was performed on the various compounds to determine the amounts of Mg(OH)2 that formed. 相似文献
10.
Gong WT Li XC Ning GL Zhu L Wang L Lin Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):835-839
Two novel phenylated pyrylium compounds, silver (I)-bridged 2,3,4,5-tetraphenylpyrylium perchlorate (P1) and its silver (I)-free pyrylium ligand (P2) were prepared from 1,2,3,4-tetraphenylcyclopentadiene to examine their spectroscopic behaviors. The UV/vis absorption and fluorescent emission spectra of P1 and P2, measured in three solvents (acetonitrile, dichloromethane and toluene), reveal that the photophysical behaviors are closely related to silver (I) fragment, and strongly dependent on solvent polarity. In polar acetonitrile, P1 displays longer absorption wavelength and much lower fluorescent emission intensity than P2, although they exhibit much similarity in shape. In contrast, in nonpolar toluene, while P2 shows an apparent absorption band at 338 nm, P1 displays a tail-like line without absorption band observed. All the spectra obtained indicate a better coplanarity and a stronger intra-molecular charge transfer in P1 due to the effect of silver (I) fragment. Additionally, the 1H NMR spectra of P1 and P2, which were recorded under the same conditions, indicate that the silver (I) fragment reinforces pyrylium ring's capacity to localize the formal positive charge within the heterocyclic ring. 相似文献