全文获取类型
收费全文 | 973篇 |
免费 | 36篇 |
国内免费 | 17篇 |
专业分类
化学 | 770篇 |
晶体学 | 20篇 |
力学 | 26篇 |
数学 | 36篇 |
物理学 | 174篇 |
出版年
2024年 | 6篇 |
2023年 | 9篇 |
2022年 | 61篇 |
2021年 | 103篇 |
2020年 | 37篇 |
2019年 | 39篇 |
2018年 | 58篇 |
2017年 | 33篇 |
2016年 | 61篇 |
2015年 | 49篇 |
2014年 | 57篇 |
2013年 | 65篇 |
2012年 | 102篇 |
2011年 | 98篇 |
2010年 | 60篇 |
2009年 | 35篇 |
2008年 | 24篇 |
2007年 | 22篇 |
2006年 | 17篇 |
2005年 | 17篇 |
2004年 | 8篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 1篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1977年 | 1篇 |
1975年 | 2篇 |
1936年 | 1篇 |
1935年 | 1篇 |
1933年 | 1篇 |
排序方式: 共有1026条查询结果,搜索用时 15 毫秒
101.
The hydrolytic effect of moisture and hygrothermal aging on poly(butylene succinate)/organo-montmorillonite nanocomposites 总被引:1,自引:0,他引:1
The study of hydrolysis on biodegradable poly(butylene succinate) (PBS) is essential to predict the materials properties in a humid environment. In this study, PBS nanocomposites were exposed to different conditions of relative humidity (RH) and temperature. The moisture uptake increased with organo-montmorillonite (OMMT) loading and the RH of the testing environment. The exposure of PBS and the nanocomposites to a humid environment caused changes in the mechanical properties. The hydrolytic degradation becomes more pronounced upon hygrothermal aging at high temperature, whereby premature failure occurred. PBS nanocomposites were found to exhibit a better hydrolytic stability than neat PBS. The degradation was evaluated through Fourier transform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC). A drastic reduction in the molecular weight of PBS has revealed the occurrence of degradation after exposure to moisture and heat. This has led to an alteration of the thermal behavior as investigated using differential scanning calorimetry (DSC). 相似文献
102.
Cheong KW Leow TC Rahman RN Basri M Rahman MB Salleh AB;Enzyme Microbial Technology Research Group 《Applied biochemistry and biotechnology》2011,164(3):362-375
A thermostable lipase from Geobacillus zalihae strain T1 was chemically modified using propionaldehyde via reductive alkylation. The targeted alkylation sites were lysines,
in which T1 lipase possessed 11 residues. Far-UV circular dichroism (CD) spectra of both native and alkylated enzyme showed
a similar broad minimum between 208 and 222 nm, thus suggesting a substantial amount of secondary structures in modified enzyme,
as compared with the corresponding native enzyme. The hydrolytic activity of the modified enzymes dropped drastically by nearly
15-fold upon chemical modification, despite both the native and modified form showed distinctive α-helical bands at 208 and
222 nm in CD spectra, leading us to the hypothesis of formation of a molten globule (MG)-like structure. As cooperative unfolding
transitions were observed, the modified lipase was distinguished from the native state, in which the former possessed a denaturation
temperature (T
m) in lower temperature range at 61 °C while the latter at 68 °C. This was further supported by 8-anilino-1-naphthalenesulfonic
acid (ANS) probed fluorescence which indicated higher exposure of hydrophobic residues, consequential of chemical modification.
Based on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis, a small number
of lysine residues were confirmed to be alkylated. 相似文献
103.
Noor-ul Hasan Khan Mohd. Bismillah AnsariEko Adi Prasetyanto Hailian JinSang-Eon Park 《Tetrahedron: Asymmetry》2011,22(1):117-123
(1S,2S)-N1,N2-Bis(3-chlorobenzyl)cyclohexane-1,2-diamine 1a′ and (1S,2S)-N1,N2-bis(4-chlorobenzyl)cyclohexane-1,2-diamine 1b′ were used to prepare chiral Cu(II) complexes Cu-Y-1a, Cu-Y-1b, Cu-mZSM5-1a, and Cu-mZSM5-1b by a flexible ligand method using copper exchanged zeolite Y and mesoporous ZSM-5. The characterization of zeolite supported complexes was performed by microanalysis, IR-, diffuse reflectance spectroscopy (DRS), EPR spectroscopy, specific rotation and thermogravimetric analysis (TGA). The catalytic activity of these supported complexes was explored for the asymmetric nitroaldol reaction of various aldehydes with nitromethane at 0 °C. Excellent yields (up to 99%) of β-hydroxy nitroalkane with an ee of up to 94% were achieved in the case of benzaldehyde as substrate. Significantly, the performance of the supported catalyst was better in terms of enantioselectivity than the complex under homogenous conditions. The supported catalysts were recycled four times with no observable loss in performance and no leaching of the catalytically active complex during the nitroaldol reaction. 相似文献
104.
Arjmand F Sayeed F Muddassir M 《Journal of photochemistry and photobiology. B, Biology》2011,103(2):166-179
New Schiff base ligand L derived from the condensation reaction of 2-amino-3-formylchromone with (R)-2-amino-2-phenylethanol was synthesized and characterized which involves combination element of ammine functionality and naturally occurring heterocyclic chromone, 4H-benzopyran-4-one. Subsequently, their complexes 1 and 2 with Cu(NO?)? and Zn(NO?)?, respectively were prepared. The DNA binding studies of the ligand L and complexes 1 and 2 with CT-DNA as compared to classical anticancer drug cisplatin were carried out by employing different optical methods viz, UV-vis, fluorescence, circular dichroism and viscosity measurements. Furthermore, the absorption studies, 1H and 31P with mononucleotides were also monitored to examine the base specific interactions of the transition metal complexes which revealed a higher propensity of copper(II) complex 1 for 5'-GMP while for zinc(II) complex 2 towards 5'-TMP involving groove binding mechanism of the complexes towards DNA. The complex 1 exhibits a remarkable DNA cleavage activity with pBR322 DNA in presence of different activators and cleavage reaction involves various oxygen species suggesting the involvement of active oxygen species for the DNA scission. 相似文献
105.
Yahayu MA Rahmani M Hashim NM Amin MA Ee GC Sukari MA Akim A 《Molecules (Basel, Switzerland)》2011,16(6):4401-4407
Extraction and chromatographic separation of the extracts of dried stem barks of Glycosmis macrantha lead to isolation of two new acridone alkaloids, macranthanine and 7-hydroxynoracronycine, and a known acridone, atalaphyllidine. The structures of these alkaloids were determined by detailed spectral analysis and also by comparison with reported data. 相似文献
106.
Hammond C Lopez-Sanchez JA Ab Rahim MH Dimitratos N Jenkins RL Carley AF He Q Kiely CJ Knight DW Hutchings GJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(15):3927-3937
The reaction of glycerol with urea to form glycerol carbonate is mostly reported in the patent literature and to date there have been very few fundamental studies of the reaction mechanism. Furthermore, most previous studies have involved homogeneous catalysts whereas the identification of heterogeneous catalysts for this reaction would be highly beneficial. This is a very attractive reaction that utilises two inexpensive and readily available raw materials in a chemical cycle that overall, results in the chemical fixation of CO(2). This reaction also provides a route to up-grade waste glycerol produced in large quantities during the production of biodiesel. Previous reports are largely based on the utilisation of high concentrations of metal sulfates or oxides, which suffer from low intrinsic activity and selectivity. We have identified heterogeneous catalysts based on gallium, zinc, and gold supported on a range of oxides and the zeolite ZSM-5, which facilitate this reaction. The addition of each component to ZSM-5 leads to an increase in the reaction yield towards glycerol carbonate, but supported gold catalysts display the highest activity. For gold-based catalysts, MgO is the support of choice. Catalysts have been characterised by XRD, TEM, STEM and XPS, and the reaction has been studied with time-on-line analysis of products via a combination of FT-IR spectroscopy, HPLC, (13)C NMR and GC-MS analysis to evaluate the reaction pathway. Our proposed mechanism suggests that glycerol carbonate forms via the cyclization of a 2,3-dihydroxypropyl carbamate and that a subsequent reaction of glycerol carbonate with urea yields the carbamate of glycerol carbonate. Stability and reactivity studies indicate that consecutive reactions of glycerol carbonate can limit the selectivity achieved and reaction conditions can be selected to avoid this. The effect of the catalyst in the proposed mechanism is discussed. 相似文献
107.
Lactic acid produced by fermentation process mostly contains a number of aliphatic carboxylic acids as impurities. In this work, carboxylic acid impurities in lactic acid samples from a number of sources were determined at ppm levels. A simple HPLC method was developed that utilized a new generation polar embedded reverse phase, 20mM phosphate buffer at pH 2.20 (±0.05) and UV detection at 210 nm. The method enabled quantitative analysis of the above acids in lactic acid matrix. The experimental conditions for column temperature, mobile phase pH and flow rate were optimized. A detailed validation of the method was performed for linearity, precision, accuracy, selectivity, limit of detection (LOD), limit of quantitation (LOQ), ruggedness and repeatability and reproducibility (R&R). 相似文献
108.
Mohd. Imran Ansari Ravi Shankar Mohd. Kamil Hussain Ruchir Kant Prakash R. Maulik K. Ravi Kumar K. Hajela 《Journal of heterocyclic chemistry》2011,48(6):1336-1341
Mono‐ and bis‐diaryl‐2H‐1,4‐benzothiazines were obtained in quantitative yields through silica‐supported perchloric acid catalyzed reaction cascade of double condensation and 1,4 addition of diaroylacetylenes with 2‐aminothiophenol at room temperature. The structures were confirmed by spectroscopic analyses and X‐ray crystallographic studies. J. Heterocyclic Chem., (2011) 相似文献
109.
Bicyclams inhibit HIV replication by binding to the CXCR4 chemokine receptor, which is the main coreceptor for gp120 used by X4, T‐tropic strains of HIV for membrane fusion and cell entry. Bicyclam AMD3100 mainly interacts with the aspartic acid residues namely Asp171 and Asp262, which are located at the extracellular ends in the CXCR4 coreceptor. Incorporation of some metal ions by the macrocyclic rings of bicyclam enhances its binding affinity to the CXCR4 receptor and enhances their anti‐HIV activity because the acetate can make a strong coordination bond to the metal and one weaker hydrogen bond to nitrogen in the cyclam ring. The interaction energy (Eint) between 150 metal–bicyclam complexes and aspartic acid has been evaluated. The metal–bicyclam complexes are obtained by the incorporation of six metal ions namely Fe3+, Co3+, Ni2+, Cu2+, Zn2+, and Pd2+ in 25 well‐known bicyclams including AMD3100. In most of the cases, Fe and Co–bicyclam complexes interact best with aspartic acid. The anti‐HIV activity of metal–bicyclam complexes can be predicted on the basis of interaction energy before the synthesis of the metal–bicyclam complex. On the basis of interaction energy, the anti‐HIV activity of bicyclam complexes can be predicted in advance to their synthesis. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
110.
Saleh MI Kusrini E Mohd Sarjidan MA Abd Majid WH 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(1):52-58
A mononuclear of [Eu(NO3)(Pic)(H2O)2(EO3)](Pic)·(0.73)H2O complex, where EO3=trietraethylene glycol and Pic=picrate anion, shows a red emission when used as an active layer in a single layer of ITO/EO3-Eu-Pic/Al configuration. The crystal structure of the complex consists of [Eu(NO3)(Pic)(H2O)2(EO3)]+ cation and [Pic]- anion. The Eu(III) ion is coordinated to the 10 oxygen atoms from one EO3 ligand, one Pic anion, one nitrate anion, and two water molecules. The complex is crystallized in triclinic with space group P-1. The hybrids in thin films I and II were prepared in the respective order solution concentrations of 15 and 20 mg/mL the emissive center. Comparing the photoluminescence (PL) and electroluminescence (EL) spectra, we can find that all emissions come from the characteristic transitions of the Eu(III) ion. The EL spectra of both thin films showed the occurrence of the most intense red-light emission around at 612 nm. Comparison of organic light-emitting device (OLED) current intensity characteristics as a function of voltage (I-V) show that the thin film I is better than those found for the thin film II. The thickness of the emitting layer is an important factor to control the current-voltage curve. The sharp and intense emission of the complex at low voltage indicates that the complex is a suitable and promising candidate for red-emitting materials. 相似文献