全文获取类型
收费全文 | 1094篇 |
免费 | 38篇 |
国内免费 | 19篇 |
专业分类
化学 | 630篇 |
晶体学 | 7篇 |
力学 | 18篇 |
数学 | 356篇 |
物理学 | 140篇 |
出版年
2023年 | 10篇 |
2022年 | 38篇 |
2021年 | 48篇 |
2020年 | 52篇 |
2019年 | 49篇 |
2018年 | 54篇 |
2017年 | 51篇 |
2016年 | 58篇 |
2015年 | 40篇 |
2014年 | 45篇 |
2013年 | 87篇 |
2012年 | 67篇 |
2011年 | 66篇 |
2010年 | 58篇 |
2009年 | 36篇 |
2008年 | 61篇 |
2007年 | 42篇 |
2006年 | 34篇 |
2005年 | 36篇 |
2004年 | 19篇 |
2003年 | 14篇 |
2002年 | 16篇 |
2001年 | 10篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 4篇 |
1996年 | 10篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 5篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 4篇 |
1982年 | 9篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1976年 | 5篇 |
1975年 | 7篇 |
1973年 | 5篇 |
排序方式: 共有1151条查询结果,搜索用时 15 毫秒
41.
α-n-amylcinnamaldehyde (jasminaldehyde) was obtained with 82 % yield by solid-liquid phase transfer catalysis without solvent within 3 days at room temperature. By use of domestic microwave irradiation, the same yield was obtained within 1 minute at a power of 600 W. 相似文献
42.
Weawkamol Leelapornpisit Minh‐Tan Ton‐That Florence Perrin‐Sarazin Kenneth C. Cole Johanne Denault Benoit Simard 《Journal of Polymer Science.Polymer Physics》2005,43(18):2445-2453
The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005 相似文献
43.
Emil Byström Anna Nordborg Fredrik Limé Ngoc Phuoc Dinh Knut Irgum 《Journal of separation science》2010,33(11):1563-1570
A combined surface activation and “grafting to” strategy was developed to convert divinylbenzene particles into weak cation exchangers suitable for protein separation. The initial activation step was based on plasma modification with bromoform, which rendered the particles amenable to further reaction with nucleophiles by introducing Br to a surface content of 11.2 atom‐%, as determined by X‐ray photoelectron spectroscopy. Grafting of thiol‐terminated glydicyl methacrylate telomers to freshly plasma activated surfaces was accomplished without the use of added initiator, and the grafting was verified both by reduction in bromine content and the appearance of sulfur‐carbon linkages, showing that the surface grafts were covalently bonded. Following grafting the attached glydicyl methacrylate telomer tentacles were further modified by a two‐step procedure involving hydrolysis to 2,3‐hydroxypropyl groups and conversion of hydroxyl groups to carboxylate functionality by succinic anhydride. The final material was capable of baseline separating four model proteins in 3 min by gradient cation exchange chromatography in a fully aqueous eluent. 相似文献
44.
Ngoc Ha Nguyen Thanh Hue Tran Minh Tho Nguyen Minh Cam Le 《International journal of quantum chemistry》2010,110(14):2653-2670
The density functional theory using a plane‐waves basis set and pseudopotential has been used to study the reaction pathways for ODH of propane on the V2O5(001) surface. The calculations indicated that propane adsoprtion step was initiated by the insertion of vanadyl oxygen O (1) into methylene C? H bond forming an iso‐propanol structure. This step is the rate‐determining step with an activation energy of 23.3 kcal/mol. The subsequent step involved the abstraction of the second hydrogen by O (1) site leading the formation of propene. This process had an activation energy of 22.5 kcal/mol. The elimination of surface bound water molecule at the O (1) was a barrierless process. The energy required for this process was compensated from O2 dissociative adsorption. Finally, the electronic density of state has been applied to prove the reality of the calculated results. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
45.
46.
Christine Bressy Minh Ngoc NGuyen Brigitte Tanguy Van Giang Ngo André Margaillan 《Polymer Degradation and Stability》2010,95(7):1260-9117
Polymers containing hydrolytically labile trialkylsilyl ester side groups were synthesised via a conventional and a controlled radical polymerization. The trialkylsilyl methacrylate monomer unit was chosen for its capacity to hydrolyse into basic, acid or sea water varying the hydrophilic character of the resulting polymer backbone with time. The hydrolysis or saponification reaction of the ester bond of the trialkylsilyl methacrylate was monitored through a 1H NMR study showing the formation of siloxane side-products. Several copolymers and polymer blends were prepared as matrixes for controlled erodible systems. Their capacity to hydrolyse was demonstrated through SEM investigations with selective dissolution of free films containing hydrolysable copolymers and PMMA blends. Well-defined random and diblock copolymers with methyl methacrylate were investigated to show the effect of the microstructure on the erosion properties of the corresponding coatings. Poly(methyl methacrylate-b-tert-butyldimethylsilyl methacrylate) diblock copolymers synthesised through the RAFT process showed a better control of the erosion with a constant erosion rate over a long-time service in sea water at pH = 8.2. In addition, experiments showed that the erosion rate could be modulated by varying the molar proportion of hydrolysable side groups onto the copolymer backbone and the weight amount of copolymers mixed with PMMA in toluene solution. 相似文献
47.
Muriel De Bock Marie-Alice Meuwis Tran Quang Minh Jean-Paul Chapelle Michel Malaise Marianne Fillet 《Talanta》2010,82(1):245-594
In most diseases, the clinical need for serum/plasma markers has never been so crucial, not only for diagnosis, but also for the selection of the most efficient therapies, as well as exclusion of ineffective or toxic treatment. Due to the high sample complexity, prefractionation is essential for exploring the deep proteome and finding specific markers.In this study, three different sample preparation methods (i.e., highly abundant protein precipitation, restricted access materials (RAM) combined with IMAC chromatography and peptide ligand affinity beads) were investigated in order to select the best fractionation step for further differential proteomic experiments focusing on the LMW proteome (MW inferior to 40,000 Da). Indeed, the aim was not to cover the entire plasma/serum proteome, but to enrich potentially interesting tissue leakage proteins. These three methods were evaluated on their reproducibility, on the SELDI-TOF-MS peptide/protein peaks generated after fractionation and on the information supplied.The studied methods appeared to give complementary information and presented good reproducibility (below 20%). Peptide ligand affinity beads were found to provide efficient depletion of HMW proteins and peak enrichment in protein/peptide profiles. 相似文献
48.
Extraction and isolation of catechins from tea 总被引:1,自引:0,他引:1
Tea is a major source of catechins, which have become well known for their antioxidant potential. Numerous human, animal, and in vitro studies have linked tea catechins with prevention of certain types of cancers, reduction of the risks for obesity, diabetes, and cardiovascular disease, and improvement of the immune system. Tea catechins are widely used in various neutraceuticals, pharmaceuticals, and cosmetics for either enhancing product shelf-life or for enhancing human health. Thus, the demand for catechins has increased considerably. Catechins have been extracted and isolated from tea leaves by numerous methods through several steps including: treatment of the tea leaves, extraction of catechins from teas into solvents, isolation of catechins from other extracted components, and drying the preparations to obtain catechin extracts in a powder form. This paper outlines the physical and chemical properties of the tea catechins and reviews the extraction steps of the various extraction methods, as a basis to improve and further develop the extraction and isolation of the tea catechins. 相似文献
49.
Myriam E. Rodriguez Ping Zhang Kashif Azizuddin Grace B. Delos Santos Song-mao Chiu Liang-yan Xue Jeffery C. Berlin Xinzhan Peng Hongqiao Wu Minh Lam Anna-Liisa Nieminen Malcolm E. Kenney Nancy L. Oleinick 《Photochemistry and photobiology》2009,85(5):1189-1200
The phthalocyanine photosensitizer Pc 4 has been shown to bind preferentially to mitochondrial and endoplasmic reticulum membranes. Upon photoirradiation of Pc 4-loaded cells, membrane components, especially Bcl-2, are photodamaged and apoptosis, as indicated by activation of caspase-3 and cleavage of poly(ADP-ribose) polymerase, is triggered. A series of analogs of Pc 4 were synthesized, and the results demonstrate that Pcs with the aminopropylsiloxy ligand of Pc 4 or a similar one on one side of the Pc ring and a second large axial ligand on the other side of the ring have unexpected properties, including enhanced cell uptake, greater monomerization resulting in greater intracellular fluorescence and three-fold higher affinity constants for liposomes. The hydroxyl-bearing axial ligands tend to reduce aggregation of the Pc and direct it to lysosomes, resulting in four to six times more killing of cells, as defined by loss of clonogenicity, than with Pc 4. Whereas Pc 4-PDT photodamages Bcl-2 and Bcl-xL, Pc 181-PDT causes much less photodamage to Bcl-2 over the same dose–response range relative to cell killing, with earlier cleavage of Bid and slower caspase-3-dependent apoptosis. Therefore, within this series of photosensitizers, these hydroxyl-bearing axial ligands are less aggregated than is Pc 4, tend to localize to lysosomes and are more effective in overall cell killing than is Pc 4, but induce apoptosis more slowly and by a modified pathway. 相似文献
50.
The gas-surface reaction dynamics of NO impinging on an iron(II) phthalocyanine (FePc) monolayer were investigated using King and Wells sticking measurements. The initial sticking probability was measured as a function of both incident molecular beam energy (0.09-0.4 eV) and surface temperature (100-300 K). NO adsorption onto FePc saturates at 3% of a monolayer for all incident beam energies and surface temperatures, suggesting that the final chemisorption site is confined to the Fe metal centers. At low surface temperature and low incident beam energy, the initial sticking probability is 40% and decreases linearly with increasing beam energy and surface temperature. The results are consistent with the NO molecule sticking onto the FePc molecules via physisorption to the aromatics followed by diffusion to the Fe metal center, or precursor-mediated chemisorption. The adsorption mechanism of NO onto FePc was confirmed by control studies of NO sticking onto metal-free H2Pc, inert Au111, and reactive Al111. 相似文献