全文获取类型
收费全文 | 3464篇 |
免费 | 499篇 |
国内免费 | 360篇 |
专业分类
化学 | 1601篇 |
晶体学 | 54篇 |
力学 | 222篇 |
综合类 | 41篇 |
数学 | 470篇 |
物理学 | 1935篇 |
出版年
2024年 | 15篇 |
2023年 | 44篇 |
2022年 | 145篇 |
2021年 | 116篇 |
2020年 | 119篇 |
2019年 | 104篇 |
2018年 | 98篇 |
2017年 | 118篇 |
2016年 | 141篇 |
2015年 | 122篇 |
2014年 | 183篇 |
2013年 | 265篇 |
2012年 | 192篇 |
2011年 | 237篇 |
2010年 | 189篇 |
2009年 | 194篇 |
2008年 | 226篇 |
2007年 | 257篇 |
2006年 | 145篇 |
2005年 | 153篇 |
2004年 | 134篇 |
2003年 | 145篇 |
2002年 | 140篇 |
2001年 | 111篇 |
2000年 | 103篇 |
1999年 | 77篇 |
1998年 | 89篇 |
1997年 | 70篇 |
1996年 | 66篇 |
1995年 | 53篇 |
1994年 | 51篇 |
1993年 | 44篇 |
1992年 | 34篇 |
1991年 | 21篇 |
1990年 | 24篇 |
1989年 | 21篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 10篇 |
1985年 | 8篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 6篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1969年 | 1篇 |
排序方式: 共有4323条查询结果,搜索用时 15 毫秒
51.
A.A. FilaretovM.G. Zhizhin L.N. KomissarovaV.P. Danilov V.V. ChernyshevB.I. Lazoryak 《Journal of solid state chemistry》2002,166(2):362-368
A new ammonium indium phosphate (NH4)In(OH)PO4 was prepared by hydrothermal reaction in the In2O3-NH4H2PO4-NH3/OH system (T=200°C, autogenous pressure, 7 days). The formula (NH4)In(OH)PO4 was determined on the basis of chemical and thermal analysis (TG/DSC), X-ray powder diffraction and IR-spectroscopy. (NH4)In(OH)PO4 crystallizes in the tetragonal system with space group P43212 (No. 96); a=9.4232(1) Å, c=11.1766(1) Å, V=992.45(2) Å3; Z=8. The crystal structure was refined by the Rietveld method (Rw=6.35%, Rp=5.10%). The second-harmonic generation study confirmed that structure of (NH4)In(OH)PO4 does not have a center of symmetry. The cis-InO4(OH)2 octahedra form helical chains, parallel to the c-axis. The In-O-In bonds are nearly equidistant. The chains are interconnected by phosphate tetrahedra and create tunnels containing the NH4+ ions along the c-axis. (NH4)In(OH)PO4 is isostructural with RbIn(OH)PO4. 相似文献
52.
Sample evaporation in splitless injection of large volumes is rapid: depending on the experiment, results indicate that 200 μl of hexane, for instance, evaporates in 2–10 s, producing vapor at a rate of many hundreds of milliliters per minute. A 60 × 4 mm packed bed of 20–35 mesh Tenax TA enabled injection of 200 μl volumes of all solvents tested, and even 1 ml injections were possible provided they were performed over a period of 30 s. Retention of volatile sample components depends on the sample solvent, the injection volume, and the injection speed, but only little on the injector temperature. Losses of n-tridecane varied from hardly 15 % (when dissolved in pentane) to ca 60 % (ethyl acetate); losses of n-heptadecane were usually below 20 %. The column temperature during injection should be at least ca 20–30°C above the standard solvent boiling point. 相似文献
53.
Ródenas-Torralba E Cava-Montesinos P Morales-Rubio A Cervera ML De La Guardia M 《Analytical and bioanalytical chemistry》2004,379(1):83-89
The aim of this study is to show the advantages of the emerging multicommutation methodology based on the use of solenoid valves for Te determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS). The delivery of a series of alternating sequential insertions of small volumes of samples and reagents gives rise to new hydrodynamic processes and exciting analytical potentials by controlling the time of flow through the on/off-switched solenoid valves. This drastically reduces the reagent consumption by a factor of 4 and the generation of effluents (590 mL h–1 instead of 750 mL h–1 generated by the continuous-mode measurement) and also provides an improvement in the laboratory productivity by an increase of the sample throughput (85 h–1 compared to 20 h–1 found in the continuous mode). So, multicommutation is an environmentally and economically sustainable alternative to the methodology based on continuous measurements. The multicommutation-based method developed was applied to tellurium determination in commercially available milk samples; a calibration range of 0.0–0.5 ng mL–1 and a detection limit of 0.20 ng L–1 with average relative standard deviation of 2.1% were found. Comparable results were obtained for a series of samples using both continuous and multicommutation HG-AFS modes. 相似文献
54.
Vapor pressure data were measured for water, methanol and ethanol as well as their binary mixtures with an ionic liquid (IL) 1-ethyl-3-methylimidazolium dimethylphosphate ([EMIM][DMP]) at varying temperature and IL-content ranging from mass fraction of 0.10–0.70 by a quasi-static method. The vapor pressure data for the IL-containing binary systems were correlated using NRTL equation with average absolute relative deviation (ARD) within 0.0076, and the binary NRTL parameters was used for predicting the vapor pressure of the IL-containing ternary systems with reasonable accuracy. In addition, the infinite activity coefficients of solvents in [EMIM][DMP] and isobaric vapor–liquid equilibrium for IL-containing ternary systems at 101.325 kPa and mass fraction of IL being 0.5 were predicted with the regressed NRTL parameters. The results indicate that ionic liquid [EMIM][DMP] can depress the volatility of the solvents of water, methanol and ethanol but to a varying degree, leading to the variation of relative volatility of a solvent and even removal of azeotrope for water–ethanol mixture. 相似文献
55.
This paper describes some thermal analysis experiments conducted on high explosive samples. These employ differential scanning calorimetry to monitor thermal effects at elevated temperatures (around 200 °C) and heat conduction calorimetry to record thermal effects at much lower temperatures (below 100 °C).The work shows that, due to the generally high thermal stability of many high explosive compositions, heat generation rates are very low, if detectable at all, at normal storage temperatures, even when using a very sensitive instrument. The sensitivity and reproducibility of this technique has been investigated in detail by Wilker et al. [S. Wilker, U. Ticmanis, G. Pantel, Detailed investigation of sensitivity and reproducibility of heat flow calorimetry, in: Proceedings of the 11th Symposium on Chemical Problems Connected with the Stability of Explosives, Sweden, 1998] and shown to be capable of recording heat generation rates of less than a microwatt. This allows continuous measurement of decomposition processes in nitrate ester based propellants at temperatures as low as 40 °C. However, the measurement of very low levels of heat generation is difficult, time consuming and therefore expensive. If the assumption is made that the life limiting process is invariably the slow decomposition of the energetic component, this will frequently lead to very long service lifetime predictions.A number of possible complications are identified. Firstly, due to its low detection threshold, a heat conduction calorimeter may detect other reactions which will not lead to failure, but which may still dominate the heat flow signal. Secondly, the true failure process may generate little energy and be overlooked. In view of these considerations, at present it seems unwise to rely on heat conduction microcalorimetry as the only tool for the assessment of the life of high explosive energetic systems.Based on examples of life terminating processes in high explosives during storage and use, it is clear that decomposition of the energetic material is not invariably the cause of system failure. It is also by no means the only reaction that may take place in, and be observed by, a heat conduction calorimeter. 相似文献
56.
The two independent elements of the second-order nonlinear optical susceptibility tensor of a range of contact poled, donor–acceptor substitued side-chain polymers are reported. The susceptibilities were measured by second harmonic generation from thin films, typically less than 0.5 μm thick, at a fundamental wavelength of 1064 nm. The largest value was χ = 2.64 pm/V which is three times greater than the χ value of KDP and was measured in a nitrobenzylidene side chain, polyhydroxystyrene polymer with an eleven unit alkyl chain spacer attaching the side group to the backbone. Typical susceptibility values obtained were χ~0.3 pm/V and X(2)33~1 pm/V. The coherence lengths of the materials, which lay in the range 4–12 μm, were measured at 1064 nm by the maker fringe technique using thick, wedge-shaped samples. 相似文献
57.
本文使用涂金石墨管,自制氢化物石墨炉进样系统及连续流动氢化物发生器,直接测定了粮食,植物及水中的痕量汞。该法实用性强,线性范围宽,精密度好,准确度高。灵敏度为1.1ng/L,检出限(3σ)为0.8ng/L。 相似文献
58.
《Electroanalysis》2004,16(16):1305-1310
A novel amperometric biosensor was constructed for the determination of phenols in pure organic phase. This biosensor was fabricated by immobilizing tyrosinase in a titania sol‐gel membrane which was obtained with a vapor deposition method. This method was facile and avoided the calcination step needed in conventional titania sol‐gel process. The titania sol‐gel membrane could effectively retain the essential water layer around the enzyme molecule needed for maintaining its activity in organic phase. The experimental parameters such as solvent and operating potential were optimized. At ?100 mV this biosensor showed a good amperometric response to phenols in pure chloroform without any mediator and rehydration of the enzyme. For catechol determination the sensor exhibited a fast response of less than 5 seconds. The sensitivity of different phenols was as follows: catechol > phenol > p‐cresol. Additionally, the apparent Michaelis‐Menten constants of the encapsulated tyrosinase to catechol, phenol and p‐cresol were found to be 0.15±0.003, 0.17±0.008 and 0.21±0.004 mM, respectively. The biosensor had also good reproducibility and stability. This work provided a promising platform for the construction of pure organic phase biosensors and the determination of substrates with poor water solubility. 相似文献
59.
Summary A genetic algorithm has been designed which generates molecular structures within constraints. The constraints may be any useful function, for example an enzyme active site, a pharmacophore or molecular properties from pattern recognition or rule-induction analyses. The starting point may be random or may utilise known molecules. These are modified to grow into families of structures which, using the evolutionary operators of selection, crossover and mutation evolve to better fit the constraints. The basis of the algorithm is described together with some applications in lead generation, 3D database construction and drug design. Genetic algorithms of this type may have wider applications in chemistry, for example in the design and optimisation of new polymers, materials (e.g. superconducting materials) or synthetic enzymes. 相似文献
60.
El Houssaine Aghezzaf Thomas L. Magnanti Laurence A. Wolsey 《Mathematical Programming》1995,71(2):113-126
Given a treeG = (V, E) and a weight function defined on subsets of its nodes, we consider two associated problems. The first, called the rooted subtree problem, is to find a maximum weight subtree, with a specified root, from a given set of subtrees.The second problem, called the subtree packing problem, is to find a maximum weight packing of node disjoint subtrees chosen from a given set of subtrees, where the value of each subtree may depend on its root.We show that the complexity status of both problems is related, and that the subtree packing problem is polynomial if and only if each rooted subtree problem is polynomial. In addition we show that the convex hulls of the feasible solutions to both problems are related: the convex hull of solutions to the packing problem is given by pasting together the convex hulls of the rooted subtree problems.We examine in detail the case where the set of feasible subtrees rooted at nodei consists of all subtrees with at mostk nodes. For this case we derive valid inequalities, and specify the convex hull whenk 4.Research supported in part by Nato Collaborative Research Grant CRG 900281, Science Program SC1-CT91-620 of the EEC, and contract No 26 of the programme Pôle d'attraction interuniversitaire of the Belgian government. 相似文献