全文获取类型
收费全文 | 781篇 |
免费 | 20篇 |
国内免费 | 2篇 |
专业分类
化学 | 700篇 |
晶体学 | 3篇 |
力学 | 7篇 |
数学 | 55篇 |
物理学 | 38篇 |
出版年
2023年 | 3篇 |
2022年 | 22篇 |
2021年 | 28篇 |
2020年 | 21篇 |
2019年 | 19篇 |
2018年 | 6篇 |
2017年 | 10篇 |
2016年 | 15篇 |
2015年 | 21篇 |
2014年 | 27篇 |
2013年 | 69篇 |
2012年 | 37篇 |
2011年 | 42篇 |
2010年 | 39篇 |
2009年 | 29篇 |
2008年 | 38篇 |
2007年 | 38篇 |
2006年 | 44篇 |
2005年 | 44篇 |
2004年 | 34篇 |
2003年 | 37篇 |
2002年 | 31篇 |
2001年 | 11篇 |
2000年 | 8篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 8篇 |
1996年 | 12篇 |
1995年 | 12篇 |
1994年 | 14篇 |
1993年 | 15篇 |
1992年 | 10篇 |
1991年 | 6篇 |
1989年 | 2篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有803条查询结果,搜索用时 15 毫秒
81.
Pitois A de las Heras LA Zampolli A Menichetti L Carlos R Lazzerini G Cionini L Salvatori PA Betti M 《Analytical and bioanalytical chemistry》2006,384(3):751-760
Boron neutron capture therapy (BNCT) is a bimodal radiotherapeutic treatment based on the irradiation of neoplastic tissues
with neutrons after the tissues have selectively accumulated molecules loaded with nuclides with large neutron capture cross-sections
(such boron-10). Boron-10 carriers have been tested to a limited extent, and clinical trials have been conducted on sulfhydryl
borane (10B-BSH) and boronophenylalanine (10B-BPA). However, precise and accurate measurements of boron-10 concentrations (0.1–100 μg/g) in specimens and samples of limited
size (μg scale) are needed in order to be able to biologically characterise new compounds in predictive tissue dosimetry,
toxicology and pharmacology studies as well as in clinical investigations. A new approach based on fast separation and detection
of 10B-BPA performed by coupling capillary electrophoresis to electrospray mass spectrometry is reported. This method allows the
quantitative analysis and characterisation of 10B-BPA in a short time with a high separation efficiency. Detection limits of 3 μM for 10B-BPA and 30 ng/mL for 10B were obtained with CE–ESI–MS. A quantification limit of 10 μM for 10B-BPA (100 ng/mL for 10B) was attained. The total boron-10 concentration was determined by high-resolution inductively coupled mass spectrometry
in order to validate the method. Boron-10 isotope measurements were carried out by HR–ICP–MS at medium resolution (R=4000)
due to the presence of an isobaric interference at mass 10. Good agreement was obtained between the values from CE–ESI–MS
and those from HR–ICP–MS. The method has been successfully used to determine the 10B-BPA in two lines of cultured cells. 相似文献
82.
Deganello G Giannici F Martorana A Pantaleo G Prestianni A Balerna A Liotta LF Longo A 《The journal of physical chemistry. B》2006,110(17):8731-8739
The catalyst Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is studied by CO-temperature programmed reduction (CO-TPR), isothermal oxygen storage complete capacity (OSCC), X-ray absorption spectroscopy (XAS) at the Pt L(III) edge, and in situ X-ray diffraction (in situ XRD), with the aim of elucidating the role of supported metal in CO oxidation by ceria-based three-way catalysts (TWC). The redox behavior of Pt(1 wt %)/Ce(0.6)Zr(0.4)O(2) is compared to that of bare ceria-zirconia. OSCC of redox-aged Pt/ceria-zirconia is twice that of bare ceria-zirconia, and the maximum of CO consumption occurs at a temperature about 300 K lower than redox-aged ceria-zirconia. XAS analysis allows one to evidence the formation of a platinum-cerium alloy in redox-aged samples and the stability of the metal particles toward oxidation and sintering during high-temperature treatments. Under CO flux at 773 K, bare ceria-zirconia shows a continuous drift of diffraction peaks toward smaller Bragg angles, due to a progressive increase of Ce(III) content. Under the same treatment, the structural rearrangement of Pt-supported ceria-zirconia starts after an induction time and takes place with an abrupt change of the lattice constant. The experimental evidence points to the role of supported Pt in modifying the redox properties of ceria-zirconia with respect to the bare support. It is proposed that the much faster bulk reduction observed by in situ XRD for redox-aged Pt/ceria-zirconia can be attributed to an easier release of reacted CO(2), producing a more effective turnover of reactants at the catalyst surface. 相似文献
83.
Curulli Antonella Montesperelli Giampiero Ronca Sara Cavalagli Nicola Ubertini Filippo Padeletti Giuseppina Vecchio Ciprioti Stefano 《Journal of Thermal Analysis and Calorimetry》2020,142(5):1721-1737
Journal of Thermal Analysis and Calorimetry - In the frame of the HERACLES (HEritage Resilience Against CLimate Events on Site) project, a set of cultural heritage sites was studied to improve... 相似文献
84.
Emiliano Bedini Antonella Carabellese Marialuisa Schiattarella Michelangelo Parrilli 《Tetrahedron》2005,61(23):5439-5448
3-Acetamido-3,6-dideoxy-d-galactopyranose (d-Fucp3NAc) is an aminosugar almost exclusively found in phytopathogenic O-antigens. The glycosylation reaction involving d-Fucp3NAc donors was studied with several rhamnosyl acceptors, revealing that the best yields and highest α-stereoselectivity were obtainable by coupling a N-phenyl trifluoroacetimidate glycosyl donor in a ternary mixture (dioxane/DME/toluene 4:1:1) as solvent. For the first time a synthetic access to α-d-Fucp3NAc containing oligorhamnans, that are interesting molecules for studying the effects of O-antigen model oligosaccharides on the modulation of plant response to bacteria, was reported. An example is the pentasaccharide repeating unit of the major O-antigen component from Pseudomonas syringae pv. holci IMV 8300, which was synthesized as its methyl glycoside. 相似文献
85.
86.
Kujawa P Moraille P Sanchez J Badia A Winnik FM 《Journal of the American Chemical Society》2005,127(25):9224-9234
The layer-by-layer growth of multilayer assemblies of two polysaccharides, the polyanion hyaluronan (HA) and the polycation chitosan (CH), was investigated using atomic force microscopy (AFM) and surface plasmon resonance (SPR) spectroscopy, with primary emphasis on the effect of the polysaccharide molecular weights on the film thickness and surface morphology. The HA/CH multilayers exhibit an exponential increase of the optical film thickness with the number of deposited bilayers. We show that the multilayer thickness at a given stage depends on the size of both CH, the diffusing polyelectrolyte, and HA, the non-diffusing species. Assemblies (12 bilayers) of high molecular weight polysaccharides (HA, 360,000; CH, 160,000) were twice as thick (approximately 900 nm vs approximately 450 nm) as those obtained with low molecular weight polymers (HA, 30,000; CH, 31,000), as assessed by AFM scratch tests. The exponential growth rate is the same for the high and low molecular weight pairs; the larger film thicknesses observed by SPR and by AFM arising from an earlier onset of the steep exponential growth phase in the case of the high molecular weight pair. In all cases, isolated islets form during the deposition of the first CH layer onto the underlying HA. Upon further film growth, individual islets coalesce into larger vermiculate features. The transition from distinct islands to vermiculate structures depends on the molecular weights of the polysaccharides and the lower molecular weight construct presents larger worm-like surface domains than the high molecular weight pair. 相似文献
87.
Gallo P Nasi A Vinci F Guadagnuolo G Brambilla G Fiori M Serpe L 《Rapid communications in mass spectrometry : RCM》2005,19(4):574-579
In this work we present a method for confirmatory analysis of chloramphenicol (CAP) in bovine and buffalo raw milk. CAP is extracted in acetonitrile and purified by affinity chromatography on an alpha-1-acid glycoprotein (AAG) column, then is identified and determined by ion-trap liquid chromatography/electrospray ionisation tandem mass spectrometry (LC/ESI-MS/MS) analysis in the negative ion mode. CAP was identified at the minimum required performance limit (MRPL) of 0.30 ppb, by monitoring the [M-H]- ion and at least two product ions, meeting the qualitative and quantitative criteria set by the European Commission in Decision 2002/657/EC for confirmation of prohibited veterinary drugs. The trueness and within-day and between-day repeatability data are also reported. Moreover, the loading capacity of affinity columns towards CAP was tested. This method, based on the molecular recognition between drug and AAG during the purification step to improve sample cleanup, represents a quantitative and repeatable procedure for confirmatory analysis, and fits the requirements for the routine official control of CAP residues in raw milk. 相似文献
88.
This paper shows the results of underground waters last monitoring in the province of Lecce (Apulia, Southern Italy). We carried out the physical-chemical characterization of the aquifers and their classification in accordance to limit values sanctioned by Italian legislation in force, by European directives and by FAO, in order to define their quality and to establish their possible use for drinkable and irrigation purposes. The attention has been focused on salinity evaluation and underground waters contamination phenomena, due to sea-water intrusion and to the use of fertilizers. Salinity and nitrates concentrations are high in a few wells. Iron and manganese concentrations are very high for almost every sample and this is due to corrosion phenomena of artesian wells metallic structure. For a better interpretation of data, multivariate statistical analysis has been used, in order to obtain the correlation among analytical results, soils hydro-geological properties and anthropic conditions. 相似文献
89.
Maccotta A Fantazzini P Garavaglia C Donato ID Perzia P Brai M Morreale F 《Annali di chimica》2005,95(3-4):117-124
Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood. 相似文献
90.
We study the prolongation of semibasic projectable tangent valued k-forms on fibered manifolds with respect to a bundle functor F on local isomorphisms that is based on the flow prolongation of vector fields and uses an auxiliary linear r-th order connection on the base manifold, where r is the base order of F. We find a general condition under which the Frölicher-Nijenhuis bracket is preserved. Special attention is paid to the curvature of connections. The first order jet functor and the tangent functor are discussed in detail. Next we clarify how this prolongation procedure can be extended to arbitrary projectable tangent valued k-forms in the case F is a fiber product preserving bundle functor on the category of fibered manifolds with m-dimensional bases and local diffeomorphisms as base maps. 相似文献