全文获取类型
收费全文 | 799篇 |
免费 | 0篇 |
国内免费 | 16篇 |
专业分类
化学 | 469篇 |
晶体学 | 2篇 |
力学 | 35篇 |
数学 | 139篇 |
物理学 | 170篇 |
出版年
2023年 | 2篇 |
2022年 | 11篇 |
2021年 | 12篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 11篇 |
2017年 | 7篇 |
2016年 | 11篇 |
2015年 | 9篇 |
2014年 | 21篇 |
2013年 | 49篇 |
2012年 | 45篇 |
2011年 | 56篇 |
2010年 | 37篇 |
2009年 | 27篇 |
2008年 | 50篇 |
2007年 | 58篇 |
2006年 | 51篇 |
2005年 | 42篇 |
2004年 | 54篇 |
2003年 | 38篇 |
2002年 | 34篇 |
2001年 | 9篇 |
2000年 | 8篇 |
1999年 | 7篇 |
1998年 | 9篇 |
1997年 | 16篇 |
1996年 | 6篇 |
1995年 | 11篇 |
1994年 | 11篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 8篇 |
1990年 | 4篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1985年 | 7篇 |
1984年 | 5篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 6篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有815条查询结果,搜索用时 15 毫秒
11.
Biosensors based on enzyme field-effect transistors for determination of some substrates and inhibitors 总被引:3,自引:0,他引:3
Dzyadevych SV Soldatkin AP Korpan YI Arkhypova VN El'skaya AV Chovelon JM Martelet C Jaffrezic-Renault N 《Analytical and bioanalytical chemistry》2003,377(3):496-506
This paper is a review of the authors' publications concerning the development of biosensors based on enzyme field-effect transistors (ENFETs) for direct substrates or inhibitors analysis. Such biosensors were designed by using immobilised enzymes and ion-selective field-effect transistors (ISFETs). Highly specific, sensitive, simple, fast and cheap determination of different substances renders them as promising tools in medicine, biotechnology, environmental control, agriculture and the food industry.The biosensors based on ENFETs and direct enzyme analysis for determination of concentrations of different substrates (glucose, urea, penicillin, formaldehyde, creatinine, etc.) have been developed and their laboratory prototypes were fabricated. Improvement of the analytical characteristics of such biosensors may be achieved by using a differential mode of measurement, working solutions with different buffer concentrations and specific agents, negatively or positively charged additional membranes, or genetically modified enzymes. These approaches allow one to decrease the effect of the buffer capacity influence on the sensor response in an aim to increase the sensitivity of the biosensors and to extend their dynamic ranges.Biosensors for the determination of concentrations of different toxic substances (organophosphorous pesticides, heavy metal ions, hypochlorite, glycoalkaloids, etc.) were designed on the basis of reversible and/or irreversible enzyme inhibition effect(s). The conception of an enzymatic multibiosensor for the determination of different toxic substances based on the enzyme inhibition effect is also described.We will discuss the respective advantages and disadvantages of biosensors based on the ENFETs developed and also demonstrate their practical application. 相似文献
12.
Romero I Dubois L Collomb MN Deronzier A Latour JM Pécaut J 《Inorganic chemistry》2002,41(7):1795-1806
Reactions of Mn(II)(PF(6))(2) and Mn(II)(O(2)CCH(3))(2).4H(2)O with the tridentate facially capping ligand N,N-bis(2-pyridylmethyl)ethylamine (bpea) in ethanol solutions afforded the mononuclear [Mn(II)(bpea)](PF(6))(2) (1) and the new binuclear [Mn(2)(II,II)(mu-O(2)CCH(3))(3)(bpea)(2)](PF(6)) (2) manganese(II) compounds, respectively. Both 1 and 2 were characterized by X-ray crystallographic studies. Complex 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 11.9288(7) A, b = 22.5424(13) A, c =13.0773(7) A, alpha = 90 degrees, beta = 100.5780(10 degrees ), gamma = 90 degrees, and Z = 4. Crystals of complex 2 are orthorhombic, space group C222(1), with a = 12.5686(16) A, b = 14.4059(16) A, c = 22.515(3) A, alpha = 90 degrees, beta = 90 degrees, gamma = 90 degrees, and Z = 4. The three acetates bridge the two Mn(II) centers in a mu(1,3) syn-syn mode, with a Mn-Mn separation of 3.915 A. A detailed study of the electrochemical behavior of 1 and 2 in CH(3)CN medium has been made. Successive controlled potential oxidations at 0.6 and 0.9 V vs Ag/Ag(+) for a 10 mM solution of 2 allowed the selective and nearly quantitative formation of [Mn(III)(2)(mu-O)(mu-O(2)CCH(3))(2)(bpea)(2)](2+) (3) and [Mn(IV)(2)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](3+) (4), respectively. These results have shown that each substitution of an acetate group by an oxo group is induced by a two-electron oxidation of the corresponding dimanganese complexes. Similar transformations have been obtained if 2 is formed in situ either by direct mixing of Mn(2+) cations, bpea ligand, and CH(3)COO(-) anions with a 1:1:3 stoichiometry or by mixing of 1 and CH(3)COO(-) with a 1:1.5 stoichiometry. Associated electrochemical back-transformations were investigated. 2, 3, and the dimanganese [Mn(III)Mn(IV)(mu-O)(2)(mu-O(2)CCH(3))(bpea)(2)](2+) analogue (5) were also studied for their ability to disproportionate hydrogen peroxide. 2 is far more active compared to 3 and 5. The EPR monitoring of the catalase-like activity has shown that the same species are present in the reaction mixture albeit in slightly different proportions. 2 operates probably along a mechanism different from that of 3 and 5, and the formation of 3 competes with the disproportionation reaction catalyzed by 2. Indeed a solution of 2 exhibits the same activity as 3 for the disproportionation reaction of a second batch of H(2)O(2) indicating that 3 is formed in the course of the reaction. 相似文献
13.
A new method was developed for the analysis of pesticide residues in tobacco. The objective was to significantly increase the number of samples that can be processed by the laboratory and to enable the extension of the current coverage to additional pesticides. A new analytical approach was therefore defined based on two main axes, the automation of the sample preparation and the selectivity of the analyte detection using tandem mass spectrometry. This latter aspect reduces the stringency of the requirements placed on the clean-up of the extracts and on the chromatographic resolution when less selective detectors are used. The extraction of the analytes from the matrix is performed using the pressurized liquid extraction technique. Tobacco samples are extracted at elevated temperature and pressure (100 C and 100 atm; 1 atm = 101,325 Pa) using acetone as an extraction solvent. The resulting extract is then concentrated using a Vortex evaporator. Three different solid-phase extraction (SPE) procedures, adjusted to the chemical properties of the different active ingredients to be measured, are applied to the concentrated extract, thus leading to three extract fractions. The first fraction contains such main classes of active ingredients as organohalogenated and 2,6-dinitroaniline compounds while the second one collects the organophosphorus and acylalanines residues; these two fractions are analyzed by capillary gas chromatography coupled to tandem mass spectrometry using negative chemical ionization and electron impact ionization in the positive mode, respectively. The third extract fraction gathers the N-methylcarbamates residues which are analyzed by HPLC with post-column derivatization and fluorescence detection. The different sample preparation stages from extraction to SPE clean-up have been automated through the use of recent analytical technologies. In combination with the analysis by tandem mass spectrometry, this provided a potential for a high sample throughput. 相似文献
14.
Négrier F Marceau E Che M Giraudon JM Gengembre L Löfberg A 《The journal of physical chemistry. B》2005,109(7):2836-2845
1.5 Ni wt %/Al2O3 catalysts have been prepared by incipient wetness impregnation using [Ni(diamine)x(H2O)(6-2x)]Y2 precursors (diamine = 1,2-ethanediamine (en) and trans-1,2-cyclohexanediamine (tc); x = 0, 1, and 2; Y = NO3- and Cl-), to avoid the formation, during calcination, of difficult-to-reduce nickel aluminate. N2 was chosen for thermal treatment to help reveal and take advantage of the reactions occurring between Ni2+, ligands, counterions, and support. In the case of [Ni(en)2(H2O)2]Y2 salts used as precursors, in situ UV-vis and DRIFT spectroscopies show that after treatment at 230 degrees C Ni(II) ions are grafted to alumina via two OAl bonds and that the diamine ligands still remain coordinated to grafted nickel ions but in a monodentate way, bridging the cation with the alumina surface. With Y = Cl-, the chloride counterions desorb as hydrogen chloride, and hydrogen released upon decomposition of the en ligands is able to reduce a fraction of nickel ions into metal as evidenced by XPS. In contrast, with Y = NO3-, compounds such as CO or NO are formed during thermal treatment, indicating that nitrate ions burn the en ligands. After thermal treatment at 500 degrees C, a surface phase containing Ni(II) ions forms, characterized by XPS and UV-vis spectroscopy. Temperature-programmed reduction shows that these ions can be quantitatively reduced to the metallic state at 500 degrees C, in contrast with the aluminate obtained when the preparation is carried out from [Ni(H2O)6]2+, which is reduced only partly at 950 degrees C. On the other hand, a total self-reduction of nickel complexes leading to 2-5-nm metal particles is obtained upon thermal treatment via the hydrogen released by a hydrogen-rich ligand such as tc, whatever the Y counterion. An appropriate choice of the ligand and the counterion allows then to obtain selectively Ni(II) ions or a dispersed reduced nickel phase after treatment in N2, as a result of the reactions occurring between the chemical partners present on alumina. 相似文献
15.
16.
We report on a molecular simulation study of the homogeneous nucleation of CO2 in the supercooled liquid at low pressure (P = 5 MPa) and for degrees of supercooling ranging from 32% to 60%. In all cases, regardless of the degree of supercooling, the structure of the crystal nuclei is that of the Pa3 phase, the thermodynamically stable phase. For the more moderate degree of supercooling of 32%, the nucleation is an activated process and requires a method to sample states of high free energy. In this work, we apply a series of bias potentials, which promote the ordering of the centers of mass of the molecules and allow us to gradually grow crystal nuclei. The reliability of the results so obtained is assessed by studying the evolution of the nuclei in the absence of any bias potential, and by determining their probability of growth. We estimate that the size of the critical nucleus, for which the probability of growth is 0.5, is approximately 240 molecules. Throughout the nucleation process, the crystal nuclei clearly exhibit a Pa3 structure, in apparent contradiction with Ostwald's rule of stages. The other polymorphs have a much larger free energy. This makes their formation highly unlikely and accounts for the fact that the nucleation of CO2 proceeds directly in the stable Pa3 structure. 相似文献
17.
Shaymaa Khazaal Julien Harb Mohamad Rima Cdric Annweiler Yingliang Wu Zhijian Cao Ziad Abi Khattar Christian Legros Herv Kovacic Ziad Fajloun Jean-Marc Sabatier 《Molecules (Basel, Switzerland)》2022,27(9)
COVID-19 has expanded across the world since its discovery in Wuhan (China) and has had a significant impact on people’s lives and health. Long COVID is a term coined by the World Health Organization (WHO) to describe a variety of persistent symptoms after acute SARS-CoV-2 infection. Long COVID has been demonstrated to affect various SARS-CoV-2-infected persons, independently of the acute disease severity. The symptoms of long COVID, like acute COVID-19, consist in the set of damage to various organs and systems such as the respiratory, cardiovascular, neurological, endocrine, urinary, and immune systems. Fatigue, dyspnea, cardiac abnormalities, cognitive and attention impairments, sleep disturbances, post-traumatic stress disorder, muscle pain, concentration problems, and headache were all reported as symptoms of long COVID. At the molecular level, the renin-angiotensin system (RAS) is heavily involved in the pathogenesis of this illness, much as it is in the acute phase of the viral infection. In this review, we summarize the impact of long COVID on several organs and tissues, with a special focus on the significance of the RAS in the disease pathogenesis. Long COVID risk factors and potential therapy approaches are also explored. 相似文献
18.
Ferid Abidi Nayssene Aissaoui Jean-Charles Gaudin Jean-Marc Chobert Thomas Haertlé Mohamed Nejib Marzouki 《Applied biochemistry and biotechnology》2013,170(2):231-247
Prot-2 protease previously purified to homogeneity from Botrytis cinerea showed potentiality to be used in detergency and for production of bioactive peptides. To extend the characterization of Prot-2 protease, antifungal and antibacterial assays were performed in vitro using protein hydrolysates prepared from muscle of mackerel (Scomber scomborus) treated with this enzyme. The most active hydrolysate (degree of hydrolysis of 8 %) exhibited inhibition effect towards bacteria and phytopathogenic fungi, demonstrating that Prot-2 proteolysis generated bioactive peptides. Biochemical and molecular characterization of the purified Prot-2, by SDS-PAGE/Tryptic in gel-digestion and LC-MS/MS analysis, was investigated. The peptide amino acid sequence alignment search in database revealed a moderate homology between the determined amino acid sequence of Prot-2 protease and the known fungal trypsin/chymotrypsin in particular from Glomerella, Metarhizium and Streptomyces. From peptide sequence data obtained by mass spectrometry and sequences homologies, primers were defined and a cDNA fragment of 786 bp was amplified by RT-PCR. The cDNA nucleotide sequence analysis revealed an open reading frame coding for 262 amino acid residues. The deduced amino acid sequence of Prot-2 showed moderate identity with trypsin of Glomerella graminicola (74 %) and with chymotrypsin from Metarhizium anisopliae (71 %). Prot-2 exhibited a Ser protease homology and showed in addition the specific His motif of trypsin/chymotrypsin family. 相似文献
19.
Nuzillard JM 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,187(2):193-198
The SERF experiment is a variant of the homonuclear J-resolved experiment, in which a single coupling constant is measured. It consists of a single chemical shift selective excitation that is followed by a biselective spin echo. Recent articles mention the existence of artefacts in SERF spectra that are supposedly related to pulse imperfections. This article presents a detailed study of the biselective refocusing pulses. It also reports a method for predicting the position and amplitude of the expected and unexpected 2D spectral peaks in SERF spectra. Artefacts can be partially eliminated by phase cycling or by the introduction of static field gradient pulses in the acquisition sequence. A procedure to obtain of pure absorption peaks in SERF spectra is proposed. 相似文献
20.