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131.
Andrew J. Thompson Jerome Dabin Javier Iglesias‐Fernndez Albert Ardvol Zoran Dinev Spencer J. Williams Omprakash Bande Aloysius Siriwardena Carl Moreland Ting‐Chou Hu David K. Smith Harry J. Gilbert Carme Rovira Gideon J. Davies 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2012,124(44):11333-11333
132.
Karina Nesprias Mariángeles Iglesias Sonia Rivas Elida Alvarez Gastón Barreto Nora Eyler Adriana Cañizo 《国际化学动力学杂志》2011,43(11):657-666
Cyclic organic peroxides have interesting pharmacological properties and are used at industrial level as polyfunctional initiators of polymerization, and so their preparation through novel methods has attracted the attention of numerous researchers. White crystals of 4‐heptanone cyclic diperoxide (HDP) can be obtained in acidic media at ?1°C by a reaction between 4‐heptanone and hydrogen peroxide. Its thermal decomposition was studied in acetone, cyclohexane, acetonitrile, ethyl acetate, ethanol, 2‐propanol, 2‐butanol, and 1,4‐dioxane at temperatures higher than 120°C, showing a behavior accordingly with a pseudo‐first‐order kinetic law up to at least 80% HDP conversion. It was demonstrated that an increase in solvent polarity is accompanied by an increase in reaction rates. The effect of solvent polarity on the thermal decomposition rate constant values can be associated with a reaction mechanism involving a more dipolar‐activated complex than the diperoxide initial molecule. The activation parameters varied widely from 31.2 to 46.6 kcal mol?1 and ?1.33 to 31.7 cal mol?1 K?1 when going from ethanol to cyclohexane as reaction solvents, respectively. An enthalpy–entropy compensation effect was observed in all solvents. Specific interactions between the oxygen atoms from the peroxidic bond and the hydrogen atom bonded to C2 and/or from the OH group can be taken into account to explain that the existence of the compensation effect does not mean that an isokinetic relationship consequently can be established. The kinetic results showed that an isokinetic relationship is observed only for a group of solvents. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 657–666, 2011 相似文献
133.
Emilia Iglesias 《国际化学动力学杂志》2012,44(10):668-679
The keto–enol tautomerism of 3‐chloro‐pentane‐2,4‐dione (ClPD) was studied in aqueous micellar solutions of cationic, anionic, and nonionic surfactants. The enol of ClPD tautomerizes rapidly in water to the equilibrium proportions of the keto form, KE=0.55; whereas the keto–enol conversion of 3‐ethyl‐pentane‐2,4‐dione (EPD) is a much slower reaction than the enol nitrosation. Kinetics of enol –nitrosation of both ClPD and EPD in aqueous acid medium using nitrous acid shows first‐order dependence upon [ketone] and linear or curve relationships of the observed rate constant, ko, as a function of [nitrite] or [H+]; the observed behavior depends on the molecular structure of diketone and varies with the experimental conditions. The reaction is strongly catalyzed by Cl?, Br?, or SCN?, and the observed rate constant shows a curve dependence on [Br?] or [SCN?], which is more pronounced at high acidity. The results are consistent with a reaction mechanism in which the nitrosation occurs initially on the enol–oxygen and releasing a proton to form a chelate–nitrosyl complex intermediate in steady state. Fine differences on the mechanistic spectrum of enols nitrosation are considered on the basis of the molecular structure of the diketone. © 2012 Wiley Periodicals, Inc. Int J Chem Kinet 44: 668–679, 2012 相似文献
134.
José M. Goenaga Ana Gayol Raquel G. Concha Miguel Iglesias José M. Resa 《Monatshefte für Chemie / Chemical Monthly》2007,88(2):403-436
Speeds of sound, densities, and refractive indices of the binary mixtures containing ethanol+(2-methyl-1-propanol, 2-methyl-1-butanol,
1-pentanol, or 3-methyl-1-butanol) were measured at 288.15 ≤ T/K ≤ 323.15 and atmospheric condition in the whole compositional range. The effect of temperature was analyzed by several
chemical terms. 相似文献
135.
Carmen M. Andújar Snchez Ma Jos Iglesias Fernando Lpez Ortiz 《Tetrahedron letters》2002,43(52):9611-9614
Functionalised 1,3- and 1,4-cyclohexadienes have been prepared through dearomatisation of benzonitriles by sequential conjugate addition of -lithium alkyl(diphenyl)phosphine borane in the presence of HMPA and capture of the intermediate anion with protonating and alkylating reagents. 相似文献
136.
137.
J. Iglesias A. Portela A. Rovella 《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2008
The perturbations of complex polynomials of one variable are considered in a wider class than the holomorphic one. It is proved that under certain conditions on a polynomial p of the plane, the Cr conjugacy class of a map f in a C1 neighborhood of p depends only on the geometric structure of the critical set of f. This provides the first class of examples of structurally stable maps with critical points and nontrivial nonwandering set in dimension greater than one. 相似文献
138.
139.
A Facile and Cost‐effective Electroanalytical Strategy for the Quantification of Deoxyguanosine and Deoxyadenosine in Oligonucleotides Using Screen‐printed Graphite Electrodes 下载免费PDF全文
Ariadna Brotons Ignacio Sanjuán Christopher W. Foster Craig E. Banks Francisco José Vidal‐Iglesias José Solla‐Gullón Jesús Iniesta 《Electroanalysis》2016,28(12):3066-3074
The development of electroanalytical methods for the detection and quantification of nucleotides in DNA offers vital implications in assessing the degree of oxidation or epigenetic modification in DNA. Unfortunately, the electrochemical response of oligonucleotides is strongly influenced by the size, composition and nucleic base sequence. In this article, an optimized analytical procedure for the enzymatically breakdown of the oligonucleotides to their corresponding nucleotides for the evaluation of the electrochemical response through the use of square wave voltammetry (SWV) is presented. Enzymatic digestion of oligonucleotides has been optimized in terms of buffer composition, digestion time, strategy for stopping the enzymatic reaction and filtration requirement for enzyme removal, and then compared to an established protocol. Under the optimized protocol SWV response of a number of untreated and enzymatically digested six‐mer oligonucleotides, namely 5′‐GGGGGG‐3′, 5′‐AAAAAA‐3′, 5′‐CGCGCG‐3′ and 5′‐AAACGC‐3′ have been analysed, providing a higher sensitivity for the determination of guanosine and adenosine monophosphate species under digestion conditions with a more facile and cost effective procedure. The novel strategy for the enzymatically treated oligonucleotides in combination with the SWV response provides a proof of principle for feasible applications in the diagnosis of methylated guanosine in DNA as a potential biomarker due to its relation with cancer. 相似文献
140.
Development of a solid-phase microextraction method for determination of volatile oxidation compounds in fish oil emulsions 总被引:1,自引:0,他引:1
Headspace solid-phase microextraction (HS-SPME) is proposed for isolating and determining the headspace volatiles formed during oxidation of fish-oil-in-water emulsions. Three different fiber coatings were tested and compared for sensitivity and reproducibility. A carboxen/polydimethylsiloxane (CAR-PDMS) fiber coating was found to be the most suitable for the analysis of emulsion volatiles. The main factors affecting the microextraction process on CAR-PDMS were then evaluated by a factorial design: amount of sample, time and temperature of extraction and stirring. The incubation of 0.5 g of emulsion at 60 degrees C during 30 min leads to the most effective extraction of volatiles associated with lipid oxidation of fish oil emulsions. The HS-SPME method coupled with GC-MS allowed the qualitative and quantitative analysis of the volatiles derived from oxidation of real fish oil enriched foods such as milk and mayonnaise. The method here proposed is very fast and simple and yields high sensitivity, with good repeatability for all target compounds. 相似文献