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91.
Separation of natural antioxidants using PDMS electrophoresis microchips coupled with amperometric detection and reverse polarity 下载免费PDF全文
Bruno Gabriel Lucca Susan Marie Lunte Wendell Karlos Tomazelli Coltro Valdir Souza Ferreira 《Electrophoresis》2014,35(23):3363-3370
This report describes the use of PDMS ME coupled with amperometric detection for rapid separation of ascorbic, gallic , ferulic, p‐coumaric acids using reverse polarity. ME devices were fabricated in PDMS by soft lithography and detection was accomplished using an integrated carbon fiber working electrode aligned in the end‐channel configuration. Separation and detection parameters were investigated and the best conditions were obtained using a run buffer consisting of 5 mM phosphate buffer (pH 6.9) and a detection voltage of 1.0 V versus Ag/AgCl reference electrode. All compounds were separated within 70 s using gated injection mode with baseline resolution and separation efficiencies between 1200 and 9000 plates. Calibration curves exhibited good linearity and the LODs achieved ranged from 1.7 to 9.7 μM. The precision for migration time and peak height provided maximum values of 4% for the intrachip studies. Lastly, the analytical method was successfully applied for the analysis of ascorbic and gallic acids in commercial beverage samples. The results achieved using ME coupled with amperometric detection were in good agreement with the values provided by the supplier. Based on the data reported here, the proposed method shows suitability to be applied for the routine analysis of beverage samples. 相似文献
92.
Eric Iván Sánchez‐Flores Rodrigo Chávez‐Calvillo Todd A. Keith Gabriel Cuevas Tomás Rocha‐Rinza Fernando Cortés‐Guzmán 《Journal of computational chemistry》2014,35(10):820-828
The topological analysis of the electron density for electronic excited states under the formalism of the quantum theory of atoms in molecules using time‐dependent density functional theory (TDDFT) is presented. Relaxed electron densities for electronic excited states are computed by solving a Z‐vector equation which is obtained by means of the Sternheimer interchange method. This is in contrast to previous work in which the electron density for excited states is obtained using DFT instead of TDDFT, that is, through the imposition of molecular occupancies in accordance with the electron configuration of the excited state under consideration. Once the electron density of the excited state is computed, its topological characterization and the properties of the atoms in molecules are obtained in the same manner that for the ground state. The analysis of the low‐lying singlet and triplet vertical excitations of CO and C6H6 are used as representative examples of the application of this methodology. Altogether, it is shown how this procedure provides insights on the changes of the electron density following photoexcitation and it is our hope that it will be useful in the study of different photophysical and photochemical processes. © 2014 Wiley Periodicals, Inc. 相似文献
93.
Validation of a confirmatory method for lipophilic marine toxins in shellfish using UHPLC-HR-Orbitrap MS 总被引:1,自引:0,他引:1
Gabriel Orellana Julie Vanden Bussche Lieven Van Meulebroek Michiel Vandegehuchte Colin Janssen Lynn Vanhaecke 《Analytical and bioanalytical chemistry》2014,406(22):5303-5312
Lipophilic marine toxins are produced by harmful microalgae and can accumulate in edible filter feeders such as shellfish, leading to an introduction of toxins into the human food chain, causing different poisoning effects. During the last years, analytical methods, based on liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS), have been consolidated by interlaboratory validations. However, the main drawback of LC-MS/MS methods remains the limited number of compounds that can be analyzed in a single run. Due to the targeted nature of these methods, only known toxins, previously considered during method optimization, will be detected. Therefore in this study, a method based on ultra-high-performance liquid chromatography coupled to high-resolution Orbitrap mass spectrometry (UHPLC-HR-Orbitrap MS) was developed. Its quantitative performance was evaluated for confirmatory analysis of regulated lipophilic marine toxins in shellfish flesh according to Commission Decision 2002/657/EC. Okadaic acid (OA), dinophysistoxin-1 (DTX-1), pectenotoxin-2 (PTX-2), azaspiracid-1 (AZA-1), yessotoxin (YTX), and 13-desmethyl spirolide C (SPX-1) were quantified using matrix-matched calibration curves (MMS). For all compounds, the reproducibility ranged from 2.9 to 4.9 %, repeatability from 2.9 to 4.9 %, and recoveries from 82.9 to 113 % at the three different spiked levels. In addition, confirmatory identification of the compounds was effectively performed by the presence of a second diagnostic ion (13C). In conclusion, UHPLC-HR-Orbitrap MS permitted more accurate and faster detection of the target toxins than previously described LC-MS/MS methods. Furthermore, HRMS allows to retrospectively screen for many analogues and metabolites using its full-scan capabilities but also untargeted screening through the use of metabolomics software. Figure
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94.
Russell G. Baughman Gabriel B. Hall 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(10):975-977
Structural studies performed in this laboratory of organophosphorus pesticides continue with these related compounds. The –NO2 groups of methyl parathion (systematic name: dimethyl 4‐nitrophenyl phosphorothioate, C8H10NO5PS) and dicapthon (systematic name: 2‐chloro‐4‐nitrophenyl dimethyl phosphorothioate, C8H9ClNO5PS) make dihedral angles of 10.67 (8) and 5.8 (1)°, respectively, with the planes of their attached rings, which accompanies angular distortion at the ring C atoms to which the –NO2 groups are attached. Similar distortions are observed at the C atom to which the thiophosphate groups are attached. Significant differences in distances and angles around the phenolic O, versus the –OMe groups, explain why it is the site of hydrolysis for these compounds. A comparison of a torsion angle involving the thiophosphate group and phenolic O atom with similar pesticide structures is given and indicates steric influences on that angle. 相似文献
95.
Investigation of fill factor losses on 20.2% efficient n‐type mono‐like silicon solar cells with laser contact opening 下载免费PDF全文
Alexander Frey Josh Engelhardt Gabriel Micard Giso Hahn Barbara Terheiden 《固体物理学:研究快报》2016,10(2):143-147
Large area (243.36 cm2) back‐junction passivated emitter, rear totally diffused (PERT) solar cells with laser contact opening (LCO) on n‐type mono‐like crystalline Si with efficiencies of 20.2% are presented. Boron emitters with high electrical quality (implied open circuit voltage iVOC up to 700 mV) are formed during a co‐diffusion step using SiOx:B layers. Increasing the rear metal contact coverage, we observed a decrease in fill factor (FF) instead of the expected increase due to the decrease of the back side series resistance. We show that it can be attributed to recombination centers (RCs) in the space charge region underneath the contact spots inducing an increasing second diode contribution. The presented empirical model for the RCs implemented in Synopsys Sentaurus TCAD allows for a successful reproduction of the FF, pseudo FF and VOC behaviour with contact coverage. According to this model, the RCs induced by laser ablation and subsequently evaporation of Al have a shallow exponential distribution with a characteristic length of LT = 0.2 µm and an effective surface density of N *T0 = 25 cm–1. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
96.
Baudat Emilie Gautier Céline Fichet Pascal Destrel Eric Colin Christèle Giuliani Margaux Lambrot Gabriel 《Journal of Radioanalytical and Nuclear Chemistry》2021,328(2):637-650
Journal of Radioanalytical and Nuclear Chemistry - 90Sr radiochemical method using nitric acid for Sr and Ca separation was optimized using design of experiments methodology. Nitric acid... 相似文献
97.
Sauleh Siddiqui Steven A Gabriel Shapour Azarm 《The Journal of the Operational Research Society》2015,66(4):664-673
Uncertainty and integer variables often exist together in economics and engineering design problems. The goal of robust optimization problems is to find an optimal solution that has acceptable sensitivity with respect to uncertain factors. Including integer variables with or without uncertainty can lead to formulations that are computationally expensive to solve. Previous approaches for robust optimization problems under interval uncertainty involve nested optimization or are not applicable to mixed-integer problems where the objective or constraint functions are neither quadratic, nor linear. The overall objective in this paper is to present an efficient robust optimization method that does not contain nested optimization and is applicable to mixed-integer problems with quasiconvex constraints (? type) and convex objective funtion. The proposed method is applied to a variety of numerical examples to test its applicability and numerical evidence is provided for convergence in general as well as some theoretical results for problems with linear constraints. 相似文献
98.
Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study 下载免费PDF全文
Yeljair Monascal Alexis Maldonado José R. Mora Tania Córdova Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(1):40-46
The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log10 k (s?1) = 13.56 ± 0.31 and Ea (kJ mol?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking Cδ+‐‐‐δ‐OCH3 with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
99.
Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride 下载免费PDF全文
Libia L. Julio José R. Mora Alexis Maldonado Gabriel Chuchani 《Journal of Physical Organic Chemistry》2015,28(4):261-265
The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
100.
Back Cover: Exploring Excited‐State Tunability in Luminescent Tris‐cyclometalated Platinum(IV) Complexes: Synthesis of Heteroleptic Derivatives and Computational Calculations (Chem. Eur. J. 52/2014) 下载免费PDF全文