全文获取类型
收费全文 | 3060篇 |
免费 | 144篇 |
国内免费 | 2篇 |
专业分类
化学 | 2281篇 |
晶体学 | 27篇 |
力学 | 84篇 |
数学 | 372篇 |
物理学 | 442篇 |
出版年
2023年 | 27篇 |
2022年 | 20篇 |
2021年 | 32篇 |
2020年 | 51篇 |
2019年 | 48篇 |
2018年 | 58篇 |
2017年 | 48篇 |
2016年 | 116篇 |
2015年 | 77篇 |
2014年 | 84篇 |
2013年 | 199篇 |
2012年 | 269篇 |
2011年 | 274篇 |
2010年 | 147篇 |
2009年 | 126篇 |
2008年 | 215篇 |
2007年 | 217篇 |
2006年 | 172篇 |
2005年 | 169篇 |
2004年 | 155篇 |
2003年 | 113篇 |
2002年 | 101篇 |
2001年 | 76篇 |
2000年 | 83篇 |
1999年 | 49篇 |
1998年 | 38篇 |
1997年 | 22篇 |
1996年 | 29篇 |
1995年 | 16篇 |
1994年 | 23篇 |
1993年 | 18篇 |
1992年 | 20篇 |
1991年 | 15篇 |
1990年 | 11篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 5篇 |
1986年 | 8篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1980年 | 4篇 |
1979年 | 1篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 3篇 |
1969年 | 1篇 |
排序方式: 共有3206条查询结果,搜索用时 15 毫秒
161.
Ch. Jesús F. Socorro M. Rodríguez de Rivera 《Journal of Thermal Analysis and Calorimetry》2013,113(3):1003-1007
A calorimetric sensor has been developed for local and direct measurement of calorific dissipations in different parts of the human body. The constructed prototype has a detection surface of 36 cm2. The calibration of the sensor is based on a semi-empirical model that permits to simulate the operation of the device, making easier an operational functioning method. The device is modeled as a system with two inputs and two outputs. The inputs are the calorific power (W) that is intended to be measured and the power (W pid) that dissipates a resistance, keeping constant the thermostat temperature through the use of a PID controller. The outputs are the thermostat temperature (T pid) and the calorimetric signal (y) that provides the thermopile that is in contact with the body. 相似文献
162.
The Thorpe-Ziegler reaction has been used in the preparation of enaminonitriles and cyclic ketones for many years. A wide variety of bases1 have been employed to acomplish this reaction, the most effective being the alkali metal salts of aralkyl amines. The reaction conditions vary from room temperature to toluene reflux temperature for long periods of time1. 相似文献
163.
A convenient synthesis of the cyclohexyl, (1R,3R,4S)-3-P-menthyl and (15-endo)-2-bomyl glyoxylates, from the respective alcohols and other very available materials, as a model applicable to that of other chiral, sensitive giyoxylates, is described. 相似文献
164.
Photoactive materials based on dye molecules incorporated into thin films or bulk solids are useful for applications as photosensitization, photocatalysis, solar cell sensitization and fluorescent labeling, among others. In most cases, high concentrations of dyes are desirable to maximize light absorption. Under these circumstances, the proximity of dye molecules leads to the formation of aggregates and statistical traps, which dissipate the excitation energy and lower the population of excited states. The search for enhancement of light collection, avoiding energy wasting requires accounting the photophysical parameters quantitatively, including the determination of quantum yields, complicated by the presence of light scattering when particulate materials are considered. In this work we summarize recent advances on the photophysics of dyes in light‐scattering materials, with particular focus on the effect of dye concentration. We show how experimental reflectance, fluorescence and laser‐induced optoacoustic spectroscopy data can be used together with theoretical models for the quantitative evaluation of inner filter effects, fluorescence and triplet formation quantum yields and energy transfer efficiencies. 相似文献
165.
Noelia Negreira Isaac Rodríguez Rosario Rodil Elisa Rubí Rafael Cela 《International journal of environmental analytical chemistry》2013,93(11):1174-1188
A low solvent consumption method for the determination of eight ultraviolet (UV) filters, displaying low to medium polarities, in freeze-dried samples of marine bivalves and fish is proposed. Matrix solid-phase dispersion (MSPD) and gas chromatography with mass spectrometry (GC-MS) were used as sample preparation and determination techniques, respectively. This work describes the influence of several parameters (type and amount of dispersant and clean-up sorbents, as well as elution solvent) on the yield and the selectivity of the MSPD extraction. Under optimized conditions, samples (0.5?g) were ground with 2?g of Florisil in a mortar with a pestle and transferred into a polypropylene syringe, which contained 1?g of C18 as clean-up sorbent. Analytes were eluted with 5?mL of acetonitrile. This extract was concentrated to dryness, re-constituted with 1?mL of ethyl acetate and injected in the GC-MS system without any further clean-up. The global average recoveries, measured for three different biota samples, spiked at three different levels (between 50 and 1000?ng?g?1), ranged from 80% to 101% with associated standard deviations below 10%. The inter-day precision of the method varied from 4% to 15% and the achieved LOQs (defined for a signal to noise ratio of 10) ranged from 4 to 28?ng?g?1, referred to the freeze-dried matrix. Octocrylene (OCR) was found in some samples of fish and mussels at concentrations between 15 and 20?ng?g?1, referred to dry mass. 相似文献
166.
Álvaro Sánchez Rodríguez Zoraida Sosa Ferrera 《International journal of environmental analytical chemistry》2013,93(12):1166-1177
A solid phase extraction (SPE) technique for seawater samples coupled to quantification using liquid chromatography tandem-mass spectrometry (LC-MS/MS) is described to quantify relevant antifouling booster biocides of ecotoxicological concern (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid). The optimised methodology provides a sensitive, easy to use and efficient analytical procedure with detection limits in the range of between 0.1 and 0.2?ng?L?1 and appropriate reproducibility (with analytical standard deviations of less than 10%). Spiked recoveries for all compounds exceeded 72%. The method was tested through a thorough monitoring regime of commercial port and marinas on the island of Gran Canaria (off the north-west coast of Africa) over a period of several months in 2008. Results provide the first data for antifouling booster biocides in the Canary Islands. Concentrations of Diuron and Irgarol 1051 in samples ranged between 2 and 195?ng?L?1 and 2 and 146?ng?L?1, respectively. TCMTB and Dichlofluanid were not detected. 相似文献
167.
Y. Arroyo Gómez J. A. López Sastre J. F. Rodríguez Amo M. A. Sanz Tejedor 《Journal of carbohydrate chemistry》2013,32(7):1051-1058
Abstract The asymmetric oxidation reaction of D-glyceraldehyde diethyl dithioacetal 1 and its di-O-acetyl derivative with a Sharpless reagent to produce the corresponding D-glyceraldehyde diethyl dithioacetal S-oxide derivatives takes place with high stereoselectivity. The configuration of the two new chiral centres formed is deduced. 相似文献
168.
Dr. Ángel J. Jiménez Michael Sekita Dr. Esmeralda Caballero Dr. M. Luisa Marcos Dr. M. Salomé Rodríguez‐Morgade Prof. Dr. Dirk M. Guldi Prof. Tomás Torres 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14506-14514
In a novel electron‐donor–acceptor conjugate, phthalocyanine (Pc) and perylenediimide (PDI) are connected through a trans‐platinum(II) diacetylide linker to yield Pc‐Pt‐PDI 1 . In the ground state, the presence of PtII disrupts the electronic communication between the two electroactive components, as revealed by UV/Vis spectroscopy and electrochemical studies. The photophysical behavior of 1 is compared with that of the corresponding Pc‐PDI electron‐donor–acceptor conjugate 2 in terms of charge separation and charge recombination. The insertion of PtII between Pc and PDI impacts the results in a longer‐lived Pc . +/PDI . ? radical ion‐pair state. In addition, the intermediately formed Pc triplet excited state is formed with higher quantum yields in 1 than in 2 . 相似文献
169.
Determination of estrogens in environmental water samples using 1,3‐dipentylimidazolium hexafluorophosphate ionic liquid as extraction solvent in dispersive liquid–liquid microextraction
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Bárbara Socas‐Rodríguez Javier Hernández‐Borges María Asensio‐Ramos Antonio V. Herrera‐Herrera Jose A. Palenzuela Miguel Ángel Rodríguez‐Delgado 《Electrophoresis》2014,35(17):2479-2487
In this work, the potential of a symmetric dialkyl‐substituted ionic liquid (IL), 1,3‐dipenthylimidazolium hexafluorophosphate ([PPIm][PF6]), as extraction solvent in dispersive liquid–liquid microextraction (DLLME) has been studied for the analysis of a group of three natural (estriol, 17β‐estradiol, and 17α‐estradiol) and four synthetic (17α‐ethynylestradiol, diethylstibestrol, dienestrol, and hexestrol) estrogenic compounds as well as one mycotoxin with estrogenic activity (zearalenone) in different types of water samples (Milli‐Q, mineral, and wastewater). Separation, determination, and quantification were developed by HPLC‐DAD and a fluorescence detector (FD) connected in series. Factors influencing the IL‐DLLME procedure (sample pH, amount of IL, type and volume of disperser solvent, ionic strength, and assistance of vortex agitation) were investigated and optimized by means of a step‐by‐step approach. Once the optimum extraction conditions were established (10 mL of water at pH 8, 60 mg of [PPIm][PF6], 500 μL of ACN as disperser solvent and vortex agitation for 1 min), the calibration curves of the whole method (IL‐DLLME‐HPLC‐DAD/FD) were obtained and precision and accuracy were evaluated. It was demonstrated that the developed methodology was repeatable, accurate, and selective with limits of detection in the 0.30–0.57 μg/L and 13.8–37.1 μg/L range for FD and DAD, respectively. Relative recovery values were higher than 85% for the different types of water samples and the Student's t test demonstrated that there were not significant differences between the added and the found concentration. 相似文献
170.
Alba Campo‐Cacharrón Enrique M. Cabaleiro‐Lago Jesús Rodríguez‐Otero 《Journal of computational chemistry》2014,35(21):1533-1544
Complexes formed by substituted buckybowls derived from corannulene and sumanene with sodium cation or chloride anion have been computationally studied by using a variety of methods. Best results have been obtained with the SCS‐MP2 method extrapolated to basis set limit, which reproduces the highest‐level values obtained with the MP2.X method. All bowls form stable complexes with chloride anion, with stabilities ranging from ?6 kcal/mol in the methylated corannulene derivative to ?45 kcal/mol in the CN‐substituted sumanene. The opposite trend is observed in sodium complexes, going from deeply attractive complexes with the methylated derivatives (?36 kcal/mol with sumanene derivative) to slightly repulsive ones in the CN‐substituted bowls (2 kcal/mol in the corannulene derivative). Anion complexes are stabilized by large electrostatic interactions combined with smaller though significant dispersion and induction contributions. Conversely, cation complexes are stabilized by large induction contributions capable of holding together the bowl and the cation even in cases where the electrostatic interaction is repulsive. The effect of substitution is mainly reflected on changes in the molecular electrostatic potential of the bowl and, thus, in the electrostatic contribution to the interaction. Therefore, the variations in the stability of the complexes on substitution could be roughly predicted just considering the changes in the electrostatic interaction. However, other contributions also register changes mainly as a consequence of displacements on the position of the ion at the minimum, so the accurate prediction of the stability of this kind of complexes requires going further than the electrostatic approach. © 2014 Wiley Periodicals, Inc. 相似文献