全文获取类型
收费全文 | 2224篇 |
免费 | 70篇 |
国内免费 | 6篇 |
专业分类
化学 | 1717篇 |
晶体学 | 18篇 |
力学 | 38篇 |
数学 | 276篇 |
物理学 | 251篇 |
出版年
2023年 | 18篇 |
2022年 | 31篇 |
2021年 | 83篇 |
2020年 | 61篇 |
2019年 | 56篇 |
2018年 | 45篇 |
2017年 | 34篇 |
2016年 | 82篇 |
2015年 | 84篇 |
2014年 | 72篇 |
2013年 | 155篇 |
2012年 | 155篇 |
2011年 | 141篇 |
2010年 | 113篇 |
2009年 | 98篇 |
2008年 | 141篇 |
2007年 | 126篇 |
2006年 | 125篇 |
2005年 | 103篇 |
2004年 | 85篇 |
2003年 | 67篇 |
2002年 | 62篇 |
2001年 | 24篇 |
2000年 | 28篇 |
1999年 | 18篇 |
1998年 | 16篇 |
1997年 | 13篇 |
1996年 | 27篇 |
1995年 | 14篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 20篇 |
1991年 | 9篇 |
1990年 | 10篇 |
1989年 | 17篇 |
1988年 | 16篇 |
1987年 | 11篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 10篇 |
1983年 | 5篇 |
1982年 | 7篇 |
1980年 | 6篇 |
1979年 | 9篇 |
1978年 | 4篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1975年 | 4篇 |
1974年 | 8篇 |
1973年 | 4篇 |
排序方式: 共有2300条查询结果,搜索用时 233 毫秒
21.
Screening and analytical confirmation of sulfonamide residues in milk by capillary electrophoresis-mass spectrometry 总被引:1,自引:0,他引:1
A new methodology is proposed to automate the monitoring of sulfonamide residues in milk samples. It combines a screening unit for the total amount of sulfonamide with capillary electrophoresis-mass spectrometry (CE-MS) equipment for processing the samples containing a detectable level of sulfonamide. The screening unit consists of continuous-flow system (CFS) to precipitate the proteins connected on-line to the CE-MS equipment, in which a common characteristic ion of all sulfonamides was monitored with the MS detector by flushing the sample through the capillary. The confirmatory method is based on the purification and preconcentration of sulfonamides in a CFS unit and posterior analysis by CE-MS. The sample treatment unit was also on-line connected to the CE-MS equipment. In order to increase sensitivity, the flow rate of the sheath liquid was diminished from 0.5 to 0.2 microL.min(-1) by increasing the content in water from 0 to 50% and the formic acid from 0.5 to 1.5% in this liquid and by applying an overimposed pressure of 5 mbar during the electrophoretic separation. The method allowed the analysis of 30 samples per hour. 相似文献
22.
A spectrofluorimetrical selective method was designed for determination of paracetamol in tablets. This important technique can be characterized by its sensitivity, simplicity, celerity and cheaper cost than current official methods. The employed methodology involves coumarinic compound formation obtained by reaction between paracetamol and ethylacetoacetate (EAA) in the presence of sulphuric acid as catalyst. The reaction product is highly fluorescent at 478 nm, being excited at 446 nm.The linear concentration range of the application was 0.1-0.4 μg/ml of paracetamol and the detection limit was 57 ng/ml.The influence of different variables was studied and optimized through chemometric techniques. Applying the above-mentioned method good results were obtained with regard to pharmaceutical formulations containing paracetamol. Therefore, it is relevant to suggest this profitable technique for medicament control analysis. 相似文献
23.
This work shows the potentiality of As as internal standard to compensate errors from sampling of sparkling drinking water samples in the determination of selenium by graphite furnace atomic absorption spectrometry. The mixture Pd(NO3)2/Mg(NO3)2 was used as chemical modifier. All samples and reference solutions were automatically spiked with 500 μg l−1 As and 0.2% (v/v) HNO3 by the autosampler, eliminating the need for manual dilutions. For 10 μl dispensed sample into the graphite tube, a good correlation (r=0.9996) was obtained between the ratio of analyte absorbance by the internal standard absorbance and the analyte concentrations. The relative standard deviations (R.S.D.) of measurements varied from 0.05 to 2% and from 1.9 to 5% (n=12) with and without internal standardization, respectively. The limit of detection (LD) based on integrated absorbance was 3.0 μg l−1 Se. Recoveries in the 94-109% range for Se spiked samples were obtained. Internal standardization (IS) improved the repeatability of measurements and increased the lifetime of the graphite tube in ca. 15%. 相似文献
24.
Mulrooney CA Li X DiVirgilio ES Kozlowski MC 《Journal of the American Chemical Society》2003,125(23):6856-6857
By using oxygen as the terminal oxidant, copper complexes derived from chiral 1,5-diaza-cis-decalin catalyze the enantioselective oxidative biaryl coupling of highly functionalized naphthols to provide octa- and decasubstituted binaphthalenes with high selectivity (86-90% ee). Products containing very electron-rich naphthalenes were prone to epimerization under the reaction conditions. This epimerization could be suppressed by employing naphthol starting materials with phenol protecting groups that attenuated the electron-rich nature of the naphthalenes. Direct oxidation of the resultant chiral 1,1'-binaphthol framework completed the first asymmetric synthesis of a perylenequinone containing only an axial chirality element. 相似文献
25.
Carol A. Loeschorn Charles J. Kelley Robert N. Hanson Michael A. Davis 《Tetrahedron letters》1984,25(32):3387-3390
The addition of methyl Grignard to diethyl acetamido(cyanoselenobenzyl)malonates 3 and 4 at ?78° followed by hydrolysis yields the 3-(4-and 3-methylselenophenyl)alanines 1 and 2. 相似文献
26.
The kinetics of the reaction of manganese(III) with oxalic acid (OA) has been studied in H2SO4 solutions. Under the experimental conditions of 6 × 10–3 <>0 < 0.4=" mol=">–3 and [H2SO4]0 0.2 mol dm–3 the observed pseudo-first order rate constant k
obs follows the expression
相似文献
27.
Liliana Cseh Carol Csunderlik Ingo Pantenburg Gerd Meyer Otilia Costisor 《无机化学与普通化学杂志》2003,629(6):985-988
The complex Co(C14H13NO)2Cl2 with the protonated N‐salicylidene‐p‐toluidine ligand was synthesized from an ethanolic solution of CoCl2·6H2O and N‐salicylidene‐p‐toluidine. The crystal structure was determined from X‐ray single crystal data (monoclinic, space group Cc, a = 1496.2(3) pm, b = 1257.4(4) pm, c = 1544.6(3) pm, β = 115.01(1)°, Z = 4). Co2+ adopts a distorted tetrahedral geometry. The UV‐Vis and IR spectra of the complex are discussed. 相似文献
28.
G. Graziano G. Barone F. Catanzano A. Riccio 《Journal of Thermal Analysis and Calorimetry》1995,44(4):765-775
A general feature of temperature-induced reversible denaturation of small globular proteins is its all-or-none character. This strong cooperativity leads to think that protein molecules, possessing only two accessible thermodynamic states, the native and the denatured one, resemble ‘crystal molecules’ that melt at raising temperature. An analysis, grounded on mean field theory, allows to conclude that the two-state transition is a first-order phase transition. The implication of this conclusion are briefly discussed. 相似文献
29.
Carlo Bruno Eleonora Ussano Gianni Barucca Davide Vanossi Giovanni Valenti Edward A. Jackson Andrea Goldoni Lucio Litti Simona Fermani Luca Pasquali Moreno Meneghetti Claudio Fontanesi Lawrence T. Scott Francesco Paolucci Massimo Marcaccio 《Chemical science》2021,12(23):8048
The presence of non-hexagonal rings in the honeycomb carbon arrangement of graphene produces rippled graphene layers with valuable chemical and physical properties. In principle, a bottom-up approach to introducing distortion from planarity of a graphene sheet can be achieved by careful insertion of curved polyaromatic hydrocarbons during the growth of the lattice. Corannulene, the archetype of such non-planar polyaromatic hydrocarbons, can act as an ideal wrinkling motif in 2D carbon nanostructures. Herein we report an electrochemical bottom-up method to obtain egg-box shaped nanographene structures through a polycondensation of corannulene that produces a new conducting layered material. Characterization of this new polymeric material by electrochemistry, spectroscopy, electron microscopy (SEM and TEM), scanning probe microscopy, and laser desorption-ionization time of flight mass spectrometry provides strong evidence that the anodic polymerization of corannulene, combined with electrochemically induced oxidative cyclodehydrogenations (Scholl reactions), leads to polycorannulene with a wavy graphene-like structure.A bottom-up synthesis of wavy graphene structures obtained through an anodic polymerization process, combined with an electrochemically triggered oxidative cyclodehydrogenation, of the bowl-shaped polyaromatic hydrocarbon corannulene. 相似文献
30.
Takehiko Yamato Carol Pérez-Casas Shofiur Rahman Zeng Xi Mark R. J. Elsegood Carl Redshaw 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(1-2):193-197
A novel receptor possessing two complexation sites and bearing 1,3-alternate conformation based on thiacalix[4]arene, confirmed by single crystal X-ray analysis, was prepared. The tetrathiacalix[4]arene
diamide shows strong intramolecular hydrogen bonding. The binding behavior towards K+ and halides has been examined by 1H NMR titration experiments. 相似文献
|