全文获取类型
收费全文 | 899篇 |
免费 | 23篇 |
国内免费 | 1篇 |
专业分类
化学 | 676篇 |
晶体学 | 3篇 |
力学 | 9篇 |
数学 | 109篇 |
物理学 | 126篇 |
出版年
2017年 | 6篇 |
2016年 | 15篇 |
2015年 | 19篇 |
2014年 | 20篇 |
2013年 | 37篇 |
2012年 | 30篇 |
2011年 | 46篇 |
2010年 | 28篇 |
2009年 | 31篇 |
2008年 | 38篇 |
2007年 | 18篇 |
2006年 | 29篇 |
2005年 | 19篇 |
2004年 | 48篇 |
2003年 | 24篇 |
2002年 | 21篇 |
2001年 | 26篇 |
2000年 | 27篇 |
1999年 | 13篇 |
1997年 | 7篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 12篇 |
1992年 | 5篇 |
1991年 | 12篇 |
1990年 | 11篇 |
1989年 | 18篇 |
1988年 | 8篇 |
1986年 | 15篇 |
1985年 | 12篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 8篇 |
1981年 | 11篇 |
1980年 | 16篇 |
1979年 | 13篇 |
1978年 | 11篇 |
1977年 | 18篇 |
1976年 | 26篇 |
1975年 | 17篇 |
1974年 | 15篇 |
1973年 | 17篇 |
1972年 | 7篇 |
1971年 | 13篇 |
1970年 | 9篇 |
1968年 | 7篇 |
1967年 | 5篇 |
1943年 | 5篇 |
1939年 | 6篇 |
排序方式: 共有923条查询结果,搜索用时 328 毫秒
41.
A simple method for analysis of anatoxin-a in aqueous samples was developed using solid-phase microextraction (SPME) and high-performance liquid chromatography (HPLC) with fluorescence detection. Anatoxin-a was derivatized to a fluorogenic agent on the surface of the SPME fiber. In the method an SPME fiber was immersed for 30 min in the aqueous sample. The fluorogenic derivatizing reagent (4-fluoro-7-nitro-2,1,3-benzoxadiazole, 1.0 mg/ml in methanol) was dropped or sprayed onto the fiber containing extracted analytes. The fiber was then heated for 10 min in an empty vial at 70 degrees C in a waterbath to promote derivatization. The derivatives formed on the fiber were desorbed in a SPME-HPLC interface. The interface was filled with methanol-1 mM hydrochloric acid (7:3, v/v) before inserting of the fiber into the interface. For desorption, the fiber was inserted in the interface for 5 min. For anatoxin-a in an aqueous sample, the calibration curve showed linearity in the range of 50-1500 ng/ml and the limit of detection of anatoxin-a was 20 ng/ml. No interferences were found, and the time for analysis was 55 min for one sample. 相似文献
42.
43.
Dr. Michael L. Lejkowski Dr. Ronald Lindner Dr. Takeharu Kageyama Dr. Gabriella É. Bódizs Dipl.‐Chem. Philipp N. Plessow Dr. Imke B. Müller Dr. Ansgar Schäfer Dr. Frank Rominger Prof. Dr. Peter Hofmann Dr. Cornelia Futter Dr. Stephan A. Schunk Dr. Michael Limbach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(44):14017-14025
For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C1 building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO2, ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal. 相似文献
44.
45.
46.
Roland Hellinger Jeannie Horak Wolfgang Lindner 《Analytical and bioanalytical chemistry》2013,405(25):8105-8120
The fluorescent tag 6-aminoquinolyl-N-hydroxysuccinimidyl carbamate (AQC; AccQ Fluor reagent kit from Waters) is a commercial N-terminal label for proteinogenic amino acids (AAs), designed for reversed-phase separation and quantification of the AA racemates. The applicability of AQC-tagged AAs and AA-type zwitterionic compounds was tested for enantiomer separation on the tert-butyl carbamate modified quinine and quinidine based chiral stationary phases, QN-AX and QD-AX employing polar-organic elution conditions. The investigated test analytes included the enantiomers of the positional isomers of isoleucine (Ile), threonine, homoserine, and 4-hydroxyproline. Furthermore, β-AAs, cyclic, and heterocyclic AAs including trans-2-amino-cyclohexane carboxylic acid and trans-2-aminocyclohexyl sulfonic acid, phenylalanine derivatives substituted with halides with increasing electronegativity and 3,4-dihydroxyphenylalanine, cysteine-related derivatives including homocysteic acid, methionine sulfone, cysteine-S-acetic acid, and cysteine-S-acetamide as well as a small range of aminophosphonic acids were enantioseparated. A mechanistic interaction study of AQC-AAs in comparison with fluoresceine isothiocyanate-labeled AAs was performed. The chiral and chemoselective recognition processes involved in enantiomer separation and retention was systematically discussed. Special emphasis was set on the influential factors exhibited by the chemistry, branching position, and spatial properties of the investigated zwitterionic analytes. The general interest to separate and distinguish between different types of branched-chained AAs and metabolic side products thereof lies in the toxicity of some of these compounds, which makes for instance allo–Ile an attractive candidate in disease-related biomarker research. Figure
Separation of the four AQC-tagged isomers of 4-hydroxyproline (trans-D, cis-D, trans-L and cis-L) on the chiral stationary phase QD-AX 相似文献
47.
Uwe Lindner Jana Lingott Silke Richter Norbert Jakubowski Ulrich Panne 《Analytical and bioanalytical chemistry》2013,405(6):1865-1873
Hydrophilic interaction chromatography (HILIC) coupled with inductively coupled plasma mass spectrometry (ICP-MS) was optimized for speciation analysis of gadolinium-based contrast agents in environmental samples, in particular surface river waters and plants. Surface water samples from the Teltow channel, near Berlin, were investigated over a distance of 5 km downstream from the influx of a wastewater treatment plant. The total concentration of gadolinium increased significantly from 50 to 990 ng?L?1 due to the influx of the contrast agents. After complete mixing with the river water, the concentration remained constant over a distance of at least 4 km. Two main substances [Dotarem® (Gd-DOTA) and Gadovist® (Gd-BT-DO3A)] have been identified in the river water using standards. A gadolinium-based contrast agent, possibly Gd-DOTA (Dotarem®), was also detected in water plant samples taken from the Teltow channel. Therefore, uptake of contrast agents [Gadovist® (Gd-BTDO3A), Magnevist® (Gd-DTPA), Omniscan® (Gd-DTPA-BMA), Dotarem® (Gd-DOTA), and Multihance® (Gd-BOPTA)] by plants was investigated in a model experiment using Lepidium sativum (cress plants). HILIC–ICP-MS was used for identification of different contrast agents, and a first approach for quantification using aqueous standard solutions was tested. For speciation analysis, all investigated contrast agents could be extracted from the plant tissues with a recovery of about 54 % for Multihance® (Gd-BOPTA) up to 106 % for Gadovist® (Gd-BT-DO3A). These experiments demonstrate that all contrast agents investigated are transported from the roots to the leaves where the highest content was measured. 相似文献
48.
49.
W. Lindner H. Ruckendorfer W. Lechner W. Posch 《International journal of environmental analytical chemistry》2013,93(2-4):235-249
Abstract In continuation of our work dealing with multicolumn HPLC (MC[sbnd]HPLC) we describe in this paper an on-line on-column fraction trapping technique based on effluent mixing. To a normal two-column switching set-up (in this case with two RP columns) an additional high-pressure pump gets inserted into the connection line between column A and column B via a low dead volume mixing tee. The in-line respectively off-line switching of pump B and the mobile phase B is time controlled by using a high pressure switching valve. With this set-up it is possible to mix on-line an effluent fraction from column A and transferred onto column B with a highly polar and pH-controlled (e.g. aqueous buffer) new effluent, to reduce or adjust significantly the overall elution strength of this mixed transferred solvent. Thus, several chromatographically effective possibilities can be created in a simple manner, which are for example: (a) pronounced peak compression respectively on-column concentration on column B; (b) due to low elution strength and/or pH adjustment during the trapping period on column B, increments to the overall selectivity of the column switching set-up can be added creating multidimensionality via mobile phase switching; (c) combining the heart cut with the effluent mixing technique enables analysis of trace peaks eluted on the back flank of an overloaded main peak. 相似文献
50.