全文获取类型
收费全文 | 913篇 |
免费 | 19篇 |
国内免费 | 2篇 |
专业分类
化学 | 795篇 |
晶体学 | 2篇 |
力学 | 6篇 |
数学 | 80篇 |
物理学 | 51篇 |
出版年
2022年 | 6篇 |
2021年 | 11篇 |
2020年 | 10篇 |
2019年 | 15篇 |
2017年 | 4篇 |
2016年 | 23篇 |
2015年 | 22篇 |
2014年 | 19篇 |
2013年 | 46篇 |
2012年 | 49篇 |
2011年 | 56篇 |
2010年 | 34篇 |
2009年 | 35篇 |
2008年 | 45篇 |
2007年 | 45篇 |
2006年 | 38篇 |
2005年 | 42篇 |
2004年 | 40篇 |
2003年 | 43篇 |
2002年 | 24篇 |
2001年 | 19篇 |
2000年 | 18篇 |
1999年 | 15篇 |
1998年 | 10篇 |
1997年 | 10篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 8篇 |
1992年 | 12篇 |
1991年 | 11篇 |
1990年 | 20篇 |
1989年 | 5篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 15篇 |
1985年 | 14篇 |
1984年 | 13篇 |
1983年 | 9篇 |
1982年 | 17篇 |
1981年 | 7篇 |
1980年 | 12篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 10篇 |
1976年 | 7篇 |
1973年 | 6篇 |
1972年 | 4篇 |
1971年 | 4篇 |
1968年 | 5篇 |
排序方式: 共有934条查询结果,搜索用时 578 毫秒
51.
Christina Haberhauer-Troyer Marizela Delic Brigitte Gasser Diethard Mattanovich Stephan Hann Gunda Koellensperger 《Analytical and bioanalytical chemistry》2013,405(6):2031-2039
A novel method for the simultaneous quantification of both glutathione (GSH) and its oxidized form glutathione disulfide (GSSG) by hydrophilic interaction chromatography–MS/MS has been developed and is critically discussed. Internal standardization based on isotopically labeled standards for both analytes is an absolute prerequisite for accurate quantification of this redox pair. Hence, a highly efficient and selective miniaturized procedure for the synthesis of isotopically labeled GSSG from commercially available glutathione-(glycine-13C2,15N) was established using H2O2 as oxidant and NaI as catalyst. Moreover, a tool is presented to monitor and hence uncover artifactual GSSG formation due to oxidation of GSH during sample preparation, which is the main source of systematic error in GSSG analysis. For this purpose, we propose to monitor the oxidation product formed by reaction of naturally occurring GSH with the isotopically labeled GSH used as internal standard. For the determination of GSH/GSSG ratios in yeast, different extraction methods based on (1) hot extraction with aqueous, acidic, or organic solvents, (2) mechanical cell lysis, and (3) extraction at subambient temperature were investigated in terms of recovery, extraction efficiency, and artifactual formation of GSSG. Total combined uncertainties of as low as 25–30 % (coverage factor?=?2) for the determination of GSH/GSSG ratios without derivatization were made possible by the addition of the internal standards early in the analytical procedure (before extraction) and immediate analysis of the analytes. 相似文献
52.
In order to obtain liquid-crystalline polymers without using classical mesogenic groups, comb copolymers consisting of a polyacrylamide main chain and lipoamino acid side chains have been synthesized. These copolymers were obtained by the polymerization of lipoamino acid macromonomers. These macromonomers were obtained from, α,ω-aliphatic amino acids by linking a polymerizable group at the amino end and an α-amino acid at the carboxyl end. The macromonomers were then transformed into comb copolymers by free-radical polymerization. These comb copolymers exhibit mesophases both in aqueous solution and in the anhydrous state. The range of stability and the structures of the mesophases were determined by X-ray diffraction. Two types of structures were found, corresponding to the lyotropic lamellar and hexagonal mesophases. The influences of the nature of the amino acid and the water concentration on the domain of stability and the geometrical parameters of the mesomorphic structures were investigated. 相似文献
53.
Sergei V. Kostjuk Hui Yee Yeong Brigitte Voit 《Journal of polymer science. Part A, Polymer chemistry》2013,51(3):471-486
This review highlights recent approaches toward polyisobutylene (PIB) by an energy efficient room temperature cationic polymerization. Special focus is laid on our own work using modified Lewis acids and nitrile‐ligated metal complexes associated with weakly coordinating anions. In both cases, suitable conditions have been found for efficient production of PIB characterized by medium to low molar masses and a high content of exo double bonds as end groups—the typical features of highly reactive PIB, an important commercial intermediate toward oil and gasoline additives. These and other approaches demonstrate that the cationic polymerization of isobutylene is still not fully explored, and new innovative catalyst systems can lead to surprising results of high commercial interest. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 相似文献
54.
Peggy Cénac Brigitte Chauvin Frédéric Paccaut Nicolas Pouyanne 《Random Structures and Algorithms》2015,46(1):117-141
Common assumptions on the source producing the words inserted in a suffix trie with n leaves lead to a height and saturation level. We provide an example of a suffix trie whose height increases faster than a power of n and another one whose saturation level is negligible with respect to . Both are built from VLMC (Variable Length Markov Chain) probabilistic sources and are easily extended to families of tries having the same properties. The first example corresponds to a “logarithmic infinite comb” and enjoys a non uniform polynomial mixing. The second one corresponds to a “factorial infinite comb” for which mixing is uniform and exponential. © 2013 Wiley Periodicals, Inc. Random Struct. Alg., 46, 117–141, 2015 相似文献
55.
Marko Stojkovic Israel Joel Koenka Wolfgang Thormann Peter C. Hauser 《Electrophoresis》2014,35(4):482-486
A CE system featuring an array of 16 contactless conductivity detectors was constructed. The detectors were arranged along 70 cm length of a capillary with 100 cm total length and allow the monitoring of separation processes. As the detectors cannot be accommodated on a conventional commercial instrument, a purpose built set‐up employing a sequential injection manifold had to be employed for automation of the fluid handling. Conductivity measurements can be considered universal for electrophoresis and thus any changes in ionic composition can be monitored. The progress of the separation of Na+ and K+ is demonstrated. The potential of the system to the study of processes in CZE is shown in two examples. The first demonstrates the differences in the developments of peaks originating from a sample plug with a purely aqueous background to that of a plug containing the analyte ions in the buffer. The second example visualizes the opposite migration of cations and anions from a sample plug that had been placed in the middle of the capillary. 相似文献
56.
57.
Dr. Andrea Hornemann Dr. Diane M. Eichert Arne Hoehl Dr. Brigitte Tiersch Prof. Gerhard Ulm Prof. Maxim G. Ryadnov Dr. Burkhard Beckhoff 《Chemphyschem》2022,23(4):e202100815
Synchrotron radiation-based Fourier transform infrared spectroscopy enables access to vibrational information from mid over far infrared to even terahertz domains. This information may prove critical for the elucidation of fundamental bio-molecular phenomena including folding-mediated innate host defence mechanisms. Antimicrobial peptides (AMPs) represent one of such phenomena. These are major effector molecules of the innate immune system, which favour attack on microbial membranes. AMPs recognise and bind to the membranes whereupon they assemble into pores or channels destabilising the membranes leading to cell death. However, specific molecular interactions responsible for antimicrobial activities have yet to be fully understood. Herein we probe such interactions by assessing molecular specific variations in the near-THz 400–40 cm−1 range for defined helical AMP templates in reconstituted phospholipid membranes. In particular, we show that a temperature-dependent spectroscopic analysis, supported by 2D correlative tools, provides direct evidence for the membrane-induced and folding-mediated activity of AMPs. The far-FTIR study offers a direct and information-rich probe of membrane-related antimicrobial interactions. 相似文献
58.
Friederike A. Sandbaumhüter Claudia Gittel M. Paula Larenza-Menzies Regula Theurillat Wolfgang Thormann Christina Braun 《Electrophoresis》2021,42(17-18):1826-1831
The enantioselectivity of the pharmacokinetics of methadone was investigated in anesthetized Shetland ponies after a single intravenous (0.5 mg/kg methadone hydrochloride; n = 6) or constant rate infusion (0.25 mg/kg bolus followed by 0.25 mg/kg/h methadone hydrochloride; n = 3) administration of racemic methadone. Plasma concentrations of l -methadone and d -methadone and their major metabolites, l - and d -2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP), respectively, were analyzed by CE with highly sulfated γ-cyclodextrin as chiral selector and electrokinetic analyte injection from liquid/liquid extracts prepared at alkaline pH. In both trials, the d -methadone concentrations were lower than those of l -methadone and the d -EDDP levels were lower than those of L-EDDP. For the case of a single intravenous bolus injection, the plasma concentration versus time profile of methadone enantiomers was analyzed with a two-compartment pharmacokinetic model. l -methadone showed a slower elimination rate constant, a lower body clearance, and a smaller steady-state volume of distribution than d -methadone. d -methadone and d -EDDP were eliminated faster than their respective l -enantiomers. This is the first study that outlines that the disposition of racemic methadone administered to anesthetized equines is enantioselective. 相似文献
59.
α‐Halogenoacetanilides as Hydrogen‐Bonding Organocatalysts that Activate Carbonyl Bonds: Fluorine versus Chlorine and Bromine
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Sylvain Koeller Dr. Coralie Thomas Dr. Fréderic Peruch Dr. Alain Deffieux Dr. Stéphane Massip Prof. Dr. Jean‐Michel Léger Dr. Jean‐Pierre Desvergne Prof. Dr. Anne Milet Dr. Brigitte Bibal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(10):2849-2859
α‐Halogenoacetanilides (X=F, Cl, Br) were examined as H‐bonding organocatalysts designed for the double activation of C?O bonds through NH and CH donor groups. Depending on the halide substituents, the double H‐bond involved a nonconventional C?H???O interaction with either a H?CXn (n=1–2, X=Cl, Br) or a H?CAr bond (X=F), as shown in the solid‐state crystal structures and by molecular modeling. In addition, the catalytic properties of α‐halogenoacetanilides were evaluated in the ring‐opening polymerization of lactide, in the presence of a tertiary amine as cocatalyst. The α‐dichloro‐ and α‐dibromoacetanilides containing electron‐deficient aromatic groups afforded the most attractive double H‐bonding properties towards C?O bonds, with a N?H???O???H?CX2 interaction. 相似文献
60.
Jochen Schölhammer Brigitte Baretzky Wolfgang Gust Eric Mittemeijer Boris Straumal 《Interface Science》2001,9(1-2):43-53
The atomic force microscopy (AFM) was used to study the grain boundary (GB) groove profiles far away from the melting temperature T
m. It is shown that AFM allows one to measure the temperature dependence of the GB energy in a rather broad temperature interval (from 0.85 T
m to T
m). The GB energy and GB segregation of Bi were measured at 1123 K in the interval of the Bi bulk concentration x
v
Bi from 5 to 140 ppm Bi. The transition from monolayer to multilayer adsorption is observed for the 19a GB at 1123 K and x
v
Bi = 60 at. ppm Bi. At the same point (1123 K and x
v
Bi = 60 at. ppm Bi) a discontinuity of the first derivative of the GB energy is observed. These features were explained using the model of GB prewetting phase transformation developed previously. 相似文献