全文获取类型
收费全文 | 172篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 130篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 29篇 |
物理学 | 20篇 |
出版年
2023年 | 3篇 |
2022年 | 8篇 |
2021年 | 13篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 4篇 |
2017年 | 1篇 |
2016年 | 8篇 |
2015年 | 4篇 |
2014年 | 9篇 |
2013年 | 7篇 |
2012年 | 26篇 |
2011年 | 13篇 |
2010年 | 9篇 |
2009年 | 11篇 |
2008年 | 6篇 |
2007年 | 4篇 |
2006年 | 7篇 |
2005年 | 7篇 |
2004年 | 5篇 |
2003年 | 2篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 3篇 |
1982年 | 1篇 |
排序方式: 共有184条查询结果,搜索用时 213 毫秒
61.
62.
Gottardo R Polettini A Sorio D Pascali JP Bortolotti F Liotta E Tagliaro F 《Electrophoresis》2008,29(19):4078-4087
A new method for the determination of illicit and abused drugs in blood by capillary zone electrophoresis-electrospray ionization-time-of-flight mass spectrometry is proposed, in view of its application in clinical and forensic toxicology. The analytes (methamphetamine, methylenedioxyamphetamine, methylenedioxyethylamphetamine, methylenedioxymethamphetamine, methadone, cocaine, morphine, codeine, 6-acethylmorphine, benzoylecgonine) were separated with capillary zone electrophoresis by applying 15 kV within 25 min, in an uncoated fused-silica capillary (75 microm x 100 cm) using a 25 mM ammonium formate electrolyte solution (pH 9.5). The capillary electropherograph was coupled to time-of-flight mass spectrometry through an orthogonal electrospray ionization source, with a coaxial sheath liquid interface. The sheath liquid was composed of isopropanol-water (1:1 v/v) containing 0.5% formic acid delivered at 4 microL/min. Forensic drugs were identified by exact mass determination (mass accuracy typically < or =5 ppm) and by matching of the isotopic pattern. Under optimized conditions, linearity was assessed in the range 10-2000 ng/mL, with correlation coefficients between 0.9744 and 0.9982 for all the analytes. LODs were in the range of 2-10 ng/mL (S/N > or =3) and LOQs of 10-30 ng/mL. The CVs (tested at 40 and 800 ng/mL in biological matrix) were below 2.97% for migration times and below 14.61% for peak area ratios (analyte/internal standard). Blood samples were extracted by using a liquid-liquid extraction procedure and injected under field-amplified sample stacking conditions. The method was successfully applied to real cases. 相似文献
63.
Biver T Friani R Gattai C Secco F Tiné MR Venturini M 《The journal of physical chemistry. B》2008,112(38):12168-12173
The equilibria and kinetics for the process of In(3+) exchange between nitrilotriacetic acid (NTA) and bovine serum transferrin (T) have been investigated in aqueous solution containing sodium bicarbonate. The metal exchange equilibria have been measured by difference ultraviolet spectroscopy at 25 degrees C, pH=7.4, and I=0.2 M (NaClO4). The acid dissociation constants of NTA and the binding constants of In(III) to NTA have also been measured. Kinetic experiments revealed that the process of In(3+) uptake by transferrin from [In(NTA)2](3-) is biphasic, the fast phase being completed in a few seconds, the slow phase lasting for hours. The fast phase has been investigated by the stopped-flow method and results in monoexponential kinetics. It involves rapid interaction of the 1:1 complex ML (M=In, L=NTA) with TB (T=transferrin, B=CO3(2-)) to give a quaternary intermediate MLTB which then evolves to an "open" MTB* ternary complex complex with expulsion of L. In turn, this complex interconverts to a "closed", more stable, form MTB. Neither the prevailing complex M2L nor the TB2 form of transferrin are directly involved in the exchange process but act as metal and protein reservoirs. The pH dependence of the reaction has been also investigated. The slow phase has not been investigated in detail; it takes several hours to go to the completeness, its slowness being ascribed to metal redistribution between the C-site and N-site of the protein, and/or metal release from polynuclear In(III) species. 相似文献
64.
Self‐(Un)rolling Biopolymer Microstructures: Rings,Tubules, and Helical Tubules from the Same Material 下载免费PDF全文
Dr. Chunhong Ye Svetoslav V. Nikolov Dr. Rossella Calabrese Dr. Amir Dindar Prof. Alexander Alexeev Prof. Bernard Kippelen Prof. David L. Kaplan Prof. Vladimir V. Tsukruk 《Angewandte Chemie (International ed. in English)》2015,54(29):8490-8493
We have demonstrated the facile formation of reversible and fast self‐rolling biopolymer microstructures from sandwiched active–passive, silk‐on‐silk materials. Both experimental and modeling results confirmed that the shape of individual sheets effectively controls biaxial stresses within these sheets, which can self‐roll into distinct 3D structures including microscopic rings, tubules, and helical tubules. This is a unique example of tailoring self‐rolled 3D geometries through shape design without changing the inner morphology of active bimorph biomaterials. In contrast to traditional organic‐soluble synthetic materials, we utilized a biocompatible and biodegradable biopolymer that underwent a facile aqueous layer‐by‐layer (LbL) assembly process for the fabrication of 2D films. The resulting films can undergo reversible pH‐triggered rolling/unrolling, with a variety of 3D structures forming from biopolymer structures that have identical morphology and composition. 相似文献
65.
Cirilli R Alcaro S Fioravanti R Ferretti R Bolasco A Gallinella B Faggi C 《Journal of chromatography. A》2011,1218(33):5653-5657
A set of ten C5-chiral 4,5-dihydro-(1H)-pyrazole derivatives was synthesized and analyzed by high-performance liquid chromatography (HPLC) on the polysaccharide-based Chiralcel OJ-H chiral stationary phase (CSP). The enantioseparations were carried out using pure ethanol as eluent. Different structural elements of the investigated compounds were recognized for obtaining a very high enantioselectivity. In order to clarify some aspects of the chiral discrimination process, the thermodynamic parameters associated to the enantiorecognition and the enantiomer elution order were established. 相似文献
66.
C Ye I Drachuk R Calabrese H Dai DL Kaplan VV Tsukruk 《Langmuir : the ACS journal of surfaces and colloids》2012,28(33):12235-12244
We studied the pH-responsive behavior of layer-by-layer (LbL) microcapsules fabricated from silk fibroin chemically modified with different poly amino acid side chains: cationic (silk-poly l-lysine, SF-PL) or anionic (silk-poly-l-glutamic acid, SF-PG). We observed that stable ultrathin shell microcapsules can be assembled with a dramatic increase in swelling, thickness, and microroughness at extremely acidic (pH < 2.5) and basic (pH > 11.0) conditions without noticeable disintegration. These changes are accompanied by dramatic changes in shell permeability with a 2 orders of magnitude increase in the diffusion coefficient. Moreover, the silk ionomer shells undergo remarkable softening with a drop in Young's modulus by more than 1 order of magnitude due to the swelling, stretching, and increase in material porosity. The ability to control permeability and mechanical properties over a wide range for the silk-based microcapsules, with distinguishing stability under harsh environmental conditions, provides an important system for controlled loading and release and applications in bioengineering. 相似文献
67.
Tom P. Carberry Rossella Tarallo Dr. Annarita Falanga Dr. Emiliana Finamore Prof. Dr. Massimiliano Galdiero Prof. Dr. Marcus Weck Prof. Dr. Stefania Galdiero 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(43):13678-13685
A poly(amide)‐based dendrimer was synthesized and functionalized with the membrane‐interacting peptide gH(625–644) (gH625) derived from the herpes simplex virus type 1 (HSV‐1) envelope glycoprotein H, which has previously been shown to assist in delivering large cargoes across the cellular membrane. We demonstrate that the attachment of the gH625 peptide sequence to the termini of a dendrimer allows the conjugate to penetrate into the cellular matrix, whereas the unfunctionalized dendrimer is excluded from translocation. The peptide‐functionalized dendrimer is rapidly taken into the cells mainly through a non‐active translocation mechanism. Our results suggest that the presented peptidodendrimeric scaffold may be a promising material for efficient drug delivery. 相似文献
68.
The present work is aimed at investigating the influence of the background electrolyte composition and concentration on the separation efficiency and resolution and mass spectrometric detection of illicit drugs in a capillary zone electrophoresis-electrospray ionization-time of flight mass spectrometry (CZE-ESI-TOF MS) system. The effect of phosphate, borate and Tris buffers on the separation and mass spectrometry response of a mixture of 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, methadone, cocaine, morphine, codeine and 6-monoacetylmorphine was studied, in comparison with a reference ammonium formate separation buffer. Inorganic non-volatile borate and Tris buffers proved hardly suitable for capillary electrophoresis-mass spectrometry (CE-MS) analysis, but quite unexpectedly ammonium phosphate buffers showed good separation and ionization performances for all the analytes tested. Applications of this method to real samples of hair from drug addicts are also provided. 相似文献
69.
Mello R Alcalde-Aragonés A Olmos A González-Núñez ME Asensio G 《The Journal of organic chemistry》2012,77(10):4706-4710
Anhydrous 2-percarboxyethyl-functionalized silica (2b), a recyclable supported peracid, is a suitable reagent to perform the epoxidation of alkenes 1 in supercritical carbon dioxide at 250 bar and 40 °C under flow conditions. This procedure simplifies the isolation of the reaction products and uses only carbon dioxide as a solvent under mild conditions. The solid reagent 2b can be easily recycled by a reaction with 30% hydrogen peroxide in an acid medium. 相似文献
70.
D Witkowska R Politano M Rowinska-Zyrek R Guerrini M Remelli H Kozlowski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(35):11088-11099
Hpn, one of Helicobacter pylori's nickel-accessory proteins, is an amazingly peculiar protein: Almost half of its sequence consists of polyhistidyl (poly-His) residues. Herein, we try to understand the origin of this naturally occurring sequence, thereby shedding some light on the bioinorganic chemistry of Hpn's numerous poly-His repeats. By using potentiometric, mass spectrometric, and various spectroscopic techniques, we studied the Ni(II) - and Cu(II) complexes of the wild-type Ac-THHHHYHGG-NH(2) fragment of Hpn and of its six analogues, in which consecutive residues (His or Tyr) were replaced by Ala (Ala-substitution or Ala-scan approaches), thereby resulting in Ac-TAHHHYHGG-NH(2) , Ac-THAHHYHGG-NH(2) , Ac-THHAHYHGG-NH(2) , Ac-THHHAYHGG-NH(2) , Ac-THHHHAHGG-NH(2) , and Ac-THHHHYAGG-NH(2) peptides. We found that the His4 residue is critical for both Ni(II) - and Cu(II) -ion binding and the effectiveness of binding varies even if the substituted amino acid does not take part in the direct binding interactions. 相似文献