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991.
Helmut Beckers Dr. Xiaoqing Zeng Dr. Helge Willner Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(5):1506-1520
Pure sym‐N2O4 isolated in solid Ne was obtained by passing cold neon gas over solid N2O4 at ?115 °C and quenching the resulting gaseous mixture at 6.3 K. Filtered UV irradiation (260–400 nm) converts sym‐N2O4 into trans‐ONONO2, a weakly interacting (NO2)2 radical pair, and traces of the cis‐N2O2?O2 complex. Besides the weakly bound ON?O2 complex, cis‐N2O2?O2 was also obtained by co‐deposition of NO and O2 in solid Ne at 6.3 K, and both complexes were characterised by their matrix IR spectra. Concomitantly formed cis‐N2O2 dissociated on exposure to filtered IR irradiation (400–8000 cm?1), and the cis‐N2O2?O2 complex rearranged to sym‐N2O4 and trans‐ONONO2. Experiments using 18O2 in place of 16O2 revealed a non‐concerted conversion of cis‐N2O2?O2 into these species, and gave access to four selectively di‐18O‐substituted trans‐ONONO2 isotopomers. No isotopic scrambling occurred. The IR spectra of sym‐N2O4 and of trans‐ONONO2 in solid Ne were recorded. IR fundamentals of trans‐ONONO2 were assigned based on experimental 16/18O isotopic shifts and guided by DFT calculations. Previously reported contradictory measurements on cis‐ and trans‐ONONO2 are discussed. Dinitroso peroxide, ONOONO, a proposed intermediate in the IR photoinduced rearrangement of cis‐N2O2?O2 to the various N2O4 species, was not detected. Its absence in the photolysis products indicates a low barrier (≤10 kJ mol?1) for its exothermic O? O bond homolysis into a (NO2)2 radical pair. 相似文献
992.
José Luis Palacios José Miguel Renom 《International journal of quantum chemistry》2010,110(9):1637-1641
Using probabilistic tools, we give tight upper and lower bounds for the Kirchhoff index of any d‐regular N‐vertex graph in terms of d, N, and the spectral gap of the transition probability matrix associated to the random walk on the graph. We then use bounds of the spectral gap of more specialized graphs, available in the literature, in order to obtain upper bounds for the Kirchhoff index of these specialized graphs. As a byproduct, we obtain a closed‐form formula for the Kirchhoff index of the d‐dimensional cube in terms of the first inverse moment of a positive binomial variable. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
993.
W. Russ Algar 《Analytica chimica acta》2010,673(1):1-25
A comprehensive review of the development of assays, bioprobes, and biosensors using quantum dots (QDs) as integrated components is presented. In contrast to a QD that is selectively introduced as a label, an integrated QD is one that is present in a system throughout a bioanalysis, and simultaneously has a role in transduction and as a scaffold for biorecognition. Through a diverse array of coatings and bioconjugation strategies, it is possible to use QDs as a scaffold for biorecognition events. The modulation of QD luminescence provides the opportunity for the transduction of these events via fluorescence resonance energy transfer (FRET), bioluminescence resonance energy transfer (BRET), charge transfer quenching, and electrochemiluminescence (ECL). An overview of the basic concepts and principles underlying the use of QDs with each of these transduction methods is provided, along with many examples of their application in biological sensing. The latter include: the detection of small molecules using enzyme-linked methods, or using aptamers as affinity probes; the detection of proteins via immunoassays or aptamers; nucleic acid hybridization assays; and assays for protease or nuclease activity. Strategies for multiplexed detection are highlighted among these examples. Although the majority of developments to date have been in vitro, QD-based methods for ex vivo biological sensing are emerging. Some special attention is given to the development of solid-phase assays, which offer certain advantages over their solution-phase counterparts. 相似文献
994.
Diabetes, a multifunctional disease and a major cause of morbidity and mortality in the industrialized countries, strongly associates with the development and progression of atherosclerosis. One of the consequences of high level of glucose in the blood circulation is glycation of long-lived proteins, such as collagen I, the most abundant component of the extracellular matrix (ECM) in the arterial wall. Glycation is a long-lasting process that involves the reaction between a carbonyl group of the sugar and an amino group of the protein, usually a lysine residue. This reaction generates an Amadori product that may evolve in advanced glycation end products (AGEs). AGEs, as reactive molecules, can provoke cross-linking of collagen I fibrils. Since binding of low-density lipoproteins (LDLs) to the ECM of the inner layer of the arterial wall, the intima, has been implicated to be involved in the onset of the development of an atherosclerotic plaque, collagen modifications, which can affect the affinity of native and oxidized LDL for collagen I, can promote the entrapment of LDLs in the intima and accelerate the progression of atherosclerosis.In this study, open tubular capillary electrochromatography is proposed as a new microreactor to study in situ glycation of collagen I. The kinetics of glycation was first investigated in a fused silica collagen I-coated capillary. Dimethyl sulphoxide, injected as an electroosmotic flow marker, gave information about the charge of coating. Native and oxidized LDL, and selected peptide fragments from apolipoprotein B-100, the protein covering LDL particles, were injected as marker compounds to clarify the interactions between LDLs and the glycated collagen I coating. The method proposed is simple and inexpensive, since only small amounts of collagen and LDL are required. Atomic force microscopy images complemented our studies, highlighting the difference between unmodified and glycated collagen I surfaces. 相似文献
995.
This paper presents a new sample preparation procedure for determination of selected acidic pharmaceuticals (ibuprofen, naproxen, ketoprofen, and diclofenac) in sewage sludge using microwave assisted solvent extraction, dispersive matrix extraction (DME) followed by the conventionally applied solid phase extraction (SPE), derivatization, and gas chromatography-mass spectrometry. The recoveries calculated from analytical data of spiked sludge samples changed in the range of 80-105% ± 15% for the four pharmaceuticals in mixed and activated sludge depending on the efficiency of the clean-up procedure. The measured concentration values of ibuprofen and naproxen were identical in the mixed and the activated sludge samples. However, ketoprofen and diclofenac showed about twice as high concentration in activated sludge than in the mixed one independently of the applied extraction method. The typical concentration ranges of ibuprofen, naproxen, ketoprofen and diclofenac in sewage sludge were 10-30 ng/g, 30-50 ng/g, 50-130 ng/g, and 50-140 ng/g respectively. 相似文献
996.
Francisco J. Salgado Sara Vázquez Amparo Pérez-Díaz Pilar Arias 《Analytica chimica acta》2010,658(1):18-3648
Serum is a typical sample for non-invasive studies in clinical research. Its proteome characterization is challenging, since requires extensive protein depletion. Methods used nowadays for removal of high-abundance proteins are expensive or show quite often a low loading capacity, which has strong repercussions on the number of samples and replicates per analysis.In order to deplete immunoglobulins (Igs) and albumin (HSA) from 1 mL serum samples, we have developed a protocol based on a combination of thiophilic chromatography, not previously used in clinical proteomics, and a HSA-specific resin. Ig/HSA-depleted samples, immunoglobulinome and albuminone were analyzed by 2-DE. Thiophilic chromatography, coupled with HSA-depletion, allows a good 2-DE resolution as well as the visualization of new spots. Moreover, it yields enough protein to evaluate technical variability and facilitate subsequent protein identification. To validate the protocol, we carried out a preliminary comparative study between triplicate Igs/HSA-depleted serum samples from healthy control individuals and recently diagnosed/untreated rheumatoid arthritis (RA) patients. RA patients showed several acute phase proteins, as well as additional serum proteins, differentially and significantly regulated.Therefore, thiophilic chromatography can be used as an efficient and economical method in 2-DE to deplete immunoglobulins from large human serum samples before a more extensive fractioning. 相似文献
997.
The interactions of water molecule with platinum dioxygen complex and dioxide molecule are investigated by means of matrix isolation infrared spectroscopy and density functional calculations. The platinum atoms reacted with dioxygen to form the previously reported Pt(O2) complex. The Pt(O2) complex reacted with water molecule to give the Pt(O2)–H2O complex, which was characterized to involve hydrogen bonding between one O atom of Pt(O2) and one H atom of H2O (structure A ). Upon visible light irradiation, the hydrogen bonded Pt(O2)???HOH complex rearranged to another Pt(O2)–H2O isomer (structure B ), which involves (O2)Pt???OH2 interaction. The Pt(O2)–H2O complex in structure B can be isomerized to the weakly bound platinum dioxide‐water complex (structure C ) under UV irradiation. 相似文献
998.
Junoh Kim Jongwon Shim Yong‐Jin Kim Kookheon Char Kyung‐Do Suh Jin‐Woong Kim 《Macromolecular bioscience》2010,10(10):1171-1176
This study reports a facile and practical means to non‐invasively deliver biologically active ingredients through the skin using polymer‐based nanocarriers. For this, polymer nanocapsules were fabricated with different surface charges as well as glass transition temperatures and we observed their ability to deliver the encapsulated active ingredient, coenzyme Q10, through the skin layer. Direct imaging of a probe molecule, Nile Red, and a matrix polymer labeled with fluorescence moiety, Lucifer Yellow, allowed us to demonstrate that the probe molecule readily permeates into the deep skin, while the matrix polymer stays in the stratum corneum layer due to electrostatic interactions. Quantitative characterization of the penetrating amount of coenzyme Q10 using the Frantz cell method proved that, to achieve improved delivery efficiency, the nanocapsule should have a low glass transition temperature as well as positive surface charges.
999.
Helena Řehulková Jana Chalupová Marek Šebela Pavel Řehulka 《Journal of mass spectrometry : JMS》2010,45(1):104-111
Peptide samples derived from enzymatic in‐gel digestion of proteins resolved by gel electrophoresis often contain high amount of salts originating from reaction and separation buffers. Different methods are used for desalting prior to matrix‐assisted laser desorption/ionization (MALDI) mass spectrometry (MS), e.g. reversed‐phase pipette tip purification, on‐target washing, adding co‐matrices, etc. As a suitable matrix for MALDI MS of peptides, α‐cyano‐4‐hydroxycinnamic acid (CHCA) is frequently used. Crystalline CHCA shows the ability to bind peptides on its surface and because it is almost insoluble in acidic water solutions, the on‐target washing of peptide samples can significantly improve MALDI MS signals. Although the common on‐target washing represents a simple, cheap and fast procedure, only a small portion of the available peptide solution is efficiently used for the subsequent MS analysis. The present approach is a combination of the on‐target washing principle carried out in a narrow‐end pipette tip (e.g. GELoader tip) and preconcentration of peptides from acidified solution by passing it through small CHCA crystals captured inside the tip on a glass microfiber frit. The results of MALDI MS analysis using CHCA‐tip peptide preconcentration are comparable with the use of homemade POROS R2 pipette tip microcolumns. Advantages and limitations of this approach are discussed. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
1000.