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91.
A few years back T. Vértesi et al. (J Phys Chem A 2005, 109, 3476) gave an elegant procedure to derive the adiabatic‐to‐diabatic transformation angle (ADT‐angle) for lowest two states, γ12, in presence of their interaction with the higher states. In this article, we explicitly solved the coupled differential equations involving the ADT‐angles describing the mixing of four interacting states for the first time to get all the ADT‐angles, γij's (including the γ12) associated with well‐defined topological phases. In application to a suitable configuration space (CS) of a molecular system, we have demonstrated well‐defined Berry phases (Berry M. V., R Soc London Ser A 1984, 45, 392) for an isolated system with as many as four strongly interacting states. © 2012 Wiley Periodicals, Inc. 相似文献
92.
Isabelle Hladezuk Veronique Chastagner Stuart G. Collins Stephen J. Plunkett Alan Ford Sebastien Debarge Anita R. Maguire 《Tetrahedron》2012,68(7):1894-1909
Development of rhodium catalysed O–H insertion reactions employing α-diazophosphonates with appropriately protected adenosine, uridine and thymidine derivatives is described. This synthetic methodology leads, following deprotection, to novel phosphononucleoside derivatives bearing a carboxylic acid moiety adjacent to the phosphonate. Protection strategies are critical to the success of the key O–H insertion. There are two important aspects: avoiding competing insertion pathways or catalyst poisoning, and being able to achieve deprotection without degradation of the phosphononucleosides. 相似文献
93.
94.
Erica D. Couch Dr. Tyler J. Auvil Prof. Anita E. Mattson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(27):8283-8287
The enhanced catalytic activity of difluoroboronate ureas proved to be essential as an acidity amplifier to promote metal‐free O?H and S?H insertion reactions of α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester. 相似文献
95.
96.
Here we report the characterization of an electrochemical mercury (Hg2+) sensor constructed with a methylene blue (MB)-modified and thymine-containing linear DNA probe. Similar to the linear probe electrochemical DNA sensor, the resultant sensor behaved as a “signal-off” sensor in alternating current voltammetry and cyclic voltammetry. However, depending on the applied frequency or pulse width, the sensor can behave as either a “signal-off” or “signal-on” sensor in square wave voltammetry (SWV) and differential pulse voltammetry (DPV). In SWV, the sensor showed “signal-on” behavior at low frequencies and “signal-off” behavior at high frequencies. In DPV, the sensor showed “signal-off” behavior at short pulse widths and “signal-on” behavior at long pulse widths. Independent of the sensor interrogation technique, the limit of detection was found to be 10 nM, with a linear dynamic range between 10 nM and 500 nM. In addition, the sensor responded to Hg2+ rather rapidly; majority of the signal change occurred in <20 min. Overall, the sensor retains all the characteristics of this class of sensors; it is reagentless, reusable, sensitive, specific and selective. This study also highlights the feasibility of using a MB-modified probe for real-time sensing of Hg2+, which has not been previously reported. More importantly, the observed “switching” behavior in SWV and DPV is potentially generalizable and should be applicable to most sensors in this class of dynamics-based electrochemical biosensors. 相似文献
97.
Lucas Martins Monica Arrais Alexandre de Souza Anita Marsaioli 《Magnetic resonance in chemistry : MRC》2014,52(11):665-672
Binary and ternary systems composed of dapsone, sulfobutylether‐β‐cyclodextrin (SBE‐β‐CD), β‐CD and egg phosphatidylcholine (EPC) were evaluated using 1D ROESY, saturation transfer difference NMR and diffusion experiments (DOSY) revealing the binary complexes Dap/β‐CD (Ka 1396 l mol?1), Dap/SBE‐β‐CD (Ka 246 l mol?1), Dap/EPC (Ka 84 l mol?1) and the ternary complex Dap/β‐CD/EPC (Ka 18 l mol?1) in which dapsone is more soluble. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
98.
Emerald ash borer (EAB), Agrilus planipennis Fairmaire, is an invasive insect that has killed millions of ash trees in Canada and the USA. (3Z)-Dodecen-12-olide is a known female-produced pheromone of this insect, and a concise, three-step synthesis of a 2:1 blend of (3Z)-dodecen-12-olide and (3E)-dodecen-12-olide starting from commercially available (2-carboxyethyl)triphenylphosphonium bromide and 10-bromo-1-decene is described. The key steps in this synthesis are a lithium-salt-free Wittig reaction and an intramolecular SN2 esterification. Both of these macrocyclic lactones are behaviorally active toward EAB, and the 2:1 blend whose synthesis is described here has the potential to be a detection agent, mating disruptor, or mass trapping agent, which could be used in the control of EAB. 相似文献
99.
Rotem Shemesh Maksym Krepker Diana Goldman Yael Danin‐Poleg Yechezkel Kashi Nadav Nitzan Anita Vaxman Ester Segal 《先进技术聚合物》2015,26(1):110-116
Active antimicrobial packaging is a promising form of active packaging that can kill or inhibit microorganism growth in order to maintain product quality and safety. One of the most common approaches is based on the release of volatile antimicrobial agents from the packaging material such as essential oils. Due to their highly volatile nature, the challenge is to preserve the essential oils during the high‐temperature melt processing of the polymer, while maintaining high antimicrobial activity for a desired shelf life. This study suggests a new approach in order to achieve this goal. Antimicrobial active films are developed based on low‐density polyethylene (LDPE), organo‐modified montmorillonite clays (MMT) and carvacrol (used as an essential oil model). In order to minimize carvacrol loss throughout the polymer compounding, a pre‐compounding step is developed in which clay/carvacrol hybrids are produced. The hybrids exhibit a significant increase in the d‐spacing of clay and enhanced thermal stability. The resulting LDPE/(clay/carvacrol) films exhibit superior and prolonged antibacterial activity against Escherichia coli and Listeria innocua, while polymer compounded with pure carvacrol loses the antibacterial properties within days. The films also present an excellent antifungal activity against Alternaria alternata, used as a model plant pathogenic fungus. Furthermore, infrared spectroscopy analysis of the LDPE/(clay/carvacrol) system displayed significantly higher carvacrol content in the film as well as a slower out‐diffusion of the carvacrol molecules in comparison to LDPE/carvacrol films. Thus, these new films have a high potential for antimicrobial food packaging applications due to their long‐lasting and broad‐spectrum antimicrobial efficacy. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
100.
Andreas Klitgaard Anita Iversen Mikael R. Andersen Thomas O. Larsen Jens Christian Frisvad Kristian Fog Nielsen 《Analytical and bioanalytical chemistry》2014,406(7):1933-1943
In natural-product drug discovery, finding new compounds is the main task, and thus fast dereplication of known compounds is essential. This is usually performed by manual liquid chromatography-ultraviolet (LC-UV) or visible light-mass spectroscopy (Vis-MS) interpretation of detected peaks, often assisted by automated identification of previously identified compounds. We used a 15 min high-performance liquid chromatography–diode array detection (UHPLC–DAD)–high-resolution MS method (electrospray ionization (ESI)+ or ESI?), followed by 10–60 s of automated data analysis for up to 3000 relevant elemental compositions. By overlaying automatically generated extracted-ion chromatograms from detected compounds on the base peak chromatogram, all major potentially novel peaks could be visualized. Peaks corresponding to compounds available as reference standards, previously identified compounds, and major contaminants from solvents, media, filters etc. were labeled to differentiate these from compounds only identified by elemental composition. This enabled fast manual evaluation of both known peaks and potential novel-compound peaks, by manual verification of: the adduct pattern, UV–Vis, retention time compared with log D, co-identified biosynthetic related compounds, and elution order. System performance, including adduct patterns, in-source fragmentation, and ion-cooler bias, was investigated on reference standards, and the overall method was used on extracts of Aspergillus carbonarius and Penicillium melanoconidium, revealing new nitrogen-containing biomarkers for both species. 相似文献