Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Influence of Polarity and Activation Energy in Microwave–Assisted Organic Synthesis (MAOS)

The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol⁻¹ and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation.     

从废水到新能源:光催化燃料电池的优化与应用

随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。     

A paper-based resonance energy transfer nucleic acid hybridization assay using upconversion nanoparticles as donors and quantum dots as acceptors

Monodisperse aqueous upconverting nanoparticles (UCNPs) were covalently immobilized on aldehyde modified cellulose paper via reduction amination to develop a luminescence resonance energy transfer (LRET)-based nucleic acid hybridization assay. This first account of covalent immobilization of UCNPs on paper for a bioassay reports an optically responsive method that is sensitive, reproducible and robust. The immobilized UCNPs were decorated with oligonucleotide probes to capture HPRT1 housekeeping gene fragments, which in turn brought reporter conjugated quantum dots (QDs) in close proximity to the UCNPs for LRET. This sandwich assay could detect unlabeled oligonucleotide target, and had a limit of detection of 13 fmol and a dynamic range spanning nearly 3 orders of magnitude. The use of QDs, which are excellent LRET acceptors, demonstrated improved sensitivity, limit of detection, dynamic range and selectivity compared to similar assays that have used molecular fluorophores as acceptors. The selectivity of the assay was attributed to the decoration of the QDs with polyethylene glycol to eliminate non-specific adsorption. The kinetics of hybridization were determined to be diffusion limited and full signal development occurred within 3 min.     

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery,density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum‐sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure‐decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 389–399     

Synthesis,Electronic Properties and WOLED Devices of Planar Phosphorus‐Containing Polycyclic Aromatic Hydrocarbons

We describe the synthesis and the physical properties of polyaromatic hydrocarbons (PAHs) containing a phosphorus atom at the edge. In particular, the impact of the successive addition of aromatic rings on the electronic properties was investigated by experimental (UV/Vis absorption, fluorescence, cyclic voltammetry) and theoretical studies (DFT). The physical properties recorded in solution and in the solid state showed that the P‐containing PAHs exhibit properties expected for an emitter in white organic light‐emitting diodes (WOLEDs).     

Arbitrage‐free call option surface construction using regression splines

In this work, we suggest a novel quadratic programming‐based algorithm to generate an arbitrage‐free call option surface. The empirical performance of the proposed method is evaluated using S&P 500 Index call options. Our results indicate that the proposed method provides a more precise fit to observed option prices than other alternative methodologies. Copyright © 2014 John Wiley & Sons, Ltd.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

Novel halogenated cyclopentasilylene-2,4-dienes via DFT

In view of immense importance of silylenes and the fact that their properties undergo significant changes on substitution with halogens, here, we have used B3LYP/6-311++G** level of theory to access the effects of 1–4 halogens (X = F, Cl, Br, and I) on four unprecedented sets of cyclopentasilylene-2,4-dienes; with the following formulas: SiC₄H₃X ( 1 _X ), SiC₄H₂X₂ ( 2 _X ), SiC₄HX₃ ( 3 _X ), and SiC₄X₄ ( 4 _X ). In going down from F to I, the singlet (s)-triplet (t) energy gap (ΔE_s-t, a possible indication of stability), and band gap (ΔE_H-L) decrease while nucleophilicity (N), chemical potential (μ), and proton affinity (PA) increase. The overall order of N, μ, and PA for each X is 2 _X > 1 _X > 3 _X > 4 _X . Precedence of 2 _X over 1 _X is attributed to the symmetric cross conjugation in the former. The highest and lowest N are shown by 2 _I and 4 _F . The trend of divalent angle () for each X is 4 _X > 1 _X > 3 _X > 2 _X . The results show that in going from electron withdrawing groups (EWGs) to electron donating groups (EDGs), the ΔE_s-t and ΔE_H-L decrease while N, μ, and PA increase. Also, rather high N of our scrutinized silylenes may suggest new promising ligands in organometallic chemistry.