Magnetic field dependence of electron spin polarization generated through radical-triplet interactions

The magnetic field dependence of electron spin polarization (ESP), generated in free radicals when they encounter photoexcited triplets, was measured experimentally and analyzed theoretically. The time-resolved electron paramagnetic resonance measurements were performed with a microwave setup consisting of low-loss dielectric ring resonators with tunable microwave frequencies and the corresponding magnetic fields. The ESP of the radical was found in the magnetic field range of 170-370 mT, and the results of the calculation based on the numerical solution of the stochastic Liouville equation were found to be in line with the experimental data showing that ESP decreases when the magnetic field increases.     

一种适用于飞行器航电综合的故障检测和重构方法

鉴于特殊的飞行任务需求,某型号航电综合单一的故障逻辑难以满足多元故障状态下自主重构需求,降低了系统容错性。为解决航电综合多元故障模式难以量化表征影响故障重构的工程难题,创新的提出了一种适用于航电综合的故障检测和重构方法,基于决策表数据挖掘技术的航电综合故障预测流程和多源信息故障检测技术确保常规故障检测率大于98%,航电系统重构状态的量化表征分类方式确保了系统快速重构设计,本文提出的故障检测和重构方法极大地提高航电综合系统的故障检测率与容错能力。     

Kinetic resolution and chemoenzymatic dynamic kinetic resolution of functionalized gamma-hydroxy amides

[reaction: see text] An efficient kinetic resolution of racemic gamma-hydroxy amides 1 was performed via Pseudomas cepacia lipase (PS-C)-catalyzed transesterification. The enzyme PS-C tolerates both variation in the chain length and different functionalities giving good to high enantioselectivity (E values of up to >250). The combination of enzymatic kinetic resolution with a ruthenium-catalyzed racemization led to a dynamic kinetic resolution. The use of 2,4-dimethyl-3-pentanol as a hydrogen source to suppress ketone formation in the dynamic kinetic resolution yields the corresponding acetates in good yield and good to high enantioselectivity (ee's up to 98%). The synthetic utility of this procedure was illustrated by the practical synthesis of the versatile intermediate gamma-lactone (R)-5-methyltetrahydrofuran-2-one.     

Switchable ionic liquids enable efficient nanofibrillation of wood pulp

Use of switchable ionic liquid (SIL) pulp offers an efficient and greener technology to produce nanofibers via ultrafine grinding. In this study, we demonstrate that SIL pulp opens up a mechanically efficient route to the nanofibrillation of wood pulp, thus providing both a low cost and chemically benign route to the production of cellulose nanofibers. The degree of fibrillation during the process was evaluated by viscosity and optical microscopy of SIL treated, bleached SIL treated and a reference pulp. Furthermore, films were prepared from the fibrillated material for characterization and tensile testing. It was observed that substantially improved mechanical properties were attained as a result of the grinding process, thus signifying nanofibrillation. Both SIL treated and bleached SIL treated pulps were fibrillated into nanofibers with fiber diameters below 15 nm thus forming networks of hydrophilic nature with an intact crystalline structure. Notably, it was found that the SIL pulp could be fibrillated more efficiently than traditional pulp since nanofibers could be produced with more than 30% less energy when compared to the reference pulp. Additionally, bleaching reduced the energy demand by further 16%. The study demonstrated that this switchable ionic liquid treatment has considerable potential in the commercial production of nanofibers due to the increased efficiency in fibrillation.     

Measuring the pollutant transport capacity of dissolved organic matter in complex matrixes

Dissolved organic matter (DOM) facilitated transport in contaminated groundwater was investigated through the measurement of the binding capacity of landfill leachate DOM (Vejen, Denmark) towards two model pollutants (pyrene and phenanthrene). Three different methods for measuring binding capacity were used and evaluated, head-space solid-phase micro-extraction (HS-SPME), enhanced solubility (ES) and fluorescence quenching (FQ). It was concluded that for samples with complex matrixes it was possible to measure the net effect of the DOM binding capacity and the salting out effect of the matrix. It was further concluded that DOM facilitated transport should be taken into account for non-ionic PAHs with lg?K?_OW above 5, at DOM concentrations above 250?mg?C/L. The total DOM concentration was found to be more important for the potential of facilitated transport than differences in the DOM binding capacity.     

Sugar Puckering Drives G-Quadruplex Refolding: Implications for V-Shaped Loops

A DNA G-quadruplex adopting a (3+1) hybrid structure was modified in two adjacent syn positions of the antiparallel strand with anti-favoring 2′-deoxy-2′-fluoro-riboguanosine (^FrG) analogues. The two substitutions promoted a structural rearrangement to a topology with the 5′-terminal G residue located in the central tetrad and the two modified residues linked by a V-shaped zero-nucleotide loop. Strikingly, whereas a sugar pucker in the preferred north domain is found for both modified nucleotides, the ^FrG analogue preceding the V-loop is forced to adopt the unfavored syn conformation in the new quadruplex fold. Apparently, a preferred C3′-endo sugar pucker within the V-loop architecture outweighs the propensity of the ^FrG analogue to adopt an anti glycosidic conformation. Refolding into a V-loop topology is likewise observed for a sequence modified at corresponding positions with two riboguanosine substitutions. In contrast, 2′-F-arabinoguanosine analogues with their favored south-east sugar conformation do not support formation of the V-loop topology. Examination of known G-quadruplexes with a V-shaped loop highlights the critical role of the sugar conformation for this distinct structural motif.     

Probing the photoexcited states of rhodium corroles by time-resolved Q-band EPR. Observation of strong spin-orbit coupling effects

The photoexcited states of two 5,10,15-tris(pentafluorophenyl)corroles (tpfc), hosting Rh(III) in their core, namely Rh(pyr)(PPh 3)(tpfc) and Rh(PPh 3)(tpfc), have been studied by time-resolved electron paramagnetic resonance (TREPR) combined with pulsed laser excitation. Using the transient nutation technique, the spin polarized spectra are assigned to photoexcited triplet states. The spectral widths observed for the two Rh(III) corroles crucially depend on the axial ligands at the Rh(III) metal ion. In case of Rh(PPh 3)(tpfc), the TREPR spectra are found to extend over 200 mT, which exceeds the spectral width of non-transition-metal corroles by more than a factor of 3. Moreover, the EPR lines of the Rh(III) corroles are less symmetric than those of the non-transition-metal corrroles. The peculiarities in the TREPR spectra of the Rh(III) corroles can be rationalized in terms of strong spin-orbit coupling (SOC) associated with the transition-metal character of the Rh(III) ion. It is assumed that SOC in the photoexcited Rh(III) corroles effectively admixes metal centered (3)dd-states to the corrole centered (3)pipi*-states detected in the TREPR experiments. This admixture leads to an increased zero-field splitting and a large g-tensor anisotropy as manifested by the excited Rh(III) corroles.     

The nanostructures of amorphous silicas.

Topologically modeled amorphized silica structures have been refined using a molecular dynamics simulation technique. Several metastable structures with substantially different medium-range connectivities, as characterized by primitive ring statistics, were obtained. Whereas the total correlation function is insensitive to these differences, the first step diffraction peak derived from energy-filtered electron diffraction shows a promising correlation to medium-range structure.     

Twin families of bisolitons in dispersion-managed systems

We calculate bisoliton solutions by using a slowly varying stroboscopic equation. The system is characterized in terms of a single dimensionless parameter. We find two branches of solutions and describe the structure of the tails for the lower-branch solutions.