Experimental evidence for competitive N–O and O–C bond homolysis in gasphase alkoxyamines

The extensive use of alkoxyamines in controlled radical polymerisation and polymer stabilisation is based on rapid cycling between the alkoxyamine (R1R2NO–R3) and a stable nitroxyl radical (R1R2NO•) via homolysis of the labile O–C bond. Competing homolysis of the alkoxyamine N–O bond has been predicted to occur for some substituents leading to production of aminyl and alkoxyl radicals. This intrinsic competition between the O–C and N–O bond homolysis processes has to this point been difficult to probe experimentally. Herein we examine the effect of local molecular structure on the competition between N–O and O–C bond cleavage in the gas phase by variable energy tandem mass spectrometry in a triple quadrupole mass spectrometer. A suite of cyclic alkoxyamines with remote carboxylic acid moieties (HOOC–R1R2NO–R3) were synthesised and subjected to negative ion electrospray ionisation to yield [M – H]− anions where the charge is remote from the alkoxyamine moiety. Collision-induced dissociation of these anions yield product ions resulting, almost exclusively, from homolysis of O–C and/or N–O bonds. The relative efficacy of N–O and O–C bond homolysis was examined for alkoxyamines incorporating different R3 substituents by varying the potential difference applied to the collision cell, and comparing dissociation thresholds of each product ion channel. For most R3 substituents, product ions from homolysis of the O–C bond are observed and product ions resulting from cleavage of the N–O bond are minor or absent. A limited number of examples were encountered however, where N–O homolysis is a competitive dissociation pathway because the O–C bond is stabilised by adjacent heteroatom(s) (e.g., R3 = CH2F). The dissociation threshold energies were compared for different alkoxyamine substituents (R3) and the relative ordering of these experimentally determined energies is shown to correlate with the bond dissociation free energies, calculated by ab initio methods. Understanding the structure-dependent relationship between these rival processes will assist in the design and selection of alkoxyamine motifs that selectively promote the desirable O–C homolysis pathway.

Variation in the OC locus of Acinetobacter baumannii genomes predicts extensive structural diversity in the Lipooligosaccharide

Lipooligosaccharide (LOS) is a complex surface structure that is linked to many pathogenic properties of Acinetobacter baumannii. In A. baumannii, the genes responsible for the synthesis of the outer core (OC) component of the LOS are located between ilvE and aspS. The content of the OC locus is usually variable within a species, and examination of 6 complete and 227 draft A. baumannii genome sequences available in GenBank non-redundant and Whole Genome Shotgun databases revealed nine distinct new types, OCL4-OCL12, in addition to the three known ones. The twelve gene clusters fell into two distinct groups, designated Group A and Group B, based on similarities in the genes present. OCL6 (Group B) was unique in that it included genes for the synthesis of L-Rhamnosep. Genetic exchange of the different configurations between strains has occurred as some OC forms were found in several different sequence types (STs). OCL1 (Group A) was the most widely distributed being present in 18 STs, and OCL6 was found in 16 STs. Variation within clones was also observed, with more than one OC locus type found in the two globally disseminated clones, GC1 and GC2, that include the majority of multiply antibiotic resistant isolates. OCL1 was the most abundant gene cluster in both GC1 and GC2 genomes but GC1 isolates also carried OCL2, OCL3 or OCL5, and OCL3 was also present in GC2. As replacement of the OC locus in the major global clones indicates the presence of sub-lineages, a PCR typing scheme was developed to rapidly distinguish Group A and Group B types, and to distinguish the specific forms found in GC1 and GC2 isolates.

QE and Suns-V-oc study on the epitaxial CSiTF solar cells

In order to clarify the major factors having confined the efficiencies of as-prepared crystalline silicon thin film (CSiTF) solar cells on the SSP (silicon sheets from powder) ribbons, QE (quantum efficiency) and Suns-V-oc study were performed on the epitaxial CSiTF solar cells fabricated on the SSP ribbons, the SSP ribbons after surface being zone melting recrystallized (ZMR) and single crystalline silicon (sc-Si) substrates. The results show that the epi-layers deposited on the SSP ribbons have rough surfaces, which not only increases the diffusion reflectance on the surfaces but also makes the anti-reflection coatings become structure-loosened, both of which would deteriorate the light trapping effect; in addition, the epi-layers deposited on the SSP ribbons possess poor crystallographic quality, so the heavy grain boundary (GB) recombination limits the diffusion length of the minority carriers in the epi-layers, which makes the as-prepared CSiTF solar cells suffer the worse spectra response at long-wavelength range. Nearly all the dark characteristic parameters of the CSiTF solar cells are far away from the ideal values. The performances of the CSiTF solar cells are especially affected by too high I-02 (the dark saturation current of space charge region) values and too low R-sh (parallel resistance) values. The higher 102 values are mainly caused by the heavy GB recombination resulting from the poor crystallographic qualities of the silicon active layers in the space charge regions, while the lower R-sh values are attributed to the electrical leakage at the un-passivated PN junction or solar cell edges after the solar cells are cut by the laser scriber.

A CMOS front-end circuit for SONET OC-96 receiver

An optical receiver front-end for SONET OC-96 receivers was analyzed and designed in 0.18 mu m CMOS process. It consists of a transimpedance amplifier (TIA) and a limiting amplifier (LA). The TIA takes a fully differential configuration, and regulated cascode (RGC) input stage is implemented. The LA was realized by five cascaded identical gain stages with active inductor load. The TIA achieved 4.2GHz bandwidth for 0.5pF photodiode (PD) capacitance and 1.2k 0 transimpedance gain. The LA achieved 5.4GHz bandwidth and 29dB voltage gain. The optical sensitivity is -19dBm at 5-Gb/s for a bit-error rate of 10(-12), and it dissipates 45.5mW for I.8V supply.

Rededication oc Chapman College Chapel, Orange, California

Rededication of Chapman College Chapel, Orange, California, February, 1978. The wooden-shingled church, constructed in 1909 for the congregation of Trinity Episcopal Church, is located on the northeast corner of East Maple Avenue and North Grand Street. Chapman College (now Chapman University) purchased the church for their chapel when the congregation moved to a new church on Canal Street.

Energy Efficient Cache Discovery in Wireless Mobile Ad oc Networks

Data caching is an attractive solution for reducing bandwidth demands and network latency in mobile ad hoc networks. Deploying caches in mobile nodes can reduce the overall traf c considerably. Cache hits eliminate the need to contact the data source frequently, which avoids additional network overhead. In this paper we propose a data discovery and cache management policy for cooperative caching, which reduces the power usage, caching overhead and delay by reducing the number of control messages flooded into the network .A cache discovery process based on position cordinates of neighboring nodes is developed for this .The stimulstion results gives a promising result based on the metrics of the studies.

Buscar el oc??ano : la formaci??n espiritual como base integradora de nuestra acci??n

Resumen en ingl??s y catal??n. Monogr??fico con el t??tulo: Espiritualidad y acci??n social

La escuela se acerca al oc??ano : ballenas y delfines de nuestros mares, un recurso educativo

Se pretende acercar el medio natural marino al alumnado que por vivir en una isla rodeada de mar dispone de un lugar atractivo para crear situaciones de aprendizaje y de concienciaci??n y cuidado del entorno. No se trata de una simple visita para que el alumnado adquiera comportamientos y valores positivos hacia la conservaci??n del mismo, si no que existe un compendio de tareas educativas relacionadas entre s?? y que gu??an al alumnado en su proceso de aprendizaje antes, durante y despu??s de la salida. Se parte de un dise??o de tarea, desde el aula, donde el alumnado es protagonista, interpreta los datos y obtiene informaci??n necesaria para llevar un trabajo de campo productivo.

Substitutional Impurities in PPV Crystals: An Intrinsic Donor-Acceptor System for High V(oc) Photovoltaic Devices

Defects are usually present in organic polymer films and are commonly invoked to explain the low efficiency obtained in organic-based optoelectronic devices. We propose that controlled insertion of substitutional impurities may, on the contrary, tune the optoelectronic properties of the underivatized organic material and, in the case studied here, maximize the efficiency of a solar cell. We investigate a specific oxygen-impurity substitution, the keto-defect -(CH(2)-C=O)- in underivatized crystalline poly(p-phenylenevinylene) (PPV), and its impact on the electronic structure of the bulk film, through a combined classical (force-field) and quantum mechanical (DFT) approach. We find defect states which suggest a spontaneous electron hole separation typical of a donor acceptor interface, optimal for photovoltaic devices. Furthermore, the inclusion of oxygen impurities does not introduce defect states in the gap and thus, contrary to standard donor-acceptor systems, should preserve the intrinsic high open circuit voltage (V(oc)) that may be extracted from PPV-based devices.