Adaptation of a load-inject valve for a flow injection chemiluminescence system enabling dual-reagent injection enhances understanding of environmental Fenton chemistry

Environmental Fenton chemistry has been poorly constrained within the marine environment at a multi-component level. A simple, unique, reconfiguration of a flow-injection analytical system combined with luminol chemiluminescence allows quasi-simultaneously the measurement, using a single load-inject valve and a single photon multiplier tube, of reduced iron, Fe(II), and hydrogen peroxide. The system enables rapid, every 22 s, measurements with good accuracy at environmentally relevant concentrations, less than 5% relative standard deviations on both a 5 nM Fe(II) standard and a 60 nM hydrogen peroxide standard. Limits of detection were as low as 40 pM Fe(II) and 100 pM hydrogen peroxide. The system showed excellent capability by measuring from within an organic rich seawater the photochemically induced production of Fe(II) and hydrogen peroxide and their subsequent cycling and Fenton like interactions.     

Effects of different composition ratio on the dielectric relaxation and dynamic mechanical properties of poly(ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers

The molecular dynamics of new poly (ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers (DL/CL/PAC) has been investigated by using dynamic mechanical thermal analysis (DMTA) and dielectric relaxation spectroscopy (DRS) measurements. The copolymers were synthesized via anionic polymerization of relevant lactams activated with carbamoyl derivatives of telechelic hydroxyl terminated polypropylene oxide with isophorone diisocyanate (PAC). The calorimetric, X‐ray diffraction, and DMTA measurements were performed to recognize the influence of the composition ratio and the type of PAC on the physical, thermal, and mechanical properties of the synthesized copolymers. The DRS was used to study the frequency dependence of the dielectric permittivity of some isotherms from ?110 to 145 °C. Copolymerization of ε‐caprolactam with about 10 wt % ω‐dodecalactam results in a copolymer that has lower water absorption, a melting point close to that of polyamide 6 and has a high enough degree of crystallinity in respect to high storage modulus. Five dielectric relaxations have been observed in the dielectric spectra, three at lower temperature and two at higher temperature. The copolymers have two glass transition temperatures for polyamide segments and polyether blocks, indicating microphase separation in the copolymers. Other studies directed toward molecular dynamics of polyamide DL/CL/PAC copolymers have not been reported. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

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A guided wave monolithic resonator ruby fiber laser

Single crystal ruby fibers, cooled with liquid nitrogen, have been operated as end pumped lasers. The fiber laser is a guided wave device with a length of 15 mm and a mean diameter of 60 μm. The laser resonator structure is monolithic, consisting of an aluminium mirror coated on one fiber end face and an uncoated opposite end face serving as an output coupler. Using an argon ion laser pump source, cw output powers of several mW were obtained.     

On the feasibility of remote palpation using acoustic radiation force

A method of acoustic remote palpation, capable of imaging local variations in the mechanical properties of tissue, is under investigation. In this method, focused ultrasound is used to apply localized (on the order of 2 mm3) radiation force within tissue. and the resulting tissue displacements are mapped using ultrasonic correlation based methods. The tissue displacements are inversely proportional to the stiffness of the tissue, and thus a stiffer region of tissue exhibits smaller displacements than a more compliant region. In this paper, the feasibility of remote palpation is demonstrated experimentally using breast tissue phantoms with spherical lesion inclusions, and in vitro liver samples. A single diagnostic transducer and modified ultrasonic imaging system are used to perform remote palpation. The displacement images are directly correlated to local variations in tissue stiffness with higher contrast than the corresponding B-mode images. Relationships between acoustic beam parameters, lesion characteristics and radiation force induced tissue displacement patterns are investigated and discussed. The results show promise for the clinical implementation of remote palpation.     

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.     

A stable droplet reactor for high temperature nanocrystal synthesis

We report a versatile capillary-based droplet reactor for the controlled synthesis of nanoparticles over a wide range of flow conditions and temperatures. The reactor tolerates large flow-rate differentials between individual reagent streams, and allows droplet composition to be varied independently of residence time and volume. The reactor was successfully applied to the synthesis of metal (Ag), metal-oxide (TiO(2)) and compound semiconductor (CdSe) nanoparticles, and in each case exhibited stable droplet flow over many hours of operation without fouling, even for reactions involving solid intermediates. For CdSe formed by the reaction of Cd oleate and Se, highly controlled growth could be achieved at temperatures of up to 250 °C, with emission spectra varying smoothly and reproducibly with temperature and flow-rate. The droplet reactor showed exceptional stability when operated under constant flow-rate and temperature conditions, yielding particles with well-defined band-edge emission spectra that did not vary over the course of a full day's continuous operation.     

Reactions of 14-hydroxy-14-azadispiro[5.1.5.2]pentadec-9-ene-7,15-dione and related compounds. II

3 When 11-diethyl- and 3, 11-di-n-propyl-14-hydroxy-14-azadispiro[5.1. 5.2]pentadec-9-ene-7, 15-dione (E-IV and n-Pr-IV) are heated with polyphosphoric acid at 55–65°, the 14-hydroxyl group cyclizes at the 11-carbon to form E-VI and n-Pr-VI, the structures of which have been established. Compounds P-IV, i-Pr-IV and t-B-IV do not cyclize under these conditions. The Beckmann rearrangement of 12-hydroxy-12-azadispiro[4.1.4.2]tridec-8-ene-6, 13-dione-6-oxime (P-I) with polyphosphoric acid at 40–50° formed only the normal product, P-II, which could not be cyclized. Compound P-IV was the only ketone of this series which would add hydrogen cyanide to form a cyanohydrin.