Analytical method for carbamate pesticides in processed foods by LC/MS/MS

A rapid analytical method for the simultaneous determination of carbamate pesticides in processed foods was established by liquid chromatography coupled with tandem mass spectrometry (LC/MS/MS). The pesticides were extracted from samples with acetonitrile using accelerated solvent extract equipment, except for the fine powder type spices, which were extracted in an ultrasonic bath. The crude extract was cleaned up with a multi-solvent GPC column (Shodex Asahipak GF-310 HQ) using acetonitrile as a mobile phase. The eluent from the column at the retention time between 13 to 18 min was concentrated under nitrogen gas and dissolved in a mixture of acetonitrile-water-0.2 mol/L ammonium formate buffer pH 6.0 (10 : 9 : 1). An aliquot was injected into the LC/MS/MS using electrospray ionization (ESI) with acquisition in the positive mode.The recoveries of 29 kinds of pesticide from dried fruits (raisin, prune and mango) and spices (turmeric, masala, sage, thyme and red pepper) fortified at levels of 0.1 and 0.01 microg/g were mostly in the range of 50 to 150% and those from soybean paste and soy sauce fortified at 0.01 microg/g were 46.9 to 122.6% (C.V. 3.8 to 37.6%), except for 4 kinds of pesticide. The determination limits (S/N> or =10) corresponded to 0.001 to 0.05 mug/g of the pesticides in red pepper.     

LQ optimal control for a class of pulse width modulated systems

We consider linear quadratic optimal control for a class of pulse width modulated systems. The problem is motivated from a practical application—digital control of switching power converters. The control synthesis problem is posed based on a sampled data model of the original switching dynamics and a linear quadratic criterion that takes the intersampling behavior into account.     

Determination of unsaturation in ethylene-propylene terpolymers and butyl rubber by time-averaged 1H n.m.r. measurements

The time-averaged ¹H n.m.r. spectra of ethylene-propylene-dicyclopentadiene, ethylene-propylene-ethylidene norbornene and isobutylene-isoprene copolymers were measured. Assignments of the olefinic resonances were carried out by comparing the spectra with those of each homopolymer and strarting monomers. The concentration of the olefinic unit in copolymer was determined by measuring the intensity ratio between the olefinic proton signal and the signal of trichloroethylene which was added as an internal standard of intensity measurements. The concentrations of unsaturation in copolymers determined by using the iodine-mercuric acetate method were proportional to those determined by the n.m.r. method. The accuracy and precision of the n.m.r. measurements were shown to be better than 10% for a mixture of polyisobutylene and polyisoprene containing 1.24 mol % of unsaturation as a model compound of isobutylene-isoprene copolymer.     

Single-trial analysis of voice-stimulus-evoked potentials

We are developing a brain-computer interface (BCI) for event-related potentials (P300) using speech stimulus in the Japanese language based on the need to investigate amyotrophic lateral sclerosis (ALS) patients. Previously, we studied a single-trial analysis of P300 with a 4-Hz lowpass filter in order to improve the entry speed of the BCI. However, the problem was a low detection accuracy, i.e., approximately 30%–80%. In this article, we reviewed the application of independent component analysis (ICA) in order to improve the accuracy of single-trial analysis of P300. As a result, the detection ratio improved from 54.2% for the traditional 4-Hz low-pass filter to 90.9% in the choice of one between two. Furthermore, in an off-line experiment, the detection ratio of the P300 response to each sound of “a, i, u, e and o” improved in the task to choose one among five with synthetic speech stimulus. The maximum detection ratio was 94.7%, and the detection ratio per sound improved from 47.0% to 85.1%.     

Chemical composition and its distribution of emulsion copolymers composed of styrene and ethyl acrylate as hydrophobic and hydrophilic comonomers

Summary Chemical composition and its distribution of styrene (St)-ethyl acrylate (EA) copolymers synthesized by emulsion copolymerization under different monomer ratios and polymerization conditions were examined by ¹H-NMR and high-performance liquid chromatography (HPLC), respectively, and compared with those of bulk copolymers. It was newly found that the chemical composition of copolymer at early stage is affected by the concentration of emulsifier (SDS, sodium dodecyl sulfate) and monomer/water ratio, and is almost independent of the concentration of initiator or polymerization temperature. The EA fraction decreased with the increase of SDS concentration and converged to the value calculated using distribution factor (f_d) when SDS concentration was extrapolated to zero. These results indicate that the EA fraction in micelle decreased compared to the expected value from f_d due to the interaction of EA monomer with emulsifier. From HPLC, it was found that each copolymer showed a sharp single peak at an early stage of polymerization indicating that no homopolymer or copolymer with different composition was produced.     

H Robust servo problem with H∞ norm constraint

A robust servo problem with an H-infinity norm constraint is investigated based on the LMI (Linear Matrix Inequality) approach to the H-infinity control problem. The following results are obtained. (1) A necessary and sufficient condition for the existence of an H-infinity controller with robust tracking property is derived. It consists of the following two indepent conditions: (i) the existence of an H-infinity controller; (ii) a boundary constraint at the reference mode. (2) If there exists an H-infinity controller with robust tracking performance, there exists one whose order equals the sum of an H-infinity controller and the internal model.     

Synthesis and characterization of polytriphenylamine containing ether bond in the main chain

Four triarylamine monomers that have an ether linkage, bis(N-phenyl-N-4-t-butylphenyl-4-aminophenoxy)ethane (TPAE), bis(N-phenyl-N-4-t-butylphenyl-4-aminophenoxy)butane (TPAB), bis(N-phenyl-N-4-t-butylphenyl-4-aminophenyl)ether (TPAO), and bis(N-4-tolyl-N-1-naphtyl-4-aminophenoxy)ether (NPAO) were prepared and polymerized using iron (III) chloride as an oxidant. Polymers, which are soluble in common organic solvents, were obtained at the yields of higher than 70%, and with glass transition temperatures of higher than 170 °C. The hole mobility decreased in the order of PNPAO > PTPAO > PTPAE = PTPAB > PBTPA, which indicates that the ether oxygen increases mobility.     

Biodegradable polymer made of styrene and N‐benzyl‐4‐vinylpyridinium chloride

A copolymer of styrene with N‐benzyl‐4‐vinylpyridinium chloride (BVP), poly(styrene‐co‐N‐benzyl‐4‐vinylpyridinium chloride) (PST‐co‐BVP), was degradable by activated sludge in soil when the oligo‐styrene portion was sufficiently small. The degradation of the equimolar copolymer followed first‐order kinetics when the polymer sample was 1.0 or 0.5 g/kg and gave a half‐life of 5.6 days. The degradation of PST‐co‐BVP with a reduced BVP content did not follow first‐order kinetics under the aforementioned conditions but appeared to follow the kinetics when the amount of the polymer sample was sufficiently small. Under the ultimate conditions, the half‐life of PST‐co‐BVP that contained 10.6 mol % BVP was estimated to be 12.5 days, and the half‐life of PST‐co‐BVP that contained 5 mol % BVP was expected to be 30–40 days. The incorporation of 5 mol % BVP appeared sufficient for making PST‐co‐BVP substantially biodegradable if we did not expect exceptionally rapid degradation. PST‐co‐BVP was different from conventional polystyrene but possessed biodegradability. Random scission of the main chain much predominated over uniform scission from the end of the polymer chain in the biodegradation of PST‐co‐BVP. The cleavage of the main chain at BVP appeared predominant over that of oligo‐styrene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 554–559. 2006     

Inverse micro-emulsion polymerization of acrylamide in the presence of a mixture of oleophilic/hydrophilic surfactants

The effect of sodium dodecyl sulphate (SDS) on the formation of inverse micro-emulsion toluene/sodium bis(2-ethylhexyl)sulphosuccinate (AOT)/water/acrylamide (AAm)/SDS and on polymerization of acrylamide initiated by oil soluble dibenzoyl peroxide was studied. The presence of SDS shifts the value of the volume fraction of aqueous phase (Φ_aw) at which a two-phase Winsor II system forms, to higher values. It was shown that an increase of the mass ratio of SDS/water led to a decrease of acrylamide polymerization rate, of polyacrylamide particle size and of polyacrylamide molecular mass distribution. It was also found that in the presence of SDS, a nearly constant value for acrylamide polymerization rate in inverse micro-emulsion in the range of Φ_aw values between 5% and 50% can be obtained. The polymerization kinetics and polymer particle formation were explained as consequences of the initiation of acrylamide polymerization in two reaction loci—in inverse micelles and in the oil macrophase of the inverse micro-emulsion. © 1998 SCI.