Organic/inorganic hybrid nano-microstructured coatings on insulated substrates by electrospray deposition

Organic/inorganic hybrid nano-microstructured coatings on insulated polymer films were prepared by electrospray deposition (ESD) from an acrylic resin/silica sol blend solution. The surface morphologies of the coated films were observed using scanning electron microscopy (SEM). The SEM images showed that a nano-microscaled fibrous structure was formed on the film. The fiber diameter decreased from 4.4 microm to 600 nm with the increase in the silica sol content. Energy-dispersive X-ray analysis also revealed that silica atoms were homogeneously distributed in the fibrous structure on the polymer film. These results indicated that the ESD method is potentially a useful option for producing nano-microstructured coatings on not only conductive, but also insulating surfaces.     

Asymmetric total synthesis of sperabillins B and D via lithium amide conjugate addition

Diastereoselective conjugate addition of homochiral lithium (R)-N-allyl-N-alpha-methylbenzylamide to methyl (2E,5E)-hepatadienoate, followed by protecting group manipulation and subsequent iodocyclocarbamation allows a concise route to the core fragment, methyl (3R,5R,6R)-3,6-diamino-5-hydroxyheptanoate, of sperabillins B and D. Differentiation between the C-3 and C-6 primary amino groups of this core amino acid was readily achieved by treatment with acetone, giving the 5,6-isopropylidene and C-3-imine protected diamine, with subsequent regioselective acylation of the C-6-nitrogen facilitating the total synthesis of sperabillin D in 10.8% overall yield, and the first asymmetric synthesis of sperabillin B in 5.8% overall yield.     

Membrane potential of a bipolar membrane: the effect of concentration perturbation of the intermediate phase around a certain value

A new model of a sandwich-type bipolar membrane potential was constructed by assuming the potential behavior of a bipolar membrane as a combination of each layer potential between two different states, i.e. the different concentrations of the bulk solution. Hence, we introduced the coion exclusion parameter that is derived from the Donnan equilibrium as a combinatorial function, which combined all the potential equations involved in our system. We assumed that the existence of the intermediate phase due to its volume would allow the Donnan equilibrium to play an important role, i.e. the vanishing of the coion exclusion effect of the membrane layer facing the bulk solution phase in high concentration. Sandwich-type bipolar membranes, which consist of a cation- (K-501) and an anion-exchange layer (A-501) were used in this study. A series of concentration perturbations of the intermediate phase was performed to examine the membrane potential behavior of the bipolar membrane experimentally. The experimental results showed a good agreement with the theoretical results, which led to the conclusion that explained the contribution of the intermediate phase to the membrane potential behavior through its volume and electrochemical properties.     

Analysis of triazines and associated metabolites with electrospray ionization field-asymmetric ion mobility spectrometry/mass spectrometry

Triazines comprise an important pollutant class owing to continued use in certain countries, and owing to strong environmental persistence that leads to problems even in countries like Sweden where the use of triazines has been prohibited for some years. We investigated mass-selective detection for analysis of triazines. More specifically, we studied the background reduction and sensitivity enhancement that result from the use of a new interface technique, field-asymmetric ion mobility spectrometry (FAIMS), in conjunction with electrospray ionization ion-trap mass spectrometry. This technique allows for ion sorting and discrimination against the considerable "chemical noise", nonspecific cluster and fragment ions, which are typically generated in electrospray ionization. This paper presents results of a pilot study of triazines and some metabolites in ideal solvents. Our long-range goal is automated analysis with mass-selective detection coupled to membrane-based sample cleanup and enrichment for additional enhancement in sensitivity.     

Study of the dissociation of a charge-reduced phosphopeptide formed by electron transfer from an alkali metal target

Doubly protonated phosphopeptide (YGGMHRQET(p)VDC) ions obtained by electrospray ionization were collided with Xe and Cs targets to give singly and doubly charged positive ions via collision-induced dissociation (CID). The resulting ions were analyzed and detected by using an electrostatic analyzer (ESA). Whereas doubly charged fragment ions resulting from collisionally activated dissociation (CAD) were dominant in the CID spectrum with the Xe target, singly charged fragment ions resulting from electron transfer dissociation (ETD) were dominant in the CID spectrum with the Cs target. The most intense peak resulting from ETD was estimated to be associated with the charge-reduced ion with H2 lost from the precursor. Five c-type fragment ions with amino acid residues detached consecutively from the C-terminal were clearly observed without a loss of the phosphate group. These ions must be formed by N--Calpha bond cleavage, in a manner similar to the cases of electron capture dissociation (ECD) and ETD from negative ions. Although the accuracy in m/z of the CID spectra was about +/-1 Th because of the mass analysis using the ESA, it is supposed from the m/z values of the c-type ions that these ions were accompanied by the loss of a hydrogen atom. Four z-type (or y--NH3, or y--H2O) ions analogously detached consecutively from the N-terminal were also observed. The fragmentation processes took place within the time scale of 4.5 micros in the high-energy collision. The present results demonstrated that high-energy ETD with the alkali metal target allowed determination of the position of phosphorylation and the amino acid sequence of post-translational peptides.     

Chronopotentiometry study of a cation-exchange membrane in the presence of cationic surfactant in membrane surface vicinity

In this study, the effect of cationic surfactant (benzalkonium chloride) on the transport of KCl through a sulfonated styrene-divinyl benzene cation-exchange membrane was investigated. The presence of benzalkonium chloride as the cationic surfactant, which interacts with the sulfonic groups on membrane surface, has to disturb the transport of K⁺ ions and directly gives responses in its chronopotentiogram. The electrodialysis of the cationic surfactant solution showed an irreversible monotonous increase of the total system potential due to the fouling phenomena. However, a small amount of cationic surfactant in the membrane surface vicinity was observed to give a fluctuating chronopotentiogram at the high current density. This fluctuation is started by a steep increase and followed by the decrease of potential, which finally relaxed to reach a steady state. This potential fluctuation is proposed to be the response of a structural transformation of surfactant micelles on the membrane surface under perturbation of the externally applied electric field, which is discussed and examined qualitatively in this report.     

An SOS-QE Approach to Nonlinear Gain Analysis for Polynomial Dynamical Systems

Combined use of the method of sum of squares (SOS) and quantifier elimination (QE) is discussed with regard to the problem of nonlinear gain analysis for a class of dynamical systems. SOS, a numerical method, is used to search for the structure of a gain function quickly, and QE, a symbolic method, determines all gain functions in the structure to find the minimum gain function. QE can also be used for the infeasibility check of gain structures. A proposed analysis procedure for polynomial dynamical systems prevents unnecessary searching for a gain structure. Two illustrative examples show the effectiveness of the proposed gain analysis procedure.     

Comparison of enzymatic recycling electrodes for measuring aminophenol: development of a highly sensitive natriuretic peptide assay system.

Several redox enzymes were examined for enzymatic/electrochemical-recycling systems in order to measure p-aminophenol (PAP) with high sensitivity. Glucose oxidase (GOD) and diaphorase (DI) worked well as catalysts for recycling electrode systems: these enzymes effectively reduced p-iminoquinone (PIQ), the electrochemically-oxidized form of PAP, and caused an enhancement in the electrochemical signals (anodic currents in the voltammogram and amperogram) by approximately 100 fold. The lower detection limits for PAP were estimated to be 50 nM with the GOD system and 2 nM with the DI system. We combined the enzymatic-recycling electrode using DI with an enzyme immunoassay system to measure atrial natriuretic peptide (ANP), an important marker peptide hormone involved in heart diseases. ANPs from serum samples at ppt-levels were determined appropriately using the present assay system.