Design and synthesis of labeling reagents (MS probes) for highly sensitive electrospray ionization mass spectrometry and their application to the detection of carbonyl, alcohol, carboxylic acid and primary amine samples.

Novel labeling reagents, called MS probes, which possess a positively charged quaternary amine moiety and can transform a neutral analyte into a charged compound by simply mixing with the analyte and allowing the mixture to stand from several minutes to 30 min at room temperature or while heating to 50 degrees C, were designed and synthesized for the highly sensitive detection of carbonyl, alcohol, carboxylic acid and primary amine samples by electrospray ionization mass spectrometry (ESI-MS). The positively charged products can be detected with high sensitivity in an ESI-MS system, which is the most popular liquid MS instrument. All of the labeled products showed a remarkably large increase in the molecular-ion peak abundance detection sensitivity of over 500-fold at picomolar concentration levels compared to that of unlabeled analytes in an ESI-MS system. These MS probes, used together with liquid MS detection, are widely applicable as a convenient method for the highly sensitive detection of less than picomolar levels of analytes, and therefore greatly enhance the power of ESI-MS analysis.     

Cerasome as an Organic-Inorganic Vesicular Nanohybrid: Characterization of Cerasome-Forming Lipids having a Single or a Dual Trialkoxysilyl Head

Morphological characterization of the organic-inorganic vesicular nanohybrids, Cerasomes, was performed in aqueous media from two aspects. Firstly, a novel Cerasome-forming lipid having two triethoxysilyl groups in the head moiety was synthesized and the physical property of the Cerasome was investigated. While the morphological stability of the Cerasomes, as evaluated from the vesicular collapse behavior against a micelle-forming nonionic surfactant, Triton-X 100, was extremely higher than that of the conventional phospholipid liposome, the stabilities were comparable to each other for the Cerasomes derived from the dual- and single-head lipids. On the other hand, the surface property of the Cerasome formed with the dual-head lipid more closely resembled the colloidal silica particles rather than that derived from the single-head lipid, as suggested by zeta-potential measurements. Secondly, the effect of the media pH on the morphological stability of the Cerasome formed with the single-head lipid was evaluated and appeared as a time difference in obtaining the morphological stability of the Cerasome. These morphological characteristics of the Cerasomes could be mainly owing to the development of the siloxane network on the vesicular surface.     

Determination of the degree of cure under dynamic and isothermal curing conditions with electrical impedance spectroscopy

This article presents a new methodology for the quantitative determination of the progress of the curing reaction of a thermosetting resin, using the results of electrical impedance spectroscopy. The method is an extension of the use of the imaginary impedance maximum as a reaction progress indicator and is based on the demonstration of a close correlation between the reaction rate, as measured by conventional differential scanning calorimetry, and the rate of change of the value of the imaginary impedance spectrum maximum. Tests on a commercial aerospace epoxy resin under both isothermal and dynamic heating conditions with calorimetry and impedance spectroscopy have demonstrated the validity of the method and set the accuracy limits involved. This technique can be used as a real-time online control tool for thermoset composite manufacturing. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 146–154, 2004     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 2004     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

Bio‐based nanocomposites from functionalized plant oils and layered silicate

Some discovery work was done on the synthesis of clay nanocomposites based on renewable plant oils. Functionalized triglycerides, such as acrylated epoxidized soybean oil, maleinized acrylated epoxidized soybean oil, and soybean oil pentaerythritol maleates, combined with styrene were used as the polymer matrix. The miscibility of these monomers and clay organomodifier was assessed by solubility parameters. The formation of nanocomposites was confirmed by both X‐ray data and transmission electron microscopy. The morphology showed a mix of intercalated and partially exfoliated sheets. The flexural modulus increased 30% at only 4 vol % clay content, but there was no significant effect on flexural strength, glass‐transition temperature, and thermal stability. Property enhancement was related to the degree of exfoliation that depends on both the polarity and flexibility of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1441–1450, 2004     

Ultrahigh‐molecular‐weight‐polyethylene‐fiber surface treatment by electron‐beam‐irradiation‐induced graft polymerization and its effect on adhesion in a styrene–butadiene rubber matrix

Aiming to develop a high‐performance fiber‐reinforced rubber from styrene–butadiene rubber (SBR), we applied a special technique using electron‐beam (EB)‐irradiation‐induced graft polymerization to ultrahigh‐molecular‐weight‐polyethylene (UHMWPE) fibers. The molecular interaction between the grafted UHMWPE fibers and an SBR matrix was studied through the evaluation of the adhesive behavior of the fibers in the SBR matrix. Although UHMWPE was chemically inert, two monomers, styrene and N‐vinyl formamide (NVF), were examined for graft polymerization onto the UHMWPE fiber surface. Styrene was not effective, but NVF was graft‐polymerized onto the UHMWPE fibers with this special method. A methanol/water mixture and dioxane were used as solvents for NVF, and the effects of the solvents on the grafting percentage of NVF were also examined. The methanol/water mixture was more effective. A grafting percentage of 16.4% was the highest obtained. This improved the adhesive force threefold with respect to that of untreated UHMWPE fibers. These results demonstrated that EB irradiation enabled graft polymerization to occur even on the inert surface of UHMWPE fibers. However, the mechanical properties of the fibers could be compromised according to the dose of EB irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2595–2603, 2004     

Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.     

Photodegradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid in aqueous suspensions of titanium dioxide

The photocatalytic degradation of a herbicide derivative, 2,4-dichlorophenoxy acetic acid (2,4-D, 1), has been investigated in aqueous suspensions of titanium dioxide. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis and decrease in Total Organic Carbon (TOC) content as a function of irradiation time in the presence of UV light source. The degradation kinetics was investigated under a variety of conditions, such as different types of TiO₂, pH, catalyst and substrate concentrations. Higher photonic efficiencies were observed with Degussa P25 as compared with other photocatalysts. The degradation products were analysed by GC-MS and probable pathways for the formation of different products were proposed.     

On the influence of the surfactant''s polar group on the local and terminal velocities of bubbles

The local and the terminal velocities, the size and the degree of bubbles’ shape deformations were determined as a function of distance from the position of the bubble formation (capillary orifice) in solutions of n-octyltrimethylammonium bromide, n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside and n-octanoic acid.

These surface-active compounds have different polar groups but an identical hydrocarbon chain (C8) in the molecule. The motion of the bubbles was monitored and recorded using a stroboscopic illumination, a CCD camera, and a JVC professional video. The recorded bubble images were analyzed by the image analysis software. The bubbles accelerated rapidly and their shape was deformed immediately after detachment from the capillary. The extent of the bubbles’ shape deformation (ratio of horizontal and vertical diameters) was 1.5 in distilled water and dropped rapidly down to a level of ca. 1.05–1.03 with increasing surfactant concentration. After the acceleration period the bubbles either attained a constant value of the terminal velocity (distilled water and high concentrations of the solutions), or a maximum in the velocity profiles was observed (low concentrations). The values of the terminal velocity diminished drastically with increasing concentration, from the value of 35 cm/s in water down to about 15 cm/s, while the bubble diameter decreased by ca. 10% only. The surfactant adsorption at the surface of the bubbles was evaluated and the minimum adsorption coverages required to immobilize the bubbles’ surface were determined. It was found that this minimum adsorption coverage was ca. 4% for n-octyldimethylphosphine oxide, n-octyl-β-D-glucopyranoside, n-octanoic acid and 25% for n-octyltrimethylammonium bromide. The difference in the adsorption coverage together with the surfactants’ surface activities indicate that it is mainly the adsorption kinetics of the surfactants that governs the fluidity of interfaces of the rising bubbles.