Sharper approximation of extreme points by far points

This research was supported in part by the National Science Foundation, U.S.A.     

Hexaphyrin(1.0.1.0.0.0). A new colorimetric actinide sensor

Hexaphyrin(1.0.1.0.0.0) (isoamethyrin) undergoes a significant color change in the presence of UO₂²⁺, PuO₂²⁺, and NpO₂²⁺. The complexation of the first of these dioxo actinide cations was studied in semi-quantitative fashion in 1:1 MeOH-CH₂Cl₂. Under these conditions, the detection limit for UO₂²⁺ was found to be ca. 5.8 ppm by naked eye monitoring and <28 ppb by UV-vis spectroscopy. Isoamethyrin does not undergo a color change in the presence of most transition metals or when exposed to Gd(III). Isoamethyrin thus constitutes an attractive alternative to 2,2′(1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo)-bisbenzenarsonic acid (AzIII) and 2-(5-bromo-2-pyridylazo)-5-(diethylamino)phenol (BrPADAP), systems currently used as actinide cation sensors.     

Asymmetric responses of international stock markets to trading volume

The major goal of this paper is to examine the hypothesis that stock returns and return volatility are asymmetric, threshold nonlinear, functions of change in trading volume. A minor goal is to examine whether return spillover effects also display such asymmetry. Employing a double-threshold GARCH model with trading volume as a threshold variable, we find strong evidence supporting this hypothesis in five international market return series. Asymmetric causality tests lend further support to our trading volume threshold model and conclusions. Specifically, an increase in volume is positively associated, while decreasing volume is negatively associated, with the major price index in four of the five markets. The volatility of each series also displays an asymmetric reaction, four of the markets display higher volatility following increases in trading volume. Using posterior odds ratio, the proposed threshold model is strongly favored in three of the five markets, compared to a US news double threshold GARCH model and a symmetric GARCH model. We also find significant nonlinear asymmetric return spillover effects from the US market.     

Influence of trans-cis photoisomerizations of solubilized compounds on transition temperatures in the system cetyltrimethylammonium bromide-water: Light-induced phase transitions

Transition temperatures (TN1) from the nematic lyotropic liquid-crystalline phase to the isotropic phase were measured for the system cetyltrimethylammonium bromide (CTAB) water in the presence of small amounts of 3-stilbene carboxylic acid (3SC), 4-stilbene carboxylic acid (4SC) and Δ2/2'-bi-(2H-l,4-benzothiazine) (BT). TNI, increases as a function of trans-3SC or trans-4SC concentration, ranging from 01 to 08 wt %, by up to 12°C. A further increase in TNI between 2 and 5°C can be achieved by photochemically converting the solubilized trans stilbene derivatives to the cis isomers. Irradiation of a trans-3SC containing sample at a temperature just above TNl leads to a light-induced phase transition to the lyotropic liquid-crystalline phase. Solubilization of trans-BT causes a slight decrease of TNI while photoisomerization to cis-BT increases T_NI by 1°C.     

Synthesis and characterization of poly(vinyl alcohol)‐graft‐[poly(D,L‐lactide)/poly(D,L‐lactide‐co‐glycolide)] hydrogels

Poly(D ,L ‐lactide) and poly(D ,L ‐lactide‐co‐glycolide) with various composition and with one methacrylate and one carboxylate end group were synthesized and grafted onto poly(vinyl alcohol) (PVA) via the carboxylate group. The graft copolymers were crosslinked via the methacrylate groups using a free radical initiator. The polymer networks were characterized by means of NMR and studied qualitatively by means of IR spectroscopy. The influence of the glycolide content in the polyester grafts and of the number of ester units in the grafts on thermal properties and swellability were studied as well. The high swellability in water is characteristic of all hydrogels. Differential scanning calorimetry (DSC) showed a single glass transition temperature that occurs in the range between 51 and 69 °C. Thermogravimetric analysis (TGA) of the networks showed the main loss in weight in the temperature range between 290 and 370 °C. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4536–4544, 2007     

Review: mass spectrometry of step-growth polymers

For at least two decades different mass spectrometric techniques have been applied for polymer analysis, including the qualitative determination of chemical compositions, end group identification, functionality type distribution and the determination of the cyclisation extend at each degree of polymerisation. Molecular weights exceeding 100 KDa are provable by MALDI-ToF mass spectrometry. Further, molecular weight distributions are determined by MADLI-ToF. However, there are some hints that, there is a discrimination against higher molecular weight species in samples with polydispersity of more than 1.2. Furthermore, pathways for dendritic and hyper-branched polymers, supramolecular polymers and nano condensates are analysed by help of mass spectrometry.     

High-speed microwave-promoted hetero-Diels-Alder reactions of 2(1H)-pyrazinones in ionic liquid doped solvents

Inter- and intramolecular hetero-Diels-Alder reactions in a series of functionalized 2(1H)-pyrazinones were investigated under controlled microwave irradiation. The cycloaddition reactions were efficiently performed in sealed tubes, utilizing either a combination of 1,2-dichloroethane and a thermally stable ionic liquid, or 1,2-dichlorobenzene as reaction medium. In all cases, a significant rate-enhancement using microwave flash heating as compared to thermal heating was observed.     

Far-infrared spectroscopy of CH3OD in highly excited torsional states and the atlas of the Fourier transform spectra in the range 200-350 cm(-1)

The high resolution Fourier transform far-infrared (FIR) spectrum of the torsion rotation band of CH3OD has been analyzed for the highly excited torsion states (n > or = 2) in the vibrational ground state. The spectrum shows splitting of the lines due to strong torsional-rotational-vibrational interactions in the molecule. Assignments were possible for rotational sub-bands in the torsional state as high as n = 4 and for K values up to 8 and J values of up to approximately 30 in most cases, for all the symmetry species. For the third excited torsional state n = 3 assignments were possible to K = 10. The data were analyzed with the help of the energy expansion model, which has been proven very successful in methanol. The state dependent expansion parameters are presented. These molecular parameters were able to reproduce the observed wavenumbers almost to within experimental accuracy of 0.0002 cm(-1) for clean unblended lines. These expansion coefficients should prove valuable in the calculation of precise energy values for excited torsional states up to n = 4, which is way above the torsional barrier. The detailed high-resolution spectral atlas of CH3OD has been presented in the range 200-350 cm(-1). This atlas is an extension of our earlier atlas in the range 20-205 cm(-1). The availability of this atlas in the journal will be very valuable for spectroscopists and astrophysicists seeking information in the infrared (IR) region in the laboratory and in outer space.