Emulsion polymerization of vinyl acetate using iodine‐transfer and RAFT radical polymerizations

This study deals with control of the molecular weight and molecular weight distribution of poly(vinyl acetate) by iodine‐transfer radical polymerization and reversible addition‐fragmentation transfer (RAFT) emulsion polymerizations as the first example. Emulsion polymerization using ethyl iodoacetate as the chain transfer agent more closely approximated the theoretical molecular weights than did the free radical polymerization. Although ¹H NMR spectra indicated that the peaks of α‐ and ω‐terminal groups were observed, the molecular weight distributions show a relatively broad range (M_w/M_n = 2.2–4.0). On the other hand, RAFT polymerizations revealed that the dithiocarbamate 7 is an excellent candidate to control the polymer molecular weight (M_n = 9.1 × 10³, M_w/M_n = 1.48), more so than xanthate 1 (M_n = 10.0 × 10³, M_w/M_n = 1.89) under same condition, with accompanied stable emulsions produced. In the M_n versus conversion plot, M_n increased linearly as a function of conversion. We also performed seed‐emulsion polymerization using poly(nonamethylene L ‐tartrate) as the chiral polyester seed to fabricate emulsions with core‐shell structures. The control of polymer molecular weight and emulsion stability, as well as stereoregularity, is also discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Thermal Behaviour and Analytical Study of the Production of TiSnOx from the Mixed 8-Hydroxyquinolinates

Solubility and pH precipitation studies were carried out to obtain the binuclear complex {[TiO(C₉H₆NO)₂][Sn(C₉H₆NO)₂]} involving 8-hydroxyquinoline as chelating agent. The compound, the individual mononuclear complexes and their physical mixture were evaluated by means of techniques such as TG, DTA, elemental analysis, X-ray diffraction, IR spectroscopy. The properties of the original compounds and also the thermoanalytical conditions exerted a great influence on the degree of crystallinity and on the crystalline phase of the mixed oxide obtained as final product of the thermal decomposition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Multipartite Generalized Bell Inequality with an Arbitrary Number of Settings

We derive a generalized Bell inequality for N qubits which involves an arbitrary number of settings for each of the local measuring apparatuses. The inequality forms a necessary condition for the existence of a local realistic model for the values of a correlation function, given in a n-setting Bell experiment. We show that a local realistic model for the values of a correlation function, given in a two-setting Bell experiment, cannot construct a local realistic model for the values of a correlation function, given in an arbitrary number of n-setting Bell experiment, even though there exist two-setting models for the n measurement directions chosen in the given n-setting experiment. Therefore, the property of two-setting model is different from the property of n-setting model. We discuss classification of local realistic theories in further detail more than the result presented in (J. Phys. A: Math. Theor. 41:155308, 2008). The generalized Bell inequality covers the previous results correctly.     

Grazing-exit X-ray spectrometry for surface and thin-film analyses.

Electron-probe x-ray micro analysis (EPMA) and particle-induced x-ray emission analysis (PIXE) were performed under grazing-exit conditions. To control the exit angle (take-off angle), a new sample holder having a stepping motor was developed for grazing-exit EPMA. A carefully polished surface of a stainless-steal sample was measured. The surface of stainless steel is normally covered with a thin native oxide layer. The intensity ratio of Cr K(alpha) to Fe K(alpha) increases significantly at the grazing angle, becoming about 5-times larger at 0.2 degrees than at 40 degrees. This result indicates that grazing-exit EPMA is useful for surface analysis. In addition, a new PIXE equipment was developed for grazing-exit x-ray measurements. The sample is fixed and the x-ray detector is moved by applying a linear stage. Preliminary experimental results of grazing-exit PIXE are also shown.     

Ion-induced self-organized ripple patterns on graphite and diamond surfaces

In order to investigate the allotropic effect on ripple pattern formation, highly oriented pyrolytic graphite (HOPG) and single crystalline diamond were irradiated with 10-200 keV Xe⁺ at an incident angle of 60° with respective to the surface normal. The irradiation fluence was 2 × 10¹⁷ cm⁻² for all irradiations. Ripple patterns were observed on both HOPG and diamond surfaces. However, large differences in ripple wavelengths, amplitudes and surface roughnesses between HOPG and diamond were recognized. The reason for these differences is discussed.     

Solvent‐ and concentration‐sensitive fluorescence of 2‐(3,4,5,6‐tetrafluoro‐2‐hydroxyphenyl)benzoxazole

2‐(3,4,5,6‐Tetrafluoro‐2‐hydroxyphenyl)benzoxazole ( 2 ) emits the long wavelength fluorescence around 500 nm in nonpolar solvent via the intramolecular proton transfer process in the excited state of 2 (enol‐form) and also emits the intermediate wavelength fluorescence around 440 nm in polar solvent, which is assumed to originate from the excited state of 2 (anion). The ease of formation of 2 (anion), compared to 2‐(2‐hydroxyphenyl)benzoxazole ( 1 ), is explained by the strongly inductive fluorine atoms. In a solvent with the intermediate polarity, 2 emits both fluorescences and their relative intensity is dependent on the concentration of 2 , which is supposed to be caused by the high sensitivity of the intermediate wavelength emission to the concentration quenching.     

Anthracene‐Attached Persistent Tricyclic Aromatic Hydrocarbon Radicals

Anthracene‐attached tricyclic aromatic hydrocarbon radicals having different central polygons, Ant‐5 , Ant‐6 , and Ant‐7 , were synthesized to evaluate the role of an anthracene substituent group in the stability and reactivity of tricyclic aromatic hydrocarbon radicals. The bulky anthryl group effectively protects a carbon atom with high spin density, resulting in high persistence of the radicals. On the other hand, the combination of the anthryl group and the tricyclic aromatic scaffold makes the molecular structure drastically change from a twisted form to a folded form and an unpaired electron moves into the anthryl moiety, eventually affording a tail‐to‐tail σ‐dimer.     

Simultaneous measurements of reactive scalar and velocity in a planar liquid jet with a second-order chemical reaction

This paper presents a new experimental approach for simultaneous measurements of velocity and concentration in a turbulent liquid flow with a chemical reaction. For the simultaneous measurements, we developed a combined probe consisting of an I-type hot-film probe and an optical fiber probe based on the light absorption spectrometric method. In a turbulent planar liquid jet with a second-order chemical reaction $(\mathrm{A}+\mathrm{B}\rightarrow \mathrm{R})$ , streamwise velocity and concentrations of all reactive species are measured by the combined probe. The turbulent mass fluxes of the reactive species are estimated from the simultaneous measurements. The results show that the influence of the chemical reaction on the turbulent mass flux of the reactant species near the jet exit is different from its influence in other regions, and the turbulent mass flux of the product species has a negative value near the jet exit and a positive value in other regions.     

Analyzing atomic liquids and solids by means of two-dimensional Raman spectra in frequency domain

A practical method to evaluate the contributions of the nonlinear polarizability and anharmonicity of potentials from the experimental and simulation data by using double Fourier transformation is presented. In a Lennard-Jones potential system, an approximated expression of the fifth-order response function using the ratio between nonlinear polarizability and anharmonicity exhibits a good agreement with the results of the molecular dynamics simulation. In a soft-core case, the fifth-order Raman signal indicates that the system consists of the delocalized and localized modes, and only the delocalized mode affects the dramatic change of the fifth-order Raman response functions between solid and liquid phases through nonlinear polarizability.     

Characteristics of all-optical 3R regenerators using cascaded second-order nonlinear effect in quasi-phase matched lithium niobate devices

We numerically show that quasi-phase matched (QPM) lithium niobate (LN) devices employing the cascaded second-order nonlinear effect of second harmonic generation (SHG) and difference frequency mixing (DFM) have all-optical decision gate characteristics. The decision gate function is realized by a parabolic transmittance for a low-power region and a limiting characteristic for a high-power region. The limiter function is attributed to the large group-velocity mismatch between the fundamental and second harmonic pulses. This operation principle differs from those of other all-optical 2R (reamplification and reshaping) or 3R (2R and retiming) regenerators that have been proposed in the past. Furthermore, we show that an initial time offset between the signal and clock pulses can improve the output signal power or the switching efficiency of the device. Based on the numerical results, we propose a method for designing all-optical 3R regenerators using the cascade of SHG and DFM in the QPM-LN devices. Following the design method, all-optical 3R operation at the bit rate of 200 Gbps can be achieved using a 1-cm-long waveguide device.