Dipole moments of (styrene-p-chlorostyrene) triblock copolymers in solutions

(Styrene-p-chlorostyrene) triblock copolymers of the ABA and BAB types (A—polystyrene; B—poly-p-chlorostyrene) were prepared by anionic polymerization and their conformational behaviours in solutions were studied from measurements of the dipole moments. Two solvents, toluene and cumene, were used for the study; toluene is a good solvent for both polystyrene and poly-p-chlorostyrene whereas cumene is a selective solvent, good for polystyrene but poor for poly-p-chlorostyrene. It was found that the dipole moments of the block copolymers measured in toluene are the same for the ABA and BAB copolymers; in cumene however the dipole moment of the BAB copolymer is smaller than that of the ABA copolymer. The results give an additional support to our previous conclusion that the conformation of the block copolymers in a good solvent such as toluene could be approximated with a pseudo-random coil form; in a selective solvent, however, some anomalies take place in the conformation of the block copolymers, as deduced from intrinsic viscosity, osmotic pressure and light scattering measurements.     

Multielemental analyses of Lonomia obliqua (Lepidoptera,Saturniidae) caterpillar using EDXRF and INAA techniques

In this study, multielemental analysis of Lonomia obliqua (Lepidoptera, Saturniidae) caterpillar was performed using energy dispersive X-ray fluorescence and instrumental neutron activation analysis techniques. This caterpillar is poisonous and has the ability to cause fatal hemorrhagic effects in humans after contact. The need of this study is related to morphological changes (mainly size and color) observed in some caterpillars used for preparation of antilonomic serum (antivenom). The samples were classified as healthy (caterpillars of control) and unhealthy (caterpillars visibly modified). The XRF measurements were performed in an energy dispersive X-ray fluorescence spectrometer and the instrumental neutron activation analysis using the IEA-R1 nuclear reactor at IPEN. The results show significant differences for several elements (mainly, P, Cl, Ca, Ti, Mn, Fe, Ni, and Zn) in unhealthy caterpillars that can affect the development of this species as well as the quality and yield of the antivenom. Furthermore, its elemental characterization contributes for the understanding the potential pharmacological (procoagulant and antithrombotic) in the prevention of life-threatening blood clots.     

Modification by H-termination in growth process of titanium silicide on Si(0 0 1)-2 × 1 observed with scanning tunneling microscopy

Formation processes of titanium silicide on hydrogen-terminated H/Si(0 0 1)-2 × 1 surface are studied at the atomic scale with a scanning tunneling microscopy (STM). Square-shaped nanoislands were observed on the Ti/H/Si(0 0 1) surface after annealed at 873-1073 K. These are the epitaxial nanoislands moderately grown due to the local orientation relationship between C49-TiSi₂ and Si(0 0 1), because passivation by surface hydrogen on Si(0 0 1) suppresses active and complex bond formation of Ti-Si.     

Low-lying spectrum of the Y-string three-quark potential using hyper-spherical coordinates

We calculate the energies of three-quark states with definite permutation symmetry (i.e. of SU(6) multiplets) in the N=0, 1, 2 shells, confined by the Y-string three-quark potential. The exact Y-string potential consists of one term, the so-called three-string term, and three angle-dependent two-string terms. Due to this technical complication we treat the problem at three increasingly accurate levels of approximation: (1) the (approximate) three-string potential expanded to first order in trigonometric functions of hyper-spherical angles; (2) the (approximate) three-string potential to all orders in the power expansion in hyper-spherical harmonics, but without taking into account the transition(s) to two-string potentials; (3) the exact minimal-length string potential to all orders in a power expansion in the hyper-spherical harmonics, and taking into account the transition(s) to two-string potentials. We show the general trend of improvement of these approximations: the exact non-perturbative corrections to the total energy are of the order of one per cent, as compared with approximation (2), yet the exact energy differences between the [20,1⁺],[70,2⁺],[56,2⁺],[70,0⁺]-plets are shifted to 2:2:0.9, from the Bowler and Tynemouth separation rule 2:2:1, which is obeyed by approximation (2) at the one per cent level. The precise value of the energy separation of the first radial excitation (“Roper”) [56^′,0⁺]-plet from the [70,1⁻]-plet depends on the approximation, but does not become negative, i.e. the “Roper” remains heavier than the odd-parity [70,1⁻]-plet in all of our approximations.     

Natural and anthropogenic consequences of tropical forest soils in Northern Peru using environmental radionuclides as radiotracers

Environmental radionuclides (⁴⁰K, ¹³⁷Cs, ²¹⁰Pb, ²²⁶Ra) were determined in soils under semi-arid stands, a transition area from thorn to deciduous forest in El Angolo, and heath stands in the Alto Mayo in Northern Peru in order to elucidate their activity level in soil, and to trace underground environment in remote areas of little anthropogenic intervention. Anthropogenic ¹³⁷Cs was only found in the uppermost portion of the soils in small amount, whereas the ²¹⁰Pb activity was exceptionally high at the soil surfaces in a tropical stand of Alto Mayo. The results suggest a fallout nuclide, ²¹⁰Pb, having been transported from local source(s) not to be specified yet.     

Aromaticity and diatropicity of <Emphasis Type="Italic">p</Emphasis>-polyphenyl-α,ω-quinododimethides

p-Polyphenyl-α,ω-quinododimethides were predicted to be moderately aromatic and diatropic, although they exist only in a single classical resonance structure with no aromatic conjugated circuits. Such a dichotomy was resolved using our graph theory of aromaticity and ring-current diamagnetism. Six-site non-conjugated circuits were found to contribute appreciably to aromaticity and ring-current diamagnetism. Within each quinododimethide molecule, local aromaticity increases on going from the outermost to inner phenylene rings.     

Determination of the phenolic-group capacities of humic substances by non-aqueous titration technique

The phenolic-group capacities of five humic substances, such as, the Aldrich humic acid, the humic and fulvic acids extracted from a soil, the humic and fulvic acids extracted from a peat have been precisely determined by the non-aqueous potentiometric titration technique. The titration by KOH in the mixed solvent of DMSO:2-propanol:water = 80:19.3:0.7 at [K⁺] = 0.02 M enabled to measure the potential change in a wide range of pOH (=−log [OH⁻]), and thus to determine the capacities of phenolic groups which could not be precisely determined in the aqueous titration. The results of the titration revealed that the mean protonation constants of the phenolic groups were nearly the same for all humic substances and close to that of phenol in the same medium, indicating that each phenolic-group in the humic substances is rather isolated and is not electronically affected by other affecting groups in the humic macromolecule.     

Capacitive micromachined ultrasonic transducers with novel membrane design

This paper presents a novel membrane design for capacitive micromachined ultrasonic transducers (cMUTs). The proposed design is composed of a thick membrane with reinforcing beams supported by a circumferential thin membrane to improve transducer sensitivity without degrading the membrane resonance frequency. Analytical formulation of sensitivity for the proposed design was newly derived and its validity was verified by finite element analysis (FEA). From the analysis, we confirmed that this thick membrane structure achieved three times higher sensitivity compared to the conventional design by decreasing 70 % of the mass of the thick membrane part with keeping the resonance frequency same.     

Aromaticity on the pancake-bonded dimer of neutral phenalenyl radical as studied by MS and NMR spectroscopies and NICS analysis

We have demonstrated the first MS and NMR observation of a face-to-face pi-bonded dimer of an organic radical (pancake-bonded dimer coined by R. S. Mulliken) in solution, using tri-tert-butylated phenalenyl radical 1, a 3-fold symmetric neutral hydrocarbon. In addition to the direct detection of the dimer signal by cold-spray ionization mass spectrometry (CSI-MS), 1H and 13C NMR spectra in solution gave definitive evidence of a well-defined D3d dimer structure with a 12-center-2-electron-long C-C bond formation, which is the same symmetry as seen in the crystalline state. On the basis of the NMR peaks of the dimer in the aromatic region (6.47 ppm for 1H NMR and 120-143 ppm for 13C NMR), we carried out nucleus-independent chemical shift (NICS) analysis, which showed that the ring center of the dimer became more aromatic (-7.1 ppm) than that of the monomer (-3.8 ppm). The trend of aromaticity generation was more pronounced in the interior of the dimer, which has been interpreted by the negative electron density induced in the bonding region as seen in the electrostatic potential surface.     

Circular dichroism of optically active poly(dialkylsilane) aggregates in microcapsules

Poly[n-hexyl-(S)-3-methylpentylsilane] aggregates confined in microcapsules to keep the aggregation number and ranging in average polymer mass m(p) in a microcapsule from 2 x 10(-)(16) to 2 x 10(-)(14) g were studied by circular dichroism measurements in ethanol (a nonsolvent) and tetrahydrofuran (an associative solvent at low temperature) at various temperatures. The weight-average molecular weight M(w) and the polydispersity index (the ratio of M(w) to the number-average molecular weight) of the polysilane sample were 6.6 x 10(4) and 1.07, respectively, and the average number of polymer molecules in each capsule was estimated to be 1.9 x 10(3) for m(p) = 2 x 10(-)(16) g and 1.7 x 10(5) for m(p) = 2 x 10(-)(14) g. The size of each aggregate did not affect the optical activity because the circular dichroism thus obtained was proportional to m(p) under the same conditions in the investigated m(p) range; on the other hand, the peak height of the circular dichroism in tetrahydrofuran had a significant hysteresis between 0 and 25 degrees C. Moreover, the circular dichroism appreciably reflected the prepared method, that is, the temperature and solvent; in other words, the aggregates memorized the initial conditions in their stacking structures.