Reaction control in radical polymerization of di‐n‐butyl itaconate utilizing a hydrogen‐bonding interaction

We have reported that intramolecular chain‐transfer reaction takes place in radical polymerization of itaconates at high temperatures and/or at low monomer concentrations. In this article, radical polymerizations of di‐n‐butyl itaconate (DBI) were carried out in toluene at 60 °C in the presence of amide compounds. The ¹³C‐NMR spectra of the obtained poly(DBI)s indicated that the intramolecular chain‐transfer reaction was suppressed as compared with in the absence of amide compounds. The NMR analysis of DBI and N‐ethylacetamide demonstrated both 1:1 complex and 1:2 complex were formed at 60 °C through a hydrogen‐bonding interaction. The ESR analysis of radical polymerization of diisopropyl itaconate (DiPI) was conducted in addition to the NMR analysis of the obtained poly(DiPI). It was suggested that the suppression of the intramolecular chain‐transfer reaction with the hydrogen‐bonding interaction was achieved by controlling the conformation of the side chain at the penultimate monomeric unit of the propagating radical with an isotactic stereosequence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4895–4905, 2004     

Landau levels in a novel two-dimensional electron system interacting with charged quantum dots

Landau levels have been theoretically investigated in a two-dimensional electron gas near a quantum dot (QD) layer. By a diagrammatical method, we have formulated the self-energy for the Landau level and deduced its relation to the AC conductivity σ_loc(ω) in the QD layer. As an example, we have examined the density of states in the case where σ_loc(ω) is described by Aω^S(S=0.8). It is found that the Landau levels are broadened due to the interaction with the localized electrons in the QDs.     

Soft-sputtering of insulin films in argon-cluster secondary ion mass spectrometry

In secondary ion mass spectrometry (SIMS) of organic substances, the dissociation of the sample molecules is crucial. We have developed SIMS equipment capable of bombardment, where the primary ions are argon cluster ions with kinetic energy per atom controllable down to 1 eV. We previously reported the detection of intact ions of insulin and cytochrome C using this equipment. In this paper, we present a detailed characterization of the emission of secondary ions from insulin, focusing on the difference in secondary ion yield between intact ions and fragment ions by varying the incident angle of the cluster ions. The emission intensity of the intact ions was changed drastically due to the exposed dosage and incident angle of the cluster ions in contrast to the fragment ions. We discuss these results based on the manner in which the argon-cluster ions collide with the organic solid.     

Highly efficient enzymatic synthesis of 3'-deoxyapionucleic acid (apioNA) having the four natural nucleobases

The synthesis of the 3'-deoxyapionucleoside 3'-triphosphates (apioNTPs) having the four natural nucleobases and their enzymatic incorporation into a DNA-DNA primer-template have been tried. Therminator DNA polymerase was shown to incorporate these apioNTPs effectively giving 43mer DNA-apioNA chimera.     

Polymorphism of 4-Fluorophenylpyruvic Acid Studied by X-Ray Crystallography and Vibrational Spectroscopy

Two polymorphic forms (I and II) of 4-fluorophenylpyruvic acid (F-PPA) were obtained by crystallization from different solvents, showing a melting point at 163.2 and 171.0 °C. Crystal structures of polymorphs I and II were determined by X-ray crystallography. IR and Raman spectra of the two polymorphs were measured and the spectral characteristics were compared with those of phenylpyruvic acid. the two polymorphs show similar molecular and crystal structures to each other, except for the molecular geometries of the enol and the carboxylic acid moieties. Distinct IR spectral differences which result from the crystal field splitting were observed between the two polymorphs.     

James-Stein estimators for time series regression models

The least squares (LS) estimator seems the natural estimator of the coefficients of a Gaussian linear regression model. However, if the dimension of the vector of coefficients is greater than 2 and the residuals are independent and identically distributed, this conventional estimator is not admissible. James and Stein [Estimation with quadratic loss, Proceedings of the Fourth Berkely Symposium vol. 1, 1961, pp. 361-379] proposed a shrinkage estimator (James-Stein estimator) which improves the least squares estimator with respect to the mean squares error loss function. In this paper, we investigate the mean squares error of the James-Stein (JS) estimator for the regression coefficients when the residuals are generated from a Gaussian stationary process. Then, sufficient conditions for the JS to improve the LS are given. It is important to know the influence of the dependence on the JS. Also numerical studies illuminate some interesting features of the improvement. The results have potential applications to economics, engineering, and natural sciences.     

Novel dating method for speleothems with microscopic fluorescent annual layers.

Terrestrial carbonate deposits with a banded layer structure can be good tools for the extraction of past environmental information on global and local scales using trace element concentrations and stable isotope ratios. The absolute age dating is most important for the reconstruction of an environmental chronicle. The measurements of fluorescent annual bandings in stalagmites using a microscopic spectrofluorometer with an XY-stage can be a convenient dating method and are especially effective for young samples whose absolute age is very difficult to be determined by other methods. The number of annual bandings was objectively counted using a personal computer. The optimal conditions for the measurements are discussed. The annual banding in stalagmites is caused by the seasonal differences in the fulvic acid concentrations in the dripping water which forms speleothems.     

Biferrocene-M(mnt)2 charge-transfer complexes (M = Ni, Co; mnt = maleonitriledithiolate). structure, valence states, and magnetic properties

Charge-transfer salts of branched-alkyl biferrocenes, (1',1' '-R2-1,1' '-biferrocene)[Ni(mnt)2] (1a, R = isopropyl; 2a, R = dineopentyl) and (1',1' '-R2-1,1' '-biferrocene)2[Co(mnt)2]2 (1b, R = isopropyl; 2b, R = dineopentyl), were prepared. Their valence states were investigated using X-ray crystallography and M?ssbauer spectroscopy. Complexes 1a and 1b show segregated-stack crystal structures that contain columns of acceptors, whereas structures of 2a and 2b, which contain bulky donors, are rather discrete. All of the complexes contain mixed-valent biferrocenium monocations. A two-step valence transition was found in complex 1a. The crystal contains two crystallographically independent cations: one undergoes valence localization below room temperature; the other undergoes valence localization below ca. 130 K. The former transition is derived from asymmetry of the crystal environment around the cation, whereas the latter one is caused by symmetry lowering coupled with a spin-Peierls transition (T(C) = 133.2 K) associated with the dimerization of the acceptors. This compound was found to exhibit a dielectric response based on valence tautomerization. Other complexes (1b, 2a, and 2b) show a valence-trapped state. In all complexes, charge localization was found to occur through local electrostatic interactions between the donor's cationic moiety and the acceptor's electronegative moieties.