A multilayered element resonator for CW-ESR and longitudinally detected ESR at radio frequency

The design and evaluation of a multilayered element resonator (MLR), which consists of multiple layers of half-loop conductor plates and insulator sheets, are presented. An MLR and a bridge shielded loop-gap resonator (BLGR), which have similar sizes and resonant frequencies, were fabricated to compare their performances. Using the MLR and the BLGR, the modulation field width and signal intensity of a phantom containing a nitroxide radical were measured by employing a continuous-wave electron spin resonance (CW-ESR) technique at a radio frequency of 300 MHz. Using the same resonators, the longitudinally detected ESR (LODESR) signal intensities of the phantom were also compared. The loadedQ values of the resonators were almost the same. The modulation widths in the MLR were significantly wider than those in the BLGR when the modulation coils were driven at the same voltage. The signal intensities of CW-ESR and LODESR from the phantom in the MLR were significantly greater than those from the BLGR. Since eddy currents disturb the penetration of the modulation field in CW-ESR or detection of changes in magnetization in LODESR observations, these results show that, in the MLR, the eddy currents were suppressed to a greater degree than in the BLGR.     

Is the hematin derived from dodecaphenylporphyrin a μ-oxo dimer?

We have prepared DPP-hematin (DPP?=?2, 3, 5, 7, 8, 10, 12, 13, 15, 17, 18, 20-dodecaphenylporphyrin), and characterized it by Mössbauer and magnetic measurements. It is concluded that DPP-hematin is most likely a monomer, as is expected from the distorted nonplanar structure of the porphyrin, in contrast to usual hematins: hematins derived from usual porphyrins are μ-oxo dimers.     

Spectroscopic and excited-state properties of tri-9-anthrylborane II: Electroabsorption and electrofluorescence spectra

Electroabsorption and electrofluorescence spectroscopies were conducted for tri-9-anthrylborane (TAB) doped in poly(methyl methacrylate) films (1.0 mol %) to reveal the spectroscopic and excited-state properties of the compound. TAB showed three distinct absorption bands: bands I [(19 - 25) x 10(3) cm(-1)], II [(25-31) x 10(3) cm(-1)], and III (>31 x 10(3) cm(-1)). The electroabsorption spectrum demonstrated that the electronic transitions in bands I and III accompanied electric dipole moment changes (Deltamu), while the change in the molecular polarizability contributed mainly to electroabsorption band II. Because of the similarities of the electroabsorption spectrum of band II with that of anthracene itself, band II was assigned to the electronic transition to the locally excited (LE) state of the anthryl group. On the other hand, bands I and III were best described by the electronic transitions to the excited charge-transfer (CT) states. The study demonstrated furthermore that the Deltamu value of TAB accompanied by the lowest-energy electronic transition was as large as 7.8 D, which agreed very well with that determined by the solvent dependences of the absorption and fluorescence maximum energies of TAB (approximately 8.0 D, ref 1): Deltamu = 7.8-8.0 D. The results proved explicitly that the excited state of TAB was localized primarily on the p orbital of the boron atom. Despite the dipole moment change (Deltamu = 7.8-8.0 D) for the lowest-energy electronic transition (band I), the electrofluorescence of TAB accompanied the change in the molecular polarizability. The spectroscopic and excited-state properties of TAB including the curious behavior of the electrofluorescence spectrum as mentioned above were discussed on the basis of theoretical considerations.     

In vivo temporal EPR imaging of the brain of rats by using two types of blood-brain barrier-permeable nitroxide radicals

In vivo temporal EPR imaging was conducted on the brain of rats that received one of two kinds of blood-brain barrier-permeable nitroxide radicals via the tail vein-one is a water-soluble 3-hydroxymethyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl (hydroxymethyl-PROXYL); and the other is a non-water-soluble 3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-1-oxyl (PCAM). From temporal EPR imaging data, temporal changes in the distribution of the nitroxide radical in the cerebral cortex, striatum, and hippocampus in the brain were investigated. It was found that the half-lives of the three parts in the brain of hydroxymethyl-PROXYL are longer and their EPR signal intensities are greater than those of PCAM.     

Electronic structure of light-induced lophyl radical derived from a novel hexaarylbiimidazole with pi-conjugated chromophore

A novel photochromic hexaarylbiimidazole with a bithienyl group as an extended pi-conjugation unit was synthesized and the light-induced lophyl radical was found to be stabilized due to the delocalization of an unpaired electron, and to strongly absorb near-infrared light.     

Magnetic hyperfine field of arsenic in nickel by NMR/ON of71,72As

The magnetic hyperfine splitting frequencies of⁷¹AsNi and⁷²AsNi in a 0.11 Tesla external magnetic field have been determined by NMR/ON method as 66.00(6) MHz and 106.17(13) MHz respectively. Using the known magnetic moments of μ(⁷¹As)=1.6735(18) and μ(⁷²As)=−2.1566(3), the hyperfine fields were deduced asB _hf(⁷¹AsNi)=12.824(19) Tesla andB _hf(⁷²AsNi)=12.807(16) Tesla.     

Fibers from polyblends containing nylon 6 as basic component. I. Melt spinning and physical properties of blend fibers

Five series of two-component blend filaments, comprising nylon 6 (N6) and nylon 66 (N66), nylon 610 (N610), nylon 11 (N11), nylon 12 (N12), or poly(ethylene terephthalate) (PET), were prepared by using a research spinning machine and a conventional drawing machine. The microstructure and the physical properties of the resultant filaments were evaluated with a tensile tester, a optical microscope, a density-gradient column, and a DTA instrument. When both components were mixed homogeneously so that they would form a three-dimensional network, the tensile properties of the blend filament were at least equivalent to the values predicted from those of both components. On the other hand, as in the cases of 30/70 and 70/30 N6–PET, when the minor component was discretely distributed as short fibrils in the matrix of the major component, the blend filament had an extremely weak tenacity. A supertenacity filament was obtained from 50/50 N6–N610. The marked increase of the tensil strength and the initial modulus of 50/50 N6–N610, about 12 g/den and 520 kg/mm², respectively, may be due to a significant increase in the crystallinity and the orientation of the blend.     

Electroreductive intramolecular coupling of aromatic beta- and gamma-imino esters: a new synthetic method for N-alkoxycarbonyl-2-aryl-3-ones and cis-2-aryl-3-ols of pyrrolidines and piperidines

The electroreduction of aromatic beta- and gamma-imino esters prepared from beta-alanine and GABA in the presence of chlorotrimethylsilane and subsequent N-alkoxycarbonylation of the resulting five- and six-membered cyclized amines gave mixed ketals of N-alkoxycarbonyl-2-arylpyrrolidin-3-ones and 2-arylpiperidin-3-ones, respectively. The best result of the electroreductive intramolecular coupling was achieved using Bu(4)NClO(4) as a supporting electrolyte and a Pb cathode in THF. Acid hydrolysis of the mixed ketals afforded N-alkoxycarbonyl-2-arylpyrrolidin-3-ones and 2-arylpiperidin-3-ones in good yields. The reduction of these ketones with NaBH(4) in methanol afforded the corresponding N-alkoxycarbonyl-cis-2-arylpyrrolidin-3-ols and cis-2-arylpiperidin-3-ols diastereospecifically.