Oxygen‐sensing properties of 5,10,15,20‐tetraphenylporphinato platinum(II) and palladium(II) covalently bound on poly(isobutyl‐co‐2,2,2‐trifluoroethyl methacrylate)

A novel methacrylate monomer bearing 5,10,15,20‐tetraphenylporphyrinato palladium(II) (PdTPP) (monomer 1a ) was synthesized and copolymerized with isobutyl methacrylate (IBM) and 2,2,2‐trifluoroethyl methacrylate (TFEM) to give poly (IBM‐co‐TFEM) bearing PdTPP (copolymer 2a ) as a dye‐conjugated oxygen‐permeable polymer for pressure‐sensitive paint applications. The introduction of PdTPP into copolymer 2a was confirmed by UV–vis spectroscopy and extended X‐ray absorption fine structure analysis. The Stern–Volmer plots of the copolymer 2a and a mixture of PdTPP and poly(IBM‐co‐TFEM) both showed downward curvature, unlike that of the platinum complex analogue (copolymer 2b ) previously reported. The plots were successfully fitted with a two‐site model to give two distinct Stern–Volmer constants (K_SV1 and K_SV2) and the partition ratio f₁. Interestingly, the f₁ values for the copolymer 2a were almost constant at about 0.98, whereas those of the mixture of PdTPP and poly(IBM‐co‐TFEM) increased from 0.889 to 0.967 as the temperature was increased. This finding suggests that there are two distinct microheterogeneities, one temperature‐dependent and the other temperature‐independent, in the mixture of PdTPP and poly(IBM‐co‐TFEM). The dye‐conjugation approach effectively eliminates the temperature‐dependent, but not the temperature‐independent microheterogeneity. The luminescence decays of copolymers 2a and 2b and the corresponding mixtures in the absence of oxygen indicated that the temperature‐dependent microheterogeneity involves an oxygen diffusion process, whereas the temperature‐independent one appears to be inherent nature in PdTPP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 663–670, 2010     

Flow structure of knuckling effect in footballs

The flight trajectory of a non-spinning or slow-spinning soccer ball might fluctuate in unpredictable ways, as for example, in the many free kicks of C. Ronaldo. Such anomalous horizontal shaking or rapid falling is termed the ‘knuckling effect’. However, the aerodynamic properties and boundary-layer dynamics affecting a ball during the knuckling effect are not well understood. In this study, we analyse the characteristics of the vortex structure of a soccer ball subject to the knuckling effect (knuckleball), using high-speed video images and smoke-generating agents. Two high-speed video cameras were set at one side and in front of the ball trajectory between the ball position and the goal; further, photographs were taken at 1000 fps and a resolution of 1024×512 pixels. Although in a previous study (Taneda, 1978), shedding of horseshoe vortices was observed for smooth spheres in the Reynolds number (Re) range of 3.8×10⁵<Re<10⁶, in the case of the soccer ball, the vortex structure, which consisted of distorted loop vortices, appeared in the wake behind the ball in the supercritical Re number region. Moreover, after the knuckleballs were airborne, large-scale undulations were observed in the vortex trail visualised with a smoke technique. On the other hand, aerodynamic forces acting on the ball were estimated from the data of the ball’s flight trajectory, and a statistically high correlation (r=0.94, p<0.01) between the fluctuation frequency of the lift and side forces and the undulation frequency of the vortex trail was shown to exist. This fact suggests that the phenomenon of large-scale undulations of the vortex trail is closely related to the cause of the unsteady aerodynamic forces acting on the knuckle ball.     

99Ru,61Ni,57Fe,and119Sn Mössbauer studies of Heusler alloys containing ruthenium

⁹⁹Ru,⁶¹Ni,⁵⁷Fe and¹¹⁹Sn Mössbauer spectroscopic studies were made on ternary intermetallic compounds containing ruthenium, Ru_xY_3?xZ (Y=Fe, Ni; Z=Si, Sn). In the system of Ru_xFe_3?xSi, two different hyperfine magnetic fields were observed at the⁹⁹Ru nuclei (H _hf[Ru]) in the range ofx≤1.0 and the magnitude of eachH _hf[Ru] was found to decrease with an increase in the ruthenium concentrationx. Both the⁹⁹Ru and¹¹⁹Sn Mössbauer spectra of Ru₂FeSn could be analyzed with two sets of magnetically split lines. The⁶¹Ni Mössbauer spectra of Ru₂NiSn were obtained at 5 and 77 K.     

System size and energy dependence of jet-induced hadron pair correlation shapes in Cu+Cu and Au+Au collisions at square root sNN=200 and 62.4 GeV

We present azimuthal angle correlations of intermediate transverse momentum (1-4 GeV/c) hadrons from dijets in Cu+Cu and Au+Au collisions at square root sNN=62.4 and 200 GeV. The away-side dijet induced azimuthal correlation is broadened, non-Gaussian, and peaked away from Delta phi=pi in central and semicentral collisions in all the systems. The broadening and peak location are found to depend upon the number of participants in the collision, but not on the collision energy or beam nuclei. These results are consistent with sound or shock wave models, but pose challenges to Cherenkov gluon radiation models.     

A Near-Infrared Dye That Undergoes Multiple Interconversions through Acid–Base Equilibrium and Reversible Redox Processes

A near-infrared (NIR) polymethine dye ( 1 ), consisting of a cyclohepta[1,2-b;4,3-b′]dithiophene and two phenol moieties, was synthesized. This dye exhibited pH-responsive changes in its photophysical properties due to a two-step acid–base equilibrium that produced a protonated cation ( 1H⁺ ) and an anion ( 1⁻ ). While 1H⁺ showed an intense fluorescence in the red region of the visible spectrum, 1⁻ exhibited a strong absorption in the NIR region. The tropylium ion character in 1H⁺ induces high pK_a1 and pK_a2 values for 1 . Moreover, a stable radical ( 1^. ) was prepared, which showed a NIR absorption band with a maximum at circa 1600 nm. The cyclic voltammogram of 1^. revealed a two-step reversible redox process that produced 1⁻ and the cation 1⁺ , which is different from 1H⁺ . These redox processes accompany drastic electrochromic changes in the vis–NIR region. Overall, 1 is susceptible to multiple interconversions between five forms, due to the multifaceted character of the cycloheptadithiophene skeleton.     

Preparation of highly dispersible and tumor-accumulative, iron oxide nanoparticles Multi-point anchoring of PEG-b-poly(4-vinylbenzylphosphonate) improves performance significantly

This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments.     

Heavy element nuclear chemistry at JAERI

The present status of heavy element nuclear chemistry research at JAERI (Japan Atomic Energy Research Institute) is reviewed. Production of the transactinide nuclei ²⁶¹Rf and ²⁶²Db via the reactions of ²⁴⁸Cm(¹⁸O,5n) and ²⁴⁸Cm(¹⁹F, 5n), respectively, at the JAERI tandem accelerator is reported. Study of the aqueous chemistry of Rf is being carried out with a newly developed rapid ion-exchange separation apparatus. Anion-exchange behavior of Rf in acidic solution is briefly discussed. Recent experimental results on decay studies of neutron-deficient actinide nuclei using the gas-jet coupled JAERI-ISOL are given. We also discuss characteristics of nuclear deformation properties at scission in symmetric and asymmetric fission of actinides. Prospects for studies in the near future are briefly considered.     

Artabotryols A – E,New Lanostane Triterpenes from the Seeds of Artabotrys odoratissimus

Six new lanostane triterpenes, artabotryols A, B, C1, C2, D, and E ( 1, 2, 3a, 3b, 4 , and 5 , resp.) have been isolated from the seeds of Artabotrys odoratissimus (Annonaceae). Their structures have been established as (3α,22S,25R)‐3‐hydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 1 ), (3α,22S,25R)‐22,26‐epoxylanost‐8‐ene‐3,26‐diol ( 2 ), (3α,22S,25R,26R)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3a ), (3α,22S,25R, 26S)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3b ), (3α,22S,25R)‐3,22‐dihydroxylanost‐8‐en‐26‐oic acid ( 4 ) and (3α,7α,11α,22S,25R)‐3,7,11‐trihydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 5 ) by spectroscopic studies and chemical correlations.     

Superconductivity in bulk T′-(La,Sm)2CuO4 prepared via a molten alkaline hydroxide route

We have synthesized La_2?xSm_xCuO₄ (0 ? x ? 2.0) with the Nd₂CuO₄ structure via a molten alkaline hydroxide route at temperatures as low as 400–480 °C. After reduction heat treatment in vacuum at 600–750 °C for removal of excess oxygen atoms at the interstitial apical site, superconductivity with T_c = 20–24 K was observed in the samples with x = 0.05–1.0. The superconducting volume fraction is nearly 100% for x = 0.3–0.7. Our results demonstrate that La_2?xSm_xCuO₄ with no nominal carrier doping is a bulk superconductor.