Type-II Red Phosphorus: Wavy Packing of Twisted Pentagonal Tubes

Elemental phosphorus exhibits fascinating structural varieties and versatile properties. The unique nature of phosphorus bonds can lead to the formation of extremely complex structures, and detailed structural information on some phosphorus polymorphs is yet to be investigated. In this study, we investigated an unidentified crystalline phase of phosphorus, type-II red phosphorus (RP), by combining state-of-the-art structural characterization techniques. Electron diffraction tomography, atomic-resolution scanning transmission electron microscopy (STEM), powder X-ray diffraction, and Raman spectroscopy were concurrently used to elucidate the hidden structural motifs and their packing in type-II RP. Electron diffraction tomography, performed using individual crystalline nanowires, was used to identify a triclinic unit cell with volume of 5330 ų, which is the largest unit cell for elemental phosphorus crystals up to now and contains approximately 250 phosphorus atoms. Atomic-resolution STEM imaging, which was performed along different crystal-zone axes, confirmed that the twisted wavy tubular motif is the basic building block of type-II RP. Our study discovered and presented a new variation of building blocks in phosphorus, and it provides insights to clarify the complexities observed in phosphorus as well as other relevant systems.     

Dispersion of functional tetraphenylporphyrin-ligated metal into ultra-thin flexible acrylate films. 2. Oxygen-uptake properties

Cobalt(II) meso-tetraphenylporphyrin (CoTPP)/acrylate hybrid thin films were prepared by CoTPP sublimation and reactive monomer evaporation onto the glass substrate in vacuum conditions. Deposited CoTPP/acrylate thin films were in situ photopolymerized. The oxygen-uptake behaviors of CoTPP/acrylate films were investigated by means of sorption measurements, monitored by gravimetric means, and analyzed using dual mode sorption model. The loading percent of CoTPP in the film was adjusted up to 60% by controlling the CoTPP sublimation rate. The thickness of the CoTPP/acrylate hybrid film was about 200 nm and oxygen-uptake data obtained from the sorption measurements indicated that CoTPP molecules in the CoTPP/acrylate hybrid films were able to bind oxygen molecules reversibly.     

Synthesis of highly crosslinked monodisperse polymer particles: Effect of reaction parameters on the size and size distribution

Monodisperse polystyrene particles crosslinked with different concentrations of divinylbenzene were synthesized in the 3.2–9.1 μm size range by dispersion polymerization in an isopropyl alcohol/toluene mixed‐dispersion medium with poly(N‐vinylpyrrolidone) as a steric stabilizer and 2,2′‐azobisisobutyronitrile as a radical initiator. The effects of the reaction parameters such as the crosslinking agent concentration, media solvency (controlled by varying the amount of toluene addition), the initiator concentration, and the stabilizer concentration on the particle size and size distribution were investigated with reference particles with a monodisperse size distribution and crosslinked by 1.5 wt % divinylbenzene. The appropriate increase in media solvency was a prerequisite for preparing crosslinked particles without coagulated and/or odd‐shaped particles. The investigation of the effects of the polymerization parameters also shows that only specific sets of conditions produce particles with a monodisperse size distribution. The glass‐transition temperatures of the particles increased with increasing divinylbenzene concentration. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4368–4377, 2002     

Direct observation of Barkhausen avalanche in Co thin films

We report direct full-field magneto-optical observations of Barkhausen avalanches in Co polycrystalline thin films at criticality. We provide experimental evidence for the validity of a phenomenological model of the Barkhausen avalanche originally proposed by Cizeau, Zapperi, Durin, and Stanley [Phys. Rev. Lett. 79, 4669 (1997)]], where the model describes a 180 degrees -type flexible domain wall deformed by a localized defect with consideration of long-range dipolar interaction. The Barkhausen jump areas show a power-law scaling distribution with critical exponent tau approximately 1.33 for all the samples having different thickness from 5 to 50 nm, which is in accord with the two-dimensional prediction of the model.     

Assessment of metabolic changes in the striatum of a MPTP-intoxicated canine model: in vivo ¹H-MRS study of an animal model for Parkinson's disease

Parkinson's disease (PD) is a neurodegenerative disorder characterized by the progressive loss of the dopaminergic neurons in the substantia nigra pars compacta, which projects to the striatum. We induced a selective loss of nigrostriatal dopamine neurons, by infusing the mitochondrial complex 1 inhibitor 1-methyl 4-phenyl 1,2,3,6-tetrahydropyridine (MPTP) into adult beagle dogs (N=5). Single voxel ¹H water suppressed magnetic resonance spectroscopy (¹H-MRS) at 3 T was used to assess the metabolic changes in the striatum of canine before and after MPTP intoxication. The metabolite spectra obtained from the striatum (voxel size: 2 cm³) showed a lower N-acetyl aspartate to total creatine (creatine+phosphocreatine) ratio after MPTP intoxication. There were no significant differences in other metabolite ratios such as glutamate+glutamine, choline-containing compounds (glycerophosphocholine+phophorylcholine and myo-inositol). Our findings indicated that ¹H-MRS is a sensitive, noninvasive measure of neural toxicity and biochemical alterations of the striatum in a canine model of PD, and further studies are needed to confirm brain metabolic changes in association with progression of MPTP-intoxication.     

Nano-sized polystyrene prepared using bifunctional vinyl urethane macromonomer in emulsion polymerization

The linear-type bifunctional vinyl urethane macromonomer (L-VUM: Mw; 40,453) was synthesized and applied to emulsion polymerization of styrene in DDI water. The structure of L-VUM was confirmed using ¹H NMR and FT-IR. The macromonomer served as a good nonionic surfactant resulted in stable polystyrene nanospheres. Polystyrene particles were prepared with various concentrations of macromonomoer (1–30 wt% refer to monomer), initiator (0.5–2 wt%) and different temperatures (60–80 °C). Monodisperse PS nanospheres with 30 wt% L-VUM have a number-average diameter (D_n) of 200 nm with good uniformity (1.011) and molecular weight (M_w) 231,180 g/mol. The particle morphology, molecular weight and distribution, uniformity and the stability of the nanospheres upon the reaction temperature and concentration of L-VUM will be thoroughly discussed.     

Performance of ionic liquid as catalyst in the copolymerization of phenyl glycidyl ether with carbon dioxide

Summary Selective ammoxidation of ethylene over Co-ZSM-5 prepared by aqueous and solid-state ion exchange has been studied. The catalyst prepared using solid-state exchange showed higher activity and selectivity to acetonitrile. Catalysts tested in the ammoxidation of ethylene were previously characterized by chemical analysis, XRD, N₂-BET measurements and FTIR. TPD of ammonia and FTIR of pyridine used as probe molecule showed that solid-state ion exchange of H-ZSM-5 with cobalt generates new Lewis acid sites which seem to play a role in the ammoxidation reaction.     

Blockade of translationally controlled tumor protein attenuated the aggressiveness of fibroblast-like synoviocytes and ameliorated collagen-induced arthritis

Histamine releasing factor/translationally controlled tumor protein (HRF/TCTP) stimulates cancer progression and allergic responses, but the role of HRF/TCTP in rheumatoid arthritis (RA) remains undefined. In this study, we explored the pathogenic significance of HRF/TCTP and evaluated the therapeutic effects of HRF/TCTP blockade in RA. HRF/TCTP transgenic (TG) and knockdown (KD) mice with collagen-induced arthritis (CIA) were used to determine the experimental phenotypes of RA. HRF/TCTP levels in the sera of RA patients were measured and compared to those from patients with osteoarthritis (OA), ankylosing spondylitis, Behçet’s disease, and healthy controls. HRF/TCTP expression was also assessed in the synovium and fibroblast-like synoviocytes (FLSs) obtained from RA or OA patients. Finally, we assessed the effects of HRF/TCTP and dimerized HRF/TCTP-binding peptide-2 (dTBP2), an HRF/TCTP inhibitor, in RA-FLSs and CIA mice. Our clinical, radiological, histological, and biochemical analyses indicate that inflammatory responses and joint destruction were increased in HRF/TCTP TG mice and decreased in KD mice compared to wild-type littermates. HRF/TCTP levels in the sera, synovial fluid, synovium, and FLSs were higher in patients with RA than in control groups. Serum levels of HRF/TCTP correlated well with RA disease activity. The tumor-like aggressiveness of RA-FLSs was exacerbated by HRF/TCTP stimulation and ameliorated by dTBP2 treatment. dTBP2 exerted protective and therapeutic effects in CIA mice and had no detrimental effects in a murine tuberculosis model. Our results indicate that HRF/TCTP is a novel biomarker and therapeutic target for the diagnosis and treatment of RA.Subject terms: Translational research, Autoimmunity     

Migration phenomena of surfactants in polyethylene film

Migration diffusion coefficients of two surfactants (sorbitan laurate, SPAN‐20 and sorbitan palmitate, SPAN‐40) in polyethylene blend are calculated in the desorption process by means of Fourier transform infrared (FT‐IR) spectroscopy technique at 25°C. They are 2.31 and 2.24 × 10⁻¹¹ cm²/s, respectively, which show no significant dependency of molecular weights of the surfactants on diffusion. The composition of LLDPE (linear low‐density polyethylene) and LDPE (low‐density polyethylene) in LLDPE blend is a 7 : 3 ratio, and ethylene acrylic acid (EAA) copolymer is used to verify its role as a migration controller. The key factor affecting the diffusion of the surfactant is suggested to be the segmental mobility by the semicrystalline LLDPE blend. Incorporation of 20 wt% EAA in the LLDPE blend retards the migration rate of the surfactants by reducing the diffusion coefficients to be 9.6 and 7.7 × 10⁻¹² cm²/s and this is believed to be due to the blocking effect of EAA. Although the diffusion coefficient was varied from system to system, the migration kinetics of the surfactants in short times obeys the Fickian behavior if the experimental error is allowed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1387–1395, 1999