STM-based molecular detection of "catch-and-release" of protons for bipyridine bound to phenylene-ethynylene thiol

The protonation/deprotonation response of a novel bipyridine containing (phenylene-ethynylene) thiol adsorbed to a Au surface was investigated with scanning tunneling microscopy (STM), showing reversible changes in the average heights (approximately 50 spots) and the height distribution arising from protonation/deprotonation.     

Reliability of mean transit time obtained using perfusion-weighted MR imaging; comparison with positron emission tomography

The purpose of this project was to assess the reliability of the cerebral mean transit time (MTT) obtained using perfusion-weighted MR imaging by comparing it with the MTT obtained when performing positron emission tomography (PET). Ten patients with chronic occlusive cerebrovascular disease were investigated. They had either unilateral internal carotid artery occlusion or middle cerebral artery occlusion. The regions-of-interest were placed in non-infarcted areas within the territory of the middle cerebral artery on the affected side. Control regions-of-interest were placed in mirrored regions of the contralateral side. Linear regression analyses were performed using the parameters of the MTT obtained with perfusion-weighted MR imaging and the MTT, cerebral blood flow, vascular reactivity, and oxygen extraction fraction obtained with PET. The respective MTTs of the affected and non-affected sides obtained with perfusion-weighted MR imaging versus those with PET were 7.3 +/- 2.2 s and 6.0 +/- 1.2 s versus 8.2 +/- 3.0 s and 6.4 +/- 1.7 s. The MTT obtained using perfusion-weighted MR imaging and PET demonstrated statistically significant correlation (r = 0.87, p < 0.0001). The MTT obtained with perfusion-weighted MR imaging correlated statistically with cerebral blood flow (r = -0.74, p < 0.001), vascular reactivity (r = -0.73, p < 0.001) and oxygen extraction fraction (r = 0.61, p < 0.01). Similarly, the MTT obtained using PET statistically correlated with cerebral blood flow (r = -0.78, p < 0.0001), vascular reactivity (r = -0.51, p < 0.05) and oxygen extraction fraction (r = 0.68, p < 0.01). The reliability of the MTT obtained using perfusion-weighted MR imaging appears to be approximately equal to that obtained with positron emission tomography.     

On Sobolev and Capacitary Inequalities for Contractive Besov Spaces over d-sets

We derive Sobolev inequalities for Besov spaces B ^p,p (F), 0<<1, 1p< on d-sets F in R ⁿ , dn, from a metric property of the Bessel capacity on R ⁿ . We first extend Kaimanovitch's result on the equivalence of Sobolev and capacitary inequalites for contractive p-norms in a general setting allowing unbounded Lévy kernels. A simple part of the Jonsson–Wallin trace theorem for Besov spaces and some basic properties of Bessel and Besov capacities on R ⁿ are then utilized in getting the desired inequalities. When p=2, the Besov space being considered is a non-local regular Dirichlet space and gives rise to a jump type symmetric Markov process M over the d-set. The upper bound of the transition function of M and metric properties of M -polar sets are then exhibited.     

Electronic structure of substitutional nitrogen impurity in TiO 2 studied by the β-NMR method

In order to study the local electronic structure of nitrogen impurity in rutile TiO₂, we have measured double-quantum NMR spectra of short lived β-emitter ¹²N(I = 1, T _1/2 = 11 ms) implanted into a rutile single crystal by means of the β-NMR technique. The resonance line obtained at room temperature is well accounted for by the second order shift due to the quadrupole interaction at the oxygen substitutional site. The spectrum at 25 K has shown the other lines than the central diamagnetic line shifted by 10?15 kHz to both sides, which has been already shown in the previous data obtained with a different crystal orientation and an external field. The present results supports the existence of a paramagnetic state formed by the substitutional nitrogen impurities.     

Investigation of individual micrometer-size Kosa particle with on-site combination of electron microscope and synchrotron X-ray microscope.

The Kosa (yellow sand) aerosol affects the global environment as well as human health because it migrates from the interior of China to other areas, absorbing various atmospheric elements. Investigation into individual Kosa aerosol particles, which are submicroscopic to several tens of micrometers in diameter, is required to resolving the issue. We installed a scanning electron microscope (SEM) equipped with an energy dispersive X-ray spectrometer (EDX) on a synchrotron radiation (SR) beam line and introduced the SR beam into the SEM chamber for combinatorial application of SEM-EDX and SR X-ray fluorescence (SR-XRF) spectrometry to individual particles. It should be noted that detailed topographic observation by SEM and sensitive elemental analysis by SR-XRF, both crucial for individual particle measurement but which previously had to be carried out separately, were jointly performed inside the SEM chamber in this setup. Here, we show that SR-XRF results, in conjunction with SEM images, contributed toward resolving individual particle dispositions. Atmospheric sulfur primarily adheres to calcium in the aerosol particles and the particle surface roughens as a consequence of the chemical reaction between the two elements.     

Side chain liquid crystal poly(fumarate)s bearing tolane‐based mesogens

Cyanotolane or fluorotolane mesogens were for the first time introduced into the fumarate monomer under basic conditions. All fumarate monomers undergo radical polymerization in benzene in the presence of dimethyl 2,2′‐azobis(isobutyrate) as an initiator at 60 °C, affording the corresponding poly(fumarate)s with a molecular weight (M_n) of ～ 10⁴ and an exceptionally narrow polydispersity. The phase behaviors of the fumarate monomers and the correspoding poly(fumarate)s were comprehensively investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD) analysis. For the fumarate monomers, fluorotolane derivatives were prone to form higher‐order liquid crystal phases such as a smectic phase, while cyanotolane derivatives tended to show a wide mesophase temperature range, depending on the alkyl chain spacer length. Very surprisingly, these features dramatically weakened when they were polymerized. The mesophase temperature ranges became narrow and completely disappeared for the poly(fumarate)s with a shorter alkyl chain spacer. A nematic phase representing lower‐order arrangements became a predominant liquid crystal phase for the poly(fumarate) carrying cyanotolane mesogens. Only the poly(fumarate) carrying fluorotolane mesogens with a longer alkyl chain spacer displayed the characteristic XRD patterns of the smectic B phase. The transient photocurrent measurements of the fumarate monomer with cyanotolane mesogens displayed a hole mobility of the order of 10^?4–10^?5 cm² V^?1 s^?1 at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5101–5114, 2008     

Assembly of a Benzo-Fused Bridged Ketone Scaffold from 1,5,10-Enediynes through One-Pot Ruthenium-Catalyzed Cyclization/Iodine-Mediated Oxidative Ring Expansion

In the presence of a cationic Ru catalyst, 1,6-diynes bearing a terminal styryl moiety underwent [2+2+2] cyclization to produce dehydrobiphenylenes fused with a five-membered ring. Although the cycloadducts were unstable toward purification, their one-pot iodine-mediated ring expansion successfully afforded unprecedented bridged ketone products containing a benzo-fused bicyclo[3.2.1] framework.     

Biocatalytic reduction system for the production of chiral methyl (R)/(S)-4-bromo-3-hydroxybutyrate

An effective method for producing methyl 4-bromo-3-hydroxybutyrate enantiomers was developed using an engineered protein. Escherichia coli transformant cells containing a mutant β-keto ester reductase (KER-L54Q) from Penicillium citrinum and a cofactor-regeneration enzyme such as glucose dehydrogenase (GDH) or Leifsonia sp. alcohol dehydrogenase (LSADH) were used to produce methyl (S)-4-bromo-3-hydroxybutyrate from methyl 4-bromo-3-oxobutyrate. On the other hand, the production of methyl (R)-4-bromo-3-hydroxybutyrate was achieved by asymmetric reduction of methyl 4-bromo-3-oxobutyrate with a mutant phenylacetaldehyde reductase (PAR-HAR1) from Rhodococcus sp. ST-10.     

Volatile Organic Compound Sensing by Quartz Crystal Microbalances Coated with Nanostructured Macromolecular Metal Complexes

We report the construction of a molecular recognition layer composed of polyelectrolyte brushes and metal complexes on the surface of a quartz crystal microbalance (QCM) and the sensing abilities for various volatile organic compounds (VOCs). Atom‐transfer radical polymerization of 2‐(dimethylamino)ethyl acrylate from an initiator‐terminated self‐assembled monolayer yielded polyelectrolyte brushes on the surface of a weight‐detectable quartz crystal microbalance. One end of a poly[(2‐dimethylamino)ethyl methacrylate] brush was covalently attached onto the surface of a sensor. We found that metallophthalocyanines with four bulky pentaphenylbenzene substituents could adsorb volatile organic compounds selectively into their cavities. Macromolecular metal complexes were prepared by immersing polymer‐brush‐modified QCMs into an aqueous solution of sterically protected cobalt phthalocyanine. Anionic cobalt phthalocyanine was trapped in the polymer brushes and acted as a molecular receptor for the sensing of VOC molecules.