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.     

Recurrence-Transience for Self-similar Additive Processes Associated with Stable Distributions

For any stable distribution on the line, recurrence-transience of the selfsimilar additive process {X _t ,t0} with (X ₁)= is determined. Comparison with the stable Lévy process {Y _t ,t0} with (Y ₁)= is made: if is not strictly stable, then {Y _t } is transient but {X _t } is recurrent except the obviously transient case of monotone sample functions.     

Preparation of co‐polymethyl(alkoxy)siloxanes by acid‐catalyzed controlled hydrolytic copolycondensation of methyl(trialkoxy)silane and tetraalkoxysilane

Polymethyl(alkoxy)siloxane copolymers, poly(MTES‐co‐TEOS), and poly(MTMS‐co‐TMOS), are prepared by acid‐catalyzed controlled hydrolytic co‐polycondensation of methyl(trialkoxy)silane MeSi(OR)₃ (R = Et (MTES) and Me (MTMS)) and tetra‐alkoxysilane Si(OR)₄ (R = Et (TEOS) and Me (TMOS)), respectively. The products are purified by fractional precipitation to provide polymethyl(alkoxy)siloxane copolymers with molecular weight 1000–10,000 (poly(MTES‐co‐TEOS)) or 1700–100,000 (poly(MTMS‐co‐TMOS)) that are stable to self‐condensation. These polymers are soluble in common organic solvents except for hexane, and form flexible and transparent free‐standing films with a tensile strength of 4.0–10.0 MPa. The structure of the polymethyl(alkoxy)siloxane copolymers is thought to be a random or a block co‐polymer. They are found to provide coating films with an adhesive strength up to 10, a refractive index of 1.36–1.40, and a dielectric constant of 3.5–3.6. The products also show better weathering stability than polyethoxysiloxane due to the hydrolytic polycondensation of TEOS. Field emission‐scanning electron micrography analysis reveals that coating films are composed of a micro‐phase separated structure. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4732–4741     

Catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates using a phase-transfer catalyst

The catalytic asymmetric alkylation of α-cyanocarboxylates and acetoacetates with an alkyl halide was performed under phase-transfer conditions to afford compounds which have a chiral quaternary carbon with up to 97% and 94% ee, respectively. As applications of this method, chiral 2-oxindole derivatives and a β-lactam derivative were synthesized.     

Functionalized pyrolytic highly oriented graphite polymer film for surface‐assisted laser desorption/ionization mass spectrometry in environmental analysis

The pyrolytic highly oriented graphite polymer film (PGS) was first employed to analyze low‐mass analytes in environmental analysis by surface‐assisted laser desorption/ionization mass spectrometry (SALDI‐MS). PGS is a synthetic uniform and highly oriented graphite polymer film with high thermal anisotropic conductivity. We have found that negative ion mode SALDI‐MS using oxidized PGS (PGS‐SALDI‐MS) can be used to detect [M–H]^? ions from perfluorooctanoic acid (PFOA) and other perfluoroalkylcarboxylic acids when the PGS surface is modified with the cationic polymer polyethyleneimine (PEI). The signal intensity of PFOA when employing the PEI modification showed a ten‐fold increase over that obtained from desorption/ionization on porous silicon (DIOS). PFOA was quantified using PGS‐SALDI‐MS and the calibration curve showed a wide linear dynamic range of response (20–1000 ppb). The combination of atmospheric pressure ionization and PGS (AP‐PGS‐SALDI) showed greater signal intensity than vacuum PGS‐SALDI for deprotonated PFOA. Several other environmentally important chemicals, including perfluoroalkylsulfonic acid, pentachlorophenol, bisphenol A, 4‐hydroxy‐2‐chlorobiphenyl, and benzo[a]pyrene, were also successfully used to evaluate PGS‐SALDI‐MS. In addition, we found that nonafluoro‐1‐butanesulfonic acid was able to produce protonated peptides in positive ion PGS‐SALDI‐MS, but that perfluoropentanoic acid and trifluoroacetic acid were not. It is suggested that perfluoroalkylsulfonic acids are better protonating agents than perfluoroalkylcarboxylic acids in SALDI‐MS. Copyright © 2009 John Wiley & Sons, Ltd.     

Highly Pure Synthesis,Spectral Assignments,and Two‐Photon Properties of Cruciform Porphyrin Pentamers Fused with Benzene Units

Tetrameric porphyrin formation of 2‐hydroxymethylpyrrole fused with porphyrins through a bicyclo[2.2.2]octadiene unit gave bicyclo[2.2.2]octadiene‐fused porphyrin pentamers. Thermal conversion of the pentamers gave fully π‐conjugated cruciform porphyrin pentamers fused with benzene units in quantitative yields. UV/Vis spectra of fully π‐conjugated porphyrin pentamers showed one very strong Q absorption and were quite different from those of usual porphyrins. From TD‐DFT calculations, the HOMO level is 0.49 eV higher than the HOMO?1 level. The LUMO and LUMO+1 levels are very close and are lower by more than 0.27 eV than those of other unoccupied MOs. The strong Q absorption was interpreted as two mutually orthogonal single‐electron transitions (683 nm: 86 %, HOMO→LUMO; 680 nm: 86 %, HOMO→LUMO+1). The two‐photon absorption (TPA) cross section value (σ⁽²⁾) of the benzene‐fused porphyrin pentamer was estimated to be 3900 GM at 1500 nm, which is strongly correlated with a cruciform molecular structure with multidirectional π‐conjugation pathways.     

Equiaffine immersions of general codimension and its transversal volume element map

With an equiaffine immersion of codimension 1 into the affine space with the natural equiaffine structure, the conormal map is associated. In this paper, for an equiaffine immersion of general codimension into the space, we shall define the map corresponding to the conormal map, which is called the transversal volume element map. And we shall investigate if, an equiaffine immersion of general codimension into the space is determined by its affine fundamental form and its transversal volume element map.     

Generalized marginal homogeneity model and its relation to marginal equimoments for square contingency tables with ordered categories

For square contingency tables with ordered categories, Tomizawa (Calcutta Stat Assoc Bull 43:123–125, 1993a; Sankhyā Ser B 60:293–300, 1998) gave theorems that the marginal homogeneity (MH) model is equivalent to certain two or three models holding simultaneously. This paper proposes a generalized MH model, which describes a structure of the odds that an observation will fall in row category i or below and column category i + 1 or above, instead of in column category i or below and row category i + 1 or above. In addition, this paper gives the theorems that the MH model is equivalent to the generalized MH model and some models holding simultaneously whose each indicates: (1) the equality of m-order moment of row and column variables, (2) the equality of skewness of them and (3) the equality of kurtosis of them. When the MH model fits the data poorly, these may be useful for seeing the reason for the poor fit; for instance, the poor fit of the MH model is caused by the poor fit of the equality of row and column means rather than the generalized MH model. Examples are given.     

Platinum Nanoflowers on Scratched Silicon by Galvanic Displacement for an Effective SALDI Substrate

We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface‐assisted laser desorption/ionization‐mass spectrometry (SALDI‐MS). Surface scratching of n‐type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si? OH moieties on silicon increases because of the electron‐withdrawing nature of the Pt Nfs; hence, proton transfer from the Si? OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS‐Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS‐Pt Nf silicon hybrid plate acts 1) as a high‐affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS‐Pt Nf silicon hybrid plate for SALDI‐MS has been demonstrated by using a β‐casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity.