Synthesis and Surface Chemical Properties of Adhesive Protein of the Asian Freshwater Mussel,Limnoperna fortunei

The adhesive polydecapeptide poly(Lys‐Pro‐Thr‐Gln‐Tyr‐Ser‐Asp‐Glu‐Tyr‐Lys) (average repeating number, n = 5), which is the consensus sequence of the Asian freshwater mussel Limnoperna fortunei adhesive protein (Lffp), has been synthesized by the polycondensation of the active esters. The surface chemical experiments revealed the following characteristics of the freshwater adhesive protein: (i) wettability of the Lffp solution is affected by the polar component value (γ_s^p) of the surface free energy of the substrate, and a substrate having a γ_s^p less than 10 mJ·m^–2 exhibits a reduced wettability of the Lffp solution; (ii) the comparison of wettability of native Lffp with synthetic Lffp suggests that the decapeptide sequence, ‐Lys‐Pro‐Thr‐Gln‐Tyr‐Ser‐Asp‐Glu‐Tyr‐Lys‐, contributes to the interaction with the underwater surface; (iii) the Lffp tends to adsorb on nonpolar surfaces that have a low γ_s^p value; and (iv) the adsorption ability of the freshwater adhesive protein is less than that of the marine adhesive protein because of the higher hydrophilicity of the freshwater adhesive protein. An antifouling examination indicated that a γ_s^p value of the substrate surface of less than 10 mJ·m^–2 should achieve a higher antifouling effect towards the L. fortunei attachment. These results are the first findings for the development of a freshwater antifouling strategy based on the molecular mechanism underlying the attachment of L. fortunei.     

Synthesis of poly(styrene-b-tetrahydrofuran-b-styrene) triblock copolymers by transformation from living cationic into living radical polymerization using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl as a transforming agent

Synthesis of poly(styrene-b-tetrahydrofuran (THF)-b-styrene) triblock copolymers was performed by transformation from living cationic into living radical polymerization, using 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-hydroxy-TEMPO) as a transforming agent. Sodium 4-oxy-TEMPO, derived from 4-hydroxy-TEMPO, reacted with the living poly(THF), which was prepared by cationic polymerization of THF using trifluoromethanesulfonic acid anhydride as an initiator, resulting in quantitative formation of the poly(THF) with TEMPO at both the chain ends. The resulting polymers were able to serve as a polymeric counter radical for the radical polymerization of styrene by benzoyl peroxide, to give the corresponding triblock copolymer in quantitative efficiency. The polymerization was found to proceed in accordance with a living mechanism, because the conversion of styrene linearly increased over time, and the molar ratio of styrene to THF units in the copolymer also increased as a result of increasing the conversion. The TEM pictures demonstrated that the resulting copolymers promoted microphase segregation. It was found that the films of these copolymers showed contact angles intermediate between those of poly(THF) and of polystyrene. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2059–2068, 1998     

Application of the Perimeter Model to the Assignment of the Electronic Absorption Spectra of Gold(III) Hexaphyrins with [4n+2] and [4n] π‐Electron Systems

Expanded porphyrins : The electronic excited states of two forms of meso‐hexakis(pentafluorophenyl)‐substituted gold(III) hexaphyrin(1.1.1.1.1.1), such as that depicted, have been investigated by density functional calculations and magnetic circular dichroism spectroscopy to assign their low‐energy excited singlet states.

     

Improved prediction for a multivariate normal distribution with unknown mean and variance

The prediction problem for a multivariate normal distribution is considered where both mean and variance are unknown. When the Kullback–Leibler loss is used, the Bayesian predictive density based on the right invariant prior, which turns out to be a density of a multivariate t-distribution, is the best invariant and minimax predictive density. In this paper, we introduce an improper shrinkage prior and show that the Bayesian predictive density against the shrinkage prior improves upon the best invariant predictive density when the dimension is greater than or equal to three.     

Comparison of bifurcation and imperfection analyses of localized necking in rate-independent polycrystalline sheets

Plastic flow localization into a narrow band is investigated for a rate-independent polycrystalline sheet. Strain localization is considered to initiate at a point of bifurcation from the homogeneous deformation state or to result from the growth of a preexisting imperfection. Bifurcation analysis based on the rate-independent crystal plasticity model is found to give limit strains at a realistic strain level in the biaxial-stretching range. Limit strains predicted by the imperfection analysis are lower than those for bifurcation analysis and tend to approach those strain levels with decreasing amount of initial imperfection. Then, the bifurcation analysis is applied to the simulation of the forming limit for strongly textured sheets. The bifurcation analysis reveals the same trend of a texture dependence of limit strains as that for the imperfection analysis employing a rate-dependent model reported in the literature.     

Novel plasma biomarker surrogating cerebral amyloid deposition

Alzheimer’s disease (AD) is the most common and devastating dementia. Simple and practical biomarkers for AD are urgently required for accurate diagnosis and to facilitate the development of disease-modifying interventions. The subjects for the study were selected on the basis of PiB amyloid imaging by PET. Forty PiB-positive (PiB+) individuals, including cognitively healthy controls (HC), and mild cognitive impairment and AD individuals, and 22 PiB-negative (PiB−) HC participated. Employing our novel highly sensitive immunoprecipitation-mass spectrometry, we measured plasma amyloid β-proteins (Aβs; Aβ1-40 and Aβ1-42) and Aβ-approximate peptides (AβAPs), which were cleaved from amyloid precursor protein (APP). Among the AβAPs, APP669-711 appeared to be a good reference for deciphering pathological change of Aβ1-42. We evaluated the performance of the ratio of APP669-711 to Aβ1-42 (APP669-711/Aβ1-42) as a biomarker. APP669-711/Aβ1-42 significantly increased in the PiB+ groups. The sensitivity and specificity to discriminate PiB+ individuals from PiB− individuals were 0.925 and 0.955, respectively. Our plasma biomarker precisely surrogates cerebral amyloid deposition.     

An Iron(III)-Monoamidate Complex Catalyst for Selective Hydroxylation of Alkane CH Bonds with Hydrogen Peroxide

Selective oxidation: The success of the title reaction is caused by the strong electron donation from the amidate moiety of the dpaq ligand to the iron center (dpaq=2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamidate). This process facilitates the O?O bond heterolysis of the intermediate Fe(III) OOH species to generate a selective oxidant without forming highly reactive hydroxyl radicals.     

Magnetic resonance differentiation between T2 and T1 gallbladder carcinoma: significance of subserosal enhancement on the delayed phase dynamic study

Purpose

The aim of this study is to investigate whether subserosal enhancement on the delayed-phase dynamic magnetic resonance (MR) study (SED) can differentiate T2 from T1 gallbladder carcinoma (GBC).

Methods

The institutional research board approved this retrospective study. Between 1997 and 2006, there were surgically proven 11 T1 and 21 T2 GBC in 30 patients, all of whom had undergone preoperative contrast enhanced dynamic MR study, either with a 2D sequence (n=17) or 3D sequences (n=15). All images were reviewed by two radiologists for the presence of SED, and receiver operating characteristic (ROC) curve analysis was performed. Sensitivity, specificity, positive and negative predictive values were calculated by consensus.

Results

The areas under the ROC curves of the two readers were 0.91 and 0.86, and the kappa value was 0.78. Of the 21 T2 GBC, 18 and 3 showed positive and negative SED, respectively. Of the 11 T1 GBC, 1 and 10 showed positive and negative SED, respectively. The sensitivity, specificity, positive and negative predictive values of SED for diagnosing T2 lesions were 86%, 88%, 91% and 77%, respectively.

Conclusions

In conclusion, SED may be a useful sign to differentiate T2 from T1 GBC, which would affect the preoperative surgical planning of the patients.     

A finite type invariant of order at most 4 for genus 2 handlebody-knots is a constant map

We show that a finite type invariant of order at most 4 for genus 2 handlebody-knots is a constant map. For this purpose, we give a concrete basis for the vector space of all finite type invariants of order at most 4 for spatial theta-curves, which makes a correction to Koike?s result. Each invariant of the basis is derived from the HOMFLYPT polynomial of the associated 3-component link of a spatial theta-curve.