Molecular shape of palytoxin in aqueous solution

Palytoxin, one of the most toxic non-peptide substances, formed an associated dimer of 5 nm length in aqueous solution.     

Probability Distribution on Full Rooted Trees

The recursive and hierarchical structure of full rooted trees is applicable to statistical models in various fields, such as data compression, image processing, and machine learning. In most of these cases, the full rooted tree is not a random variable; as such, model selection to avoid overfitting is problematic. One method to solve this problem is to assume a prior distribution on the full rooted trees. This enables the optimal model selection based on Bayes decision theory. For example, by assigning a low prior probability to a complex model, the maximum a posteriori estimator prevents the selection of the complex one. Furthermore, we can average all the models weighted by their posteriors. In this paper, we propose a probability distribution on a set of full rooted trees. Its parametric representation is suitable for calculating the properties of our distribution using recursive functions, such as the mode, expectation, and posterior distribution. Although such distributions have been proposed in previous studies, they are only applicable to specific applications. Therefore, we extract their mathematically essential components and derive new generalized methods to calculate the expectation, posterior distribution, etc.     

Stochastic Model of Block Segmentation Based on Improper Quadtree and Optimal Code under the Bayes Criterion

Most previous studies on lossless image compression have focused on improving preprocessing functions to reduce the redundancy of pixel values in real images. However, we assumed stochastic generative models directly on pixel values and focused on achieving the theoretical limit of the assumed models. In this study, we proposed a stochastic model based on improper quadtrees. We theoretically derive the optimal code for the proposed model under the Bayes criterion. In general, Bayes-optimal codes require an exponential order of calculation with respect to the data lengths. However, we propose an algorithm that takes a polynomial order of calculation without losing optimality by assuming a novel prior distribution.     

Exact bounds on epsilon processes

In this paper we show that the lengths of the approximating processes in epsilon substitution method are calculable by ordinal recursions in an optimal way.     

A synthetic approach to diverse 3-acyltetramic acids via O- to C-acyl rearrangement and application to the total synthesis of penicillenol series

For the efficient approach to medicinally important α-branched 3-acyltetramic acids, the key reaction of O- to C- acyl rearrangement using α-amino-acid-derived 4-O-acyltetramic acids was extensively examined in the presence of various metal salts. Use of CaCl(2) or NaI dramatically changed the results in the reaction efficiency and rapidly brought about the desired α-branched 3-acyltetramic acids in markedly improved yields. We also discuss an epimerization at C5 stereocenter under the rearrangement conditions as well as the tolerance for structural variation at C3 and C5. In addition to the preceding success in the total synthesis of new cytotoxic tetramic acid, penicillenol A(1), this methodology could be also applied to the first total synthesis of penicillenol A(2).     

Synthesis of novel mucic acid 1,4-lactone methyl ester 3-O-ferulate related to an extractive component isolated from the peels of Citrus sudachi

Synthesis of a new type of mucic acid 1,4-lactone methyl ester 3-O-ferulate related to an extractive component isolated from Citrus sudachi, and its diastereomer has been achieved by employing stereodivergent dihydroxylation as a key step. The structures of the final products are fully characterized by spectroscopic methods and compared with that of the natural product.     

Optical properties of pentacene and perfluoropentacene thin films

The optical properties of pentacene (PEN) and perfluoropentacene (PFP) thin films on various SiO(2) substrates were studied using variable angle spectroscopic ellipsometry. Structural characterization was performed using x-ray reflectivity and atomic force microscopy. A uniaxial model with the optic axis normal to the sample surface was used to analyze the ellipsometry data. A strong optical anisotropy was observed, and enabled the direction of the transition dipole of the absorption bands to be determined. Furthermore, comparison of the optical constants of PEN and PFP thin films with the absorption spectra of the monomers in solution shows significant changes due to the crystalline environment. Relative to the monomer spectrum, the highest occupied molecular orbital to lowest unoccupied molecular orbital transition observed in PEN (PFP) thin film is reduced by 210 meV (280 meV). A second absorption band in the PFP thin film shows a slight blueshift (40 meV) compared to the spectrum of the monomer with its transition dipole perpendicular to that of the first absorption band.     

Adsorption-induced intramolecular dipole: correlating molecular conformation and interface electronic structure

The interfaces formed between pentacene (PEN) and perfluoropentacene (PFP) molecules and Cu(111) were studied using photoelectron spectroscopy, X-ray standing wave (XSW), and scanning tunneling microscopy measurements, in conjunction with theoretical modeling. The average carbon bonding distances for PEN and PFP differ strongly, that is, 2.34 A for PEN versus 2.98 A for PFP. An adsorption-induced nonplanar conformation of PFP is suggested by XSW (F atoms 0.1 A above the carbon plane), which causes an intramolecular dipole of approximately 0.5 D. These observations explain why the hole injection barriers at both molecule/metal interfaces are comparable (1.10 eV for PEN and 1.35 eV for PFP) whereas the molecular ionization energies differ significantly (5.00 eV for PEN and 5.85 eV for PFP). Our results show that the hypothesis of charge injection barrier tuning at organic/metal interfaces by adjusting the ionization energy of molecules is not always readily applicable.