Degrees of polymerization (DP) and DP distribution of cellouronic acids prepared from alkali-treated celluloses and ball-milled native celluloses by TEMPO-mediated oxidation

Various cellulose II samples, ball-milled native celluloses and ball-milled wood saw dust were subjected to 2,2,6,6-tetramethypyperidine-1-oxyl radical (TEMPO)-mediated oxidation to prepare cellouronic acid Na salts (CUAs). The TEMPO-oxidized products obtained were analyzed by ¹³C-NMR and size-exclusion chromatography (SEC). When the cellulose II samples with degrees of polymerization (DP) of 220–680 were used as the starting materials, the CUAs obtained had weight-average DP (DPw) values of only 38–79. Thus, significant depolymerization occurs on cellulose chains during the TEMPO-mediated oxidation. These DP values of CUAs correspond to the cellulose II crystal sizes along the chain direction in the original cellulose II samples, but not necessarily to their leveling-off DP values. CUAs can be obtained also from ball-milled native celluloses in good yields by TEMPO-mediated oxidation, although their DPw values are lower than about 80. On the other hand, CUA with DPw of about 170 was obtained from ball-milled wood saw dust.     

Structural and functional properties of designed globins

De novo design of artificial proteins is an essential approach to elucidate the principles of protein architecture and to understand specific functions of natural proteins and also to yield novel molecules for medical and industrial aims. We have designed artificial sequences of 153 amino acids to fit the main-chain framework of the sperm whale myoglobin structure based on the knowledge-based energy functions to evaluate the compatibility between protein tertiary structures and amino acid sequences. The synthesized artificial globins bind a single heme per protein molecule as designed, which show well-defined electrochemical and spectroscopic features characteristic of proteins with a low-spin heme. Redox and ligand binding reactions of the artificial heme proteins were investigated and these heme-related functions were found to vary with their structural uniqueness. Relationships between the structural and functional properties are discussed.     

Lower bounds for the distributions of certain multivariate test statistics

A lower (upper) bound is given for the distribution of each d_j, j = k + 1, …, p (j = 1, …, s), the jth latent root of AB^?1, where A and B are independent noncentral and central Wishart matrices having $\text{W}{}_{\mathrm{p}}\text{(q, Σ; Ω)}$ with rank $\text{(Ω) ≤ k = p ? s}$ and W_p(n, Σ), respectively. Similar bound are also given for the distributions of noncentral means and canonical correlations. The results are applied to obtain lower bounds for the null distributions of some multivariate test statistics in Tintner's model, MANOVA and canonical analysis.     

Structural analysis of polymer-brush-type cellulose β-ketoesters by molecular dynamics simulation

The reason for anomalous NMR patterns of cellulose β-ketoesters, which were prepared by reaction between cellulose and ketene dimers having long alkyl chains (AKDs) under homogeneous conditions using a cellulose solvent system, was studied by molecular dynamics simulation. Cellulose/AKD β-ketoester models with degree of substitution (DS) 2.0 and degree of polymerization (DP) 5, 10, 20 or 40, and cellulose/fatty acid ester models with DS 3.0 and DP 5, 10, 20 or 40 were assembled in the simulation. The calculated results were compared with those obtained by NMR and conformation analyses of the actually prepared cellulose derivatives. The molecular dynamics simulation data showed that the average velocities of anhydroglucose units in cellulose/AKD β-ketoesters were approximately one tenth of those in cellulose/fatty acid esters. Thus, cellulose chains in the cellulose/AKD β-ketoesters are extremely restricted in motion by the β-ketoester substituents. The solid-like behavior of cellulose chains in cellulose/AKD β-ketoesters in solution state is, therefore, explainable by strong restriction in motion of cellulose chains by long, branched and bulky substituents introduced into cellulose hydroxyls in high densities via β-ketoester bonds.     

Secreted phospholipase A<Subscript>2</Subscript>, lipoprotein hydrolysis,and atherosclerosis: integration with lipidomics

Phospholipase A₂ (PLA₂) is a group of enzymes that hydrolyze the sn-2 position of glycerophospholipids to yield fatty acids and lysophospholipids. Of many PLA₂s or related enzymes identified to date, secreted PLA₂s (sPLA₂s) comprise the largest family that contains 10 catalytically active isozymes. Besides arachidonic acid released from cellular membranes for eicosanoid synthesis, several if not all sPLA₂s have recently been implicated in hydrolysis of phospholipids in lipoprotein particles. The sPLA₂-processed low-density lipoprotein (LDL) particles contain a large amount of lysophospholipids and exhibit the property of “small-dense” or “modified” LDL, which facilitates foam cell formation from macrophages. Transgenic overexpression of these sPLA₂s leads to development of atherosclerosis in mice. More importantly, genetic deletion or pharmacological inhibition of particular sPLA₂s significantly attenuates atherosclerosis and aneurysm. In this article, we will give an overview of current understanding of the role of sPLA₂s in atherosclerosis, with recent lipidomics data showing the action of a subset of sPLA₂s on lipoprotein phospholipids.     

On using influence functions for testing multivariate normality

Changes in the joint distribution of influence functions for the mean vector and the covariance matrix are examined when the true probability distribution is contaminated. In particular, the formulas for influence functions of the first and second moments with respect to the above joint distribution are obtained and used to derive reasonable test statistics for multivariate normality. The formulas are extended by using the joint distribution of score functions for population parameters. An application of the extended formulas to the usual linear regression analysis leads to a measure of multivariate skewness which can be used to reduce the effect of non-normality of the response variable. Also, some relationship between the extended formulas and goodness-of-fit statistics is discussed and used to derive test statistics for multivariate normality.     

Effects of pressure and solvents on the infrared absorption intensity of the O-H stretching mode of phenol in solutions

Effects of pressure and solvents on the infrared spectrum of phenol in solutions have been investigated using a hydrostatic high-pressure cell with synthetic diamond windows. For the first time, we performed a quantitative investigation of the effect of pressure on the absolute intensity of O-H stretching mode up to 150 MPa (in CCl4) and 200 MPa (in CS2). For comparison, we measured the effect of solvents on the absorption intensity. The Polo-Wilson theory, which is the most traditional theory for medium effects on the intensity, was tested for present results. The pressure dependence was in sufficient agreement with their formula, while the solvent dependence is unsatisfactory. This suggests that the traditional intensity correction by Polo-Wilson's formula is practically valid for pressure-tuning infrared experiments.