Semi-parametric estimation in the compositional modeling of multicomponent systems from Raman spectroscopic data

Identification and quantification of molecular species are central applications of molecular spectroscopy. In complex multicomponent systems like tissue samples, linear parametric models are often used to estimate the relative concentrations of the biochemical components of the sample. In situations where not all of the components of the sample are known or modeled, such parametric models can suffer from omitted variable bias and result in skewed estimates of component concentrations. We propose a semi-parametric approach that tries to avoid this omitted variable bias by effectively including unknown covariates as a non-parametric term in the regression equation. Constituent concentrations estimated with such partial linear models should outperform strict parametric linear models when the user has limited information on the composition of a multi-constituent system.     

Assessment of tissue viability using near-infrared spectroscopy

Both anti-CD40 antibodies and anti-immunoglobulin (Ig) coupled to Sepharose induced proliferation of resting B cells and suppressed lipopolysaccharide (LPS)-induced B-cell differentiation to immunoglobulin secretion at comparable levels determined with the plaque-forming assay and Ig RNA steady state levels. Anti-CD40 antibodies also increased the proliferation of B cells stimulated by T helper cells in vitro while suppressing their differentiation to Ig secretion. Further, B cells preactivated by anti-Ig, anti-CD40 or a combination of the two mitogens could be restimulated by anti-CD40 but not by anti-Ig antibodies. Phenotypic divergence of Ig and CD40 signals regarding surface expression of activation markers was observed. Restimulation of anti-Ig- or anti-CD40-prestimulated cells with anti-Ig induced apoptosis whereas apoptosis could be inhibited when cells were recultivated with anti-CD40.     

Cross-validiation of the Neuropsychology Behavior and Affect Profile in stroke patients.

Internal stability and discriminant validity of the Neuropsychology Behavior and Affect Profile (L. Nelson et al, 1989) were examined in samples of 70 stroke patients and 88 elderly controls. The test is designed to yield indices of premorbid (before-item subset) and present (now-item subset) levels of emotional functioning in each of 5 scales. With coefficient alphas ranging from .76 to .87, results indicated moderate to high internal stability. The test was also able to reliably distinguish between the criterion stroke sample (n?=?42) and a matched group of elderly controls in terms of present levels of emotional functioning (2 wks poststroke). When discriminant validity was examined in terms of premorbid emotional status (before-item subset), group differences were unexpectedly obtained. Clinical and research implications of these results are discussed, noting the possibility of early, noncognitive correlates preceding stroke. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

An evaluation method of PV systems

Data evaluation methods have wide adaptations, such as feedbacks to PV system operation management and design. The authors have already developed sophisticated verification method (SV method) of PV systems, which is a simple evaluation method to identify six kinds of system loss rates using basic information and simple four measurable data. This time, the authors introduced quality diagnosis to our previous model for compensating the measurement errors in field data, and improved the algorithm of the model. Consequently, validity of the evaluation result became better than the previous model.     

Toward identification of acid/base catalysts in the active site of enolase: comparison of the properties of K345A, E168Q, and E211Q variants

High-resolution crystallographic data show that Glu 168 and Glu 211 lie on opposite surfaces of the active site from Lys 345. Two different proposals for general base catalysis have emerged from these structural studies. In one scheme, the carboxylate side chains of Glu 168 and Glu 211 are proposed to ionize a trapped water molecule and the OH- serves as the base [Lebioda, L., & Stec, B. (1991) Biochemistry 30, 2817-2822]. In the other proposal, the epsilon-amino group of Lys 345 functions in general base catalysis [Wedekind, J. E., Poyner, R. R., Reed, G. H., & Rayment, I. (1994) Biochemistry 33, 9333-9342]. Genes encoding site specific mutations of these active site residues of yeast enolase, K345A, E168Q, and E211Q, have been prepared. The respective protein products of the wild type and mutant genes were expressed in Escherichia coli and isolated in homogeneous form. All three mutant proteins possess severely depressed activities in the overall reaction- < 1 part in 10(5) of wild type activity. Properties of the three mutant proteins in partial reactions were examined to define more clearly the roles of these residues in the catalytic cycle. The K345A variant fails to catalyze the exchange of the C-2 proton of 2-phospho-D-glycerate with deuterium in D2O, whereas both the E211Q and E168Q mutant proteins are functional in this partial reaction. For E211Q and E168Q enolases, exchange is essentially complete prior to appearance of product, and this observation provides further support for an intermediate in the normal reaction. K345A enolase is inactive in the ionization of tartronate semialdehyde phosphate (TSP), whereas both E168Q and E211Q proteins alter the tautomeric state or catalyze ionization of bound TSP. Wild type enolase catalyzes hydrolysis of (Z)-3-chloro-2-phosphoenolpyruvate by addition of OH- and elimination of Cl- at C-3. This reaction mimics the addition of OH- to C-3 of phosphoenolpyruvate in the reverse reaction with the normal product. All three mutant proteins are depressed in their abilities to carry out this reaction. In single-turnover assays, the activities vary in the order K345A > E168Q > E211Q. These results suggest that Lys 345 functions as the base in the ionization of 2-PGA and that Glu 211 participates in the second step of the reaction.     

Effect of Microstructure on the Electrochemical Behavior of Ti-10 Mass% Mn Alloys in High Chloride Solution

The effect of microstructure on the corrosion of heat-treated Ti-10 mass% Mn alloys was investigated by electrochemical impedance spectroscopy (EIS) in 10% NaCl solution of pH 0.5 at 97 °C. Sample of solution heat treatment (ST) had a single β phase, and samples subjected to the aging heat treatment at 600 °C had α phase precipitation in β phases. The EIS measurements showed that the corrosion resistance of the aging heat-treated samples showed lower values than ST sample, however, much higher values than pure Ti. Thus, Mn was effective to increase the corrosion resistance of Ti alloys. Laser micrographs of heat-treated samples indicated that α phase was selectively corroded and made the pit after the corrosion test. The transmission electron microscope (TEM)-energy dispersive x-ray spectrometry (EDXS) analyses showed that the Mn content was 9 mass% in the β phase and 0.7 mass% in α phase. Hence, it was understood that less-Mn α phase was selectively corroded in the corrosion test. However, as compared with pure Ti, the aging heat-treated samples showed much higher resistance against the corrosion by the 0.7 mass% Mn in α phase. Finally, it was concluded that it was possible to keep the high corrosion resistance for heat-treated Ti-10 mass% Mn alloy by controlling the microstructure of α phase.     

Three-Dimensional Culture of Cartilage Tissue on Nanogel-Cross-Linked Porous Freeze-Dried Gel Scaffold for Regenerative Cartilage Therapy: A Vibrational Spectroscopy Evaluation

This study presents a set of vibrational characterizations on a nanogel-cross-linked porous freeze-dried gel (NanoCliP-FD gel) scaffold for tissue engineering and regenerative therapy. This scaffold is designed for the in vitro culture of high-quality cartilage tissue to be then transplanted in vivo to enable recovery from congenital malformations in the maxillofacial area or crippling jaw disease. The three-dimensional scaffold for in-plate culture is designed with interface chemistry capable of stimulating cartilage formation and maintaining its structure through counteracting the dedifferentiation of mesenchymal stem cells (MSCs) during the formation of cartilage tissue. The developed interface chemistry enabled high efficiency in both growth rate and tissue quality, thus satisfying the requirements of large volumes, high matrix quality, and superior mechanical properties needed in cartilage transplants. We characterized the cartilage tissue in vitro grown on a NanoCliP-FD gel scaffold by human periodontal ligament-derived stem cells (a type of MSC) with cartilage grown by the same cells and under the same conditions on a conventional (porous) atelocollagen scaffold. The cartilage tissues produced by the MSCs on different scaffolds were comparatively evaluated by immunohistochemical and spectroscopic analyses. Cartilage differentiation occurred at a higher rate when MSCs were cultured on the NanoCliP-FD gel scaffold compared to the atelocollagen scaffold, and produced a tissue richer in cartilage matrix. In situ spectroscopic analyses revealed the cell/scaffold interactive mechanisms by which the NanoCliP-FD gel scaffold stimulated such increased efficiency in cartilage matrix formation. In addition to demonstrating the high potential of human periodontal ligament-derived stem cell cultures on NanoCliP-FD gel scaffolds in regenerative cartilage therapy, the present study also highlights the novelty of Raman spectroscopy as a non-destructive method for the concurrent evaluation of matrix quality and cell metabolic response. In situ Raman analyses on living cells unveiled for the first time the underlying physiological mechanisms behind such improved chondrocyte performance.     

Investigation of an iron-based additive on coal pyrolysis and char oxidation at high heating rates

Iron-based catalysts have been shown to enhance coal pyrolysis and char oxidation at low to moderate temperatures and heating rates (< 1250 K and 1–1000 K/s). Such catalytic activity has not been demonstrated at high heating rates and temperatures approaching pulverized coal combustion applications. The effect of an iron-based additive on coal pyrolysis and char combustion was studied in a flat-flame burner system at high particle heating rates using a Kentucky bituminous coal. Pyrolysis and char reactivity of two treated coals with different catalyst loadings were studied and compared with the untreated coal. The total volatiles yield for the treated coals increased between 14 and 18% (absolute) on a dry ash-free basis compared to the untreated coal in experiments conducted at 1300 K. A first-order char oxidation model was used to compare the apparent char reactivities of the treated and untreated coals measured at 1500 and 1700 K. An increase in apparent char reactivity was observed for both treated samples.     

PEG Modification Effect of Silica on the Suzuki–Miyaura Coupling Reaction Using Silica-immobilized Palladium Catalysts

Abstract  

The Pd phosphine complex catalysts immobilized onto polyethylene glycol (PEG)-modified silica were prepared in order to clarify the effect of the PEG modification on the Suzuki–Miyaura coupling reaction in organic solvents. For the reaction of ethyl p-bromobenzoate and phenylboronic acid in the presence of potassium carbonate in toluene, the PEG-modified silica-immobilized Pd catalysts exhibited much higher activities than the catalysts without PEG modification.