Fast cross-validation of high-breakdown resampling methods for PCA

Cross-validation (CV) is a very popular technique for model selection and model validation. The general procedure of leave-one-out CV (LOO-CV) is to exclude one observation from the data set, to construct the fit of the remaining observations and to evaluate that fit on the item that was left out. In classical procedures such as least-squares regression or kernel density estimation, easy formulas can be derived to compute this CV fit or the residuals of the removed observations. However, when high-breakdown resampling algorithms are used, it is no longer possible to derive such closed-form expressions. High-breakdown methods are developed to obtain estimates that can withstand the effects of outlying observations. Fast algorithms are presented for LOO-CV when using a high-breakdown method based on resampling, in the context of robust covariance estimation by means of the MCD estimator and robust principal component analysis. A robust PRESS curve is introduced as an exploratory tool to select the number of principal components. Simulation results and applications on real data show the accuracy and the gain in computation time of these fast CV algorithms.     

Thermodynamic and experimental study of chemical bath deposition of Zn(S,O,OH) buffer layers in basic aqueous ammonia solutions. Cell results with electrodeposited CuIn(S,Se)2 absorbers

This paper presents a thermodynamic study of Chemical Bath Deposition (CBD) of zinc sulphide based films in aqueous ammonia solutions. The aim is a better understanding of ammonia and temperature effects on the deposition conditions and films composition. The formation of solid phases has been predicted by means of the precipitation conditions of ZnO, Zn(OH)₂ and ZnS as a function of temperature between 298 and 333 K. Films have been deposited according to calculated diagrams and preliminary results on solar cells based on electrodeposited CuIn(S,Se)₂ layers have been demonstrated. Composition and thickness of the films have been extracted to link the theoretical study with experiments.     

Lysosomal enzyme and inhibitor levels in the human trabecular meshwork

PURPOSE: To examine in the human trabecular meshwork lysosomal enzymes and one inhibitor of serine proteases that actively participate in the degradation of macromolecules into low molecular weight constituents. METHODS: Using an avidin-biotin-peroxidase technique, lysosomal proteases and alpha 1-proteinase inhibitor were examined in the trabecular meshwork of 23 human eyes with donor ages ranging from 2 to 90 years. These eyes were categorized into three age groups (< or = 20, 21 to 49, and > or = 50 years). Histochemical staining for lysosomal hydrolases was also performed on frozen sections of 20 human eyes. The staining was analyzed by an image analyzer and the levels of lysosomal proteases were further measured by biochemical assays. RESULTS: The trabecular meshwork from all the eyes stained intensely against antibodies to cathepsins B and G and alpha 1-proteinase inhibitor. The staining for elastase was weaker but evident. Image analyses revealed that the staining intensity for each protease or inhibitor was similar in all age groups. The staining in the uveal meshwork appeared to be the strongest among all the trabecular meshwork regions. Biochemical assays of tissue extracts confirmed that the enzyme and inhibitor levels were comparable among the three donor age groups. Activities of two lysosomal hydrolases, acid phosphatase and acid esterase, were also found in trabecular meshwork cells of 20 eyes. No apparent difference in enzyme activities was found with increasing age, and variation related to region was not observed. CONCLUSIONS: This study demonstrated the age-independent distribution of a variety of lysosomal enzymes and a protease inhibitor in the human trabecular meshwork. The presence of these proteins suggests a possible role in the metabolic operation of the trabecular meshwork.     

Dye–fiber interactions in PET fibers: Hydrogen bonding studied by IR‐spectroscopy

Dye–fiber interactions are studied in poly (ethylene terephthalate) fibers by FT‐IR spectroscopy. It is shown for the first time that DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) serves as an easy applicable and accurate technique for the study of fibrous structures. This article focuses on the possible hydrogen bond interactions in the dye–fiber system, where the PET fibers are dyed with anthraquinone‐based disperse dyes. The dyes and related anthraquinone structures are studied in both the dilute solution state, the solid state, and as present in the PET fibers. It is proven that 1‐amino anthraquinones show strong “chelate‐type” intramolecular hydrogen bonding in all three states. In the fibers an important supplementary intermolecular hydrogen bonding with the C?O groups in the PET fiber is observed. The extend of hydrogen bonding seems to be prone to dye concentration variations. Further analysis by modulated differential scanning calorimetry links the hydrogen bonding to an intrinsic plasticizing effect of the dyes affecting the dye diffusion process. This thus offers a tool for the fundamental understanding of the dyeing process and possible observed differences in dyeing behavior in dye–fiber systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Mechanistic study of drying of alkyd resins using (Z,Z)- and (E,E)-3,6-nonadiene as model substances

The cobalt-catalysed autoxidative drying of alkyd resins was studied using (Z,Z)-3,6-nonadiene and (E,E)-3,6-nonadiene as model compounds. A large number of reaction products were isolated from the autoxidation mixture using HPLC and preparative size exclusion chromatography and identified with ¹H- and ¹³C-NMR. The identified compounds comprised C₉ hydroperoxides, endoperoxides, epoxides, aldehydes and ketones and some other oxidation products. Their chemical structures pointed to three different types of oxidation processes taking place. Besides the main radical autoxidation reaction, evidence was found for photo-sensitized oxidation involving singlet oxygen. Thirdly, epoxidation occurs via peracids or hydroperoxides formed as intermediates. Because of the large number of possible isomers having very similar physical properties, isolation of dimers required considerable effort. Nevertheless, two dimers were isolated and characterized. Their structures indicate crosslinking to occur by recombination of radicals as termination reaction.     

The rapid synthesis of nanostructured orthorhombic KNbO3 particles by a microwave-assisted hydrothermal method and their characterization

We studied the molar ratio effects of niobium and potassium precursors on the structure and morphology of potassium niobate powders prepared via microwave-assisted hydrothermal synthesis (MaHS). KNbO₃ nanostructures in the form of nanotowers and nanocubes were obtained at reduced synthesis times (30–240 min). The products were characterized via XRD, Raman spectroscopy, SEM, and TEM; band gap calculations used diffuse reflectance data. The results indicate that KNbO₃ nanostructures were obtained with crystallite sizes ranging from 33 to 52 nm. An orthorhombic crystalline structure was formed from the increase of KOH at a molar ratio Nb₂O₅:KOH (1:8 to 1:16 M). The band-gap of 3.1–3.3 eV has potential use in photodegradation applications.     

Novel BQCA- and TBPB-Derived M1 Receptor Hybrid Ligands: Orthosteric Carbachol Differentially Regulates Partial Agonism

Recently, investigations of the complex mechanisms of allostery have led to a deeper understanding of G protein-coupled receptor (GPCR) activation and signaling processes. In this context, muscarinic acetylcholine receptors (mAChRs) are highly relevant due to their exemplary role in the study of allosteric modulation. In this work, we compare and discuss two sets of putatively dualsteric ligands, which were designed to connect carbachol to different types of allosteric ligands. We chose derivatives of TBPB [1-(1′-(2-tolyl)-1,4′-bipiperidin-4-yl)-1H-benzo[d]imidazol-2(3H)-one] as M₁-selective putative bitopic ligands, and derivatives of benzyl quinolone carboxylic acid (BQCA) as an M₁ positive allosteric modulator, varying the distance between the allosteric and orthosteric building blocks. Luciferase protein complementation assays demonstrated that linker length must be carefully chosen to yield either agonist or antagonist behavior. These findings may help to design biased signaling and/or different extents of efficacy.