Irreversible Collapse of Poly(vinyl stearate) Monolayers at the Air-Water Interface

The collapse of Langmuir monolayers of poly(vinyl stearate) (PVS) at the air-water interface has been investigated by combined measurements of the surface pressure-area isotherms and Brewster angle microscopy (BAM). Atomic force microscopy (AFM) has been used to gain out-of-plane structural information on collapsed films transferred onto a solid substrate by a modified version of the inverse Langmuir-Schaefer deposition method. At high areas per monomer repeat unit, BAM imaging revealed that the films are heterogeneous, with large solidlike domains (25-200 mum in diameter) coexisting with liquidlike domains. Upon film compression, the domains coalesced to form a homogeneous monolayer before the film collapsed at constant pressure, forming irreversible three-dimensional (3D) structures. BAM images showed that two 3D structures coexisted: buckles of varying width extending across the surface and perpendicular to the direction of the compression and dotted islandlike structures. Upon expansion, the film fractured and both 3D protrusions persisted, explaining the marked hysteresis recorded in the Langmuir isotherms. Experiments with AFM confirmed the 3D nature of both protrusions and revealed that many buckles contain substructures corresponding to narrow buckles whose heights are a multiple of a single bilayer. Additionally, many multilayer islands with diameters spanning from 0.2 mum to over 3.5 mum were characterized by varying heights between 2 nm and up to over 50 nm. The key to the formation of the irreversible 3D structures is the presence of large inhomogeneities in the PVS monolayer, and a generalized phenomenological model is proposed to explain the collapse observed.     

High capacity, charge-selective protein uptake by polyelectrolyte brushes

Surface plasmon resonance was used to measure binding of proteins from solution to poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes end-grafted from gold surfaces by atom transfer radical polymerization (ATRP). PDMAEMA brushes were prepared with a variety of grafting densities and degrees of polymerization. These brushes displayed charge selective protein uptake. The extent of uptake for net negatively charged bovine serum albumin (BSA) scaled linearly with the surface mass concentration of grafted PDMAEMA, regardless of grafting density. BSA was bound at a constant ratio of 120 DMAEMA monomer units per protein molecule for all brushes examined. The equivalent three-dimensional concentration of BSA bound in the brush (i.e., the bound BSA surface excess concentration divided by the brush thickness) decreased monotonically with decreasing grafting density. The concentration of BSA bound within brushes prepared at higher grafting densities was comparable with the aqueous protein solubility limit. BSA desorption from the brush required changes in solution pH and/or ionic strength to eliminate its net electrostatic attraction to PDMAEMA. Net positively charged lysozyme was completely rejected by the PDMAEMA brushes.     

Direct conjugation of semiconductor nanocrystals to a globular protein to study protein-folding intermediates

In this Article, we study the development of semiconductor nanocrystals (quantum dots of average diameter less than 2 nm) directly conjugated to a transporter protein human serum albumin (HSA) as fluorescent biological labels. F?rster resonance energy transfer (FRET) from the amino acid tryptophan (Trp214) to quantum dot in HSA is monitored to follow the local and global changes in the protein structure during thermal unfolding and refolding processes. This study is likely to attract widespread attention as a powerful tool for the study of protein folding.     

Covariate Transformation Diagnostics for Generalized Linear Models

Transformations of covariates are commonly applied in regression analysis. When a parametric transformation family is used, the maximum likelihood estimate of the transformation parameter is often sensitive to minor perturbations of the data. Diagnostics are derived to assess the influence of observations on the covariate transformation parameter in generalized linear models. Three numerical examples are presented to illustrate the usefulness of the proposed diagnostics.     

印度尼西亚化石树脂的光致发光特征研究

紫外灯下,化石树脂常见荧光现象,但其磷光现象仍有待表征与研究.将印度尼西亚产出的类似多米尼加蓝珀的化石树脂分为白色包体(PartⅠ)、暗色包体(PartⅡ)和基底(PartⅢ)三个部分,使用红外光谱确定其植物来源,借助三维荧光光谱仪表征化石树脂的光致发光现象(包括荧光和磷光),并探讨印尼化石树脂发光现象随地质过程变化的...     

Utility of membrane preconcentration-capillary electrophoresis-mass spectrometry in overcoming limited sample loading for analysis of biologically derived drug metabolites, peptides, and proteins

The limited loading of capillary electrophoresis (CE) leads to relatively poor concentration limits of detection. In this work a unique method for analyte preconcentration with capillary electrophoresis-mass spectrometry (CE-MS) is described. A cartridge containing an impregnated membrane is installed at the inlet of the CE capillary, and we term this approach membrane preconcentration capillary electrophoresis-mass spectrometry (mPC-CE-MS). The analysis of in vivo derived metabolites, peptides, and proteins is described showing the wide applicability of the technology in the analysis of numerous compound classes ranging in molecular weight from 200–60,000 u. In particular, we describe the direct mPC-CE-MS analysis of urine obtained from a patient receiving the neuroleptic drug haloperidol. Three metabolites were found in the urine, and two of them are implicated in the Parkinsonian-like side effects caused by taking this drug. The technique is also applied to the analysis of major histocompatibility complex class I peptides obtained from EG-7 cells. Furthermore, the clinical potential of this approach is described by the direct analysis of urine from a patient suffering from multiple myeloma, as well as aqueous humor derived from a patient undergoing surgery. Finally we show that the use of mPC-ME-MS in conjunction with either analyte stacking (small organic molecules such as metabolites) or moving-boundary transient isotachophoresis (peptides and proteins) after analytes have been eluted from the adsorptive membrane affords optimal performance and no compromise in CE mass spectrometry performance.     

The structure of solid salt eutectics — – Why lamellar or conglomerate?

Using KCl/ZnSO₄ eutectic it has been shown that cooling the melt into a room temperature enclosure forms a lamellar structure, whereas cooling into a heated enclosure (225 °C) forms a conglomerate structure, while an enclosure temperature of 125 °C gave a partially conglomerate structure with some lamellae in process of forming conglomerates.Consideration of the thermal gradients imposed on solidification and consequently the relative time available during which the ions are sufficiently mobile to rearrange their positions, can explain the observation that lamellar structures are formed by higher melting point eutectics, whereas eutectics of lower melting point form conglomerate structures.     

Load Monitoring of Impacted Carbon-Fibre-Reinforced Plastic Plates

This work deals with a new wave migration model for the determination of an impact location for non-isotropic plates. The method is based on the wave propagation after the impact. The evaluation and processing of the signals of at least four sensors allow for the calculation of the impact location from the runtime of the signals. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties of erbium-doped fluorochlorozirconate glasses

We report the optical properties of a fluorochlorozirconate (FCZ) glass with the composition 53% ZrF₄, 20% NaF, 3.5% AlF₃, 3% LaF₃, 0.5% InF₃, (20 ? x)% BaCl₂, x% BaF₂ with x varying from 0% to 2%, and doped with various amounts of trivalent erbium by the addition of ErCl₃. Annealing of the as-prepared glass in inert (N₂) or reducing (5%H₂ + 95%Ar) atmospheres at temperatures that ensure the conversion of the glass into a glass-ceramic by the nucleation of BaCl₂ nanocrystals, does not significantly change any of Er³⁺ related absorption and photoluminescence (PL) characteristics. We have carried out a Judd–Ofelt analysis of the absorption spectra and obtained Ω₂ = (1.92 ± 0.3) × 10^? 20 cm², Ω₄ = (0.88 ± 0.16) × 10^? 20 cm² and Ω₆ = (0.59 ± 0.08) × 10^? 20 cm², and also the radiative lifetimes of the ⁴I_13/2→⁴I_15/2, ⁴I_11/2→⁴I_15/2 and ⁴S_3/2→⁴I_15/2 bands. The radiative lifetime from the Judd–Ofelt analysis for the ⁴I_13/2→⁴I_15/2 band is in good agreement with the experimentally measured PL decay time. The examination of the optical properties of powdered samples with different average particle size does not show any photon trapping effects. We have determined the spectral absorption and emission cross-sections and then estimated the possible spectral optical gain for varying degrees of relative populations of the ⁴I_13/2 and ⁴I_15/2 manifolds.