Raman and Photoluminescence Spectroscopic Detection of Surface‐Bound Li+O2− Defect Sites in Li‐Doped ZnO Nanocrystals Derived from Molecular Precursors

We present a detailed study of Raman spectroscopy and photoluminescence measurements on Li‐doped ZnO nanocrystals with varying lithium concentrations. The samples were prepared starting from molecular precursors at low temperature. The Raman spectra revealed several sharp lines in the range of 100–200 cm^?1, which are attributed to acoustical phonons. In the high‐energy range two peaks were observed at 735 cm^?1 and 1090 cm^?1. Excitation‐dependent Raman spectroscopy of the 1090 cm^?1 mode revealed resonance enhancement at excitation energies around 2.2 eV. This energy coincides with an emission band in the photoluminescence spectra. The emission is attributed to the deep lithium acceptor and intrinsic point defects such as oxygen vacancies. Based on the combined Raman and PL results, we introduce a model of surface‐bound LiO₂ defect sites, that is, the presence of Li⁺O₂^? superoxide. Accordingly, the observed Raman peaks at 735 cm^?1 and 1090 cm^?1 are assigned to Li? O and O? O vibrations of LiO₂.     

Peptide‐Directed DNA‐Templated Protein Labelling for The Assembly of a Pseudo‐IgM

The development of methods for conjugation of DNA to proteins is of high relevance for the integration of protein function and DNA structures. Here, we demonstrate that protein‐binding peptides can direct a DNA‐templated reaction, selectively furnishing DNA–protein conjugates with one DNA label. Quantitative conversion of oligonucleotides is achieved at low stoichiometries and the reaction can be performed in complex biological matrixes, such as cell lysates. Further, we have used a star‐like pentameric DNA nanostructure to assemble five DNA–Rituximab conjugates, made by our reported method, into a pseudo‐IgM antibody structure that was subsequently characterized by negative‐stain transmission electron microscopy (nsTEM) analysis.     

Studies on human insulin adsorption kinetics at an organic-aqueous interface determined using a label-free electroanalytical approach

Protein adsorption represents a considerable challenge in the development and production of macromolecular drugs. From an analytical point of view the adsorption process is difficult to study in an efficient way using currently available techniques. In this work potential and time dependent adsorption and adsorption kinetics of human insulin at an 1,2-dichloroethane-aqueous interface were studied using a novel electroanalytical approach based on measurements of interfacial capacitance. Two different types of measurements were performed; potential scans and time scans. In the potential scans, the capacitance was measured over a range of applied potential differences across the interface. The interfacial potential difference is linked to the charge at the interface. Adsorption of human insulin was detectable at a bulk phase insulin concentration as low as 0.1 μM as a negative shift in the potential of zero charge (pzc). Adsorption kinetics were further studied using time scans in which the interfacial capacitance was measured at a fixed applied interfacial potential difference. Using this approach it was possible to study how the adsorption kinetics and the shape of the time scan curves were related to the bulk concentration of insulin and the interfacial potential difference. The changes in capacitance could be described phenomenologically by pseudo-first-order kinetics at low concentrations of insulin except at positive interfacial potential differences and high insulin concentrations (≥0.25 μM) where a more complex shape of the time scans curves was observed.     

N-nitrosothialdine. Synthesis,X-ray crystallography,and N-N rotational barrier

Crystalline N-nitrosothialdine ($\text{2}$) has been prepared in 38% yield by treating thialdine ($\text{1}$) with $\text{n}$-butyl nitrite and acetic acid in hexane. X-Ray crystallography of $\text{2}$ revealed that its three methyl groups are a11 $\text{cis}$ and, rather surprisingly, all equatorial; this finding contrasts sharply with results for other nitrosamine heterocycles which have been investigated, whose bulky alpha substituents are forced into a primarily axial orientation by the large steric requirement of the N-N-0 system. The equatorial methyl group both displaces the nitroso group from the C-N-C plane and twists it somewhat about the N-N bond. N-Nitrosothialdine's unusually low barrier to rotation about the N-N bond (72 kJ/mole) is attributed to this steric crowding, combined with inductive electron withdrawal by the two sulfur atoms.     

A Methodology for Obtaining Material Properties of Polymeric Foam at Elevated Temperatures

A new methodology to characterise the elastic properties of polymeric foam core materials at elevated temperatures is proposed. The focus is to determine reliable values of the tensile and compressive moduli and Poisson’s ratio based on strain data obtained using digital image correlation (DIC). In the paper a detailed coverage of the source of uncertainties in the experimental procedure is provided. The uncertainties include those associated with the load introduction, the measurement and the data processing. The design of the specimens and loading jigs are developed and assessed in terms of the introduction of uniform strain. It is shown that due to the mismatch in stiffness between the jig material and the foam the introduction of a uniform strain through the cross section of the specimens is difficult to obtain. A means for correcting for the non-uniform strain across the specimen cross section is developed. To validate the methodology, tests are firstly conducted at room temperature on Divinycell PVC H100 foam. It is shown that the material is highly anisotropic with a stiffness of 50% less in the plane of the foam sheet compared to the through-thickness direction. It is also shown that because of the compliance of the foam, jig misalignment causes large errors in the measurement, and a means for correcting for this is defined. Tests are then conducted in a temperature controlled chamber at elevated temperatures ranging from 20°C to 90°C. A nonlinear reduction in Young’s modulus is obtained with significant degradation occurring after 70°C. The Poisson’s ratio remains fairly stable at different temperatures. A strong theme in the paper is the accuracy and precision of the DIC data and the factors which introduce scatter in the data, along with the uncertainties that this introduces. Particular attention is paid to the affect of the correlation parameters on the derived strain data.     

CE frontal analysis based on simultaneous UV and contactless conductivity detection: a general setup for studying noncovalent interactions

CE frontal analysis (CE-FA) has been established as a powerful tool to study noncovalent interactions between macromolecules and small molecules such as drug substances or pharmaceutical excipients. However, when using traditional commercial CE instrumentation, a serious drawback is related to the fact that only UV-active compounds can be studied. In recent years, contactless conductivity detection has become an attractive alternative to UV detection in CE due to its high versatility. In this study, we combine contactless conductivity detection and UV detection in a highly versatile setup for profiling noncovalent interactions between low-molecular-weight molecules and macromolecules. In the case of molecules having a chromophore the setup allows determination of binding constants using two independent detectors. The new contactless conductivity detection cell is compatible with commercial CE instrumentation and is therefore easily implemented in any analysis laboratory with CE expertise.     

Representing Medical Protocols for Organizational Simulation: An Information-Processing Approach

Organizational simulations have been used in business, manufacturing, and engineering design tasks to gain insight into organizational process bottlenecks, and to improve the quality and efficiency of processes within these industries. As market pressures demand increased efficiencies within the health care industry, organizational simulation techniques could provide similar insight into the design of better medical care processes, or protocols, in medical organizations. To simulate the process of medical care within a specific organization however, requires models that can represent (1) unpredictable patient responses to care, (2) the flexibility needed to adapt to different patients, and (3) different preferences of health care professionals and the implicit preferences contained within the protocol. Using previous work on simulation in the Virtual Design Team (VDT), and an example protocol drawn from an existing protocol in bone marrow transplantation, we describe extensions to the VDT information-processing representation that will allow us to simulate the performance characteristics of a medical protocol used within a medical organization. Our representational extensions capture the uncertainty of medical care for patients, the activity flexibility within the organization, and the preferences of health care professionals that will make information-processing organizational simulations in the medical domain possible. We believe our representation will provide a robust simulation tool box that can be used to investigate the performance of specific medical protocols within different hospital settings, and explore organizational theory within the health care industry.