Direct chemical method for preparing 2,3-epoxyamides using sodium chlorite

A direct method for preparing 2,3-epoxyamides from tertiary allylamines via a tandem C-H oxidation/double bond epoxidation using sodium chlorite is reported. Apparently, the reaction course consists of two steps: (i) allylic oxidation of the starting allylamine to corresponding unsaturated allylamide with sodium chlorite followed by (ii) epoxidation of the allylamide to the 2,3-epoxyamide mediated by hypochlorite ion, which is formed in situ by reduction of sodium chlorite. The reaction conditions tolerate the presence of free hydroxyl groups and typical functional groups such as TBS, aryl, alkyl, allyl, acetyl, and benzyl groups; however, when an activated aromatic ring (e.g., sesamol) is present in the substrate, the use of a scavenger is necessary.     

Vibrational interactions in dimethylgold(III) halides and carboxylates

The far-infrared and Raman spectra of binuclear molecules [Me₂AuX]₂ (X = Cl, Br, I) and [Me₂Au(OOCR)]₂ (R = Me, CF₃, Bu^t, Ph) in the 600–70 cm⁻¹ region are reported. The experimentally measured vibrational frequencies of [Me₂AuX]₂ are in a good agreement with density functional theory predictions. The Au…Au vibrational interactions predicted to be in the 270–60 cm⁻¹ region of [Me₂AuX]₂ far-IR and Raman spectra have been observed. The Raman-active Au…Au vibrations of the [Me₂Au(OOCR)]₂ molecules were found to be in the same region as those of [Me₂AuX]₂. The Au–X stretching modes were observed between 100 and 250 cm⁻¹ in accordance with the DFT predictions. Their frequencies in the IR spectra of [Me₂AuX]₂ increase in the sequence I < Br < Cl while the AuC₂ stretching frequencies decrease in the same order. This fact might be an evidence of the decreasing covalent character of the gold-halogen bridges. The Au–O stretching bands of dimethylgold(III) carboxylates have been observed in the 500–250 cm⁻¹ region, and Au–C stretching frequencies of both [Me₂AuX]₂ and [Me₂Au(OOCR)]₂ compounds have been found between 600 and 500 cm⁻¹.     

Kojic acid derivatives as histamine H(3) receptor ligands

The histamine H(3) receptor (H(3)R) is a promising target in the development of new compounds for the treatment of mainly centrally occurring diseases. However, emerging novel therapeutic concepts have been introduced and some indications in the H(3)R field, e.g. migraine, pain or allergic rhinitis, might take advantage of peripherally acting ligands. In this work, kojic acid-derived structural elements were inserted into a well established H(3)R antagonist/inverse agonist scaffold to investigate the bioisosteric potential of γ-pyranones with respect to the different moieties of the H(3)R pharmacophore. The most affine compounds showed receptor binding in the low nanomolar concentration range. Evaluation and comparison of kojic acid-containing ligands and their corresponding phenyl analogues (3-7) revealed that the newly integrated scaffold greatly influences chemical properties (S Log P, topological polar surface area (tPSA)) and hence, potentially modifies the pharmacokinetic profile of the different derivatives. Benzyl-1-(4-(3-(piperidin-1-yl)propoxy)phenyl)methanamine ligands 3 and 4 belong to the centrally acting diamine-based class of H(3)R antagonist/inverse agonist, whereas kojic acid analogues 6 and 7 might act peripherally. The latter compounds state promising lead structures in the development of H(3)R ligands with a modified profile of action.     

Gutzwiller theory of band magnetism in LaOFeAs

We use the Gutzwiller variational theory to calculate the ground-state phase diagram and quasiparticle bands of LaOFeAs. The Fe3d-As4p Wannier-orbital basis obtained from density-functional theory defines the band part of our eight-band Hubbard model. The full atomic interaction between the electrons in the iron orbitals is parametrized by the Hubbard interaction U and an average Hund's-rule interaction J. We reproduce the experimentally observed small ordered magnetic moment over a large region of (U,J) parameter space. The magnetically ordered phase is a stripe spin-density wave of quasiparticles.     

Intrinsic Fluorescence of Protoporphyrin IX from Blood Samples Can Yield Information on the Growth of Prostate Tumours

Prostate cancer is one of the most common types of cancer in men, and unfortunately many prostate tumours remain asymptomatic until they reach advanced stages. Diagnosis is typically performed through Prostate-Specific Antigen (PSA) quantification, Digital Rectal Examination (DRE) and Transrectal Ultrasonography (TU). The antigen (PSA) is secreted by all prostatic epithelial cells and not exclusively by cancerous ones, so its concentration also increases in the presence of other prostatic diseases. DRE and TU are not reliable for early detection, when histological analysis of prostate tissue obtained from a biopsy is necessary. In this context, fluorescence techniques are very important for the diagnosis of cancer. In this paper we explore the potential of using endogenous phorphyrin blood fluorescence as tumour marker for prostate cancer. Substances such as porphyrin derivatives accumulate substantially more in tumours than in normal tissues; thus, measuring blood porphyrin concentration by autofluorescence intensity may provide a good parameter for determining tumour stage. In this study, the autofluorescence of blood porphyrin was analyzed using fluorescence and excitation spectroscopy on healthy male NUDE mice and in those with prostate cancer induced by inoculation of DU145 cells. A significant contrast between the blood of normal and cancer subjects could be established. Blood porphyrin fluorophore showed an enhancement on the fluorescence band around 632 nm following tumour growth. Fluorescence detection has advantages over other light-based investigation methods: high sensitivity, high speed and safety. However it does carry the drawback of low specificity of detection. The extraction of blood porphyrin using acetone can solve this problem, since optical excitation of further molecular species can be excluded, and light scattering from blood samples is negligible.     

An efficient local time-stepping scheme for solution of nonlinear conservation laws

We develop an efficient local time-stepping algorithm for the method of lines approach to numerical solution of transient partial differential equations. The need for local time-stepping arises when adaptive mesh refinement results in a mesh containing cells of greatly different sizes. The global CFL number and, hence, the global time step, are defined by the smallest cell size. This can be inefficient as a few small cells may impose a restrictive time step on the whole mesh. A local time-stepping scheme allows us to use the local CFL number which reduces the total number of function evaluations. The algorithm is based on a second order Runge–Kutta time integration. Its important features are a small stencil and the second order accuracy in the L² and L^∞ norms.     

Temperature phase transition model for the DNA-CNTs-based nanotweezers

DNA and Carbon nanotubes (CNTs) have unique physical, mechanical and electronic properties that make them revolutionary materials for advances in technology. In state-of-the-art applications, these physical properties can be exploited to design a type of bio-nanorobot. In this paper, we present the behavior of DNA-based nanotweezers and show the capabilities of controlling this robotic device. The theoretical calculations are based on the Peyrard-Bishop model for DNA dynamics. Furthermore, the influence of the van der Waals force between two CNTs on the opening and closing of nanotweezers is studied in comparison with the stretching forces of DNA.     

Error Estimation for Discontinuous Galerkin Solutions of Two-Dimensional Hyperbolic Problems

We analyze the discretization errors of discontinuous Galerkin solutions of steady two-dimensional hyperbolic conservation laws on unstructured meshes. We show that the leading term of the error on each element is a linear combination of orthogonal polynomials of degrees p and p+1. We further show that there is a strong superconvergence property at the outflow edge(s) of each element where the average discretization error converges as O(h ^2p+1) compared to a global rate of O(h ^p+1). Our analyses apply to both linear and nonlinear conservation laws with smooth solutions. We show how to use our theory to construct efficient and asymptotically exact a posteriori discretization error estimates and we apply these to some examples.     

Thermogravimetric and kinetic study of new bis(iminophosphorane)ethane solvates

Journal of Thermal Analysis and Calorimetry - Thermal and crystallographic characterization of one solvent-free bis(iminophosphorane)ethane (BIPE) form and three solvates with acetonitrile (ACN),...     

Monitoring of residual stresses in injection-molded plastics with holographic interferometry

Residual stresses are often trapped in injection-molded plastic parts due to the rapid cooling of the material in this manufacturing process. These stresses are a common source of failure in plastic components in automobiles, appliances and computers and are difficult to measure with conventional residual-stress experimental methods. Real-time holographic interferometry appears to be a viable technique to identify and monitor these stresses in plastic parts. In this investigation, holographic interferometry was used to monitor the relaxation of residual stresses in the plastic-molded actuator arm of a computer hard drive. In the first phase of this study, the relaxation of these residual stresses as a function of temperature was observed. In the second phase, the time to completely relax the residual stresses in the plastic part at an elevated temperature, the annealing temperature, was determined. In the third phase of this investigation, the rate of relaxation of these residual stresses as a function of time at various operating temperatures, was studied. Based on the results of this study, holographic interferometry appears to be a powerful research tool in the study of residual stresses in plastic parts. It also has the potential to be a practical tool for the inspection of manufactured plastic parts for the presence of residual stress.