Osmotic Pressure and Phase Boundary Determination of Multiphase Systems by Analytical Ultracentrifugation

We show that analytical ultracentrifugation can be applied to derive full equations of state of colloids in a single sedimentation equilibrium experiment, by determination of single‐phase boundaries as well as of osmotic pressure versus concentration at fixed temperatures. A continuous dependence of the osmotic pressure, over orders of magnitude between at least ～10¹ and 10⁴ Pa, and a wide concentration range, are determined in agreement with standard theoretical considerations. Two model experimental colloidal systems are investigated: For a well‐known synthetic clay system (laponite), it is shown that two regimes—counter‐ion ideal gas and interacting double layers—can easily be identified in the equation of state, whereas metastable glass‐ or microphase‐separated gel states previously encountered in osmotic stress measurements of laponite are circumvented. For the case of rigid, crystallized catanionic bilayers, single phase domains can be identified. Osmotic pressure results in this case disagree with results obtained using the classical osmotic stress technique, as a result of sample adhesion to the ultracentrifuge cell windows and uncertainty due to possible micromolar ion contamination.     

On a chip demonstration of a functional role for Odorant Binding Protein in the preservation of olfactory receptor activity at high odorant concentration

The molecular mechanisms underlying odorant detection have been investigated using the chip based SPR technique by focusing on the dynamic interactions between transmembrane Olfactory Receptor OR1740, odorant ligands and soluble Odorant-Binding Protein (OBP-1F). The OR1740 present in the lipid bilayer of nanosomes derived from transformed yeasts specifically bound OBP-1F. The receptor preferential odorant ligand helional released bound OBP-1F from the OR-OBP complex, while unrelated odorants failed to do so. OBP-1F modified the functional OR1740 dose-response to helional, from a bell-shaped to a saturation curve, thus preserving OR activity at high ligand concentration. This unravels an active role for OBPs in olfaction, in addition to passive transport or a scavenger role. This sensorchip technology was applied to assessing native OBP-1F in a biological sample: rat olfactory mucus also displayed significant binding to OR1740 nanosomes, and the addition of helional yielded the dissociation of mucus OBP from the receptor.     

Flavylium chromophores as species markers for dragon's blood resins from Dracaena and Daemonorops trees

A simple and rapid liquid chromatographic method with diode-array UV-vis spectrophotometric detection has been developed for the authentication of dragon's blood resins from Dracaena and Daemonorops trees. Using this method it was discovered that the flavylium chromophores, which contribute to the red colour of these resins, differ among the species and could be used as markers to differentiate among species. A study of parameters, such as time of extraction, proportion of MeOH and pH, was undertaken to optimise the extraction of the flavyliums. This method was then used to make extracts from samples of dragon's blood resin obtained from material of known provenance. From the samples analysed 7,6-dihydroxy-5-methoxyflavylium (dracorhodin), 7,4'-dihydroxy-5-methoxyflavylium (dracoflavylium) and 7,4'-dihydroxyflavylium were selected as species markers for Daemonorops spp., Dracaena draco and Dracaena cinnabari, respectively. The chromatograms from these samples were used to build an HPLC-DAD database. The ability to discriminate among species of dragon's blood using the single marker compounds was compared with a principal components analysis of the chromatograms in the HPLC-DAD database. The results from the HPLC-DAD method based on the presence of these flavylium markers was unequivocal. The HPLC-DAD method was subsequently applied to 37 samples of dragon blood resins from the historical samples in the Economic Botany Collection, Royal Botanic Gardens, Kew. The method identified anomalies in how samples in this collection had been labelled. It is clear that the method can be used to evaluate the provenance of samples used in different areas of cultural heritage. It also could be used to monitor the trade of endangered species of dragon's blood and the species being used in complex formulations of traditional Chinese medicine.     

Flow cytometric immunoassay for sulfonamides in raw milk

Sulfonamide antibiotics are applied in veterinary medicine for the treatment of microbial infections. For the detection of residues of sulfonamides in milk, a multi-sulfonamide flow cytometric immunoassay (FCI) was developed using the Luminex MultiAnalyte Profiling (xMAP) technology. In this automated FCI, a previously developed biotinylated multi-sulfonamide mutant antibody (M.3.4) was applied in combination with fluorescent beads, directly coated with a sulfathiazole derivative, and streptavidin–phycoerythrin (SAPE) for the detection. With this FCI, at least 11 different sulfonamides could be detected (more than 50% inhibition at the 100 ng mL⁻¹ level) and, after an incubation of 1 h, measurements were rapid (10 s per sample). For the application with raw milk, a 96-well microplate-based filtration step was included into the protocol to remove disturbing milk fat particles. Because of differences in sensitivity towards different sulfonamides, the FCI was considered and validated as a qualitative screening assay. For sulfadoxine, the most applied sulfonamide in Dutch dairy cattle, the detection capability (CCβ) was <50 μg L⁻¹ and this level seems feasible for five other sulfonamides. For sulfadiazine, the CCβ was <200 μg L⁻¹ and this level seems feasible for four other sulfonamides. A major advantage of the applied xMAP-technology, with its 100 different color-coded bead sets, is the possibility to develop multiplex immunoassays for the simultaneous detection of several antibiotics.     

Probing organization and communication at layered interfaces

We have investigated the local organization intrinsic to a variety of interfacial structures, by both electrochemical and spectroscopic means. Our focus has been on the design and construction of biomimetic interfaces, where a lipid bilayer or a hybrid bilayer membrane can be bound to an interface. The goal of this work is ultimately to create an interface on a transducer surface that can support an enzyme in its active form. To this point, we have examined the extent of organization that is achievable in monolayers that will be used to bind bilayer structures to a transducer surface. Our electrochemical data point to the important role of the substrate surface in determining adlayer organization. We have also investigated the fluidity and structural heterogeneity of lipid bilayers using time-resolved and steady state fluorescence spectroscopy. Our data point to the highly interactive nature of lipid bilayer constituents, where perturbations introduced to one region have significant consequences on other regions of the bilayer. Such information is directly relevant to the existence and properties of lipid raft structures in both model and biological bilayers.     

Quantum and classical fidelity for singular perturbations of the inverted and harmonic oscillator

Let us consider the quantum/versus classical dynamics for Hamiltonians of the form

(0.1)     

Characterization of titanium dioxide nanoparticles dispersed in organic ligand solutions by using a diffusion-ordered spectroscopy-based strategy

Diffusion-ordered NMR spectroscopy (DOSY NMR) is presented as a tool for the determination of the diffusion coefficients of organic ligands in suspensions of titanium dioxide nanoparticles. The nanoparticles were prepared by a sol-gel process by hydrolysis and condensation reactions of titanium tetra-n-butoxide in the presence of pentane-2,4-dione (acacH: acetylacetone), as well as para-toluenesulfonic acid (pTsA) and n-butanol (nBuOH). NMR spectroscopic studies were performed in various deuterated solvents, on both dispersed xerosols and diluted sols. The bipolar-pulsed field gradient longitudinal eddy-current delay (LED) pulse sequence was used for data acquisition. The data were processed by inverse Laplace transformation (ILT), by using a maximum entropy algorithm, to afford 2D DOSY spectra. Different diffusion regimes for organic ligands in the bound and unbound states were successfully discriminated, more particularly in [D3]acetonitrile, thus allowing assessment of their interactions with the nanoparticles.     

A Phase-Space Study of the Quantum Loschmidt Echo in the Semiclassical Limit

The notion of Loschmidt echo (also called “quantum fidelity”) has been introduced in order to study the (in)-stability of the quantum dynamics under perturbations of the Hamiltonian. It has been extensively studied in the past few years in the physics literature, in connection with the problems of “quantum chaos”, quantum computation and decoherence. In this paper, we study this quantity semiclassically (as ), taking as reference quantum states the usual coherent states. The latter are known to be well adapted to a semiclassical analysis, in particular with respect to semiclassical estimates of their time evolution. For times not larger than the so-called “Ehrenfest time” , we are able to estimate semiclassically the Loschmidt Echo as a function of t (time), (Planck constant), and δ (the size of the perturbation). The way two classical trajectories merging from the same point in classical phase-space, fly apart or come close together along the evolutions governed by the perturbed and unperturbed Hamiltonians play a major role in this estimate. We also give estimates of the “return probability” (again on reference states being the coherent states) by the same method, as a function of t and . Submitted: April 27, 2006; Accepted: May 11, 2006     

On Representation Formulas and Radiation Conditions

Solutions of linear elliptic partial differential equations in unbounded domains can be represented by boundary potentials if they satisfy certain conditions at infinity. These radiation conditions depend on the fundamental solution chosen for the integral representation. We prove some basic results about radiation conditions in a rather general framework. Fundamental solutions G are considered that are defined only on the complement of a compact set. It turns out, however, and we present examples for this, that the more interesting results only hold if G is defined on all of ℝⁿ or if it is a Green function for an exterior boundary value problem. © 1997 by B.G. Teubner Stuttgart-John Wiley & Sons, Ltd.