Combined use of liquid chromatography-nuclear magnetic resonance spectroscopy and liquid chromatography-mass spectrometry for the characterization of an acarbose degradation product

Directly coupled LC-MS and LC-NMR were applied to identify and structurally characterize an acarbose degradation product A in acidic media. A comparative analysis of the stop-flow LC-NMR (1H and TOCSY) and LC-MS data provided evidence that A is structurally related to acarbose, differing from the parent compound in a number of subunits present in the molecule. Spectral analysis revealed that A was the alpha-glucosidase inhibitor amylostatin XG. Complementary information obtained from the two methods led to the structural elucidation of A which was later corroborated by high-resolution NMR spectroscopy of the isolated molecule.     

Chalcogenide glass photonic crystals

All-optical switching devices are based on a material possessing a nonlinear optical response, enabling light to control light, and are enjoying renewed interest. Photonic crystals are a promising platform for realizing compact all-optical switches operating at very low power and integrated on an optical integrated circuit. In this review, we show that by making photonic crystals from a highly nonlinear chalcogenide glass, we have the potential to integrate a variety of active devices into a photonic chip. We describe the fabrication and testing of two-dimensional Ge₃₃As₁₂ Se₅₅ chalcogenide glass photonic crystal membrane devices (waveguides and microcavities). We then demonstrate the ability to post-tune the devices using the material photosensitivity. In one proposal we hope to introduce a double-heterostructure microcavity using the photosensitivity alone.     

Low energy alkali ion scattering investigation of Au nanoclusters grown on silicon oxide surfaces

The atomic and electronic structures of Au nanostructures grown by deposition onto various silicon oxide surfaces were probed with low energy alkali ion scattering. Charge state-resolved time-of-flight spectra of scattered 2 keV ³⁹K⁺ ions were collected from Au deposited onto an untreated Si wafer with a native oxide, a thermally grown oxide surface, and atomically-clean Si(111). It is shown that nanoclusters form on both oxides, but not on the clean Si. A quantitative analysis of the ion scattering spectra indicates that the nanoclusters are initially flat, two-dimensional structures that start to develop a second layer at about 0.5 Å of deposited Au and then form three-dimensional islands. The neutral fraction of scattered 2 keV ³⁹K⁺ ions decreases with deposition indicating changes in the quantum state occupancy with cluster size. The shapes of the clusters differ on the native and thermal oxides, leading to shape-dependent neutralization.     

Surface modification of microspheres with steric stabilizing and cationic polymers for gene delivery

In this paper, we describe surface modification of poly( D,L-lactide- co-glycolide) (PLG) microspheres, intended for DNA vaccine application, with two functionalities: a steric stabilizing component, provided by poly(vinyl alcohol) (PVA) and a cationic component, aimed at subsequent DNA surface loading. The cationic functionality arises from polycations, such as PEI, poly( L-lysine), trimethyl chitosan, and (dimethylamino)ethyl methacrylate, introduced into the water phase of classical oil-in-water (o/w) solvent evaporation method of PLG microsphere fabrication. By systematic evaluation of production variables, a system was produced with balanced properties in terms of microsphere size appropriate for uptake by antigen presenting (e.g., dendritic) cells, colloidal stability, and relatively high DNA loading. The polycation (PEI) molecular weight and preparation concentration were both found to increase the surface polycation content and DNA binding capacity; however, they lead to an increased tendency for aggregation, particularly when the microsphere size was decreased. DNA loading of almost 100% efficiency was achieved under optimized conditions in physiologically acceptable buffers, resulting in a surface DNA loading appropriate for vaccine purposes. A further increase in surface DNA loading was however associated with an increase in the particles negative potential, indicating the surface presence of DNA charges not neutralized by the polycation and hence potentially not protected from in vivo enzymatic degradation. The internalization of surface-loaded DNA into the target cells was confirmed by monitoring fluorescent DNA after the microspheres were endocytosed by the cells in culture.     

The gas-phase interactions of TEMPO radicals with Fe+ ions

The gas-phase ligation of the 2,2,6,6-tetramethylpiperidyl-1-oxide (TEMPO) radical (1) and its 4-hydroxy derivative (2) with Fe+ ions in a 3 T Fourier transform ion cyclotron resonance (FTICR) mass spectrometer was investigated. Triple ligation may occur: the first ligation produces a transient species prone to either charge exchange or a stable second ligation; the third ligand adds slowly, with fragmentation. 1 and 2 differ in that 1 binds exclusively at the nitroxyl oxygen while 2 also binds at the OH site after the loss of a H-radical. Calculations combined with steric considerations support such a mechanism for 2. The site and the mechanism of the important side reaction of 1 that involves OH addition from a water impurity to yield an FeR2 + species remain unexplained.     

High-Q cavities in photosensitive photonic crystals

We propose a novel concept for creating high-Q cavities in photonic crystal slabs (PCSs) composed of photosensitive material. To date, high-Q cavities have been realized through the use of double heterostructures where the lattice geometry is altered via nanolithography. Here, we show that selective postexposure to light of a uniform PCS composed of photosensitive material, altering the refractive index permanently, can also yield high-Q microcavities. We show theoretically that high-Q cavities (up to Q = 1 x 10(6)) can be achieved with photoinduced index changes that are well within what can be achieved in chalcogenide glasses.     

New design for a variable optical attenuator based on a bent channel waveguide

We present a new method for bend loss control in a curved channel optical waveguide and employ it in a novel design of a thermo-optic variable optical attenuator. We show that the introduced asymmetric refractive index profile of the waveguide structure, combined with the optimal placement of the heating electrodes, leads to a significant increase of the dynamic range of the attenuator. PACS 42.82.Et; 42.70.Jk; 42.79.Ta     

Investigation of the interaction between peanut agglutinin and synthetic glycopolymeric multivalent ligands

The interaction between synthetic glycoplymers bearing beta-D-galactose side groups and the lectin peanut agglutinin (PNA) was investigated by UV-difference spectroscopy and isothermal titration calorimetry (ITC). UV-difference spectroscopy indicated that the polymer-lectin interaction was stronger than that between PNA and either the corresponding monomer, D-galactose or D-lactose. The thermodynamics of binding (K, DeltaG, DeltaH, DeltaS and n) were determined from ITC data by fitting with a two-site, non-cooperative binding model. It was found that the glycopolymer displayed around a 50 times greater affinity for the lectin than the parent carbohydrate, and around 10 times greater than the monomer, on a valency-corrected basis. Binding was found to be entropically driven, and was accompanied by aggregation and precipitation of protein molecules. Furthermore, interesting differences between polymers prepared either from deacetylated monomers, or by deacetylation of pre-formed polymers, were found.     

Trust and Contextualism

The objective of this paper is to apply the general idea of contextualism, as a theory of knowledge attribution, to the very specific case of testimony and trust characterized as being the procedure of the attribution of knowledge (and sincerity) to the informant. In the first part, I argue in favor of evidentialism, a viewpoint that takes epistemically responsible trust as a matter of evidence. In the second part, I consider the question of how strong an evidential basis has to be for epistemically responsible trust. I have briefly registered two main tendencies in contemporary debates regarding trust and testimony: (i) the non-unitary character of our trust; (ii) and the requirement for a refinement of evidential standards. In short, I argue in favor of the stance that any ‘undiscriminatory generalization’ (both Redian or anti-reductivist and Humean or reductivist) concerning epistemically responsible trust is a kind of inappropriate theoretical idealization, and that a certain theoretical reconciliation has to be offered. Finally, in the third part, I propose trust-contextualism as the viewpoint that optimally harmonizes both our intuitive and theoretical requirements about epistemically responsible trust.

The influence of the molecular dipole on the electronic structure of isomeric icosahedral dicarbadodecaborane and phosphacarbadodecaborane molecular films

We compare the molecular films of three different isomers of closo-dicarbadodecaborane (orthocarborane (1,2-C2B10H12), metacarborane (1,7-C2B10H12), paracarborane (1,12-C2B10H12)) and two related icosahedral cage molecules, 1-phospha-2-carbadodecaborane (1,2-PCB10H11) and 1-phospha-7-carbadodecaborane (1,7-PCB10H11) adsorbed on a variety of substrates. While the experimental electronic structure from combined photoemission and inverse photoemission studies of the molecular films are in good agreement with semiempirical calculations for the isolated molecule, there is a shift in the chemical potential for each molecule. The experimental position of the molecular chemical potential implicates an influence of both interface and adsorbate dipole.