Engineering Gram Selectivity of Mixed‐Charge Gold Nanoparticles by Tuning the Balance of Surface Charges

Nanoparticles covered with ligand shells comprising both positively and negatively charged ligands exhibit Gram‐selective antibacterial action controlled by a single experimental parameter, namely the proportion of [+] and [?] ligands tethered onto these particles. Gram selectivity is attributed to the interplay between polyvalent electrostatic and non‐covalent interactions that work in unison to disrupt the bacterial cell wall. The [+/?] nanoparticles are effective in low doses, are non‐toxic to mammalian cells, and are tolerated well in mice. These results constitute the first example of rational engineering of Gram selectivity at the (macro)molecular level.     

Interferences elimination in ion chromatography by inclusion of the interfering ion into the mobile phase—Analysis of fluoride in chloride rich dietary samples

New approach to the chloride interferences elimination by addition of the interfering ion to the mobile phase is proposed and evaluated. Different eluents for the non-suppressed ion chromatographic analysis of fluorides in chlorides rich samples were tested and compared with eluent recommended by the column manufacturer. The limit of detection, linearity range and resistance to matrix effects caused by chlorides were the comparison criteria. The applicability of the selected eluent was demonstrated through the analysis of the edible salts and various tea samples. The employment of the proposed eluent shorten the time of the analysis since the only required preparation steps for edible salts were the dissolution and appropriate dilution of the samples. The recovery test was employed to verify the obtained results.     

Generalized tight p-frames and spectral bounds for Laplace-like operators

We prove sharp upper bounds for sums of eigenvalues (and other spectral functionals) of Laplace-like operators, including bi-Laplacians and fractional Laplacians. We show that among linear images of a highly symmetric domain, our spectral functionals are maximal on the original domain. We exploit the symmetries of the domain, and the operator, avoiding the necessity of finding good test functions for variational problems. This is especially important for fractional Laplacians, since exact solutions are not even known on intervals, making it hard to find good test functions.To achieve our goals we generalize tight p-fusion frames, to extract the best possible geometric results for domains with isometry groups admitting tight p-frames. Any such group generates a tight p-fusion frame via conjugations of a fixed projection matrix. We show that generalized tight p-frames can also be obtained by conjugations of an arbitrary rectangular matrix, with the frame constant depending on the singular values of the matrix.     

Preparation and characterization of microporous fibers for sample preparation and LC‐MS determination of drugs

The aim of this study was the preparation of polypyrrole (PPy) fibers for solid phase microextraction (SPME). PPy coatings were obtained during the electrochemical polymerization process. The utility of various metal wires (Fe, Cu, Ag, Cu/Ag, kanthal and medical stainless steel) as a support for polymers was compared. Various experimental conditions of the synthesis process such as scan rate, voltage limits and number of scans and deposition time were applied. The average polymer thickness was in the range of 7–125 μm and its weight was in the scope of 0.65–5.6 mg. Different techniques, mainly elemental analysis, Fourier transform infrared spectroscopy, microscopy, and chromatography were performed for the characterization of obtained fibers with microporous structure. The extraction efficiency of cardiovascular drugs (metoprolol, propranolol, oxprenolol, propafenone and mexiletine) by means of fibers was tested. The concentration of mentioned compounds in standard solution was in the span of 10–150 ng/mL. LC‐MS was employed for determination of drugs in desorption solution. LODs varied from 0.013 to 1.51 ng/mL for metoprolol and mexiletine respectively. The repeatability of extraction was obtained with the RSD values lower than 10%.     

Symmetric Stable Processes on Unbounded Domains

Let be a symmetric -stable process in , , . We give necessary and sufficient condition under which the expectation of a very general function of the exit time from horns is finite. These domains include the symmetric domains given by increasing functions studied earlier by various authors. Our methods differ from those in earlier papers in that we obtain our results from estimates on the transition densities instead of harmonic measure. Some of this estimates are of independent interest.Supported in part by NSF grant #9700585-DMS and RTN Harmonic Analysis and Related Problems contract HPRN-CT-2001-00273-HARP.     

Intrinsic ultracontractivity of the Feynman-Kac semigroup for relativistic stable processes

Let be the relativistic -stable process in , , , with infinitesimal generator . We study intrinsic ultracontractivity (IU) for the Feynman-Kac semigroup for this process with generator , , locally bounded. We prove that if , then for every the operator is compact. We consider the class of potentials such that , and is comparable to the function which is radial, radially nondecreasing and comparable on unit balls. For in the class we show that the semigroup is IU if and only if . If this condition is satisfied we also obtain sharp estimates of the first eigenfunction for . In particular, when , , then the semigroup is IU if and only if . For the first eigenfunction is comparable to

     

Thermal degradation studies of polyurethane/POSS nanohybrid elastomers

Reported here is the synthesis of a series of polyurethane/POSS nanohybrid elastomers, the characterisation of their thermal stability and degradation behaviour at elevated temperatures using a combination of thermogravimetric Analysis (TGA) and thermal volatilisation analysis (TVA). A series of PU elastomer systems have been formulated incorporating varying levels of 1,2-propanediol-heptaisobutyl-POSS (PHIPOSS) as a chain extender unit, replacing butane diol. The bulk thermal stability of the nanohybrid systems has been characterised using TGA. Results indicate that covalent incorporation of POSS into the PU elastomer network increases the non-oxidative thermal stability of the systems. TVA analysis of the thermal degradation of the POSS/PU hybrid elastomers have demonstrated that the hybrid systems are indeed more thermally stable when compared to the unmodified PU matrix; evolving significantly reduced levels of volatile degradation products and exhibiting a ∼30 °C increase in onset degradation temperature. Furthermore, characterisation of the distribution of degradation products from both unmodified and hybrid systems indicate that the inclusion of POSS in the PU network is directly influencing the degradation pathways of both the soft and hard-block components of the elastomers: The POSS/PU hybrid systems show reduced levels of CO, CO₂, water and increased levels of THF as products of thermal degradation.