Uniform-in-Bandwidth Functional Limit Laws

We provide uniform-in-bandwidth functional limit laws for the increments of the empirical and quantile processes. Our theorems, established in the framework of convergence in probability, imply new sharp uniform-in-bandwidth limit laws for functional estimators. In particular, they yield the explicit value of the asymptotic limiting constant for the uniform-in-bandwidth sup-norm of the random error of kernel density estimators. We allow the bandwidth to vary within the complete range for which the estimators are consistent.     

Elliptical magnetic resonance spectroscopic imaging with GRAPPA for imaging brain tumors at 3 T

Magnetic Resonance Spectroscopic Imaging (MRSI) is a technique for imaging spatial variation of metabolites and has been very useful in characterizing biochemical changes associated with disease as well as response to therapy in malignant pathologies. This work presents a self-calibrated undersampling to accelerate 3D elliptical MRSI and an extrapolation-reconstruction algorithm based on the GRAPPA method. The accelerated MRSI technique was tested in three volunteers and five brain tumor patients. Acceleration allowed larger spatial coverage and consequently, less lipid contamination in spectra, compared to fully sampled acquisition within the same scantime. Metabolite concentrations measured from the accelerated acquisitions were in good agreement with measurements obtained from fully sampled MRSI scans.     

Burstiness and fractional diffusion on complex networks

Many dynamical processes on real world networks display complex temporal patterns as, forinstance, a fat-tailed distribution of inter-events times, leading to heterogeneouswaiting times between events. In this work, we focus on distributions whose averageinter-event time diverges, and study its impact on the dynamics of random walkers onnetworks. The process can naturally be described, in the long time limit, in terms ofRiemann-Liouville fractional derivatives. We show that all the dynamical modes possess, inthe asymptotic regime, the same power law relaxation, which implies that the dynamics doesnot exhibit time-scale separation between modes, and that no mode can be neglected versusanother one, even for long times. Our results are then confirmed by numericalsimulations.     

Ultra-rapid separation of an angiotensin mixture in nanochannels using shear-driven chromatography

The present paper reports on the separation of a mixture of fluorescein isothiocyanate-labeled angiotensin I and II peptides in a shear-driven nanochannel with a C18-coating and using an eluent consisting of 5% acetonitrile in 0.02 M aqueous phosphate buffer at pH 6.5. The flat-rectangular nanochannel in fused silica consisted of an etched structure in combination with a flat moving wall. The very fast separation kinetics that can be achieved in a nanochannel allowed to separate the angiotensin peptides in less then 0.2 s in a distance of only 1.8 mm. Plate heights as small as 0.4 microm were calculated after substraction of the injection effect.     

CO2 Hydroboration: Impact of the Boryl Moieties on the Reactivity of Four Bis(boryl)acetal Compounds toward 2,6-Diisopropylaniline

The hydroboration of CO₂ into bis(boryl)acetal (BBA) compounds is an important transformation, since it enabled to selectively reduce CO₂ by 4e^- and to subsequently use the BBA compounds as C₁ and C_n sources. However, the influence of the nature of the boryl moieties on the reactivity of BBA compounds has not been evaluated so far. In the present study, four BBA compounds – including two new ones – were reacted with 2,6-diisopropylaniline to afford the expected imine. Significant differences in the rate of the reaction from minutes to weeks have been observed depending on the BBA used, showing the importance of the nature of the boryl moieties. Theoretical investigations enabled to propose a mechanism involving the addition of the aniline to the BBA as the rate-determining step and to determine that the steric hindrance of the BBA compounds is the main factor driving the rate of this condensation reaction.     

Kinetic stability of complex molecular clusters

This investigation is concerned with modeling the evaporation, or decay, of n-nonane molecular clusters. We use a unique cluster decay model that was first developed to estimate the decay time scale of argon clusters using molecular-dynamics simulations. In this study we seek to enhance the model so that it represents a more complex cluster decay dynamic, suitable for n-nonane clusters. Experimental measurements of nucleation rates of n-nonane droplets have been used to deduce the rate at which a molecule escapes from the cluster. Typically for an n-nonane cluster containing 40 molecules, at an experimental temperature of 225 K, the empirical decay time, which is the inverse of the decay rate, is estimated to be 50 ns. For this time scale, the direct observation of n-nonane cluster decay from a molecular-dynamics trajectory is not feasible, since decay events are so rare. However, the cluster decay model uses a combination of molecular dynamics and stochastic dynamics in order to resolve the problem associated with long decay time scales. The model is based on a Langevin treatment that views cluster decay as single-particle escape from a confining potential of mean force. It is used to predict kinetic decay times of n-nonane clusters. We discover this result differs significantly from a classically derived decay time scale determined from a continuum thermodynamic treatment of the population balance equations of clusters. However, the dynamically generated results obtained from the kinetic decay model compare more favorably than the classical results with the empirical decay times that are deduced from experimental measurements of n-nonane clusters.     

Natural products as an inspiration in the diversity-oriented synthesis of bioactive compound libraries

The purpose of diversity-oriented synthesis is to drive the discovery of small molecules with previously unknown biological functions. Natural products necessarily populate biologically relevant chemical space, since they bind both their biosynthetic enzymes and their target macromolecules. Natural product families are, therefore, libraries of pre-validated, functionally diverse structures in which individual compounds selectively modulate unrelated macromolecular targets. This review describes examples of diversity-oriented syntheses which have, to some extent, been inspired by the structures of natural products. Particular emphasis is placed on innovations that allow the synthesis of compound libraries that, like natural products, are skeletally diverse. Mimicking the broad structural features of natural products may allow the discovery of compounds that modulate the functions of macromolecules for which ligands are not known. The ability of innovations in diversity-oriented synthesis to deliver such compounds is critically assessed.     

Progressive-convergent elucidation of stereochemistry in complex polyols. The absolute configuration of (-)-sagittamide A

The absolute stereostructure of sagittamide A (1), a O-hexacetyl long-chain hexahydroxy-alpha,omega-dicarboxylic acid, was assigned using a progressive-convergent approach that integrates three powerful regimens for stereochemical analysis of acyclic natural products: J-based analysis, 13C NMR universal database comparisons, and exciton coupling circular dichroism.     

Deposition of DNA-functionalized gold nanospheres into nanoporous surfaces

We report the deposition of DNA-conjugated gold nanospheres into arrays of surface nanopores obtained from hexagonally ordered thin polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer films on silicon. The deposition occurs spontaneously from aqueous solution and is driven by either electrostatic interactions or specific DNA hybridization events between the DNA nanospheres and the surface nanopores. To mitigate this spontaneous deposition, we have chemically modified the nanopores with either positively charged aminosilanes or oligonucleotide probe sequences. The deposition of DNA nanospheres into the surface nanopores was characterized by atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). We have observed preferential immobilization of individual DNA nanospheres within the nanopores, based on the size matching between the two entities. The inclusion density and selectivity of DNA nanosphere deposition into the surface nanopores was found to depend predominantly on the methods through which the nanoporous surfaces were prepared and chemically functionalized.     

High-density targeting of a viral multifunctional nanoplatform to a pathogenic, biofilm-forming bacterium

Nanomedicine directed at diagnosis and treatment of infections can benefit from innovations that have substantially increased the variety of available multifunctional nanoplatforms. Here, we targeted a spherical, icosahedral viral nanoplatform to a pathogenic, biofilm-forming bacterium, Staphylococcus aureus. Density of binding mediated through specific protein-ligand interactions exceeded the density expected for a planar, hexagonally close-packed array. A multifunctionalized viral protein cage was used to load imaging agents (fluorophore and MRI contrast agent) onto cells. The fluorescence-imaging capability allowed for direct observation of penetration of the nanoplatform into an S. aureus biofilm. These results demonstrate that multifunctional nanoplatforms based on protein cage architectures have significant potential as tools for both diagnosis and targeted treatment of recalcitrant bacterial infections.