Structures of small mixed krypton-xenon clusters

Structures of small mixed krypton-xenon clusters of different compositions with an average size of 30–37 atoms are investigated. The Kr 3d 5/2 and Xe 4d 5/2surface core level shifts and photoelectron intensities originating from corner, edge, and face/bulk sites are analyzed by using soft x-ray photoelectron spectroscopy. Structural models are derived from these experiments, which are confirmed by theoretical simulation taking induced dipole interactions into account. It is found that one or two small Xe cores are partly embedded in the surface of the Kr clusters. These may grow and merge leading to a phase separation between the two rare gas moieties in mixed clusters with increasing the Xe content

Experiment and theory

Photoionization of neutral atomic sulfur in the ground and metastable states was studied experimentally at a photon energy resolution of 44 meV (full width at half maximum). Relative cross section measurements were recorded by using tunable vacuum ultraviolet radiation in the energy range 9–30 eV obtained from a laser-produced plasma and the atomic species were generated by photolysis of molecular precursors. Photoionization of this atom is characterized by multiple Rydberg series of autoionizing resonances superimposed on a direct photoionization continuum. A wealth of resonance features observed in the experimental spectra are spectroscopically assigned and their energies and quantum defects tabulated. The cross section measurements are compared with state-of-the-art theoretical cross section calculations obtained from the Dirac Coulomb R-matrix method. Resonance series in the spectra are identified and compared, indicating similar features in both the theoretical and experimental spectra

Structures of mixed argon-nitrogen clusters

The structures of mixed argon-nitrogen clusters of different compositions are investigated by analyzing core level shifts and relative intensities of surface and bulk sites in the Ar 2p 3/2 regime in soft X-ray photoelectron spectroscopy. These structures are confirmed by core level shift calculations taking induced dipole interactions into account, in which several model structures of the mixed clusters are considered by Monte Carlo simulations. These results suggest that the mixed argon-nitrogen clusters show partial core-shell structures, where an argon core is partially covered by nitrogen molecules

Compressive nano-FTIR chemical mapping

Nano-Fourier-transform infrared spectroscopy (nano-FTIR) combines infrared spectroscopy with scanning probe microscopy (SPM) techniques and enables spectroscopic imaging of molecular and electronic properties of matter at nanometer spatial resolution. The spectroscopic imaging can be used to derive chemical mappings, i.e. the spatial distribution of concentrations of the species contained in a given sample. However, due to the sequential scanning principle underlying SPM, recording the complete spectrum over a large spatial area leads to long measurement times. Furthermore, the acquired spectrum often contains additional signals from species and lineshape effects that are not explicitly accounted for. A compressive chemical mapping approach is proposed for undersampled nano-FTIR data that utilizes sparsity of these additional signals in the spectral domain. The approach combines a projection technique with standard compressed sensing, followed by a spatially regularized regression. Using real nano-FTIR measurements superimposed by simulated interferograms representing the chemical mapping of the contained species, it is demonstrated that the proposed procedure performs well even in cases in which the simulated interferograms and the sparse additional signals exhibit a strong spectral overlap

pH-Sensitive Chitosan–Heparin Nanoparticles for Effective Delivery of Genetic Drugs into Epithelial Cells

Chitosan has been extensively studied as a genetic drug delivery platform. However, its efficiency is limited by the strength of DNA and RNA binding. Expecting a reduced binding strength of cargo with chitosan, we proposed including heparin as a competing polyanion in the polyplexes. We developed chitosan–heparin nanoparticles by a one-step process for the local delivery of oligonucleotides. The size of the polyplexes was dependent on the mass ratio of polycation to polyanion. The mechanism of oligonucleotide release was pH-dependent and associated with polyplex swelling and collapse of the polysaccharide network. Inclusion of heparin enhanced the oligonucleotide release from the chitosan-based polyplexes. Furthermore, heparin reduced the toxicity of polyplexes in the cultured cells. The cell uptake of chitosan–heparin polyplexes was equal to that of chitosan polyplexes, but heparin increased the transfection efficiency of the polyplexes two-fold. The application of chitosan–heparin small interfering RNA (siRNA) targeted to vascular endothelial growth factor (VEGF) silencing of ARPE-19 cells was 25% higher. Overall, chitosan–heparin polyplexes showed a significant improvement of gene release inside the cells, transfection, and gene silencing efficiency in vitro, suggesting that this fundamental strategy can further improve the transfection efficiency with application of non-viral vectors

All-optical spatio-temporal control of electron emission from SiO2 nanospheres with femtosecond two-color laser fields

Field localization by nanostructures illuminated with laser pulses of well-defined waveform enables spatio-temporal tailoring of the near-fields for sub-cycle control of electron dynamics at the nanoscale. Here, we apply intense linearly-polarized two-color laser pulses for all-optical control of the highest energy electron emission from SiO2 nanoparticles. For the size regime where light propagation effects become important, we demonstrate the possibility to control the preferential emission angle of a considerable fraction of the fastest electrons by varying the relative phase of the two-color field. Trajectory based semi-classical simulations show that for the investigated nanoparticle size range the directional steering can be attributed to the two-color effect on the electron trajectories, while the accompanied modification of the spatial distribution of the ionization rate on the nanoparticle surface has only a minor effect

Bio-Inspired Amphiphilic Block-Copolymers Based on Synthetic Glycopolymer and Poly(Amino Acid) as Potential Drug Delivery Systems

In this work, a method to prepare hybrid amphiphilic block copolymers consisting of biocompatible synthetic glycopolymer with non-degradable backbone and biodegradable poly(amino acid) (PAA) was developed. The glycopolymer, poly(2-deoxy-2-methacrylamido-D-glucose) (PMAG), was synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Two methods for modifying the terminal dithiobenzoate-group of PMAG was investigated to obtain the macroinitiator bearing a primary aliphatic amino group, which is required for ring-opening polymerization of N-carboxyanhydrides of hydrophobic α-amino acids. The synthesized amphiphilic block copolymers were carefully analyzed using a set of different physico-chemical methods to establish their composition and molecular weight. The developed amphiphilic copolymers tended to self-assemble in nanoparticles of different morphology that depended on the nature of the hydrophobic amino acid present in the copolymer. The hydrodynamic diameter, morphology, and cytotoxicity of polymer particles based on PMAG-b-PAA were evaluated using dynamic light scattering (DLS) and transmission electron microscopy (TEM), as well as CellTiter-Blue (CTB) assay, respectively. The redox-responsive properties of nanoparticles were evaluated in the presence of glutathione taken at different concentrations. Moreover, the encapsulation of paclitaxel into PMAG-b-PAA particles and their cytotoxicity on human lung carcinoma cells (A549) and human breast adenocarcinoma cells (MCF-7) were studied

Probing the Penetration of Rapamycin by Scanning Transmission X-ray Microscopy

Drug penetration in human skin ex vivo following a modification of skin barrier permeability is systematically investigated by scanning transmission X-ray microscopy. Element-selective excitation is used in the O 1s regime for probing quantitatively the penetration of topically applied rapamycin in different formulations with a spatial resolution reaching <75 nm. The data were analyzed by a comparison of two methods: (i) two-photon energies employing the Beer–Lambert law and (ii) a singular value decomposition approach making use of the full spectral information in each pixel of the X-ray micrographs. The latter approach yields local drug concentrations more reliably and sensitively probed than the former. The present results from both approaches indicate that rapamycin is not observed within the stratum corneum of nontreated skin ex vivo, providing evidence for the observation that this high-molecular-weight drug inefficiently penetrates intact skin. However, rapamycin is observed to penetrate more efficiently the stratum corneum when modifications of the skin barrier are induced by the topical pretreatment with the serine protease trypsin for variable time periods ranging from 2 to 16 h. After the longest exposure time to serine protease, the drug is even found in the viable epidermis. High-resolution micrographs indicate that the lipophilic drug preferably associates with corneocytes, while signals found in the intercellular lipid compartment were less pronounced. This result is discussed in comparison to previous work obtained from low-molecular-weight lipophilic drugs as well as polymer nanocarriers, which were found to penetrate the intact stratum corneum exclusively via the lipid layers between the corneocytes. Also, the role of the tight junction barrier in the stratum granulosum is briefly discussed with respect to modifications of the skin barrier induced by enhanced serine protease activity, a phenomenon of clinical relevance in a range of inflammatory skin disorders