Evaluation of tip-enhanced Raman spectroscopy for characterizing different virus strains

Tip-enhanced Raman spectroscopy (TERS) is a highly sensitive spectroscopic technique which combines the advantages of optical spectroscopy with the requirements needed for the characterization of biological nano-structures. In this study, TERS was used to investigate the applicability of this spectroscopic technique for the detection of different virus strains like avipoxvirus and adeno-associated virus. TERS spectra obtained from different particles of the same virus strain show variations in relative peak intensities and positions of most spectral features observed. These spectral variations were higher for the larger avipoxvirus particles (?≈350 nm) than for the smaller adeno-associated virus particles (?≈26 nm).     

Fast characterization of functionalized silica materials by silicon-29 surface-enhanced NMR spectroscopy using dynamic nuclear polarization

We demonstrate fast characterization of the distribution of surface bonding modes and interactions in a series of functionalized materials via surface-enhanced nuclear magnetic resonance spectroscopy using dynamic nuclear polarization (DNP). Surface-enhanced silicon-29 DNP NMR spectra were obtained by using incipient wetness impregnation of the sample with a solution containing a polarizing radical (TOTAPOL). We identify and compare the bonding topology of functional groups in materials obtained via a sol-gel process and in materials prepared by post-grafting reactions. Furthermore, the remarkable gain in time provided by surface-enhanced silicon-29 DNP NMR spectroscopy (typically on the order of a factor 400) allows the facile acquisition of two-dimensional correlation spectra.     

Affinity of Cu+ for the copper-binding domain of the amyloid-β peptide of Alzheimer's disease

The role of metal ions in Alzheimer's disease etiology is unresolved. For the redox-active metal ions iron and copper, the formation of reactive oxygen species by metal amyloid complexes has been proposed to contribute to Alzheimer's disease neurodegeneration. For copper, reactive oxygen species are generated by copper redox cycling between its 1+ and 2+ oxidation states. Thus, the AβCu(I) complex is potentially a critical reactant associated with Alzheimer's disease etiology. Through competitive chelation, we have measured the affinity of the soluble copper-binding domain of the amyloid-β peptide for Cu(I). The dissociation constants are in the femtomolar range for both wild-type and histidine-to-alanine mutants. These results indicate that Cu(I) binds more tightly to monomeric amyloid-β than Cu(II) does, which leads us to propose that Cu(I) is a relevant in vivo oxidation state.     

RbCN3H4: the first structurally characterized salt of a new class of guanidinate compounds

Rubidium guanidinate, RbCN(3)H(4), was synthesized from guanidine and rubidium hydride, and the crystal structure was determined from powder X-ray diffraction (PXRD) data. RbCN(3)H(4) crystallizes in the orthorhombic space group Pnma (No. 62) with four formula units per cell. The guanidinate anions are arranged in double chains running along the b axis, stacked almost perpendicularly to each other to form a three-dimensional network. The rubidium cations, coordinated by 11 N atoms, occupy the vacancies of the network in a zigzag motif along the b axis. Because the PXRD structure of the CN(3) core clearly indicates the N-atom functionalities and the location of the H-atom positions, the latter spatial parameters were determined from Perdew-Burke-Ernzerhof generalized gradient approximation (GGA-PBE) density functional theory calculations. The corresponding ν(NH) stretching modes can be observed in the IR spectrum, and the volume chemistry of RbCN(3)H(4) mirrors the efficient packing of the saltlike phase.     

LC-MS based quantification of 2'-ribosylated nucleosides Ar(p) and Gr(p) in tRNA

RNA nucleosides are often naturally modified into complex non-canonical structures with key biological functions. Here we report LC-MS quantification of the Ar(p) and Gr(p) 2'-ribosylated nucleosides in tRNA using deuterium labelled standards, and the first detection of Gr(p) in complex fungi.     

H atom adsorption and diffusion on Si(110)-(1×1) and (2×1) surfaces

We present a periodic density-functional study of hydrogen adsorption and diffusion on the Si(110)-(1×1) and (2×1) surfaces, and identify a local reconstruction that stabilizes the clean Si(110)-(1×1) by 0.51 eV. Hydrogen saturates the dangling bonds of surface Si atoms on both reconstructions and the different structures can be identified from their simulated scanning tunneling microscopy/current image tunneling spectroscopy (STM/CITS) images. Hydrogen diffusion on both reconstructions will proceed preferentially along zigzag rows, in between two adjacent rows. The mobility of the hydrogen atom is higher on the (2×1) reconstruction. Diffusion of a hydrogen vacancy on a monohydride Si(110) surface will proceed along one zigzag row and is slightly more difficult (0.2 eV and 0.6 eV on (1×1) and (2×1), respectively) than hydrogen atom diffusion on the clean surface.     

Hypericin-mediated photocytotoxic effect on HT-29 adenocarcinoma cells is reduced by light fractionation with longer dark pause between two unequal light doses

The present study demonstrates the in vitro effect of hypericin-mediated PDT with fractionated light delivery. Cells were photosensitized with unequal light fractions separated by dark intervals (1 or 6 h). We compared the changes in viability, cell number, survival, apoptosis and cell cycle on HT-29 cells irradiated with a single light dose (12 J/cm(2)) to the fractionated light delivery (1 + 11 J/cm(2)) 24 and 48 h after photodynamic treatment. We found that a fractionated light regime with a longer dark period resulted in a decrease of hypericin cytotoxicity. Both cell number and survival were higher after light sensitization with a 6-h dark interval. DNA fragmentation occurred after a single light-dose application, but in contrast no apoptotic DNA formation was detected with a 6-h dark pause. After fractionation the percentage of cells in the G1 phase of the cell cycle was increased, while the proportion of cells in the G2 phase decreased as compared to a single light-dose application, i.e. both percentage of cells in the G1 and G2 phase of the cell cycle were near control levels. We presume that the longer dark interval after the irradiation of cells by first light dose makes them resistant to the effect of the second illumination. These findings confirm that the light application scheme together with other photodynamic protocol components is crucial for the photocytotoxicity of hypericin.     

Recent applications of conductivity detection in capillary and chip electrophoresis

The review provides a comprehensive survey of the recent applications of contact and contactless conductivity detection in capillary electrophoretic and chip electrophoretic analyses of a broad scale of compounds, from low-molecular-mass highly mobile small inorganic and organic ions, via medium-molecular-mass peptides and oligo- and polynucleotides up to high-molecular-mass biopolymers, proteins and nucleic acids fragments. The review presents also the recent developments in the construction of different types of conductivity detectors (detectors with galvanic contact of the sensing electrodes with the BGE and sample components, contactless conductivity detectors with capacitively coupled tubular and semitubular electrodes and combined conductivity/optical detectors) applied in the capillary electromigration methods performed in classical fused silica, polytetrafluorethylene, and polyetheretherketone capillaries or on glass and polymethylmethacrylate microchips. In addition, the principle and theoretical bases of conductivity detection in capillary electromigration techniques, zone electrophoresis, ITP, micellar EKC, and electrochromatography are briefly described.