Nucleobase orientation and ordering in films of single-stranded DNA on gold

We demonstrate how the orientation and ordering of DNA bases in ultrahigh vacuum (UHV) and ambient environments can be determined using complementary spectroscopic methods. Near-edge X-ray absorption fine structure (NEXAFS) with fluorescence detection, X-ray photoelectron (XPS), and Fourier transform infrared (FTIR) spectroscopies are used to quantify the coverage, chemical composition, orientation, and ordering of thymine bases in model self-assembled monolayers of thymine homo-oligonucleotides [oligo(dT)] on gold. We find that, in monolayers of thiol-modified oligo(dT), thymine bases tend to orient parallel to the Au substrate, and this preferential orientation is significantly more pronounced in monolayers of thiolated 5-mers compared to 25-mers. We interpret this preferential orientation as a signature of significant correlations (local ordering) between individual nuleobases, which offers a way to quantify and compare nucleobase interactions in films under both ambient and UHV conditions.     

Comparison of four extraction/methylation analytical methods to measure fatty acid composition by gas chromatography in meat

Four different extraction-derivatization methods commonly used for fatty acid analysis in meat (in situ or one-step method, saponification method, classic method and a combination of classic extraction and saponification derivatization) were tested. The in situ method had low recovery and variation. The saponification method showed the best balance between recovery, precision, repeatability and reproducibility. The classic method had high recovery and acceptable variation values, except for the polyunsaturated fatty acids, showing higher variation than the former methods. The combination of extraction and methylation steps had great recovery values, but the precision, repeatability and reproducibility were not acceptable. Therefore the saponification method would be more convenient for polyunsaturated fatty acid analysis, whereas the in situ method would be an alternative for fast analysis. However the classic method would be the method of choice for the determination of the different lipid classes.     

Combined experimental and theoretical study on redox-active d8 metal dithione-dithiolato complexes showing molecular second-order nonlinear optical activity

Synthesis, characterization, NLO properties, and theoretical studies of the mixed-ligand dithiolene complexes of the nickel triad [M(II)(Bz(2)pipdt)(mnt)] (Bz(2)pipdt = 1,4-dibenzyl-piperazine-3,2-dithione, mnt = maleonitriledithiolato, M(II) = Ni, 1, Pd, 2, Pt, 3) are reported. Molecular structural characterization of 1-3 points out that four sulfur atoms are in a slightly distorted square-planar geometry. While the M-S bond distances are only slightly different, comparison of the C-C and C-S bonds in the C(2)S(2)MS(2)C(2) core allows us to point out a significant difference between the C-C and the C-S distances in Bz(2)pipdt and mnt. These findings suggest assigning a dithiolato character to mnt (pull ligand) and a dithione one (push ligand) to Bz(2)pipdt. Cyclic voltammetry of 1-3 exhibits two reversible reduction waves and a broad irreversible oxidation wave. These complexes are characterized in the visible region by a peak of moderately strong intensity, which undergoes negative solvatochromism. The molecular quadratic optical nonlinearities were determined by the EFISH technique, which provided the following values μβ(λ) (10(-48) esu) = -1436 (1), -1450 (2), and -1950 (3) converted in μβ(0) (10(-48) esu) = -463 (1), -684 (2), and -822 (3), showing that these complexes exhibit large negative second-order polarizabilities whose values depend on the metal, being highest for the Pt compound. DFT and TD-DFT calculations on 1-3 allow us to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated, and the results obtained support that the most appealing candidate as a second-order NLO chromophore is the platinum compound. This is due to (i) the most extensive mixture of the dithione/metal/dithiolato orbitals, (ii) the influence of the electric field of the solvent on the frontier orbitals that maximizes the difference in dipole moments between the excited and the ground state, and (iii) the largest oscillator strength in the platinum case vs nickel and palladium ones.     

Degradable Poly(amidoamine) Hydrogels as Scaffolds for In Vitro Culturing of Peripheral Nervous System Cells

This paper reports on the synthesis and physico‐chemical, mechanical, and biological characterization of two sets of poly(amidoamine) (PAA) hydrogels with potential as scaffolds for in vivo peripheral nerve regeneration. They are obtained by polyaddition of piperazine with N,N′‐methylenebis(acrylamide) or 1,4‐bis(acryloyl)piperazine with 1,2‐diaminoethane as cross‐linking agent and exhibit a combination of relevant properties, such as mechanical strength, biocompatibility, biodegradability, ability to induce adhesion and proliferation of Schwann cells (SCs) preserving their viability. Moreover, the most promising hydrogels, that is those deriving from 1,4‐bis(acryloyl)piperazine, allow the in vitro growth of the sensitive neurons of the dorsal root ganglia, thus getting around a critical point in the design of conduits for nerve regeneration.

     

Optical spectroscopy of lanthanide ions in ZnO-TeO2 glasses

Zinc tellurite glasses of compositions 19ZnO-80TeO2-1Ln2O3 with Ln = Eu, Er, Nd and Tm were prepared by melt quenching. The absorption spectra were measured and from the experimental oscillator strengths of the f-->f transitions the Judd-Ofelt parameters ohm(lambda) were obtained. The values of the ohm(lambda) parameters are in the range usually observed for oxide glasses. For Nd3+ and Er3+, luminescence spectra in the near infrared were measured and the stimulated emission cross sections sigma(p) were evaluated for some laser transitions. The high values of sigma(p), especially for Nd3+, make them possible candidates for optical applications. Fluorescence line narrowing (FLN) spectra of the Eu3+ doped glass were measured at 20 K, and the energies of the Stark components of the 7F1 and 7F2 states were obtained. A crystal field analysis was carried out assuming a C2v site symmetry. The behaviour of the crystal field ratios B22/B20 and B44/B40 agrees reasonably well with the values calculated using the geometric model proposed by Brecher and Riseberg. The crystal field strength at the Eu3+ sites appears to be very low compared to other oxide glasses.     

Detecting functional magnetic resonance imaging activation in white matter: Interhemispheric transfer across the corpus callosum

Background  

It is generally believed that activation in functional magnetic resonance imaging (fMRI) is restricted to gray matter. Despite this, a number of studies have reported white matter activation, particularly when the corpus callosum is targeted using interhemispheric transfer tasks. These findings suggest that fMRI signals may not be neatly confined to gray matter tissue. In the current experiment, 4 T fMRI was employed to evaluate whether it is possible to detect white matter activation. We used an interhemispheric transfer task modelled after neurological studies of callosal disconnection. It was hypothesized that white matter activation could be detected using fMRI.     

Thermal properties of Nafion–TiO<Subscript>2</Subscript> composite electrolytes for PEM fuel cell

Thermal analysis has been used to evaluate the stability, glass transition, and water retention of Nafion based polymer–ceramic electrolytes. These electrolytes are envisioned as promising replacement of Nafion in fuel cells operating above 100 °C. The polymeric matrix prepared by casting exhibits lower crystallinity than the extruded Nafion, a feature that affects the water absorption properties. The addition of titania-based nanotubes and nanoparticles to the polymer has enhanced the water retention at high temperatures (~130 °C) and the glass transition temperature, respectively. Such results are important for the design of composite electrolytes for the operation of fuel cells at high temperatures.     

Design of efficient methanol impermeable membranes for fuel cell applications

In this paper, the design of efficient composite membranes based on sulfonated polysulfone and acidic silica material with characteristics and properties such as methanol barrier, high proton conductivity and suitable fuel cells performance is presented. A positive influence of nanosized acidic silica powders, used as an additive filler in the preparation of composite membranes, due to an efficient hydrophilic inter-distribution inside the membrane when compared to pure silica, is found. A series of different techniques such as XRF, FT-IR, TGA, DSC, IEC and conductivity measurements are used to highlight the properties of acidic silica material and composite membranes. The composite membrane based on acidic silica (SPSf-SiO(2)-S) shows the lowest crossover current (only 8 mA cm(-2)), which is 43% lower than that of a pure SPSf membrane and 33% lower compared to a composite membrane based on bare silica (SPSf-SiO(2)). These significant differences are attributed to the increasing diffusion path length of MeOH/H(2)O clusters in the composite membranes. The maximum DMFC performance at 30 °C is achieved with the SPSf-SiO(2)-S membrane (23 mW cm(-2)), whereas the MEAs based on SPSf-SiO(2) and pure SPSf membranes reached 21 and 16 mW cm(-2), respectively. These significant results of the composite SPSf-SiO(2)-S membrane are ascribed at a good compromise among high proton conductivity, low swelling and low methanol crossover compared to pure SPSf and (unmodified silica)-SPSf membranes. A preliminary short durability test of 100 h performed in a cell with the composite SPSf-SiO(2)-S membrane shows remarkable performance stability during chrono-voltammetric measurements (60 mA cm(-2)) at 30 °C.