Sensing amyloid-β aggregation using luminescent dipyridophenazine ruthenium(II) complexes

The aggregation of amyloid-β (Aβ) peptides has been associated with the onset of Alzheimer's disease. Here, we report the use of a luminescent dipyridophenazine ruthenium(II) complex to monitor Aβ fibrillization. This complex is not photoluminescent in aqueous solution nor in the presence of monomeric Aβ, but it presents a strong photoluminescence in the presence of Aβ fibril aggregates. One of the advantages of this metal complex is its large Stokes shift (180 nm). Furthermore, the long-lived photoluminescence lifetime of this ruthenium complex allows its use for the detection of fibrillar proteins in the presence of short-lived fluorescent backgrounds, using time-gating technology. We will present evidence of the advantages of dipyridophenazine ruthenium(II) complexes for monitoring protein fibrillization in highly fluorescent media.     

Size controlled gold nanoparticle formation by <Emphasis Type="Italic">Avena sativa</Emphasis> biomass: use of plants in nanobiotechnology

Oat (Avena sativa) biomass was studied as an alternative to recover Au(III) ions from aqueous solutions and for its capacity to reduce Au(III) to Au(0) forming Au nanoparticles. To study the binding trend of Au(III) to oat and the possible formation of Au nanoparticles, the biomass and a solution of Au(III) were reacted for a period of 1 h at pH values ranging from 2 to 6. The results demonstrated that Au(III) ions were bound to oat biomass in a pH-dependent manner, with the highest adsorption (about 80%) at pH 3. HRTEM studies showed that oat biomass reacted with Au(III) ions formed Au nanoparticles of fcc tetrahedral, decahedral, hexagonal, icosahedral multitwinned, irregular, and rod shape. To our knowledge, this is the second report about the production of nanorods as a product of the reaction of a Au(III) solution with a biological material. These studies also showed that the pH of the reaction influenced the nanoparticle size. The smaller nanoparticles and the higher occurrence of these were observed at pH values of 3 and 4, whereas the larger nanoparticles were observed at pH 2.     

Landau levels of holes in a two-dimensional channel

A method for calculating the Landau levels in a two-dimensional channel is proposed. This method is aimed at construction of an effective two-dimensional Hamiltonian of holes H(k_x, k_y, B). The Hamiltonian is expanded in powers of the magnetic field B and noncommuting momenta k_x and k_y. The results indicate an interconnection between effective masses and g-factors of the two-dimensional holes. It is possible to account for the effects of band warping in a nonperturbative manner. The shift of phase in the Shubnikov-de Haas oscillations is explained.     

Surface-charge lithography for direct PDMS micro-patterning

Direct patterning of PDMS films is achieved by modulating the wettability of polar dielectric substrates. Periodic array structures of microbumps can be madeup by functionalizing periodically poled lithium niobate crystals. The modulation of surface wettability is obtained through the spatial distribution of the surface electric charges generated by the pyroelectric effect under electrode-less configuration. An appropriate thermal treatment of the substrates assures both the wettability patterning and the fast cross-linking of the PDMS film.     

Deuterium kinetic isotope effects in microsolvated gas-phase E2 reactions: Methanol and ethanol as solvents

The gas-phase reactions of F(-)(CH(3)OH) and F(-)(C(2)H(5)OH) with t-butyl bromide have been investigated to explore the effect of the solvent on the E2 transition state. Kinetic isotope effects (KIEs) were measured using a flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometer upon deuteration of both the alkyl halide and the alcohol. Kinetic isotope effects are significantly more pronounced than those previously observed for similar reactions of F(-)(H(2)O) with t-butyl halides. KIEs for the reaction of F(-)(CH(3)OH) with t-butyl bromide are 2.10 upon deuteration of the neutral reagent and 0.74 upon deuteration of the solvent. KIEs for the reaction of F(-)(C(2)H(5)OH) with t-butyl bromide are 3.84 upon deuteration of the neutral reagent and 0.66 upon deuteration of the solvent. The magnitude of these effects is discussed in terms of transition-state looseness. Additionally, deuteration of the neutral regent and deuteration of the solvent do not produce completely separable isotope effects, which is likely due to a crowded transition state. These results are compared to our previous work on S(N)2 and E2 solvated systems.     

Ion chemistry of 1H-1,2,3-triazole. 2. Photoelectron spectrum of the iminodiazomethyl anion and collision induced dissociation of the 1,2,3-triazolide ion

The 363.8 nm photoelectron spectrum of the iminodiazomethyl anion has been measured. The anion is synthesized through the reaction of the hydroxide ion (HO-) with 1 H-1,2,3-triazole in helium buffer gas in a flowing afterglow ion source. The observed spectrum exhibits well-resolved vibronic structure of the iminodiazomethyl radical. Electronic structure calculations have been performed at the B3LYP/6-311++G(d,p) level of theory to study the molecular structure of the ion. Equilibrium geometries of four possible conformers of the iminodiazomethyl anion have been obtained from the calculations. Spectral simulations have been performed on the basis of the calculated geometries and normal modes of these conformationally isomeric ions and the corresponding radicals. The spectral analysis suggests that the ions of two conformations are primarily formed in the aforementioned reaction. The relative abundance of the two conformers substantially deviates from the thermal equilibrium populations, and it reflects the potential energy surfaces relevant to conformational isomerization processes. The electron affinities of the ( ZE)- and ( EE)-iminodiazomethyl radicals have been determined to be 2.484 +/- 0.007 and 2.460 +/- 0.007 eV, respectively. The energetics of the iminodiazomethyl anion is compared with that of the most stable structural isomer, the 1,2,3-triazolide ion. Collision-induced dissociation of the 1,2,3-triazolide ion has also been studied in flowing afterglow-selected ion flow tube experiments. Facile fragmentation generating a product ion of m/ z 40 has been observed. DFT calculations suggest that fragmentation of the 1,2,3-triazolide ion to the cyanomethyl anion and N2 is exothermic. The stability of the ion is discussed in comparison with other azolide ions with different numbers of N atoms in the five-membered ring.     

Thermal study of polypyrrole complexes with vermiculites of different layer charge

We have studied the synthesis of polypyrrole-clay nanocomposites by the in situ oxidative polymerization of pyrrole in the interlayer space of vermiculites with different layer charges from Santa Olalla and Ojén, Spain. Moreover, the influence of different interlayer cations (Na⁺, Mg²⁺, Fe³⁺) on the interaction between pyrrole and the vermiculties was studied. The resulting materials were characterized by means of DTA-TG, XRD, FTIR and Mössbauer spectroscopy. In all samples polymerization of pyrrole was observed, presumably triggered by the structural iron. In most cases it was found to be externally deposited. An uptake of pyrrole in the interlayer space and PPy formation is observed in the case of the Fe³⁺-intercalated Ojén vermiculite, which has a lower layer charge than the Santa Olalla vermiculite.     

Copper(II) complexes with N,N-dimethylbiguanide

The N,N-dimethylbiguanide (HDMBG) complexes [Cu₂(HDMBG)₂Cl₄] (1) and respectively [Cu(HDMBG)₂]Cl₂·2H₂O (2) exhibit in vitro antimicrobial activity. The complexes were characterised by IR, electronic as well as EPR spectra. The IR spectra of complexes show the pattern of N,N-dimethylbiguanide coordinated as chelate. The electronic and EPR data are in agreement with a square pyramidal stereochemistry for (1) and a square planar one for (2). The in vitro qualitative and quantitative antimicrobial activity assays showed that the complexes exhibited variable antimicrobial activity against Gram-negative strains (Escherichia coli, Klebsiella spp. and Enterobacter sp.) isolated from the hospital environment. The thermal analysis has evidenced the thermal intervals of stability and also the thermodynamic effects that accompany them. The thermal behaviour in nitrogen is complex according to TG and DTA curves including melting, dehydration as well as compounds decomposition.     

Vibrational spectroscopy of perfluorocarboxylic acids from the infrared to the visible regions

We report here the gas-phase mid-IR, near-IR, and visible vibrational spectra of perfluoropropionic, perfluorooctanoic, and perfluorononanoic acids using Fourier transform and cavity ring-down spectroscopy. The impetus for this work was to provide insight into the behavior of environmentally persistent perfluorocarboxylic acids. Although the most intense transition for all three perfluorocarboxylic acids in the fundamental spectra is the CF3 stretch, the O-H stretch carries the most intensity in the overtone region. We record the O-H stretching transition frequencies and absorption cross-sections in the DeltavOH = 1-5 regions. Our work suggests that perfluorocarboxylic acids have more harmonic O-H bonds, smaller transition frequencies, and smaller intensities as compared to shorter-chain hydrocarbon acids, alcohols, and peroxides.     

Structural Modifications of cis‐Glycofused Benzopyran Compounds and Their Influence on the Binding to Amyloid‐β Peptide

A small library of glycofused tricyclic compounds with a central pyran ring chemically modified in the position para to the ring oxygen has been synthesised. The influence of the chemical modification on the structural conformation of the compounds and on their ability to bind Aβ peptide has been evaluated respectively using molecular mechanics (MM) and molecular dynamics (MD) simulations, and STD NMR spectroscopy. The introduction of particularly polar/charged groups leads to the loss of binding ability, without a significant change in the conformation, whilst other substitutions does not significantly affect either the structural conformation or the binding.