Adenosine Reagentless Electrochemical Aptasensor Using a Phosphorothioate Immobilization Strategy

This work deals with the characterization of a phosphorothioate anchoring strategy for aptamer molecules linked to gold, in the context of electrochemical sensors, using adenosine aptamer as model system. Surface density of immobilized phosphorothioate oligonucleotide sequences has been explored for a range of oligonucleotide concentrations (0.055–55 μM), finding a consequent variation of molecular surface density (3.5×10¹¹–2.8×10¹³ molecules/cm²). Most suitable aptamer concentration for adenosine recognition was also explored and found to be around 5.5 μM. As proof of concept of phosphorothioate strategy, electrochemical response to adenosine concentration was measured using a ferrocene‐labeled oligonucleotide sequence, and phosphorothioate anchoring thermal stability was compared to thiol immobilization.     

Unusual calibration curves observed for iron using high-resolution continuum source graphite furnace atomic absorption spectrometry

The simultaneous determination of cadmium and iron in plant and soil samples has been investigated using high-resolution continuum source graphite furnace atomic absorption spectrometry. The primary cadmium resonance line at 228.802 nm and an adjacent secondary iron line at 228.726 nm, which is within the spectral interval covered by the charge-coupled device (CCD) array detector, have been used for the investigations. Due to the very high iron content in most of the soil samples the possibility has been investigated to reduce the sensitivity and extend the working range by using side pixels for measurement at the line wings instead of the line core. It has been found that the calibration curves measured at all the analytically useful pixels of this line consisted of two linear parts with distinctly different slopes. This effect has been independent of the positioning of the wavelength, i.e., if the Cd line or the Fe line was in the center of the CCD array. The most likely explanation for this unusual behavior is a significant difference between the instrument width Δλ_Instr and the absorption line width Δλ_Abs, which is quite pronounced in the case of Fe. Using both parts of the calibration curves and simultaneous measurement at the line center and at the wings made it possible to extend the working range for the iron determination to more than three orders of magnitude.     

Harnack inequality for harmonic functions relative to a nonlinear p-homogeneous Riemannian Dirichlet form

We state a Wiener criterion for the regularity of points with respect to a relaxed Dirichlet problem for a p-homogeneous Riemannian Dirichlet form.     

Processing nanoparticles with A4F-SAXS for toxicological studies: Iron oxide in cell-based assays

Nanoparticles are not typically ready-to-use for in vitro cell culture assays. Prior to their use in assays, powder samples containing nanoparticles must be dispersed, de-agglomerated, fractionated by size, and characterized with respect to size and size distribution. For this purpose we report exemplarily on polyphosphate-stabilized iron oxide nanoparticles in aqueous suspension. Fractionation and online particle size analysis was performed in a time-saving procedure lasting 50 min by combining asymmetrical flow field-flow fractionation (A4F) and small-angle X-ray scattering (SAXS). Narrowly distributed nanoparticle fractions with radii of gyration (R(g)) from 7 to 21 nm were obtained from polydisperse samples. The A4F-SAXS combination is introduced for the preparation of well-characterized sample fractions originating from a highly polydisperse system as typically found in engineered nanoparticles. A4F-SAXS processed particles are ready-to-use for toxicological studies. The results of preliminary tests of the effects of fractionated iron oxide nanoparticles with a R(g) of 15 nm on a human colon model cell line are reported.     

Synthesis of silsesquioxanes based in (3-methacryloxypropyl)-trimethoxysilane using methacrylate monomers as reactive solvents

The polycondensation of (3-methacryloxypropyl)-trimethoxysilane in acidic conditions using different methacrylate monomers as reactive solvents resulted in incompletely condensed methacrylate-functionalized silsesquioxanes with a very large fraction of intramolecular cycles. UV-MALDI-TOF-MS analysis demonstrated that the species present after 2 weeks of reaction at 60 °C were: T₆(OH)₂, T₇(OH), T₈(OH)₂, T₉(OH), T₁₀(OH)₂ and T₁₁(OH). Analysis of samples after 30 months of storage at room temperature revealed the presence of T₁₂(OH)₂ and T₁₃(OH) species. The absence of higher molar mass oligomers after prolonged storage periods is attributed to dilution of the reacting medium, which discourages bimolecular reactions that lead to polymer growth. ²⁹Si NMR spectroscopy showed that the conversion in the polycondensation reaction was in the range 0.91-0.96. The methacrylate monomers are not involved in the hydrolysis-condensation reactions with MPTMS and therefore can be polymerized by thermal or photochemical means, thereby cross-linking the preformed nanosized cagelike silsesquioxanes. The formulations containing silsesquioxanes showed a markedly reduced content of extractable monomer after photopolymerization, which makes these resins very attractive for dental filling materials.     

Almost periodic viscosity solutions of nonlinear evolution equations in Carnot groups

The aim of this paper is to establish existence and uniqueness of time almost periodic viscosity solutions to first-order evolution equations in Carnot groups.     

Validation of the antifactor Xa and antifactor IIa assays for the potency assessment of nadroparin in pharmaceutical formulations

The low-molecular weight heparin nadroparin calcium is used clinically for the prevention and treatment of venous and arterial thrombosis. The antifactor Xa and antifactor IIa assays were validated by investigating the parameters of range, linearity (r2 = 0.9905 and r2 = 0.9914, respectively) precision, accuracy, and robustness. The 2 methods incorporated a chromogenic endpoint and detection at 405 nm, yielding good results with detection limits of 0.004 and 0.01 IU/mL and quantitation limits of 0.01 and 0.03 IU/mL, respectively, for the antifactor Xa and antifactor IIa assays. Nadroparin calcium pharmaceutical products were evaluated by the antifactor Xa assay and the antifactor IIa assay, giving potencies between 93.86 and 109.88%, with an antifactor Xa/antifactor IIa ratio between 3.2 and 3.7. The results demonstrated the validity of the assays that are useful methodologies for the routine quality control of nadroparin in pharmaceutical formulations.     

Hydantoin derivatives of L- and D-amino acids: synthesis and evaluation of their antiviral and antitumoral activity

3,5-Disubstituted hydantoin (1,3-imidazolidinedione) derivatives 5a-h were prepared by base induced cyclization of the corresponding N-(1-benzotriazolecarbonyl)-L- and D-amino acid amides 4a-h. Compounds 5a-h were evaluated for their cytostatic and antiviral activities. Among all the compounds evaluated, 3-benzhydryl-5-isopropyl hydantoin (5a) showed a weak but selective inhibitory effect against vaccinia virus (EC(50) = 16 microg/mL; selectivity index: 25). 3-Cyclohexyl-5-phenyl hydantoin (5g) showed inhibitory activity against cervical carcinoma (HeLa, IC(50) = 5.4 microM) and breast carcinoma (MCF-7, IC(50) = 2 microM), but also cytotoxic effects towards human normal fibroblasts (WI 38). On the contrary, the 3-benzhydryl-5-phenyl substituted hydantoin derivative 5h showed moderate inhibitory activity towards HeLa, MCF-7, pancreatic carcinoma (MiaPaCa-2), lung carcinoma (H 460) and colon carcinoma (SW 620) (IC(50) = 20-23 microM), but no effect on WI 38.     

Influence of N-doping on the structure and electronic properties of titania nanoparticle photocatalysts

N-containing TiO(2)-based nanostructured materials (average particle size approximately 10 nm) with an anatase-type structure were investigated using oxygen (O) K-edge and titanium (Ti) K- and L-edge X-ray absorption near-edge spectroscopy (XANES). The Ti K pre-edge features indicate that samples predominantly contain ([6])Ti with some ([5])Ti, and there is no evidence for ([4])Ti. We observed that those samples with a larger fraction of Ti in a fivefold coordination, that is, with a significant number of oxygen vacancies, also present a modified Ti environment at the medium-range scale. The presence of these defects drastically modifies the electronic structure of the conduction band, as evidenced by the O K XANES spectra, but does not result in the presence of reduced Ti(3+) states. We discuss the influence of N-doping on titania nanoparticles and their structure, electronics and photocatalytic activity.     

p doping in expanded phases of ZnO: an ab initio study

The issue of p doping in nanostructured cagelike ZnO is investigated by state-of-the-art calculations. Our study is focused on one prototypical structure, namely, sodalite, for which we show that p-type doping is possible for elements of the V, VI, and VII columns of the periodic table. However, some dopants tend to form dimers, thus impairing the stability of this kind of doping. This difference of behavior is discussed, and two criteria are proposed to ensure stable p doping.