On the spectral norm of algebraic numbers

In this paper we continue to study the spectral norms and their completions ([4]) in the case of the algebraic closure $ \overline {\mathbb Q} $ of ? in ?. Let $ \widetilde{\overline{\mathbb{Q}}} $ be the completion of $ \overline {\mathbb Q} $ relative to the spectral norm. We prove that $ \widetilde{\overline{\mathbb{Q}}} $ can be identified with the R‐subalgebra of all symmetric functions of C(G), where C(G) denotes the ?‐Banach algebra of all continuous functions defined on the absolute Galois group G = Gal$ {\overline {\mathbb Q}} / {\mathbb Q} $. We prove that any compact, closed to conjugation subset of ? is the pseudo‐orbit of a suitable element of $ \widetilde{\overline{\mathbb{Q}}} $. We also prove that the topological closure of any algebraic number field in $ \widetilde{\overline{\mathbb{Q}}} $ is of the form $\widetilde{\mathbb{Q}[x]}$ with x in $ \widetilde{\overline{\mathbb{Q}}} $.     

Effects of UV photon irradiation on SiOx (0 < x < 2) structural properties

Thin films of a-SiO_x (0 < x < 2) were prepared by reactive r.f. magnetron sputtering from a polycrystalline-silicon target in an Ar/O₂ gas mixture. The oxygen partial pressure in the deposition chamber was varied so as to obtain films with different values of x. The plasma was monitored, during depositions, by optical emission spectroscopy (OES) system. Energy dispersive X-ray (EDX) measurements and infra-red (IR) spectroscopy were used to study the compositional and structural properties of the deposited layers.Structural modifications of SiO_x thin films have been induced by UV photons’ bombardment (wavelength of 248 nm) using a pulsed laser. IR spectroscopy and X-ray photoemission spectroscopy (XPS) were used to investigate the structural changes as a function of x value and incident energy. SiO_x phase separation by spinodal decomposition was revealed. The IR peak position shifted towards high wavenumber values when the laser energy is increased. Values corresponding to the SiO₂ material (only Si⁴⁺) have been found for laser irradiated samples, independently on the original x value. The phase separation process has a threshold energy that is in agreement with theoretical values calculated for the dissociation energy of the investigated material.For high values of the laser energy, crystalline silicon embedded in oxygen-rich silicon oxide was revealed by Raman spectroscopy.     

Detection of aniline at boron-doped diamond electrodes with cathodic stripping voltammetry

Boron-doped diamond (BDD) electrodes were used to investigate the possibility of detecting aniline by linear-sweep cathodic stripping voltammetry. It was found that the dimeric species (p-aminodiphenylamine and benzidine) formed by anodic oxidation of aniline during the accumulation period are involved in electrochemically reversible redox processes and, in acidic media, the shape of the stripping voltammetric response is suitable for aniline detection in the micromolar concentration range. The low background current of conductive diamond is an advantage compared to other electrode materials and allows a detection limit of 1 μM. Weak adsorption properties and the extreme electrochemical stability are additional advantages of BDD and it was found that, even after long-time measurements, the electrode surface can regain its initial activity by an anodic polarization in the potential region of water decomposition.     

Host-guest chemistry of the chromium-wheel complex [Cr8F8(tBuCO2)16]: prediction of inclusion capabilities by using an electrostatic potential distribution determined by modeling synchrotron X-ray structure factors at 16 K

The structure and detailed electron density distribution (EDD) of the large octanuclear chromium-wheel host complex [Cr8F8(tBuCO2)16] (1) has been determined from synchrotron X-ray structure factors collected at 16(5) K. The complex has a central cavity with a minimum entry distance between carbon atoms of the pivalate methyl groups (pivalic acid = tBuCO2H) of 4.027(4) A on one side of the molecule and 7.273(4) A on the other. The screened side of the molecule can be "opened" by rotation of methyl groups to create a strained host structure, which is compensated for by improved host-guest and host-solvent interaction. The EDD of the 272-atom complex (1144 e-) was determined by multipole modeling based on the experimental structure factors. 3d orbital populations on the Cr atoms and topological analysis of the EDD show that the covalent part of the metal-ligand interactions consists mainly of sigma donation from the ligands, but that overall the interactions are predominantly electrostatic. The electrostatic potential (EP) has been calculated from the experimental EDD. Knowledge of the geometry of the naked complex 1 as well as the EP in the central cavity of this molecule allows us to deduce which characteristic properties guest molecules must have to be accepted into the void. To probe these predictions, a series of complexes of 1 with different guest inclusions were synthesized (2 = 1 + N,N'-dimethylformamide (DMF), 3 = 1 + N,N'-dimethylacetamide (DMA), 4 = 1 + DMA + DMF, 5 = 1 + 2CH3CN), and their structures were examined by using X-ray diffraction data measured at 120(1) K. Results of these studies indicate that in the crystalline state, the optimal guest molecule should be linear and possess a permanent dipole. Attempts to crystallize the host complex with cations incorporated into the cavity were fruitless, although electrospray ionization mass spectrometry showed that a [1 + potassium]+ entity pre-exists in solution and can be transferred intact into the gas phase.     

Correlation between Small-Angle X-ray Scattering spectra and apparent diffusion coefficients in the study of structure and interaction of sodium taurodeoxycholate micelles

Small-Angle X-ray Scattering (SAXS) and Dynamic Light Scattering (DLS) measurements were carried out on aqueous micellar solutions of the ionic biological detergent sodium taurodeoxycholate (NaTDC). Apparent diffusion coefficients (D(app)) and SAXS spectra of NaTDC 0.1 M solutions at different ionic strengths (0.1-0.3 M NaCl) were reported. A comparative analysis of SAXS spectra and D(app) data was performed to infer information on particle structure and interaction potential. Uniform particles with a spherical, an oblate, and a prolate symmetry were used to model the micelles in the data interpretation. A hard-core interaction shell of suitable thickness and a screened Coulomb potential of the electric double layer (EDL potential) were alternatively used to represent the long-range repulsive tail of the interaction potential. The Percus Yevick and the Rescaled Mean Spherical Approximation were applied. To compare the data of the two techniques, for each sample, a D(app) was calculated from the SAXS best-fitting geometrical parameters and interparticle structure factor of the micelles. Hence, a fitting procedure involving both the scattering and D(app) data was performed. The interpretation of SAXS spectra does not allow the discrimination between the oblate and the prolate symmetries of the aggregates. On the other hand, the comparison of calculated and experimental D(app) values indicates that the prolate ellipsoid is better suited to represent the micelle shape. Moreover, the agreement between calculated and experimental D(app) values is sensitively better at the lowest NaCl concentration when the EDL potential is used. A rodlike micellar growth and a progressive screening of the electrostatic interactions is testified by the trends of best-fitting parameters as a function of the added electrolyte.     

Micro- and nano-mechanical characterization of polyamide 11 and its composites containing cellulose nanofibers

Nanocomposites from polyamide 11 and dried cellulose nanofibers (CNs), 16–30 nm in thickness and 50–400 nm in length, were prepared via direct melt mixing and their micro- and nano-mechanical properties were studied. (PF) QNM (Quantitative Nanomechanical Mapping) method was used to map nanomechanical properties at the surface of polyamide 11 and nanocomposites. This new AFM method emphasized both the increased modulus in nanocomposites as compared to the matrix and the microstructure on different levels in polyamide 11 and its nanocomposites. PF QNM showed that their crystalline structure consists of bundles of lamellar stacks, 200–350 nm in width and 20–40 nm wide lamellar stacks. Moreover, PF QNM study emphasized higher structural order in nanocomposites with 3 and 5 wt.% CNs and lower in the nanocomposite with 8 wt.% CNs as compared to the reference. These observations were verified and are consistent with both crystallinity values determined by DSC and micro-mechanical test results. The oriented bundles of lamellar stacks, observed by PF QNM, could be considered as the main blocks determining high mechanical properties for the studied nanomaterials.     

Pd@SnO2 and SnO2@Pd Core@Shell Nanocomposite Sensors

Pd@SnO₂ and SnO₂@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO₂ shells (>150 m² g^?1) with very small SnO₂ crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO₂ matrix. Although similar by first sight, Pd@SnO₂ and SnO₂@Pd are significantly different in view of their structure with Pd inside or outside the SnO₂ shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H₂. Especially, the Pd@SnO₂ core@shell nanocomposite is unique and shows a fast response time (τ₉₀ < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO₂ nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed.     

Physical properties (thermal,thermomechanical, magnetic,and adhesive) of some smart orthodontic wires

Thermal, thermomechanical, and caloric properties of commercial orthodontic wires (produced by Natural Orthodontics Corp., USA) with cylindrical and rectangular geometry were studied. Depending on the applied forces, there were identified the range of elasticity, the elasticity–viscoelasticity coexistence domain and the domain in which a maximum force of 18 N is applied, for the orthodontic wires. When increasing the thickness of orthodontic wires, deformation decreases. The Controlled Force Module, in the tension mode, was used for the determination of the orthodontic wires elongation at application of the stretching forces from 0 to 13 N, at 35 °C, maintaining each static force value for 3 min. The increase in the cross-sectional area of the orthodontic wires disfavors the process of elongation of the sample, at the same applied static force. Using the Multi-Frequency–Strain–Stress modulus, in the tension mode, DMA cyclic heating–cooling measurements were performed. The measured physical quantities for orthodontic wires were Storage Modulus, Loss Modulus, Tanδ and Stiffness, at heating and cooling. Thus, the characteristic temperatures of the phase transitions (A_s, A_f, M_s, M_f), of all the studied orthodontic wires were identified. Also, the values of the elasticity modulus (Young’s Modulus) of the orthodontic wires were calculated at 35 °C. With the DSC Q200 device, using temperature-modulated differential scanning calorimetry method, a multi-step temperature variation program, was applied to a rectangular wire, in three stages (cooling–heating–cooling). Through the interpretation of heat fluxes (reversible, irreversible and total), the phase transitions in the formation of martensite, austenite, but also of the rombohedral phase (R-phase), were identified. Formations of austenite and martensite were also evidenced by the classical DSC method, but the classical DSC method also enabled the R-phase identification. The adherence of some food dyes on the orthodontic wires, as well as the modification of the surface roughness of the orthodontic wire after the deposition of the food dye, was also studied. By magnetic measurements, it was established that the orthodontic wires had paramagnetic properties at room temperature, and nitinol was a mixture of 49.2% austenite and 50.8% martensite.

     

Investigation of thermal stability, spectral, magnetic, and antimicrobial behavior for new complexes of Ni(II), Cu(II), and Zn(II) with a bismacrocyclic ligand

Novel complexes of type M₂LCl₄·nH₂O (M: Ni, n = 4; M: Cu, n = 2.5 and M: Zn, n = 1.5; L: ligand resulted from 1,3-phenylenediamine, 3,6-diazaoctane-1,8-diamine, and formaldehyde one-pot condensation) were synthesized and characterized. The ligand was also isolated and characterized. The complexes features have been assigned from microanalytical, electrospray ionization tandem mass spectrometry, IR, UV–vis, ¹H NMR, and EPR spectra as well as magnetic data at room temperature. Simultaneous thermogravimetric/dynamic scanning calorimetry/evolved gas analysis measurements were performed to evidence the nature of the gaseous products formed in each step. Processes as water elimination, fragmentation, and oxidative degradation of the organic ligand as well as chloride elimination were observed during the thermal decomposition. The final product of decomposition was metal(II) oxide except for copper complex where CuCl remained also in the oxide network. The complexes exhibited an improved antibacterial activity in comparison with the ligand concerning both planktonic as well as biofilm-embedded cells.     

Grain shape influence on semiconducting metal oxide based gas sensor performance: modeling versus experiment

A model for sensing with semiconducting metal oxide (SMOX)-based gas sensors was developed which takes the effect of the shape of the grains in the sensing layers into account. Its validity is limited to materials in which the grains of the SMOX sensing layer are large enough to have an undepleted bulk region (large grains). This means that in all experimental conditions, the SMOX properties ensure that the influence of surface phenomena is not extended to the whole grain. The model takes the surface chemistry and its impact on the electrical properties of the sensing material into consideration. In this way, it relates the sensor signal—defined as the relative change of the sensor’s conductance—directly to the concentration of the target gas and also exhibits meaningful chemical parameters, such as the type of reactive oxygen species, the reaction constants, and the concentration of adsorption sites. The validity of the model is confirmed experimentally by applying it to data gathered by measuring homemade sensors in relevant conditions.