Surface structure and reactivity study of phosphotungstic acid-nitrogenated ormosils

Supramolecular interactions between nitrogenated groups in hybrid ormosils bearing phosphotungstate nanocatalyst were used to tune the photocatalytical activity of these class-II hybrid materials obtained through sol–gel chemistry. Surface chemistry and morphology of the materials was studied by scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and water contact angle measurements. The photocatalytic efficiency of these hybrid films, measured by the degradation of crystal violet over-layer deposited on ormosils films, is higher for ormosils bearing neutral, more polar and less H-bonding nitrile groups than those bearing alkylamine/alkylammonium functionalities, despite the lower W/Si atomic ratio on the surface and lower tungsten percentage of the pure nitrile bearing ormosils. Such higher surface reactivity of the nitrile bearing ormosils is due to weaker interaction with the phosphotungstate and the lower activity of amine bearing ormosils is attributed to the competition among reversible photochromism and photocatalysis pathways in these materials.     

Photoelectrochemical sensing of tannic acid based on the use of TiO<Subscript>2</Subscript> sensitized with 5-methylphenazinium methosulfate and carboxy-functionalized CdTe quantum dots

The article describes a method for determination of tannic acid in extracts of medicinal plants. Tannic acid (TA) is an antioxidant and has anticancer and antimicrobial properties. Titanium dioxide nanoparticles (TiO₂) were co-sensitized with 5-methylphenazinium methosulfate (PMS) and carboxy-functionalized cadmium telluride quantum dots (CdTe QDs), and immobilized on a fluorine-doped tin oxide electrode. The surface morphology and electrochemical properties of the modified electrode were investigated by scanning electron microscopy and amperometry, respectively. A composite consisting of TiO₂, PMS and CdTe QDs in a nafion film has a response to TA under LED light higher than that observed for each separate component. Under optimized experimental conditions and at an applied voltage of +0.4 V vs Ag/AgCl, the photoelectrochemical sensor has a linear response in the 0.2 to 200 μmol L^?1 TA concentration range and a detection limit of 60 nmol L^?1. The sensor was successfully applied to the determination of TA in spiked extracts from three medicinal plants, with recovery values between 98.3 and 103.9 %.

Open image in new window

Graphical abstract Schematic diagram for photoelectrochemical detection of tannic acid based on a fluorine doped tin oxide electrode modified with titanium oxide, 5-methylphenazinium methosulfate and carboxy-functionalized cadmium telluride quantum dots

     

Preliminary investigation of the interaction between the R2R3 DNA binding domain of the oncoprotein c-Myb and DNA fragments

The interaction between the R2R3 DNA binding domain of the oncoprotein c-Myb and oligodeoxynucleotides was investigated by ¹H-NMR spectroscopy and fluorescence anisotropy assays. Titration of 12 and 16 base-pair DNA fragments containing the TAACGGTC sequence with R2R3 revealed the presence of two complexed forms (in a 40/60 ratio): either two complexes or two conformations in slow exchange at the NMR chemical shift time scale. The largest variations of imino proton chemical shifts were observed for the imino proton of the base pairs 2, 3, 4 and 6 of the DNA sequence, suggesting a direct involvement of these base pairs in the interaction. Using fluorescence anisotropy measurements, a dissociation constant of 5.12 ± 1.49 nM for the specific DNA-R2R3 complex was found, whereas a value of 2.7 ± 0.1 μM was determined for the nonspecific complex. © 1996 John Wiley & Sons, Inc.     

Benzyl N‐[(Benzyloxy)methyl]carbamate: An Improved Aminomethylation Electrophile for the Synthesis of (Benzyloxy)carbonyl (Cbz)‐Protected Chiral β2‐Amino Acids

α‐Aminomethylation of (R)‐DIOZ‐alkylated (DIOZ=4‐isopropyl‐5,5‐diphenyloxazolidin‐2‐one) substrates is a key step in the asymmetric synthesis of β²‐amino acids, but it is unfortunately often accompanied by formation of transcarbamation by‐products. Aminomethylation was tested using a range of electrophiles, and the amount of by‐product formation was assessed in each case. Benzyl N‐[(benzyloxy)methyl]carbamate electrophile 3d is unable to form this by‐product due to its inherent benzyl substitution. Use of electrophile 3d showed an improved impurity profile in aminomethylation, thus leading to easier intermediate purification.     

Broadband second harmonic generation of an optical frequency comb produced by four-wave mixing in highly nonlinear fibers

We demonstrate broadband second harmonic generation of low-energy pulses produced by injecting two single-frequency lasers into a highly nonlinear fiber. Full nonlinear conversion of the corresponding spectra, consisting of broadband (∼200 nm) optical frequency combs at ∼1580 nm, were obtained by using conventional birefringence phase-matching in two BIBO crystals (2-mm and 100-μm long) with a normal incidence configuration. The crystals were not tilted and the pulses were not compressed. This broadband conversion results from the large phase-matching bandwidth of the nonlinear BIBO crystals at ∼1550 nm, but also seems to be a consequence of a fundamental comb with small spectral phase variation.     

Road traffic: A case study of flow and path-dependency in weighted directed networks

How much can we tell about flows through networks just from their topological properties? Whereas flow distributions of river basins, trees or cardiovascular systems come naturally to mind, more complex topologies are not so immediate, especially if the network is large and heterogeneously directed. Our study is motivated by the question of how the distribution of path-dependent trails in directed networks is correlated to the distribution of network flows. As an example we have studied the path-dependencies in closed trails in four metropolitan areas in England and the USA and computed their global and spatial correlations with measured traffic flows. We have found that the heterogeneous distribution of traffic intensity is mirrored by the distribution of agglomerate path-dependency and that high traffic roads are packed along corridors at short-to-medium trail lengths from the ensemble of nodes.     

Effect of pulse current on the electrodeposition of copper from choline chloride-ethylene glycol

Deep eutectic solvents (DESs) have been considered as alternatives to classic aqueous deposition baths used at room temperature. This work describes a preliminary study about the copper deposition process from a bath based on choline chloride/ethylene glycol deep eutectic solvents. The physical properties, such as viscosity and conductivity of the bath, are compared before and after the addition of CuCl₂?·?2H₂O. The process kinetics during copper deposition was investigated. By optimizing the concentration of metallic salts and operating temperature, deposits with compact surfaces and small grain size were obtained. However, the process has a very limited current efficiency. Pulse plating was applied to improve the mass transport and refine grain size. In this case, an important improvement was achieved. Current efficiency (CE) increased significantly compared to the results obtained in direct current. This proves that pulse plating can be used as an effective method to reduce deposition time and costs. Surface morphology of deposits was observed by scanning electron microscopy (SEM), and compositional analysis was quantified by energy-dispersive X-ray spectroscopy (EDXS).