Single electron tunneling rates in multijunction circuits

The rate of electron tunneling through normal metal tunnel junctions is calculated for the case of ultrasmall junction capacitances. The so-called Coulomb blockade of electron tunneling at low temperatures is shown to be strongly affected by the external electrical circuit. Under the common experimental condition of a low impedance environment the Coulomb blockade is suppressed for single tunnel junctions. However, a Coulomb gap structure emerges for junctions embedded in a high impedance environment. For a double junction setup a Coulomb blockade of tunneling arises even for low impedance environments due to the charge quantization on the metallic island between the junctions. An approach using circuit analysis is presented which allows to reduce the calculation of tunneling rates in multijunction circuits to those of a single junction in series with an effective capacitance. The range of validity of the socalled local rule and global rule rates is clarified. It is found that the tunneling rate tends towards the global rule rate as the number of junctions is increased. Some specific results are given for a one-dimensional array of tunnel junctions.     

Impedance studies of porous lanthanum-phosphate-bonded nickel electrodes in concentrated sodium hydroxide solution

The hydrogen evolution reaction (HER) was investigated on a lanthanum-phosphate-bonded nickel (LPBN) powder electrode in 30 wt.% NaOH at 70°C using ac impedance and steady-state polarization techniques. Circuits containing one or two constant-phase elements (CPEs) in parallel with a resistance and corresponding to fractal and porous electrode models were tested in order to interpret the ac impedance data. The experimental impedance spectra were well described by the porous electrode model and the circuit containing two CPEs. The results obtained from the ac impedance and steady-state measurements allowed the mechanism and kinetics of the HER to be evaluated. Comparison of these parameters with those obtained on the polycrystalline nickel electrode in 1 M alkaline solution at 25°C indicates that an increase in activity is principally due to an increase in the real surface area.     

Complexation of an acrylic resin by tertiary amines: synthesis and characterisation of new binders for antifouling paints

Antifouling coatings are the most reliable way to prevent biofouling of immersed surfaces. As concerning the high toxicity of organotin paints, the tendency is the development of coatings, which do not present environmental risks. In this work, we prepare binders from modification of acrylic copolymers containing free carboxylic acid groups. Biocides chosen are tertiary ammonium salts; alkyl chain substituents with different length are considered. The chemical modifications of resins are carried out via a single step reaction. Modification extents are monitored through proton nuclear magnetic resonance and thermogravimetric analysis and the modified resins are characterised by Fourier transform infrared spectroscopy. The glass transition temperature of the acrylate systems is assessed by dynamical mechanical analysis (pin point method) and compared with data obtained by differential scanning calorimetry. The erosion and antifouling properties of the binders are followed during an exposure to marine environment by a visual observation.     

Ferrocene incorporating host-guest dyads with electrochemically controlled three-pole hydrogen bonding properties

We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH₂Cl₂ for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states.     

Biosynthesis of conjugatable saccharidic moieties of GM2 and GM3 gangliosides by engineered E. coli

Oligosaccharidic moieties of GM(2) and GM(3) gangliosides bearing an allyl or a propargyl aglycon, are efficiently biosynthesized on the gram scale by growing metabolically engineered Escherichia coli cells in the presence of the corresponding lactoside acceptors and sialic acid.     

(2, 1)-Separating systems beyond the probabilistic bound

Building on previous results of Xing, we give new lower bounds on the rate of linear intersecting codes over large alphabets. The proof is constructive, and uses algebraic geometry (although nothing beyond the basic theory of linear systems on curves). Then, using these new bounds within a concatenation argument, we construct binary (2,1)-separating systems of asymptotic rate exceeding the one given by the probabilistic method, which was the best lower bound available up to now. This answers (negatively) the question of whether this probabilistic bound was exact, which has remained open for more than 30 years.     

Aloe djiboutiensis: Antioxidant Activity,Molecular Networking-Based Approach and In Vivo Toxicity of This Endemic Species in Djibouti

For the first time, the study of the antioxidant activity, the characterization of the phytoconstituants, and the evaluation of in vitro and in vivo toxicity of A. djiboutiensis leave and latex are performed. The antioxidant activity of both latex (ADL) and the methanolic extract of leaves (ADM) is determined using 1-diphenyl-2-picrylhydrazyl (DPPH), 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulphonic acid (ABTS) scavenging radical methods and ferric reducing/antioxidant power (FRAP) assay. The phytochemical study of latex is done using Liquid Chromatography-Mass Spectrometry (LC-MS/MS) and a molecular networking-based approach. The evaluation of in vivo toxicity is performed on mice by oral gavage with a suspension of ADL. Our results show that weak antioxidant activity of ADL and ADM in opposition to their high polyphenol, 83.01 mg and 46.4 mg expressed in gallic acid equivalent (GAE)/g of dry weight (DW), respectively, and flavonoid contents 13.12 mg and 4.25 mg expressed in quercetin equivalent (QE)/g dry weight (DW), respectively. Using the Global Natural Products Social Molecular Networking (GNPS) website, nine (9) anthraquinones derivatives, ten (10) chromones derivatives, two (2) flavonols/ chromones isomers are annotated in the molecular network. The treated mice do not display abnormalities in their general physical appearance and biochemistry parameters, compared to the controls. Only glucose and calcium levels are slightly higher in male treated mice compared to the vehicles.     

Two‐Photon‐Induced Fluorescence in New π‐Expanded Diketopyrrolopyrroles

Structurally unique π‐expanded diketopyrrolopyrroles (EDPP) were designed and synthesized. Strategic placement of a fluorene scaffold at the periphery of a diketopyrrolopyrrole through tandem Friedel–Crafts‐dehydration reactions resulted in dyes with supreme solubility. The structure of the dyes was confirmed by X‐ray crystallography verifying a nearly flattened arrangement of the ten fused rings. Despite the extended ring system, the dye still preserved good solubility and was further functionalized by using Pd‐catalyzed coupling reactions, such as the Buchwald–Hartwig amination. Photophysical studies of these new functional dyes revealed that they possess enhanced properties when compared with expanded DPPs in terms of two‐photon absorption cross‐section. It is further demonstrated that in addition to the initial diacetals, the final electrophilic cyclization step can also be applied to diketones. By placing two amine groups at peripheral positions of the resulting dyes, values of two‐photon absorption cross‐section on the level of 2000 GM around 1000 nm were achieved, which in combination with high fluorescence quantum yield (Φ_fl), generated a two‐photon brightness of approximately 1600 GM. These characteristics in combination with strong red emission (665 nm) make these new π‐expanded diketopyrrolopyrroles of major promise as two‐photon dyes for bioimaging applications. Finally, the corresponding N‐alkylated DPPs displayed a solid‐state fluorescence.