Ammonium tetraphenylborate-naphthalene adsorbent for the preconcentration and trace determination of uranium in standard alloys and synthetic samples using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol by fourth-derivative spectrophotometry

A solid ion-pair material produced from ammonium tetraphenylborate (ATPB) and naphthalene has been used for the preconcentration of uranium from the large volume of its aqueous complex samples. Uranium reacts with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) to form a water insoluble, coloured complex. This complex is quantitatively retained on the ATPB-naphthalene adsorbent filled in a column in the pH range 7.0–9.5 and at a flow rate of 2 ml/min. The solid mass from the column is dissolved with 5 ml of dimethylformamide (DMF) and uranium is determined by fourth-derivative spectrophotometry. The calibration curve is linear over the concentration range of 0.13–15.0 g of uranium in 5 ml of the final DMF solution. Seven replicate determinations of 6 g of uranium gave a mean peak height (peak-to-peak signal between 592 nm and 582 nm) of 1.02 with a relative standard deviation of 0.95%. The sensitivity is 0.8419 (d⁴A/d⁴)/(g ml^–1) found from the slope of the calibration curve. The interference of a large number of anions and cations on the estimation of uranium has been studied and the method applied for the determination of uranium in coal fly ash, Zr-base alloy and some synthetic samples corresponding to standard alloys.     

Synthesis of 1-aryl-3H-[1,2,5]triazepino[5,4-a]benzimidazol-4(5H)-ones and quantum chemical investigation of the rotamers of the Boc-protected hydrazide key intermediate

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Mixing time of an unaligned Gibbs sampler on the square

The paper concerns a particular example of the Gibbs sampler and its mixing efficiency. Coordinates of a point are rerandomized in the unit square ${[0,1]}^2$ to approach a stationary distribution with density proportional to $exp(?A^2{(u?v)}^2)$ for $(u,v)\in {[0,1]}^2$ with some large parameter $A$.Diaconis conjectured the mixing time of this process to be $O\left(A^2\right)$ which we confirm in this paper. This improves on the currently known $O(exp\left(A^2\right))$ estimate.     

Studies of Nucleophilic Substitution Reactions of p‐Nitrophenyl Acetate with Some Dihydroxamate Ions in Cationic Micellar Media

Pseudo‐first‐order rate constants have been determined for the nucleophilic substitution reactions of p‐nitrophenyl acetate with oxalo, malono, and succinodihydroxamate ions (^?ONHC(O)(CH₂)_nC(O)NHO^?) in phosphate buffer (pH=7.9) at 27°C. The rate data of the reaction revealed that the nucleophilic reactivity sequence of these hydroxamate ions is generally ODHA>MDHA>SDHA. The k_obs value increases upon addition of cationic surfactants to the reaction medium which is typical behavior of micelle‐assisted bimolecular reactions. The pseudo‐phase ion exchange model has been successfully applied to determine binding constant.     

Biological responses to silicon and nitrogen-rich PVD silicon nitride coatings

Most structural bioceramics are comprised of metallic oxides such as alumina and zirconia. They are generally considered to be completely bioinert, but a non-oxide ceramic, silicon nitride, achieves equivalent levels of mechanical reliability while being bioactive. Silicon nitride can not only stimulate cellular proliferation but it is also antipathogenic with demonstrated efficacy against Gram-positive and Gram-negative bacteria, fungi, and viruses. In this work, three physical vapor deposition coatings with different Si:N ratios (silicon-rich, stoichiometric, and nitrogen-rich) were deposited on mirror-polished silica glass substrates. The coatings were characterized by spectroscopic and microscopic techniques and tested in vitro against E. coli and KUSA-A1 mesenchymal cells. Results showed that nitrogen-enriched Si_xN_y has a strong antibacterial effect against E. coli and contributes to cellular proliferation while silicon-enriched Si_xN_y stimulates the production of bone tissue, with higher indexes for mineralization and quality. These results suggest that Si_xN_y's biological properties can be optimized for specific applications by carefully tuning its surface chemistry.     

Incorporation of β-Alanine in Cu(II) ATCUN Peptide Complexes Increases ROS Levels,DNA Cleavage and Antiproliferative Activity**

Redox-active Cu(II) complexes are able to form reactive oxygen species (ROS) in the presence of oxygen and reducing agents. Recently, Faller et al. reported that ROS generation by Cu(II) ATCUN complexes is not as high as assumed for decades. High complex stability results in silencing of the Cu(II)/Cu(I) redox cycle and therefore leads to low ROS generation. In this work, we demonstrate that an exchange of the α-amino acid Gly with the β-amino acid β-Ala at position 2 (Gly2→β-Ala2) of the ATCUN motif reinstates ROS production (^•OH and H₂O₂). Potentiometry, cyclic voltammetry, EPR spectroscopy and DFT simulations were utilized to explain the increased ROS generation of these β-Ala2-containing ATCUN complexes. We also observed enhanced oxidative cleavage activity towards plasmid DNA for β-Ala2 compared to the Gly2 complexes. Modifications with positively charged Lys residues increased the DNA affinity through electrostatic interactions as determined by UV/VIS, fluorescence, and CD spectroscopy, and consequently led to a further increase in nuclease activity. A similar trend was observed regarding the cytotoxic activity of the complexes against several human cancer cell lines where β-Ala2 peptide complexes had lower IC₅₀ values compared to Gly2. The higher cytotoxicity could be attributed to an increased cellular uptake as determined by ICP-MS measurements.     

Use of surfactant in aniline polymerization with TiO2 to PANI-TiO2 for supercapacitor performance

Polyaniline sulphate salt titanium dioxide composite (PANI-H₂SO₄·TiO₂) was synthesized by chemical in situ polymerization of aniline in the presence of TiO₂. The effect of anionic surfactant (sodium lauryl sulphate) in this reaction was also assessed. During the polymerization reaction, sodium lauryl sulphate (SLS) is converted to dodecyl hydrogen sulphate (DHS) in the presence of acidic medium and gets doped onto polyaniline along with sulphuric acid dopant, i.e. formation of polyaniline-sulphate-dodecyl hydrogen sulphate-titanium dioxide composite (PANI-H₂SO₄-DHS·TiO₂). In the PANI-H₂SO₄-DHS·TiO₂ composite, the presence of DHS is confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and energy-dispersive X-ray analysis (EDAX) and TiO₂ is confirmed by XRD and EDAX results. In PANI-H₂SO₄-DHS·TiO₂ system, the nanoparticle of TiO₂ (10–20 nm) is uniformly embedded on nanofibres (20–60 nm) of PANI-H₂SO₄-DHS, and some part of PANI-H₂SO₄-DHS·TiO₂ forms core–shell morphology, wherein TiO₂ is in core and PANI-H₂SO₄-DHS in shell forms. Stability of PANI-H₂SO₄-DHS increases due to the incorporation of stable TiO₂. Utility of PANI-TiO₂ composite was carried out in supercapacitor cell system by performing cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopic techniques in 1 M H₂SO₄ solution. Very low values of solution resistance, charge transfer resistance and time constant are obtained between 0.2 and 0.6 V. Initial specific capacitance values for the cell carried out at low and high current densities are found to be 280 and 205 F g^?1, respectively, and after 1,700 charge–discharge cycles, its retention in the specific capacitance values is found to be the same (65–66 %) with coulombic efficiency of 98–100 %. A capacitor can work even at a high discharge rate. The efficiency of oxidizing and doping power increases with the use of a surfactant. Moreover, the use of a long chain surfactant dopant containing polyaniline as an electrode material plays an important role to increase the performance of the supercapacitor by allowing the electrolyte to easily enter and come out from PANI electrodes.     

The Random Average Process and Random Walk in a Space-Time Random Environment in One Dimension

We study space-time fluctuations around a characteristic line for a one-dimensional interacting system known as the random average process. The state of this system is a real-valued function on the integers. New values of the function are created by averaging previous values with random weights. The fluctuations analyzed occur on the scale n ^1/4, where n is the ratio of macroscopic and microscopic scales in the system. The limits of the fluctuations are described by a family of Gaussian processes. In cases of known product-form invariant distributions, this limit is a two-parameter process whose time marginals are fractional Brownian motions with Hurst parameter 1/4. Along the way we study the limits of quenched mean processes for a random walk in a space-time random environment. These limits also happen at scale n ^1/4 and are described by certain Gaussian processes that we identify. In particular, when we look at a backward quenched mean process, the limit process is the solution of a stochastic heat equation.     

Niche width and scale in organizational competition: A computational approach

In some organizational applications, the principle of allocation (PoA) and scale advantage (SA) oppose each other. While PoA implies that organizations with wide niches get punished, SA holds that large organizations gain an advantage because of scale efficiencies. The opposition occurs because many large organizations also possess wide niches. However, analyzing these theoretical mechanisms implies a possible trade-off between niche width and size: if both PoA and SA are strong, then organizations must be either focused or large to survive, resulting in a dual market structure, as proposed by the theory of resource partitioning. This article develops a computational model used to study this trade-off, and investigates the properties of organizational populations with low/high SA and low/high PoA. The model generates three expected core “corner” solutions: (1) the dominance of large organizations in the strong SA setting; (2) the proliferation of narrow-niche organizations in the strong PoA setting; and (3) a bifurcated or dual market structure if both SA and PoA are present. The model also allows us to identify circumstances under which narrow-niche (specialists) or wide-niche (generalists) organizations thrive. We also use the model to examine the claim that concentrated resource distributions are more likely to generate partitioned or bifurcated populations. We also investigate the consequences of environments comprised of ordered versus unordered positions.