Exhaustive computational search of ionic-charge clusters that mediate interactions between mammalian cytochrome P450 (CYP) and P450-oxidoreductase (POR) proteins

In this work, a model for the interaction between CYP2B4 and the FMN domain of rat P450-oxidoreductase is built using as template the structure of a bacterial redox complex. Amino acid residues identified in the literature as cytochrome P450 (CYP)–redox partner interfacial residues map to the interface in our model. Our model supports the view that the bacterial template represents a specific electron transfer complex and moreover provides a structural framework for explaining previous experimental data.We have used our model in an exhaustive search for complementary pairs of mammalian CYP and P450-oxidoreductase (POR) charge clusters. We quantitatively show that among the previously defined basic clusters, the 433K–434R cluster is the most dominant (32.3% of interactions) and among the acidic clusters, the 207D–208D–209D cluster is the most dominant (29%). Our analysis also reveals the previously not described basic cluster 343R–345K (16.1% of interactions) and 373K (3.2%) and the acidic clusters 113D–115E–116E (25.8%), 92E–93E (12.9%), 101D (3.2%) and 179E (3.2%).Cluster pairings among the previously defined charge clusters include the pairing of cluster 421K–422R to cluster 207D–208D–209D. Moreover, 433K–434R and 207D–208D–209D, respectively the dominant positively and negatively charged clusters, are uncorrelated. Instead our analysis suggests that the newly identified cluster 113D–115E–116E is the main partner of the 433K–434R cluster while the newly described cluster 343R–345K is correlated to the cluster 207D–208D–209D.     

Quartz crystal microbalance simulation of the directionality of Si etching in CF4 glow discharges

Two quartz crystal microbalances have been mounted in a planar rf discharge system in such a way that the potential of the microbalances with respect to the glow discharge can be varied. This apparatus allows a rapid simulation of the etching directionality that can be expected in real pattern transfer situations in that operating one microbalance at ground and one at a negative potential gives a measure of the sidewall and vertical etch rates, respectively. The voltage threshold for ion-assisted etching has been determined to be 20 V which is the approximate value of the plasma potential in this asymmetric system.     

On the Number of 5‐Cycles in a Tournament

We find a formula for the number of directed 5‐cycles in a tournament in terms of its edge scores and use the formula to find upper and lower bounds on the number of 5‐cycles in any n‐tournament. In particular, we show that the maximum number of 5‐cycles is asymptotically equal to , the expected number 5‐cycles in a random tournament (), with equality (up to order of magnitude) for almost all tournaments.     

Sortin1-hypersensitive mutants link vacuolar-trafficking defects and flavonoid metabolism in Arabidopsis vegetative tissues

Sortin1 is a chemical genetic-hit molecule that causes specific mislocalization of plant and yeast-soluble and membrane vacuolar markers. To better understand its mode of action, we designed a Sortin1-hypersensitive screen and identified several Sortin1-hypersensitive and flavonoid-defective mutants. Mechanistically, Sortin1 mimics the effect of the glutathione inhibitor buthionine sulfoximine and alters the vacuolar accumulation of flavonoids, likely blocking their transport through vacuole-localized ABC transporters. Structure-activity relationship studies conducted in Arabidopsis revealed the structural requirements for Sortin1 bioactivity and demonstrated that overlapping Sortin1 substructures can be used to discriminate between vacuolar-flavonoid accumulations and vacuolar-biogenesis defects. We conclude that Sortin1 is a valuable probe for dissecting novel links among flavonoid transport, vacuolar integrity, and the trafficking of vacuolar targeted cargoes in Arabidopsis.     

Biomimetic mineralisation of polymeric scaffolds using a combined soaking approach: adaptation with various mineral salts

Biomimetic strategies which utilise hydrogels have been targeted due to favourable hydrogel characteristics such as the presentation of a large surface area for crystal nucleation within a structured yet responsive scaffold. Chitosan hydrogels were prepared and mineralised using a combined method which involves alternate soaking of the films with precursor solutions, followed by treatment with saturated mineral solution. This method has been shown to be effective for the synthesis of calcium carbonate-chitosan composite materials with tensile strength comparable to nacre. The ratio of organic to inorganic is readily controlled through the presoaking solution concentrations. The ubiquity of this method is shown here with respect to switching out both the anion (CaHPO(4)) and the cation (BaSO(4)). Cation doping is also readily achieved allowing formation of Mg-rich CaCO(3). Poly(acrylic acid) added to (Mg,Ca)CO(3)-chitosan systems induces the formation of two polymorphs (vaterite and calcite) which coexist within the composite material. The mineralised scaffolds were analysed by SEM and powder XRD. The successful mineralisation of chitosan templates with various inorganic compounds shows that this combined approach is widely applicable as a biomimetic approach.     

Singular Integral Operators with Carleman Shift and Discontinuous Coefficients in the Spaces H^{\omega}_0(\Gamma,\rho)

For the singular integral operators with Carleman shift, preserving or changing orientation, and piecewise continuous coefficients we prove the theorem on Fredholmness and obtain the formula for index in the generalized Hölder spaces defined by an arbitrary continuity modulus from the Bari-Stechkin class and some general weights on a closed or open finite Lyapunov curve .     

Spectroscopic and theoretical study of Cu(II), Zn(II), Ni(II), Co(II) and Cd(II) complexes of glyoxilic acid oxime

The paper presents a detailed experimental and theoretical study of five metal complexes of glyoxilic acid oxime (gaoH2), Cu(gaoH)2(H2O)2 (1), Zn(gaoH)2(H2O)2 (2), Co(gaoH)2(H2O)2 (3), Ni(gaoH)2(H2O)2 (4) and [Cd(gaoH)2(H2O)2].H2O (5). The electronic and vibrational spectra were measured and discussed as to the most sensitive to the M-L binding bands. Two different types of coordination were considered for gaoH- ligand: bidentate through the carboxylic oxygen and oxime nitrogen in 1-4 and mixed bidentate and bridging through the COO group in 5. It is shown that the spectral behavior of the nu(COO) modes can be used to predict bridging ligand coordination. DFT(B3LYP/6-31++G(d,p)) calculations on model compounds: neutral, anionic and radical forms of gao and Cu(gaoH)2, have been carried out to correlate geometries, electronic and vibrational structures. The results obtained were used to assist the electronic and vibrational analysis of the complexes studied. The effect of the metal-ligand interactions (electrostatic and covalent) on the geometry structure of the ligand was investigated.     

Weighted Hardy operators in the local generalized vanishing Morrey spaces

In this paper we study $p\rightarrow q$ -boundedness of the multi-dimensional Hardy type operators in the vanishing local generalized Morrey spaces $V\mathcal L ^{p,\varphi }_\mathrm{{loc}}(\mathbb R ^n,w)$ defined by an almost increasing function $\varphi (r)$ and radial type weight $w(|x|)$ . We obtain sufficient conditions, in terms of some integral inequalities imposed on $\varphi $ and $w$ , for such a boundedness. In the case where the function $\varphi (r)$ and the weight are power functions, these conditions are also necessary.     

Emission from the working and counter electrodes under co-reactant electrochemiluminescence conditions

We present a new approach to explore the potential-dependent multi-colour co-reactant electrochemiluminescence (ECL) from multiple luminophores. The potentials at both the working and counter electrodes, the current between these electrodes, and the emission over cyclic voltammetric scans were simultaneously measured for the ECL reaction of Ir(ppy)₃ and either [Ru(bpy)₃]²⁺ or [Ir(df-ppy)₂(ptb)]⁺, with tri-n-propylamine as the co-reactant. The counter electrode potential was monitored by adding a differential electrometer module to the potentiostat. Plotting the data against the applied working electrode potential and against time provided complementary depictions of their relationships. Photographs of the ECL at the surface of the two electrodes were taken to confirm the source of the emissions. This provided a new understanding of these multifaceted ECL systems, including the nature of the counter electrode potential and the possibility of eliciting ECL at this electrode, a mechanism-based rationalisation of the interactions of different metal-complex luminophores, and a previously unknown ECL pathway for the Ir(ppy)₃ complex at negative potentials that was observed even in the absence of the co-reactant.

Exploration of potential-dependent, multi-colour co-reactant electrochemiluminescence from multiple luminophores at the working and counter electrodes reveals new pathways to emission.