Self-Assembly Behavior and Application of Terphenyl-Cored Trimaltosides for Membrane-Protein Studies: Impact of Detergent Hydrophobic Group Geometry on Protein Stability

Amphipathic agents are widely used in various fields including biomedical sciences. Micelle-forming detergents are particularly useful for in vitro membrane-protein characterization. As many conventional detergents are limited in their ability to stabilize membrane proteins, it is necessary to develop novel detergents to facilitate membrane-protein research. In the current study, we developed novel trimaltoside detergents with an alkyl pendant-bearing terphenyl unit as a hydrophobic group, designated terphenyl-cored maltosides (TPMs). We found that the geometry of the detergent hydrophobic group substantially impacts detergent self-assembly behavior, as well as detergent efficacy for membrane-protein stabilization. TPM-Vs, with a bent terphenyl group, were superior to the linear counterparts (TPM-Ls) at stabilizing multiple membrane proteins. The favorable protein stabilization efficacy of these bent TPMs is likely associated with a binding mode with membrane proteins distinct from conventional detergents and facial amphiphiles. When compared to n-dodecyl-β-d -maltoside (DDM), most TPMs were superior or comparable to this gold standard detergent at stabilizing membrane proteins. Notably, TPM-L3 was particularly effective at stabilizing the human β₂ adrenergic receptor (β₂AR), a G-protein coupled receptor, and its complex with G_s protein. Thus, the current study not only provides novel detergent tools that are useful for membrane-protein study, but also suggests a critical role for detergent hydrophobic group geometry in governing detergent efficacy.     

Corrigendum to “Orbital stability for the Schrödinger operator involving inverse square potential” [J. Differential Equations 259 (2015) 4989–5016]

There is an corrigendum in the paper “Orbital stability for the Schrödinger operator involving inverse square potential”, Journal of Differential Equations 259 (2015) 4989–5016.     

A study of properties of adaptive quadratic grids for three-dimensional near-surface field computations

Curved geometries and the corresponding near-surface fields typically require a large number of linear computational elements. High-order numerical solvers have been primarily used with low-order meshes. There is a need for curved, high-order computational elements. Typical near-surface meshes consist of hexahedral and/or prismatic elements. The present work studies the employment of quadratic meshes that are relatively coarse for field simulations. Directionally quadratic high-order elements are proposed for the near-surface field regions. The quadratic meshes are compared with the conventional low-order ones in terms of accuracy and efficiency. The cases considered include closed surface volume calculations, as well as computation of gradients of several analytic fields. A special method of adaptive local quadratic meshes is proposed and evaluated. Truncation error analysis for quadratic grids yields comparison with the conventional linear hexahedral/prismatic meshes, which are subject to typical distortions such as stretching, skewness, and torsion.     

Induced secondary metabolites from the endophytic fungus Aspergillus versicolor through bacterial co-culture and OSMAC approaches

Two new cryptic 3,4-dihydronaphthalen-(2H)-1-one (1-tetralone) derivatives, aspvanicin A (1) and its epimer aspvanicin B (2), as well as several known cryptic metabolites (3–8), were obtained from the ethyl acetate extract of the co-culture of the endophytic fungus Aspergillus versicolor KU258497 with the bacterium Bacillus subtilis 168 trpC2 on solid rice medium. When A. versicolor was cultured axenically in liquid Wickerham medium supplemented with 3.5% DMSO, an additional three known secondary metabolites (9–11) were isolated that were lacking when the fungus was fermented on rice medium. The structures of the new compounds were elucidated using one- and two-dimensional NMR spectroscopy as well as HRESIMS. The relative and absolute configurations of 1 and 2 were determined by the combination of NMR and electronic circular dichroism (ECD) analysis aided by DFT conformational analysis and TDDFT-ECD calculations. The ECD calculations revealed that although the sign of the blue-shifted overlapping n-π¹ ECD transition follows the helicity rule of cyclic aryl ketones, the calculation of low-energy conformers and ECD spectra was necessary to determine the stereochemistry. All metabolites were assessed for their antibacterial and cytotoxic activities; one of the new diastereomers, compound 2, showed moderate cytotoxic activity against the mouse lymphoma cell line L5178Y.     

High‐Pressure Synthesis of a Nitrogen‐Rich Inclusion Compound ReN8⋅x N2 with Conjugated Polymeric Nitrogen Chains

A nitrogen‐rich compound, ReN₈?x N₂, was synthesized by a direct reaction between rhenium and nitrogen at high pressure and high temperature in a laser‐heated diamond anvil cell. Single‐crystal X‐ray diffraction revealed that the crystal structure, which is based on the ReN₈ framework, has rectangular‐shaped channels that accommodate nitrogen molecules. Thus, despite a very high synthesis pressure, exceeding 100 GPa, ReN₈?x N₂ is an inclusion compound. The amount of trapped nitrogen (x) depends on the synthesis conditions. The polydiazenediyl chains [?N=N?]_∞ that constitute the framework have not been previously observed in any compound. Ab initio calculations on ReN₈?x N₂ provide strong support for the experimental results and conclusions.     

HPLC study of the inhibiting effect of phosphate and bicarbonate buffers on the leaching pattern of dental resin composites

A high-performance liquid chromatographic method was applied to evaluate the effect of bicarbonate (NaHCO₃) and phosphate (NaH₂PO₄, Na₂HPO₄) buffers on monomer leachability of dental resin composites. Evetric was the restorative resin composite that was investigated in current study. Forty disk-shaped resin composite specimens (n?=?40) were immersed by means of a silk string in the following solutions: Distilled water (A), phosphate buffer (B), bicarbonate buffer (C), artificial saliva (D). After seven (7) and fourteen (14) days, the eluates were analyzed by means of High Performance Liquid Chromatography (HPLC). Subsequently, new specimens were fabricated and immersed in fresh solutions in which methanol 12% (v/v) was added. After seven and fourteen days of storage, the leaching of monomers was examined by means of HPLC, which was proved to be an effective tool to buffers demonstrate the inhibiting effect of phosphate and bicarbonate ions on the leaching pattern of dental resin composites.     

Investigation of Catalytic Chain Transfer Copolymerization of Methacrylates

Batch experiments were carried out to investigate the kinetics of catalytic chain transfer copolymerization of methyl methacrylate and n‐butyl methacrylate. The Predici® model developed to represent the system describes the numerous experimental data measured at high concentrations of Co(II ) catalyst, taking into account the chain‐length dependencies of termination, propagation and catalytic chain transfer. The constants for catalytic chain transfer are determined as 2.3 × 10⁴ for both methyl methacrylate and n‐butyl methacrylate from fitting the experimental data. Two inhibition mechanisms are shown to describe the decrease of the polymerization rate in the presence of catalyst equally well, with an unknown impurity dissolved in initiator introduced to explain experimental profiles measured at high initiator concentrations.

     

Robust regression credibility: The influence function approach

In classical credibility theory we assume that the vector of claims conditionally on has independent components with identical means. However, this assumption is sometimes unrealistic. To relax this condition Hachemeister (Hachemeister, C.A., 1975. Credibility for regression models with application to trend. In: Kahn, P. (Ed.), Credibility, Theory and Applications. Academic Press, New York) introduced regressors. The presence of large claims can perturb the credibility premium estimation. The lack of robustness of regression credibility estimators, as well as the fairness of tariff evaluation, led to the development of this paper. Our proposal is to apply robust statistics to the regression credibility estimation by using the robust influence function approach of M-estimators.     

Rare tetranuclear mixed-valent [Mn(II)2Mn(IV)2] clusters as building blocks for extended networks

We report the synthesis of a series of mixed valence Mn(II/IV) tetranuclear clusters [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(EtOH)(6)Br(2)]Br(2) (), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(H(2)O)(2)Cl(4)].2EtOH.H(2)O (.2EtOH.H(2)O), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(heedH(2))(2)](ClO(4))(4) (), [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(MeCN)(2)(H(2)O)(2)(bpy)(2)](ClO(4))(4) () and [Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(bpy)(2)Br(4)].2MeOH (.2MeOH). Clusters are constructed from the tripodal ligand N,N-bis(2-hydroxyethyl)ethylene diamine (heedH(2)) and represent rare examples of tetranuclear Mn clusters possessing the linear trans zig-zag topology, being the first Mn(II/IV) mixed-valent clusters of this type. The molecular clusters can then be used as building blocks in tandem with the (linear) linker dicyanamide ([N(CN)(2)](-), dca(-)) for the formation of a novel extended network {[Mn(II)(2)Mn(IV)(2)O(2)(heed)(2)(H(2)O)(2)(MeOH)(2)(dca)(2)]Br(2)}(n) (), which exhibits a rare form of the 2D herring bone topology.