Darobactin B Stabilises a Lateral-Closed Conformation of the BAM Complex in E. coli Cells

The β-barrel assembly machinery (BAM complex) is essential for outer membrane protein (OMP) folding in Gram-negative bacteria, and represents a promising antimicrobial target. Several conformational states of BAM have been reported, but all have been obtained under conditions which lack the unique features and complexity of the outer membrane (OM). Here, we use Pulsed Electron-Electron Double Resonance (PELDOR, or DEER) spectroscopy distance measurements to interrogate the conformational ensemble of the BAM complex in E. coli cells. We show that BAM adopts a broad ensemble of conformations in the OM, while in the presence of the antibiotic darobactin B (DAR-B), BAM′s conformational equilibrium shifts to a restricted ensemble consistent with the lateral closed state. Our in-cell PELDOR findings are supported by new cryoEM structures of BAM in the presence and absence of DAR-B. This work demonstrates the utility of PELDOR to map conformational changes in BAM within its native cellular environment.     

Transition Metal Free Chemoselective Reduction of α,β‐Unsaturated Ketones to Saturated Ketones Using Tosyl Hydrazide as a Hydrogen Donor

An efficient, inexpensive and simple method for the reduction of various α,β‐unsaturated ketones to corresponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been reported. A variety of enones underwent reduction without forming undesirable side products. High chemoselectivity, broad functional group tolerance and good yields are the noteworthy features of this protocol.     

Oxidative Deselenization of Selenocysteine: Applications for Programmed Ligation at Serine

Despite the unique chemical properties of selenocysteine (Sec), ligation at Sec is an under‐utilized methodology for protein synthesis. We describe herein an unprecedented protocol for the conversion of Sec to serine (Ser) in a single, high‐yielding step. When coupled with ligation at Sec, this transformation provides a new approach to programmed ligations at Ser residues. This new reaction is compatible with a wide range of functionality, including the presence of unprotected amino acid side chains and appended glycans. The utility of the methodology is demonstrated in the rapid synthesis of complex glycopeptide fragments of the epithelial glycoproteins MUC5AC and MUC4 and through the total synthesis of the structured, cysteine (Cys)‐free protein eglin C.     

A New Method for the Syntiiesis of 1-Aryl Phthalazines

A simple versatile method for the conversion of 1 -aroyl-2-(substituted benzylidene)-hydrazines to 1-aryl-phthalazines using polyphosphate ester (PPE) is described.     

Influence of processing and clay type on nanostructure and stability of polypropylene–clay nanocomposites

Melt processing is a critical step in the manufacture of polymer articles and is even more critical when dealing with inhomogeneous polymer–clay nanocomposites systems. The chemical composition, and in particular the clay type and its organic modification, also plays a major contribution in determining the final properties and in particular the thermal and long-term oxidative stability of the resulting polymer nanocomposites. Proper selection and tuning of the process variable should, in principle, lead to improved characteristics of the fabricated product. With multiphase systems containing inorganic nanoclays, however, this is not straightforward and it is often the case that the process conditions are chosen initially to improve one or more desired properties at the expense of others.     

Quantum chemical DFT study of 4-azatricyclo [5.2.2.02,6] undecane-3,5,8-trione

Fourier-transform-Raman and infrared spectrum of 4-azatricyclo [5.2.2.0^2,6] undecane-3,5,8-trione were recorded and analyzed. The vibrational wavenumbers were examined theoretically using the Gaussian03 set of quantum chemistry codes, and the normal modes were assigned by potential energy distribution (PED) calculations. The first hyperpolarizability, predicted infrared intensities and Raman activities are reported. The calculated first hyperpolarizability is comparable with reported values of similar structures which makes this compound an attractive object for future studies of nonlinear optics. Optimized geometrical parameters of the compound are in agreement with similar reported structures. The red shift of the NH stretching wavenumber in the infrared spectrum from the computational wavenumber indicates the weakening of NH bond.     

Hamiltonian Structure and Dynamics of a Neutrally Buoyant Rigid Sphere Interacting with Thin Vortex Rings

In a previous paper, we presented a (noncanonical) Hamiltonian model for the dynamic interaction of a neutrally buoyant rigid body of arbitrary smooth shape with N closed vortex filaments of arbitrary smooth shape, modeled as curves, in an infinite ideal fluid in \mathbbR³\mathbb{R}^3. The setting of that paper was quite general, and the model abstract enough to make explicit conclusions regarding the dynamic behavior of such systems difficult to draw. In the present paper, we examine a restricted class of such systems for which the governing equations can be realized concretely and the dynamics examined computationally. We focus, in particular, on the case in which the body is a smooth sphere. The equations of motion and Hamiltonian structure of this dynamic system, which follow from the general model, are presented. Following this, we impose the constraint of axisymmetry on the entire system and look at the case in which the rings are all circles perpendicular to a common axis of symmetry passing through the center of the sphere. This axisymmetric model, in our idealized framework, is governed by ordinary differential equations and is, relatively speaking, easily integrated numerically. Finally, we present some plots of dynamic orbits of the axisymmetric system.