Spatiotemporal Propagation of a Minimal Catalytic RNA Network in GUV Protocells by Temperature Cycling and Phase Separation

Compartmentalization is key to many cellular processes and a critical bottleneck of any minimal life approach. In cells, a complex chemistry is responsible for bringing together or separating biomolecules at the right place at the right time. Lipids, nucleic acids and proteins self-organize, thereby creating boundaries, interfaces and specialized microenvironments. Exploiting reversible RNA-based liquid-liquid phase separation (LLPS) inside giant unilamellar vesicles (GUVs), we present an efficient system capable of propagating an RNA-based enzymatic reaction across a population of GUVs upon freezing-thawing (FT) temperature cycles. We report that compartmentalization in the condensed RNA-rich phase can accelerate such an enzymatic reaction. In the decondensed state, RNA substrates become homogeneously dispersed, enabling content exchange between vesicles during freeze-thawing. This work explores how a minimal reversible phase separation system in lipid vesicles could help to implement spatiotemporal control in cyclic processes, as required for minimal cells.     

NMR spectroscopy of poly(vinyl chloride) defects. 2. 1H and 13C NMR analysis of the terminal vinyl end group, 1,3-dichlorobutyl end group and chloromethyl branch

We have been able to obtain the ¹H NMR subspectra of most of the major saturated end groups in PVC. In order to assign the terminal vinyl (TV) group, CH₂CH-CHCl-, we synthesized and analyzed the symmetrical model compound 3,5-dichloro-1,6-heptadiene (4) containing a racemic (r) and a meso (m) isomer. They exhibit distinct NMR signals for the vinyl protons, which allowed us to subsequently assign the r diad and the previously unreported m diad terminal vinyl resonances present in very small amounts in commercial PVC. The study of the solvent induced chemical shifts of the vinyl protons in an experimental PVC sample containing an unusually high level of this end group allowed us to further assign it in terms of the terminal rr, rm, mm and mr triads.     

Dispersion Energy-Stabilized Boron and Phosphorus Lewis Pairs

An isostructural series of boron/phosphorus Lewis pairs was systematically investigated. The association constants of the Lewis pairs were determined at variable temperatures, enabling the extraction of thermodynamic parameters. The stabilization of the Lewis adduct increased with increasing size of the dispersion energy donor groups, although the donor and acceptor properties of the Lewis pairs remained largely unchanged. This data was utilized to challenge state-of-the-art quantum chemical methods, which finally led to an enhanced workflow for the determination of thermochemical properties of weakly bound Lewis pairs within an accuracy of 0.6 to 1.0 kcal mol⁻¹ for computed association free energies.     

A Dual-Metal-Catalyzed Sequential Cascade Reaction in an Engineered Protein Cage**

Herein, we describe the creation of an artificial protein cage housing a dual-metal-tagged guest protein that catalyzes a linear, two-step sequential cascade reaction. The guest protein consists of a fusion protein of HaloTag and monomeric rhizavidin. Inside the protein capsid, we established a ruthenium-catalyzed allylcarbamate deprotection reaction followed by a gold-catalyzed ring-closing hydroamination reaction that led to indoles and phenanthridines with an overall yield of up to 66 % in aqueous solutions. Furthermore, we show that the encapsulation stabilizes the metal catalysts against deactivation by air, proteins and cell lysate.     

Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene-Based Chiral Hydride Source

An enantioselective reduction of simple carbenium ions with cyclohexadienes containing a hydridic C−H bond at an asymmetrically substituted carbon atom is disclosed. The net reaction is a transfer hydrogenation of alkenes (styrenes) only employing chiral cyclohexadienes as dihydrogen surrogates. The trityl cation is used to initiate a Brønsted acid-promoted process, in which a delicate intermolecular capture of a carbenium-ion intermediate by the aforementioned chiral hydride source is enantioselectivity determining. Exclusively non-covalent interactions are rendering one of the transition states energetically more favored, giving the reduction products in good enantiomeric ratios. The computed reaction mechanism supports the present findings as well as previous results obtained from studies on other transfer-hydrogenation methods involving the cyclohexadiene platform.     

Practical Insights into the Impedance Response of Interdigitated Electrodes: Extraction of Relative Static Permittivity and Electrolytic Conductivity

This work aims to provide a detailed understanding of the challenges related to the computation of the relative static permittivity and electrolytic conductivity of a sample medium from its impedance response recorded with interdigitated electrode (IDE) geometries. Within the scope of the study, impedance data has been measured and evaluated for a total of nine sample media using two distinct IDE geometries. Particular emphasis is laid upon the compensation of parasitic influences affecting the impedance response. With the raw data supporting this study fully disclosed, the reader is offered the opportunity to comprehensively retrace the evaluation procedure proposed in the text.     

Pseudoelasticity of Shape Memory Alloys - a 1D Material Model and Finite Element Implementation

This contribution is concerned with the formulation of a 1D-constitutive model accounting for the pseudoelastic behavior of shape memory alloys. The stress-strain-relationship is idealized by a hysteresis both in the compression as in the tension loading range. It is characterized by an upper loading path, which is to be ascribed to the transformation of the lattice to a martensitic structure. Unloading the material, a lower path is described, because of the reverse transformation into austenitic lattice. The constitutive model is based on a switching criterion which serves as a potential function for the evolution of the internal state variables. The model distinguishes between local and global variables to describe the hysteresis effects for the compression and tension range. A strain driven algorithm which captures the complete nonlinear material behavior is presented. The boundary value problem is solved for a truss element applying the finite element method. A consistent linearization of the nonlinear equations is derived. Simple examples will demonstrate the applicability of the proposed model. For future developments the usage of shape memory alloys within civil engineering structures is aimed. The advantage of the material is the very good damping behavior and the potential to overcome great strains. Both properties are distinguished to be of engineering interest. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)