Inside Back Cover: Prolinyl Nucleotides Drive Enzyme-Free Genetic Copying of RNA (Angew. Chem. Int. Ed. 41/2023)

Proline is one of the proteinogenic amino acids. It is found in all kingdoms of life. It also has remarkable activity as an organocatalyst and is of structural importance in many folded polypeptides. Here, we show that prolinyl nucleotides with a phosphoramidate linkage are active building blocks in enzyme- and ribozyme-free copying of RNA in the presence of monosubstituted imidazoles as organocatalysts. Both dinucleotides and mononucleotides are incorporated at the terminus of RNA primers in aqueous buffer, as instructed by the template sequence, in up to eight consecutive extension steps. Our results show that condensation products of amino acids and ribonucleotides can act like nucleoside triphosphates in media devoid of enzymes or ribozymes. Prolinyl nucleotides are metastable building blocks, readily activated by catalysts, helping to explain why the combination of α-amino acids and nucleic acids was selected in molecular evolution.     

A new method to generate spin-orbit coupled potential energy surfaces: effective relativistic coupling by asymptotic representation

A new method has been developed to generate fully coupled potential energy surfaces including derivative and spin-orbit coupling. The method is based on an asymptotic (atomic) representation of the molecular fine structure states and a corresponding diabatization. The effective relativistic coupling is described by a constant spin-orbit coupling matrix and the geometry dependence of the coupling is accounted for by the diabatization. This approach is very efficient, particularly for certain systems containing a very heavy atom, and yields consistent results throughout nuclear configuration space. A first application to a diatomic system is presented as proof of principle and is compared to accurate ab initio calculations. However, the method is widely applicable to general polyatomic systems in full dimensionality, containing several relativistic atoms and treating higher order relativistic couplings as well.     

Quantum theory of light and noise polarization in nonlinear optics

We present a consistent quantum theory of the electromagnetic field in nonlinearly responding causal media, with special emphasis on Chi(2) media. Starting from QED in linearly responding causal media, we develop a method to construct the cubic Hamiltonian expressed in terms of the complex nonlinear susceptibility in a quantum mechanically consistent way. In particular, we show that the method yields the nonlinear noise polarization, which together with the linear one is responsible for intrinsic quantum decoherence.     

Optical modes in semiconductor microtube ring resonators

We demonstrate optical modes in InGaAs/GaAs microtubes acting as optical ring resonators. Self-supporting microtubes were fabricated by optical lithography and wet-etching processes utilizing the self-rolling mechanism of strained bilayers. The optical modes were probed by the photoluminescence of InAs quantum dots embedded in the tube's wall. In this novel microtube ring resonator we find a spectrum of sharp modes. They are in very good agreement with the theoretical results for a closed thin dielectric waveguide.