Extractability and Intracellular Localisation of Urea Cycle Enzym es from Rat Liver

Peer Reviewe

pi-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon

A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-πinteractions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm-1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices

Dibenzo[hi,st]ovalene as Highly Luminescent Nanographene: Efficient Synthesis via Photochemical Cyclodehydroiodination, Optoelectronic Properties, and Single-Molecule Spectroscopy

Dibenzo[hi,st]ovalene (DBOV), as a new nanographene, has demonstrated promising optical properties, such as red emission with a high fluorescence quantum yield of 79% and stimulated emission, as well as high thermal stability and photostability, which indicated its promise as a light-emitting and optical gain material. However, the previous synthetic routes required at least 12 steps. This obstructed access to different derivatives, e.g., to obtain crystals suitable for X-ray diffraction analysis and to tune the optoelectronic properties. Here, we report an efficient synthetic pathway to DBOV based on a sequential iodination-benzannulation of bi(naphthylphenyl)diyne, followed by photochemical cyclodehydroiodination (PCDHI). This protocol included a fused bischrysene as a key intermediate and furnished scalable amounts of meso-substituted DBOV derivatives with different substituents. DBOV with 2,6-dimethylphenyl groups could be used for single-crystal X-ray analysis, revealing the precise structure of the DBOV core. The optoelectronic properties of the DBOV derivatives were investigated by UV-vis absorption and fluorescence spectroscopy, cyclic voltammetry, and density functional theory calculations. Single-molecule spectroscopy at room and low temperatures provided novel insights into the photophysics of DBOV embedded in a polymer film. As a result of weak coupling of the optical transitions to the matrix, single-molecule emission spectra at 4.5 K showed narrow vibronic lines. The fluorescence autocorrelation function covering 9 orders of magnitude in time displayed high contrast photon antibunching and bunching, from which the fluorescence decay rate and the triplet population and depopulation rates could be retrieved. Remarkably, the intersystem crossing rate into the triplet state decreased by more than an order of magnitude at low temperature, demonstrating that temperature can be a crucial parameter to boost single photon emission of an aromatic hydrocarbon

Future challenges in colloid and interfacial science

This article deals with topics where I expect special future challenges, exemplifying these by experiments out of my own department. One area where I expect large progress also in view of many technical developments in the past concerns the understanding of the structure of fluid interfaces at the atomic level. It is shown by non-linear optical spectroscopies that the free water surface is ice-like and can be “liquefied” by ion adsorption. X-ray fluorescence from the interface demonstrates that ion binding is very specific which cannot be explained by existing theories. A second major area are nonequilibrium features, and one of the old and new ones here is nucleation and growth. This presentation concentrates on effects produced by ultrasound, a well-defined trigger of gas bubble formation. It exhibits high potential for chemistry at extreme conditions but with a reactor at normal conditions. It has special importance for treatment of surfaces that can be also manipulated via controlled surface energies. A third area will concern complex and smart systems with multiple functions in materials and biosciences. As next generation, I anticipate those with feedback control, and examples on this are self-repairing coatings