Though the enhanced reactivity of the complexes is contrary to the common idea of the high inertness of iridium(iii) compounds it can be seen as a consequence of the interplay between the steric hindrance induced by the ligands and the strong preference of the iridium(iii) ion for octahedral geometry. This study demonstrates that the use of bulky ligands provides access to light-harvesting iridium(iii) complexes with required extent of lability which may be promising as photocatalysts and biologically active molecules.Copper subgroup metal ions in the +1 oxidation state are classical candidates for aggregation via non-covalent metal-metal interactions, which are supported by a number of bridging ligands. LGH447 manufacturer The bridging phosphines, soft donors with a relatively labile coordination to coinage metals, serve as convenient and essential components of the ligand environment that allow for efficient self-assembly of discrete polynuclear aggregates. Simultaneously, accessible and rich modification of the organic spacer of such P-donors has been used to generate many fascinating structures with attractive photoluminescent behavior. In this work we consider the development of di- and polynuclear complexes of M(i) (M = Cu, Ag, Au) and their photophysical properties, focusing on the effect of phosphine bridging ligands, their flexibility and denticity.Our simulations reveal that two enantiomeric catechins display a better disruptive effect on Aβ42 protofibril than their stereoisomer epicatechin. Unexpectedly, we find that catechins adopt both collapsed and extended states, while epicatechin populates only an extended state. Their different protofibril-disruptive effects are mostly attributed to the steric effect caused by the conformational differences.The first fluorinated lead vanadate selenite Pb2(V2O4F)(VO2)(SeO3)3 (PVOFS) was successfully synthesized via a mild hydrothermal method. This compound crystallizes in the chiral space group P212121 of the orthorhombic system and it is the first noncentrosymmetric structure in the PbII-VV-SeIV-O-F system. PVOFS is composed of five kinds of second-order Jahn-Teller susceptible asymmetric motifs, including three distinct types of vanadium-centered polyhedral units ([VO5F], [VO6] and [VO5]), [SeO3] pyramids and Pb2+ cations. It features a unique three-dimensional open framework structure displaying three types of tunnels (10-, 8- and 7-membered rings), which enriches the structural diversity for fluorinated vanadate selenite systems. Optical property studies revealed that PVOFS shows a second-harmonic generation response of 0.3 times that of the commercial KH2PO4 with phase matching behavior, a wide transparent region covering IR windows, an optical band gap of 2.35 eV, a high laser damage threshold of 61 times that of AgGaS2, and a large birefringence of 0.105 at 1064 nm. Theoretical calculations have been performed to clarify the correlation between the molecular structure and the optical properties of PVOFS.A bimodal-pore strategy was developed for preparation of the Pt3Co/C catalyst with active Pt3Co nanoparticles located around the mass transfer channels rather than inside them, which leads to ca. 29% higher mass transfer efficiency and a superior single-cell performance under an ultralow Pt loading.Hyperbranched, biodegradable PCL-based polymers are obtained through a random but invasive migration of an in situ generated carbene end group which is unmasked via the thermolysis of its precursor diazirine moiety. These hyperbranched cores are used as macroinitiators for 'grafting-from' polymerisation using controlled radical polymerisation to achieve amphiphilic copolymers which can subsequently be self-assembled into spherical core-shell micelles.Steric hindrance induced by thiophene molecules in predesigned precursors favors the exclusive formation of a three dimensional (3D) π-conjugated cage and quasi-cage like molecules instead of a porphyrinoid macrocycle. Herein we report the synthesis of a tetrapod 3D fully π-conjugated molecular cage using a simple acid catalysed reaction. The X-Ray crystallography analysis confirmed the tetrapod cage structure and intermediates, which resemble three-fourths or half of the cage structures.We propose a conceptual model that describes the in situ formation of androstenedione in agricultural soil from a phytosterol, β-sitosterol, released after crop harvest and soil fertiliser amendment. Based on the recorded agricultural practice at a spring barley field, β-sitosterol and androstenedione concentrations were modelled over the year. While decomposition of crop residues created low soil levels, the application of pig slurry led to an androstenedione soil concentration of 54 μg kg-1. The elevated soil concentration of androstenedione is not due to the introduction of the endocrine disruptor in the fertiliser, but a result of the addition of large concentrations of β-sitosterol as a natural precursor. The limited available data on β-sitosterol and androstenedione concentration in soil prohibited their accurate prediction by our model. However, the potential implication of endocrine-disrupting steroid hormones being formed in situ from currently little considered phytosterols justifies a conceptual description and further research.Pantothenate synthetase from Escherichia coli (PSE. coli) catalyzes the ATP-dependent condensation of (R)-pantoic acid and β-alanine to yield (R)-pantothenic acid (vitamin B5), the biosynthetic precursor to coenzyme A. Herein we show that besides the natural amine substrate β-alanine, the enzyme accepts a wide range of structurally diverse amines including 3-amino-2-fluoropropionic acid, 4-amino-2-hydroxybutyric acid, 4-amino-3-hydroxybutyric acid, and tryptamine for coupling to the native carboxylic acid substrate (R)-pantoic acid to give amide products with up to >99% conversion. The broad amine scope of PSE. coli enabled the efficient synthesis of pharmaceutically-relevant vitamin B5 antimetabolites with excellent isolated yield (up to 89%). This biocatalytic amide synthesis strategy may prove to be useful in the quest for new antimicrobials that target coenzyme A biosynthesis and utilisation.