Solvent-dependent moulding of porphyrin-based nanostructures: solid state, solution and on surface self-assembly

A novel porphyrin derivative 1∙Zn was synthesised in order to mimic the self-assembly properties of natural light-harvesting antennas and its self-assembly behaviour in solution and in solid state were studied by NMR and X-Ray spectroscopies. The self-assembly of this molecule was triggered in apolar solvents and studied in solution by UV-Vis spectroscopy, suggesting it is able to form slipped face-to-face aggregates, or J-aggregates. The nanoscopic and microscopic morphology of the aggregates was elucidated by atomic force microscopy, revealing the formation of extended two-dimensional structures

Manipulating electronic states at oxide interfaces using focused micro X-rays from standard lab-sources

Recently, x-ray illumination, using synchrotron radiation, has been used to manipulate defects, stimulate self-organization and to probe their structure. Here we explore a method of defect-engineering low-dimensional systems using focused laboratory-scale X-ray sources. We demonstrate an irreversible change in the conducting properties of the 2-dimensional electron gas at the interface between the complex oxide materials LaAlO3 and SrTiO3 by X-ray irradiation. The electrical resistance is monitored during exposure as the irradiated regions are driven into a high resistance state. Our results suggest attention shall be paid on electronic structure modification in X-ray spectroscopic studies and highlight large-area defect manipulation and direct device patterning as possible new fields of application for focused laboratory X-ray sources.Comment: 12 pages, 4 figure

New Insight into a Deceptively Simple Reaction: The Coordination of bpy to RuII-Carbonyl Precursors - The Central Role of thefac-[Ru(bpy)Cl(CO)3]+Intermediate and theChloride Rebound Mechanism

This work demonstrates how a careful reexamination of well-trodden fields can fill conceptual gaps that previously escaped full understanding. The coordination of 2,2'-bipyridine (bpy) to the known Ru(II)-chlorido-carbonyl precursors \u2013 the dinuclear [RuCl2(CO)3]2 (P1) and the polymeric [RuCl2(CO)2]n (P2) \u2013 has been investigated by several groups in the past, and a remarkably large number of ruthenium mono(bpy) carbonyls were identified and fully characterized. Many were investigated as catalysts or key intermediates for the photochemical, electrochemical, and photo-electrochemical reduction of CO2, and for the water\u2013gas shift reaction. Nevertheless, even though most \u2013 if not all \u2013 the reaction products are known already, a careful exam of the literature led us to believe that a convincing general scheme interconnecting them all was still missing and important questions remained unanswered. For this reason, we investigated the reactivity of two mononuclear Ru(II)-carbonyl-dmso precursors, trans,cis,cis-[RuCl2(CO)2(dmso-O)2] (P3) and fac-[RuCl2(CO)3(dmso-O)] (P4) \u2013 that can be considered as \u2018activated forms\u2019 of P2 and P1, respectively \u2013 towards the coordination of bpy. Compounds P3 and P4, allowed us to gain new mechanistic insight and a deeper level of understanding. In particular, we found that coordination of bpy to P4 (or P1) generates first the tricarbonyl cation fac-[Ru(bpy)Cl(CO)3]+.This key intermediate undergoes the facile and selective nucleophilic attack on the CO trans to Cl (by RO\u2013 in alcoholic solvents or OH\u2013 from adventitious water in other solvents), leading to all other species. We also demonstrated that Cl\u2013 \u2013 even when in large excess \u2013 is unable to replace a carbonyl on fac-[Ru(bpy)Cl(CO)3]+. However, the chloride set free from the precursor, competes efficiently with bpy for the coordination to Ru(II) (chloride rebound mechanism)

Exercise intervention for post-acute COVID-19 syndrome – do FITT-VP principles apply? A case study

The lack of standardisation of reporting exercise interventions hampers the development of best practice guidelines for long COVID patients. This case study on the effect of an exercise intervention in a long COVID patient applied the Consensus on Exercise Reporting Template (CERT) for reporting interventions. FITT-VP exercise prescription principles for long COVID rehabilitation are also suggested. A 58-year-old male, previously hospitalised for 14 days in the ward for the intensive care for the management of severe COVID-19 infection, joined an exercise rehabilitation programme. A medical history, anthropometric, biochemical, lung function, blood pressure, cardiorespiratory fitness and strength measures were all assessed before and after the eight week exercise intervention programme. Positive changes were found in all lung function test measures. Cardiorespiratory fitness, endurance capacity and muscle strength improved. However, the greatest improvements occurred in functional status, fatigue, dyspnoea and the state of depression levels. This case study suggested that in the absence of other instruments, the FITTVP principles may be used for long COVID patients, and CERT for reporting interventions, but these should be further researched

Heliophyllite: a discredited mineral species identical to ecdemite

Abstract. The type material for heliophyllite, preserved in the Swedish Museum of Natural History in Stockholm, was re-investigated through a combined EPMA (electron probe X-ray microanalysis), Raman, and X-ray powder diffraction (XRPD) and single-crystal study. EPMA chemical data, together with Raman and single-crystal structural studies, point to heliophyllite being identical to ecdemite. XRPD synchrotron data highlight the presence of a minor quantity of finely admixed finnemanite in the analyzed material, explaining the presence of some additional diffraction peaks, not indexable with the ecdemite unit cell, reported in the literature. The discreditation of heliophyllite has been approved by the IMA Commission on New Minerals and Mineral Names (proposal 19-H, 2019)

Developing HIV-1 Protease inhibitors through stereospecific reactions in protein crystals

Protease inhibitors are key components in the chemotherapy of HIV infection. However, the appearance of viral mutants routinely compromises their clinical efficacy, creating a constant need for new and more potent inhibitors. Recently, a new class of epoxide-based inhibitors of HIV-1 protease was investigated and the configuration of the epoxide carbons was demonstrated to play a crucial role in determining the binding affinity. Here we report the comparison between three crystal structures at near-atomic resolution of HIV-1 protease in complex with the epoxide-based inhibitor, revealing an in-situ epoxide ring opening triggered by a pH change in the mother solution of the crystal. Increased pH in the crystal allows a stereospecific nucleophile attack of an ammonia molecule onto an epoxide carbon, with formation of a new inhibitor containing amino-alcohol functions. The described experiments open a pathway for the development of new stereospecific protease inhibitors from a reactive lead compound

Redistribution reaction on a six-fold coordinated Sn(IV) atom and reactions towards axially unsymmetric substituted Sn(IV) porphyrins

Abstract Investigations of the Kocheshkov redistribution reaction were performed on the six fold coordinated tin(IV) atom using the axially coordinated Sn(IV) meso-tetra-phenylporphyrin system with axially trans di-chloro and trans di-acetylido substituted derivatives. The immobile four dentate porphyrin ligand enables the detailed investigation of these typically complex reaction systems on higher coordinated tin(IV) species. The thermally activated reaction displays an equilibrium. Further on, a series of axial unsymmetrically substituted Sn(IV) porphyrins are selectively synthesized and described

Borazino-doped polyphenylenes

The divergent synthesis of two series of borazino-doped polyphenylenes, in which one or more aryl units are replaced by borazine rings, is reported for the first time, taking advantage of the decarbonylative [4 + 2] Diels− Alder cycloaddition reaction between ethynyl and tetraphenylcyclopentadienone derivatives. Because of the possibility of functionalizing the borazine core with different groups on the aryl substituents at the N and B atoms of the borazino core, we have prepared borazino-doped polyphenylenes featuring different doping dosages and orientations. To achieve this, two molecular modules were prepared: a core and a branching unit. Depending on the chemical natures of the central aromatic module and the reactive group, each covalent combination of the modules yields one exclusive doping pattern. By means of this approach, three- and hexa-branched hybrid polyphenylenes featuring controlled orientations and dosages of the doping B3N3 rings have been prepared. Detailed photophysical investigations showed that as the doping dosage is increased, the strong luminescent signal is progressively reduced. This suggests that the presence of the B3N3 rings engages additional deactivation pathways, possibly involving excited states with an increasing charge-separated character that are restricted in the full-carbon analogues. Notably, a strong effect of the orientational doping on the fluorescence quantum yield was observed for those hybrid polyphenylene structures featuring low doping dosages. Finally, we showed that Cu-catalyzed 1,3-dipolar cycloaddition is also chemically compatible with the BN core, further endorsing the inorganic benzene as a versatile aromatic scaffold for engineering of molecular materials with tailored and exploitable optoelectronic properties

Simulation of Diffusion Time of Small Molecules in Protein Crystals

SummaryA simple model for evaluation of diffusion times of small molecule into protein crystals has been developed, which takes into account the physical and chemical properties both of protein crystal and the diffusing molecules. The model also includes consideration of binding and the binding affinity of a ligand to the protein. The model has been validated by simulation of experimental set-ups of several examples found in the literature. These experiments cover a wide range of situations: from small to relatively large diffusing molecules, crystals having low, medium, or high protein density, and different size. The reproduced experiments include ligand exchange in protein crystals by soaking techniques. Despite the simplifying assumptions of the model, theoretical and experimental data are in agreement with available data, with experimental diffusion times ranging from a few seconds to several hours. The method has been used successfully for planning intermediate cryotrapping experiments in maltodextrin phosphorylase crystals

Neutral 1,3,5-Triaza-7-phosphaadamantane-Ruthenium(II) Complexes as Precursors for the Preparation of Highly Water-Soluble Derivatives

The monodentate phosphane ligand 1,3,5-triaza-7-phosphaadamantane (PTA) imparts excellent water solubility to its complexes. We aimed to prepare precursors with one or more PTA coligands for solubility and one or more labile ligands for facile replacement by a linker. For this purpose, we investigated the reactivity of the neutral isomers trans- and cis-RuCl2(PTA)4 (1 and 2) towards 2,2\u2032-bipyridine (bpy), as a model chelating diimine linker. The new derivatives mer-[Ru(bpy)Cl(PTA)3]Cl (9) and fac-[Ru(bpy)Cl(PTA)3]Cl (10) were prepared and characterized. We also found that PTA reacts rapidly with cis,fac-RuCl2(dmso-O)(dmso-S)3 (11) and trans-RuCl2(dmso-S)4 (13) under mild conditions through the replacement of pairs of mutually trans dmso ligands with high selectivity, even when in stoichiometric defect. Thus, 11 affords cis,cis,trans-RuCl2(dmso-S)2(PTA)2 (12), whereas 13 gives 1. The two dmso ligands of 12 can be replaced selectively by chelating diimines such as bpy to afford the less symmetrical all-cis product cis,cis-Ru(bpy)Cl2(PTA)2 (16)