PtII-Catalyzed Hydroxylation of Terminal Aliphatic C(sp3)−H Bonds with Molecular Oxygen

The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing Pt^IV with a more economically viable oxidant, particularly O₂. We report the potential of employing FeCl₂ as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O₂ in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O₂ in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt⁰ was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N₂ in the gaseous atmosphere. Finally, stability tests revealed the involvement of Pt^II and FeCl₂ in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O₂ is presented.     

Catalytic Adventures in Space and Time Using High Energy X-rays

Very high energy X-rays (ca. >40 keV) have long offered great promise in providing great insight into the inner workings of catalysts; insights that may complement the battery of techniques available to researchers in catalysis either in the laboratory or at more conventional X-ray wavelengths. This contribution aims to critically assess the diverse possibilities now available in the high energy domain as a result of the maturation of third generation synchrotron facilities and to look forward to the potential that forthcoming developments in synchrotron source technology may offer the world of catalysis in the near future.     

Designing and using professional development resources for inquiry-based learning

This paper describes an attempt to design, analyse and refine professional development (PD) resources that encourage the implementation of inquiry-based learning (IBL). We describe the iterative development of the resources in England with over 100 mathematics teachers from secondary, tertiary and adult education and then analyse the impact these resources had on teachers’ beliefs and practices and the issues arising. This evaluation revealed that teachers had moved away from transmission-based orientations, encouraged by the use of less structured tasks and sample lesson plans, but some found it difficult to adopt IBL pedagogies. The most significant issues for teachers may be summarised as: confusing IBL with ‘discovery’ learning; developing and managing collaborative cultures within the classroom; and planning lessons that adapt to the emerging needs of learners.     

Fractional Tikhonov regularization for linear discrete ill-posed problems

Tikhonov regularization is one of the most popular methods for solving linear systems of equations or linear least-squares problems with a severely ill-conditioned matrix A. This method replaces the given problem by a penalized least-squares problem. The present paper discusses measuring the residual error (discrepancy) in Tikhonov regularization with a seminorm that uses a fractional power of the Moore-Penrose pseudoinverse of AA ^T as weighting matrix. Properties of this regularization method are discussed. Numerical examples illustrate that the proposed scheme for a suitable fractional power may give approximate solutions of higher quality than standard Tikhonov regularization.     

Comparison between 2-hydroxypropyl-��-cyclodextrin and 2-hydroxypropyl-��-cyclodextrin for inclusion complex formation with danazol

Complexation in solution between danazol and two different cyclodextrins [2-hydroxypropyl-??-cyclodextrin (HP-??-CD) and 2-hydroxypropyl-??-cyclodextrin (HP-??-CD)] was studied using phase solubility analysis, and one- and two-dimensional ¹H-NMR. The increase of danazol solubility in the aqueous cyclodextrin solutions showed a linear relationship (A_L profile). The apparent stability constant, K _1:1, of each complex was calculated and found to be 51.7 × 10³ and 7.3 × 10³ M^?1 for danazol?CHP-??-CD and danazol?CHP-??-CD, respectively. ¹H-NMR spectroscopic analysis of varying ratios of danazol and the different cyclodextrins in a mixture of EtOD?CD₂O confirmed the 1:1 stoichiometry. Cross-peaks, from 2D ROESY ¹H-NMR spectra, between protons of danazol and H3?? and H5??of cyclodextrins, which stay inside the cyclodextrin cavity, proved the formation of an inclusion complex between danazol and the cyclodextrins. For HP-??-CD, the inclusion complex is formed by entrance of the isooxazole and the A rings of danazol in the cyclodextrin cavity. For HP-??-CD, two different inclusion structures may exist simultaneously in solution: one with the isooxazole and A ring in the cavity and the other with the C and D ring inside the cavity. DLS showed that self-aggregation of the CD??s was absent in the danazol HP-??-CD system up to a CD concentration of 10% and in the danazol HP-??-CD system up to a CD concentration of 5%.     

Disentangling the Information in Species Interaction Networks

Shannon’s entropy measure is a popular means for quantifying ecological diversity. We explore how one can use information-theoretic measures (that are often called indices in ecology) on joint ensembles to study the diversity of species interaction networks. We leverage the little-known balance equation to decompose the network information into three components describing the species abundance, specificity, and redundancy. This balance reveals that there exists a fundamental trade-off between these components. The decomposition can be straightforwardly extended to analyse networks through time as well as space, leading to the corresponding notions for alpha, beta, and gamma diversity. Our work aims to provide an accessible introduction for ecologists. To this end, we illustrate the interpretation of the components on numerous real networks. The corresponding code is made available to the community in the specialised Julia package EcologicalNetworks.jl.