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.     

Optimality of the quantified Ingham–Karamata theorem for operator semigroups with general resolvent growth

We prove that a general version of the quantified Ingham–Karamata theorem for $$C_0$$-semigroups is sharp under mild conditions on the resolvent growth, thus generalising the results contained in a recent paper by the same authors. It follows in particular that the well-known Batty–Duyckaerts theorem is optimal even for bounded $$C_0$$-semigroups whose generator has subpolynomial resolvent growth. Our proof is based on an elegant application of the open mapping theorem, which we complement by a crucial technical lemma allowing us to strengthen our earlier results.     

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.     

Error estimation in measuring strain fields with DIC on planar sheet metal specimens with a non-perpendicular camera alignment

The determination of strain fields based on displacement components obtained via 2D-DIC is subject to several errors that originate from various sources. In this contribution, we study the impact of a non-perpendicular camera alignment to a planar sheet metal specimen's surface. The errors are estimated in a numerical experiment. To this purpose, deformed images - that were obtained by imposing finite element (FE) displacement fields on an undeformed image - are numerically rotated for various Euler angles. It is shown that a 3D-DIC stereo configuration induces a substantial compensation for the introduced image-plane displacement gradients. However, higher strain accuracy and precision are obtained - up to the level of a perfect perpendicular alignment - in a proposed “rectified” 2D-DIC setup. This compensating technique gains benefit from both 2D-DIC (single camera view, basic amount of correlation runs, no cross-camera matching nor triangulation) and 3D-DIC (oblique angle compensation). Our conclusions are validated in a real experiment on SS304.