Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

Matrix Entries of Real Representations of the Groups O(3) and SO(3)

We indicate bases for spinor representations of the groups O(3), SO(3), and SU(2) in which the representation matrices are real-valued. The matrix entries in these bases are calculated. We describe the transformation of classical orthogonal harmonic polynomials in three-dimensional space by these matrix entries.     

Excitation of low-lying nuclear states by the ion line emission in femtosecond laser plasma

A scheme of nuclear excitation by the ionic X-ray lines in laser plasma using two femtosecond laser pulses is proposed. The first pulse produces plasma with a given degree of ionization, allowing the X-ray line energies of the target ions to be tuned to resonance with the nuclear transition, while the second pulse generates hot electrons that are necessary for X-ray generation.     

Phase Composition of Coatings Formed on Titanium in Borate Electrolyte by Microarch Oxidation

The effect of oxidation conditions, temperature and concentration of the electrolyte, and its transformation from the true to colloidal solution on the phase composition and electrical resistance of coatings was studied.     

Cu+(H2) and Na+(H2) adducts in exchanged ZSM-5 zeolites

Cu(I) ions in Cu-ZSM-5 form Cu+(H2) complexes, stable at room temperature and sub-atmospheric H2 pressure, which do not have any homogeneous analogue except for matrix-isolated [Cu(eta2-H2)Cl]. Comparison with the unstable Na+(H2) adducts formed in the parent Na-ZSM-5 zeolite allow the conclusion that the Cu(I)/H2 bond is governed by sigma-pi overlap forces.     

Rapid synthesis of pomalidomide-conjugates for the development of protein degrader libraries

Current methods for the preparation of heterobifunctional pomalidomide-conjugates rely on methods that are often low yielding and produce intractable byproducts. Herein we describe our strategy for the reliable and succinct preparation of pomalidomide-linkers which is essential to the formation of these conjugates. We present the preparation of 18 pomalidomide-linkers in high yield compared to current literature methods. Our findings show that secondary amines consistently afford greater yields than their primary counterparts, a trend that we were able to exploit in the synthesis of several new pomalidomide homo-dimers in enhanced yields compared to similar literature syntheses. This trend was further utilised to develop the first one-pot synthesis of JQ1-pomalidomide conjugates in yields up to 62%, providing a method that is suited to rapid preparation of conjugate libraries as is frequently required for the development of new protein degraders.

Current methods for the preparation of heterobifunctional pomalidomide-conjugates rely on methods that are often low yielding and produce intractable byproducts. Herein we describe our strategy for the succinct preparation of pomalidomide-linkers.     

Invariant operators and separation of residual stresses

We consider the equations of linear theory of elasticity in stresses for the threedimensional space. Solutions are decomposed into sums of stationary solutions not satisfying the compatibility condition (residual stresses) and nonstationary solutions satisfying the compatibility condition and hence represented through the displacements. The construction of this decomposition is reduced to solving a series of Poisson equations.     

Kinetics of the oxidative coupling of methane in the presence of model catalysts

The kinetics of the oxidative coupling of methane (OCM) in the presence of La/MgO and NaWMn/SiO₂ catalysts in a flow reactor at low reactant conversions was studied. It was found that, in spite of different compositions and properties of the test catalysts, the formation of ethane from methane and ethylene from ethane can be described within the framework of the Mars-van Krevelen redox model in both cases. The rate laws of side reactions, which lead to the formation of carbon oxides, are different from the rate laws of the target reactions of the conversion of methane into ethane and ethane into ethylene. The kinetic parameters required for the numerical simulation of the OCM process were determined for either of the catalysts.