Oxazolones in Organocatalysis,New Tricks for an Old Reagent

Oxazolones or azlactones are among the most‐common starting materials for the synthesis of quaternary amino acids. Since the seminal works of Steglich and co‐workers until the recent examples from Ooi and co‐workers, azlactones have been the focus of intense research. Oxazolones are also widely used in organometallic chemistry; however, with the “renaissance” of organocatalysis, this reagent has emerged as an important starting material for a broad range of new organocatalytic asymmetric methodologies. In this Focus Review, we aim to cover all of these new organocatalytic methodologies. We begin by discussing the dynamic kinetic resolution reactions developed with azlactones. Then, we disclose the organocatalytic rearrangements. Finally, we focus on the use of oxazolones as nucleophiles in organocatalytic processes.     

Microwave assisted synthesis and magnetic properties of octanuclear and enneanuclear Ni(II) complexes: an unprecedented coordination mode for the NO(2)(-) ligand

Octanuclear and enneanuclear Ni(II) complexes have been synthesized using a microwave reactor. The octanuclear complex Ni(8) presents a new triply bridging coordination mode for the NO(2)(-) ligand.     

Energy measurement and fragment identification using digital signals from partially depleted Si detectors

In this work we devise a new method to study quark-anti-quark interactions beyond simple ladder-exchange that yield massless pions in the chiral limit. The method is based on the requirement to have a representation of the quark-gluon vertex that is explicitly given in terms of quark dressings functions. We outline a general procedure to generate the Bethe-Salpeter kernel for a given vertex representation. Our method allows not only the identification of the mesons' masses but also the extraction of their Bethe-Salpeter wave functions exposing their internal structure. We exemplify our method with vertex models that are of phenomenological interest.     

Electrical Measurement Techniques in Atomic Force Microscopy

A conductive tip in an atomic force microscope (AFM) has extended the capability from conventional topographic imaging to electrical surface characterization. The conductive tip acts as a voltage electrode to provide stimuli and monitor electrical surface properties. In this review article, we have organized the AFM electrical techniques based on whether the electrical properties are monitored at the cantilever tip or across the sample. Furthermore, the techniques are organized based on probe detection signal. A number of acronyms are used in the literature, and the more commonly used ones are identified. The principle of each technique is described, and representative applications are presented. A better understanding of the spectrum of techniques should serve as the driver to expand the application of electrical techniques to study interdisciplinary phenomena at the nanoscale.     

Check of AGT relation for conformal blocks on sphere

The AGT conjecture identifying conformal blocks with the Nekrasov functions is investigated for the spherical conformal blocks with more than 4 external legs. The diagram technique which arises in conformal block calculation involves propagators and vertices. We evaluated vertices with two Virasoro algebra descendants and explicitly checked the AGT relation up to the third order of the expansion for the 5-point and 6-point conformal blocks on sphere confirming all the predictions of arXiv:0906.3219 relevant in this situation. We propose that U(1)$U(1)$-factor can be extracted from the matrix elements of the free field vertex operators. We studied the n-point case, and found out that our results confirm the AGT conjecture up to the third order expansions.     

Bicyclic Guanidine Promoted Mechanistically Divergent Depolymerization and Recycling of a Biobased Polycarbonate

We here report the organocatalytic and temperature-controlled depolymerization of biobased poly(limonene carbonate) providing access to its trans-configured cyclic carbonate as the major product. The base TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene) offers a unique opportunity to break down polycarbonates via end-group activation or main chain scission pathways as supported by various controls and computational analysis. These energetically competitive processes represent an unprecedented divergent approach to polycarbonate recycling. The trans limonene carbonate can be converted back to its polycarbonate via ring-opening polymerization using the same organocatalyst in the presence of an alcohol initiator, offering thus a potential circular and practical route for polycarbonate recycling.     

Preparative-Scale Biocatalytic Oxygenation of N-Heterocycles with a Lyophilized Peroxygenase Catalyst

A lyophilized preparation of an unspecific peroxygenase variant from Agrocybe aegerita (rAaeUPO-PaDa-I-H) is a highly effective catalyst for the oxygenation of a diverse range of N-heterocyclic compounds. Scalable biocatalytic oxygenations (27 preparative examples, ca. 100 mg scale) have been developed across a wide range of substrates, including alkyl pyridines, bicyclic N-heterocycles and indoles. H₂O₂ is the only stoichiometric oxidant needed, without auxiliary electron transport proteins, which is key to the practicality of the method. Reaction outcomes can be altered depending on whether hydrogen peroxide was delivered by syringe pump or through in situ generation using an alcohol oxidase from Pichia pastoris (PpAOX) and methanol as a co-substrate. Good synthetic yields (up to 84 %), regioselectivity and enantioselectivity (up to 99 % ee) were observed in some cases, highlighting the promise of UPOs as practical, versatile and scalable oxygenation biocatalysts.     

Chiral Single-Molecule Potentiometers Based on Stapled ortho- Oligo(phenylene)ethynylenes

We report on the chemical design of chiral molecular junctions with stress-dependent conductance, whose helicity is maintained during the stretching of a single molecule junction due to the stapling of both ends of the inner helix. In the reported compounds, different conductive pathways are observed, with clearly different conductance values and plateau-length distributions, attributed to different conformations of the helical structures. The large chiro-optical responses and the potential use of these molecules as unimolecular spin filters have been theoretically proved using state-of-the-art Density Functional Theory (DFT) calculations, including a fully ab-initio estimation of the CISS-originating spin polarization which is done, for the first time, for a realistic molecular system.     

ATRP Enhances Structural Correlations In Polymerization-Induced Phase Separation**

Synthetic methods to control the structure of materials at sub-micron scales are typically based on the self-assembly of structural building blocks with precise size and morphology. On the other hand, many living systems can generate structure across a broad range of length scales in one step directly from macromolecules, using phase separation. Here, we introduce and control structure at the nano- and microscales through polymerization in the solid state, which has the unusual capability of both triggering and arresting phase separation. In particular, we show that atom transfer radical polymerization (ATRP) enables control of nucleation, growth, and stabilization of phase-separated poly-methylmethacrylate (PMMA) domains in a solid polystyrene (PS) matrix. ATRP yields durable nanostructures with low size dispersity and high degrees of structural correlations. Furthermore, we demonstrate that the length scale of these materials is controlled by the synthesis parameters.