An Unusual Hydrogen Migration/C−H Activation Reaction with Group 3 Metals

A novel hydrogen migration from the phenyl ring to the pyridine ring of an yttrium pyridyl complex supported by a 1,1′-ferrocene diamide ligand is reported. Density functional theory calculations were instrumental in probing the mechanism for this transformation

Efficient Graph-Based Active Learning with Probit Likelihood via Gaussian Approximations

We present a novel adaptation of active learning to graph-based semi-supervised learning (SSL) under non-Gaussian Bayesian models. We present an approximation of non-Gaussian distributions to adapt previously Gaussian-based acquisition functions to these more general cases. We develop an efficient rank-one update for applying "look-ahead" based methods as well as model retraining. We also introduce a novel "model change" acquisition function based on these approximations that further expands the available collection of active learning acquisition functions for such methods.Comment: Accepted in ICML Workshop on Real World Experiment Design and Active Learning 202

Reaction of Group III Biheterocyclic Complexes

Group III alkyl complexes supported by a ferrocene diamide ligand (1,1′-fc(NSitBuMe_2)_2) have been found to be reactive toward aromatic N-heterocycles such as 1-methylimidazole and pyridines. These reactions were investigated experimentally and computationally. An initial C−H activation event is followed by a coupling reaction to form biheterocyclic complexes, in which one of the rings is dearomatized. In the case of 1-methylimidazole, the biheterocyclic compound could not be isolated and further led to an imidazole ring-opened product; in the case of pyridines, it transformed into an isomer with extended conjugation of double bonds. Mechanisms for both reactions are proposed on the basis of experimental and computational results. DFT calculations were also used to show that an energetically accessible pathway for the ring-opening of pyridines exists

State-of-the-art glycosaminoglycan characterization

Glycosaminoglycans (GAGs) are heterogeneous acidic polysaccharides involved in a range of biological functions. They have a significant influence on the regulation of cellular processes and the development of various diseases and infections. To fully understand the functional roles that GAGs play in mammalian systems, including disease processes, it is essential to understand their structural features. Despite having a linear structure and a repetitive disaccharide backbone, their structural analysis is challenging and requires elaborate preparative and analytical techniques. In particular, the extent to which GAGs are sulfated, as well as variation in sulfate position across the entire oligosaccharide or on individual monosaccharides, represents a major obstacle. Here, we summarize the current state-of-the-art methodologies used for GAG sample preparation and analysis, discussing in detail liquid chromatograpy and mass spectrometry-based approaches, including advanced ion activation methods, ion mobility separations and infrared action spectroscopy of mass-selected species