Oligoacenes: theoretical prediction of open-shell singlet diradical ground states

A series of oligoacenes from benzene to decacene were studied computationally with DFT and CASSCF methods. In contrast to the common view that acenes are closed-shell systems or may have a triplet ground state, these results offer the first theoretical predictions for the singlet ground state and diradical character for oligoacenes. The nature of the ground states of these molecules arises from the disjoint nature of the NBMOs that are singly occupied in the diradical.     

Erratum

Peculiar transitions in the optical spectra of Mn atoms isolated in argon matrices confirm the existence of Mn₂ molecule. The temperature variation of the absorption and MCD intensity in the range 13-27 K demonstrate that the Mn₂ molecule is antiferromagnetic and allows a precise determination of its ground-state exchange energy: J = ?10.3 ± 0.6 cm^?1.     

Synthesis and structure of 4-R,5-R-[5-(hydroxy-diphenyl-methyl)-2, 2-dimethyl-[1,3]dioxolan-4-yl]-phenyl-methanone, a chiral ligand building block

A triphenyl analog of taddol, 4-R,5-R-[5-(hydroxy-diphenyl-methyl)-2,2-dimethyl-[1,3]dioxolan-4-yl]-phenyl-methanone, has been synthesized and structurally characterized. This molecule could act as a chiral ligand building block in the creation of tuned taddol analogs. Structural analysis of the title compound reveals that the hydroxyl group is involved in an intramolecular hydrogen bond and does not take part in any intermolecular interaction. Crystal packing is influenced by C–H O hydrogen bonding and phenyl phenyl interactions. Crystal data: Triclinic, P1 (No. 1), a = 5.9343(4) Å, b = 8.2367(17) Å, c = 10.987(2) Å, = 88.290(6), = 75.442(4), = 80.655(6), V = 512.86(15) ų, Z = 1, D _calc = 1.258 mg/m³. Final residual values were R ₁ = 0.0407 for 3022 observed data (I > 2s(I) ) and wR ₂ = 0.0941 for all 3524 unique data.     

A masked-alkene metathesis-based synthesis of isopulo’upone

A metathesis-based formal synthesis of (±)-isopulo’upone has been completed featuring a masked olefin metathesis/elimination sequence followed by an intramolecular Diels-Alder reaction to construct the 5,6-fused bicyclic core.     

Chemoenzymatic Synthesis of 2-Arachidonoylglycerol, An Endogenous Ligand for Cannabinoid Receptors

A simple and efficient synthesis of 2-arachidonoyl glycerol, an endogenous agonist for cannabinoid receptors was achieved using Novozym 435, immobilized lipase from Candida antarctica.     

An ultra‐high temperature flow‐through capillary device for bacterial spore lysis

Rapid and specific characterization of bacterial endospores is dependent on the ability to rupture the cell wall to enable analysis of the intracellular components. In particular, bacterial spores from the bacillus genus are inherently robust and very difficult to lyze or solubilize. Standard protocols for spore inactivation include chemical treatment, sonication, pressure, and thermal lysis. Although these protocols are effective for the inactivation of these agents, they are less well suited for sample preparation for analysis using proteomic and genomic approaches. To overcome this difficulty, we have designed a simple capillary device to perform thermal lysis of bacterial spores. Using this device, we were able to super heat (195°C) an ethylene glycol lysis buffer to perform rapid flow‐through rupture and solubilization of bacterial endospores. We demonstrated that the lysates from this preparation method are compatible with CGE as well as DNA amplification analysis. We further demonstrated the flow‐through lysing device could be directly coupled to a miniaturized electrophoresis instrument for integrated sample preparation and analysis. In this arrangement, we were enabled to perform sample lysis, fluorescent dye labeling, and protein electrophoresis analysis of bacterial spores in less than 10 min. The described sample preparation device is rapid, simple, inexpensive, and easily integratable with various microfluidic devices.     

A simple method for the direct arylation of indoles

The scope and limitations are described for a powerful new method to access indoles bearing a quaternary center at C-3 using easily accessible bisaryl λ³-iodanes and a cheap organic base.     

Magnetic field-controlled microfluidic transport.

Several new forms of magnetohydrodynamic (MHD) flow occurring in the solution gap between two 250-microm-diameter Pt microdisk electrodes, oriented in a face-to-face geometry and immersed in a uniform magnetic field (1 T), are described. The MHD flow results from the Lorentz force generated by diffusion of electrochemically generated molecular ions through the magnetic field. Individual microscopic flow tubes ( approximately 50-microm radius) spanning the gap between the face-to-face electrodes are observed during the 1-e(-) reduction of nitrobenzene in acetonitrile solutions. The flow tubes extend up to approximately 2 cm in length and are stable for indefinite periods. Directional transport of the electrogenerated nitrobenzene radical anion over macroscopic distances within the flow tubes, with minimal diffusional broadening, is demonstrated using an ultramicroelectrode probe to map the convective flux of redox species. Pulsed MHD transport of small packets of molecules and the formation of large area (approximately 3 cm(2)), microscopically thin (25 microm) rotating sheets of solution are also demonstrated. The results suggest that electrochemical methods, in combination with magnetohydrodynamic principles, may be useful for external field-controlled microfluidic systems.     

Discovering Higher-Order Interactions Through Neural Information Decomposition

If regularity in data takes the form of higher-order functions among groups of variables, models which are biased towards lower-order functions may easily mistake the data for noise. To distinguish whether this is the case, one must be able to quantify the contribution of different orders of dependence to the total information. Recent work in information theory attempts to do this through measures of multivariate mutual information (MMI) and information decomposition (ID). Despite substantial theoretical progress, practical issues related to tractability and learnability of higher-order functions are still largely unaddressed. In this work, we introduce a new approach to information decomposition—termed Neural Information Decomposition (NID)—which is both theoretically grounded, and can be efficiently estimated in practice using neural networks. We show on synthetic data that NID can learn to distinguish higher-order functions from noise, while many unsupervised probability models cannot. Additionally, we demonstrate the usefulness of this framework as a tool for exploring biological and artificial neural networks.