Halide ion effect on the chloroform chemical shift in supramolecular complexation studies with tetra-n-butylammonium salts: a 1H NMR and X-ray study

A ¹H NMR spectroscopic study of tetra-n-butylammonium halides (TBAX: X = Cl^? , Br^?  or I^? ) in CDCl₃ solutions was conducted. Complexation studies of TBAX salts with different host molecules using ¹H NMR in CDCl₃ have previously revealed that the reference residual CHCl₃ proton signal had been shifted downfield. The aim of the study was to quantify the extent of these chemical shift changes with TBAX salts. Linear concentration–chemical shift relationships in each case were obtained from the resulting titration plots obtained from the addition of the TBAX salts alone to CDCl₃. Interactions in the solid state as determined by X-ray crystallography support the solution-state investigations indicating halide ion–chloroform proton interactions.     

Serendipitous Discovery of a Potent Influenza Virus A Neuraminidase Inhibitor

We have previously reported a potent neuraminidase inhibitor that comprises a carbocyclic analogue of zanamivir in which the hydrophilic glycerol side chain is replaced by the hydrophobic 3‐pentyloxy group of oseltamivir. This hybrid inhibitor showed excellent inhibitory properties in the neuraminidase inhibition assay (K_i=0.46 nM ; K_{i (zanamivir)}=0.16 nM ) and in the viral replication inhibition assay in cell culture at 10^?8 M . As part of this lead optimization, we now report a novel spirolactam that shows comparable inhibitory activity in the cell culture assay to that of our lead compound at 10^?7 M . The compound was discovered serendipitously during the attempted synthesis of the isothiourea derivative of the original candidate. The X‐ray crystal structure of the spirolactam in complex with the N8 subtype neuraminidase offers insight into the mode of inhibition.     

Constructing spin-adiabatic states for the modeling of spin-crossing reactions. I. A shared-orbital implementation

In the modeling of spin-crossing reactions, it has become popular to directly explore the spin-adiabatic surfaces. Specifically, through constructing spin-adiabatic states from a two-state Hamiltonian (with spin-orbit coupling matrix elements) at each geometry, one can readily employ advanced geometry optimization algorithms to acquire a “transition state” structure, where the spin crossing occurs. In this work, we report the implementation of a fully-variational spin-adiabatic approach based on Kohn-Sham density functional theory spin states (sharing the same set of molecular orbitals) and the Breit-Pauli one-electron spin-orbit operator. For three model spin-crossing reactions (predissociation of N₂O, singlet-triplet conversion in CH₂, and CO addition to Fe(CO)₄), the spin-crossing points were obtained. Our results also indicated the Breit-Pauli one-electron spin-orbit coupling can vary significantly along the reaction pathway on the spin-adiabatic energy surface. On the other hand, due to the restriction that low-spin and high-spin states share the same set of molecular orbitals, the acquired spin-adiabatic energy surface shows a cusp (ie, a first-order discontinuity) at the crossing point, which prevents the use of standard geometry optimization algorithms to pinpoint the crossing point. An extension with this restriction removed is being developed to achieve the smoothness of spin-adiabatic surfaces.     

Characterization of magnetic labels for bioassays

Magnetic nanoparticles differing by their size have been synthesized to use them for multiparametric testing, based on their differing magnetic properties. The nanoparticle has two essential roles: to act as a probe owing to its specific magnetic properties and to carry on its surface precursor groups for the covalent coupling of biological recognition molecules, such as antibodies, nucleic acids. A totally unique, newly patented, method has been used to characterize magnetic signatures using the MIAplex technology. The MIAplex reader, developed by Magnisense, measures the non-linear response of the magnetic labels when they are exposed to a multi-frequency alternating magnetic field. This specific signature based on d²B(H)/dH² was correlated to other more conventional magnetic detection methods (superconducting quantum interference devices (SQUID) and Mössbauer).     

Hierarchical Analysis of Self‐Assembled PEGylated Hexaphenylalanine Photoluminescent Nanostructures

Despite the growing literature about diphenylalanine‐based peptide materials, it still remains a challenge to delineate the theoretical insight into peptide nanostructure formation and the structural features that could permit materials with enhanced properties to be engineered. Herein, we report the synthesis of a novel peptide building block composed of six phenylalanine residues and eight PEG units, PEG₈‐F6. This aromatic peptide self‐assembles in water in stable and well‐ordered nanostructures with optoelectronic properties. A variety of techniques, such as fluorescence, FTIR, CD, DLS, SEM, SAXS, and WAXS allowed us to correlate the photoluminescence properties of the self‐assembled nanostructures with the structural organization of the peptide building block at the micro‐ and nanoscale. Finally, a model of hexaphenylalanine in aqueous solution by molecular dynamics simulations is presented to suggest structural and energetic factors controlling the formation of nanostructures.     

A Theoretical Study of ãA2 CH2

The potential energy surface and dipole moment surfaces of the ã⁴A₂ electronic state of CH₂⁺ are calculated ab initio using an augmented correlation-consistent polarized valence quadruple-ζ (aug-cc-pVQZ) basis set, with the incorporation of dynamical correlation using the coupled cluster method with single and double excitations and perturbatively connected triple excitations [CCSD(T)]. We use these surfaces in the MORBID program system to calculate rotation and rotation-vibration term values for ã-state CH₂⁺, CD⁺₂, and CHD⁺ and to simulate the rotation and rotation-vibration absorption spectrum of CH₂⁺ in the ã⁴A₂ electronic state. Our work is motivated by studies of CH₂⁺ that use the Coulomb explosion imaging technique and by the goal of predicting spectra that may be obtained from discharge sources. Although the ã state is the lowest-lying excited state above the X?/Ã ground state pair, it turns out to be relatively high-lying, and we determine that T_e(ã)=30447.5 cm⁻¹. The equilibrium bond angle for ã-state CH₂⁺ is only 77.1°; as a result the asymmetric top κ value is close to 0, and the molecule is equally far from the oblate and prolate symmetric top limits in this electronic state.     

Synthesis of a new fluorescent probe specific for catechols

[reaction: see text] The synthesis of a new fluorescent probe, specific for the catechol moiety, has been conducted by preparation of alpha,alpha-dibromomalonamides containing an appropriate fluorophore. N,N'-Bis-anthracen-9-ylmethyl-2,2-dibromomalonamide reacted with various catechols in the presence of cesium carbonate to generate highly fluorescent derivatives.