Fulvenallenyl Radical (CH)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic CH Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (CH) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the CH potential energy surface accessed by the reactions of CH with methylacetylene (CHCCH) and allene (HCCCH) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of CH with closed-shell unsaturated hydrocarbons.

Crossed molecular beam experiments and theoretical simulations on the multichannel reaction of toluene with atomic oxygen.

Despite extensive experimental and theoretical studies on the kinetics of the O(P) + CH (toluene) reaction and a pioneering crossed molecular beam (CMB) investigation, the branching fractions (BFs) of the CHCHO(methylphenoxy) + H, CHO(phenoxy) + CH, and spin-forbidden CHCH (methylcyclopentadiene) + CO product channels remain an open question, which has hampered the proper inclusion of this important reaction in the chemical modelling of various chemical environments. We report a CMB study with universal soft electron-ionization mass-spectrometric detection of the reactions O(P,D) + toluene at the collision energy of 34.7 kJ mol.

Toward an Accurate Black-Box Tool for the Kinetics of Gas-Phase Reactions Involving Barrier-less Elementary Steps.

An enhanced computational protocol has been devised for the accurate characterization of gas-phase barrier-less reactions in the framework of the reaction-path (RP) and variable reaction coordinate variational transition-state theory. In particular, the synergistic combination of density functional theory and Monte Carlo sampling to optimize reactive fluxes led to a reliable yet effective computational workflow. A black-box strategy has been developed for selecting the most suited density functional with reference to a high-level one-dimensional reference potential.

Improved synthesis of DA364, an NIR fluorescence RGD probe targeting αβ integrin.

Optical imaging (OI) is gaining increasing attention in medicine as a non-invasive diagnostic imaging technology and as a useful tool for image-guided surgery. OI exploits the light emitted in the near-infrared region by fluorescent molecules able to penetrate living tissues. Cyanines are an important class of fluorescent molecules and by their conjugation to peptides it is possible to achieve optical imaging of tumours by selective targeting.