Michael J. Ahrens

Direct Observation of the Preference of Hole Transfer over Electron Transfer for Radical Ion Pair Recombination in Donor−Bridge−Acceptor Molecules

Understanding how the electronic structures of electron donor-bridge-acceptor (D-B-A) molecules influence the lifetimes of radical ion pairs (RPs) photogenerated within them (D+*-B-A-*) is critical to designing and developing molecular systems for solar energy conversion. A general question that often arises is whether the HOMOs or LUMOs of D, B, and A within D+*-B-A-* are primarily involved in charge recombination. We have developed a new series of D-B-A molecules consisting of a 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) electron donor linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor via a series of Phn oligomers, where n = 1-4, to give DMJ-An-Phn-NI. The photoexcited charge transfer state of DMJ-An acts as a high-potential photoreductant to rapidly and nearly quantitatively transfer an electron across the Phn bridge to produce a spin-coherent singlet RP 1(DMJ+*-An-Phn-NI-*). Subsequent radical pair intersystem crossing yields 3(DMJ+*-An-Phn-NI-*). Charge recombination within the triplet RP then gives the neutral triplet state. Time-resolved EPR spectroscopy shows directly that charge recombination of the RP initially produces a spin-polarized triplet state, DMJ-An-Phn-3*NI, that can only be produced by hole transfer involving the HOMOs of D, B, and A within the D-B-A system. After the initial formation of DMJ-An-Phn-3*NI, triplet-triplet energy transfer occurs to produce DMJ-3*An-Phn-NI with rate constants that show a distance dependence consistent with those determined for charge separation and recombination.

Psa enzymatic activity: a new biomarker for assessing prostate cancer aggressiveness

With the advent of widespread prostate‐specific antigen (PSA) testing in recent decades, prostate cancer (PCa) has emerged as the most frequently diagnosed non‐skin cancer among men in the U.S. and Europe [1]. Greater screening rates coupled with improved detection methods have caused a controversial upsurge in the number of men undergoing prostate biopsy and subsequent treatment. However, current diagnostic techniques generally suffer from limited ability to identify which seemingly indolent cancers are biologically aggressive [2].

Ferrocene and Maleimide-Functionalized Disulfide Scaffolds for Self-Assembled Monolayers on Gold

A series of ferrocene-based electroactive molecules (EAMs) containing maleimide and disulfide groups in different asymmetric and branched architectures were designed and synthesized. Stable monolayers of each EAM on gold electrodes were confirmed by cyclic voltammetry. Importantly, these EAMs expand the repertoire of monolayer building blocks amenable to modular biofunctionalization for applications in electrochemical biosensor fabrication.

Electroactive self-assembled monolayers on gold via bipodal dithiazepane anchoring groups.

Novel dithiazepane-functionalized ferrocenyl-phenylethynyl oligomers 1 and 2 have been synthesized. Self-assembled monolayers (SAMs) of these ferrocene derivatives have been studied by X-ray photoelectron spectroscopy, ellipsometry, and cyclic voltammetry. It has been shown by XPS that monolayers of the dithiazepane-anchored molecules on gold electrodes contain gold-thiolate species. Cyclic voltammetry of the SAMs were characteristic of stable electroactive monolayers even for single-component SAMs of 1 and 2, with the more ideal responses recorded for the two-component SAMs diluted with undecanethiol. The small variation in peak splittings at progressively higher scan rates in these SAMs makes dithiazepane-bridged redox species promising candidates for further studies on molecular wires with bipodal anchoring.