Self-assembly of chiral diketopyrrolopyrrole chromophores giving supramolecular chains in monolayers and twisted microtapes.

Chiral diketopyrrolopyrroles appended with enantiomeric ethyl lactate functions through an ether linkage to the aryl backbone of the chromophore were synthesized via the Mitsunobu reaction. The molecules have good solubility and excellent optical properties, high molar absorption coefficients, and fluorescence quantum yields. Helical aggregates with circular dichroism arising from the supramolecular arrangement are seen in both solution and thin films, and the aggregates also display circularly polarized luminescence (glum  ≈ ±0.1). The molecules assemble to give monolayers on graphite and precipitate from solution forming supramolecular twisted tapes hundreds of microns long.

Low-Temperature Sintering of l-Alanine-Functionalized Metallic Copper Particles Affording Conductive Films with Excellent Oxidative Stability.

Here, the alpha amino acid l-alanine is employed as both a capping and stabilizing agent in the aqueous synthesis of submicron-sized metallic copper particles under ambient atmospheric conditions. The reduction of the copper(II) precursor is achieved using l-ascorbic acid (vitamin C) as the reducing agent. The nature of the complex formed between l-alanine and the copper(II) precursor, pH of the medium, temperature, and the relative proportion of capping agent are found to play a significant role in determining the size, shape, and oxidative stability of the resulting particles. The adsorbed l-alanine is shown to act as a barrier imparting excellent thermal stability to capped copper particles, delaying the onset of temperature-induced aerial oxidation. The stability of the particles is complemented by highly favorable sintering conditions, rendering the formation of conductive copper films at significantly lower temperatures (T ≤ 120 °C) compared to alternative preparation methods. The resulting copper films are well-passivated by residual surface l-alanine molecules, promoting long-term stability without hindering the surface chemistry of the copper film as evidenced by the catalytic activity. Contrary to the popular belief that ligands with long carbon chains are best for providing stability, these findings demonstrate that very small ligands can provide highly effective stability to copper without significantly deteriorating its functionality while facilitating low-temperature sintering, which is a key requirement for emerging flexible electronic applications.

Imaging deposition-dependent supramolecular chiral organisation.

Thin films of a chiral diketopyrrolopyrrole derivative were imaged with spatially-defined Mueller Matrix Polarimetry, focussing on the Circular Dichroism signal, giving unique insight into the impact that deposition techniques and thermal annealing can have on chiral supramolecular structures in the solid state, where homogeneity was observed for spun-coated films while drop-coating afforded chiroptical diversity in the material, a feature invisible to absorption spectroscopy or optical microscopy.

Ground and Excited States of Bis-4-Methoxybenzyl-Substituted Diketopyrrolopyrroles: Spectroscopic and Electrochemical Studies.

A series of symmetrically bis-4-methoxybenzyl (4MB) N-substituted 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) derivatives have been synthesized. The 4MB unit makes the DPP core soluble, and shows subtle modification of up to 0.2 eV in ground and excited states of the core when compared with related alkyl derivatives. Absorption and emission spectroscopy, as well as electrochemical and computational methods have been employed to prove the importance of the peripheral aryl units on the donor/ acceptor properties of the molecules. The 4MB products are highly fluorescent (quantum yields approaching 100 % in solution), with a unique distribution of frontier states shown by spectroelectrochemistry. The solid-state fluorescence correlates with the X-ray crystal structures of the compounds, a Stokes shift of approximately 80 nm is seen for two of the compounds. The frontier energy levels show that this subtle substitutional change could be of future use in molecular energy level tailoring in these, and related, materials for organic (opto)electronics.

Free-Wilson Analysis of Comprehensive Data on Phosphoinositide-3-kinase (PI3K) Inhibitors Reveals Importance of N-Methylation for PI3Kδ Activity.

Phosphoinositide-3-kinase δ (PI3Kδ) is a critical regulator of cell growth and transformation and has been explored as a therapeutic target for a range of diseases. Through the exploration of the thienopyrimidine scaffold, we have identified a ligand-efficient methylation that leads to remarkable selectivity for PI3Kδ over the closely related isoforms. Interrogation through the Free-Wilson analysis highlights the innate selectivity the thienopyrimidine scaffold has for PI3Kδ and provides a predictive model for the activity against the PI3K isoforms.