Oligo P-phenylenevinylene Derivatives Research Articles

Oligo p-Phenylenevinylene Derivatives as Electron Transfer Matrices for UV-MALDI.

Phenylenevinylene oligomers (PVs) have outstanding photophysical characteristics for applications in the growing field of organic electronics. Yet, PVs are also versatile molecules, the optical and physicochemical properties of which can be tuned by manipulation of their structure. We report the synthesis, photophysical, and MS characterization of eight PV derivatives with potential value as electron transfer (ET) matrices for UV-MALDI. UV-vis analysis show the presence of strong characteristic absorption bands in the UV region and molar absorptivities at 355 nm similar or higher than those of traditional proton (CHCA) and ET (DCTB) MALDI matrices. Most of the PVs exhibit non-radiative quantum yields (φ) above 0.5, indicating favorable thermal decay. Ionization potential values (IP) for PVs, calculated by the Electron Propagator Theory (EPT), range from 6.88 to 7.96 eV, making these oligomers good candidates as matrices for ET ionization. LDI analysis of PVs shows only the presence of radical cations (M+.) in positive ion mode and absence of clusters, adducts, or protonated species; in addition, M+. threshold energies for PVs are lower than for DCTB. We also tested the performance of four selected PVs as ET MALDI matrices for analytes ranging from porphyrins and phthalocyanines to polyaromatic compounds. Two of the four PVs show S/N enhancement of 1961% to 304% in comparison to LDI, and laser energy thresholds from 0.17 μJ to 0.47 μJ compared to 0.58 μJ for DCTB. The use of PV matrices also results in lower LODs (low fmol range) whereas LDI LODs range from pmol to nmol. Graphical Abstract ᅟ.

Nanocomposite made of an oligo(p-phenylenevinylene)-based trihybrid thixotropic metallo(organo)gel comprising nanoscale metal-organic particles, carbon nanohorns, and silver nanoparticles.

A silver ion (Ag(+))-triggered thixotropic metallo(organo)gel of p-pyridyl-appended oligo(p-phenylenevinylene) derivatives (OPVs) is reported for the first time. Solubilization of single-walled carbon nanohorns (SWCNHs) in solutions of the pure OPVs as well as in the metallogels mediated by π-π interactions has also been achieved. In situ fabrication of silver nanoparticles (AgNPs) in the SWCNH-doped dihybrid gel leads to the formation of a trihybrid metallogel. The mechanical strength of the metallogels could be increased stepwise in the order: freshly prepared gel<dihybrid gel<trihybrid gel. Microscopic studies of the trihybrid gel indicate the formation of three distinct morphologies, that is, nanoscale metal-organic particles (NMOPs), flowerlike aggregates of SWCNHs and AgNPs, and also their integration with each other. Detailed studies suggest lamellar organizations of the linear metal-ligand complexes in the NMOPs, which upon association create a three-dimensional network that eventually immobilizes the solvent molecules.