Mark F. Wyatt

Analysis of various organic and organometallic compounds using nanostructure-assisted laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOFMS).

Nanostructure-assisted laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOFMS) has been developed recently as a matrix-free/surface-assisted alternative to matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS). The NALDI surface of silicon nanowires is already very effective for the analysis of small to medium sized, polar organic molecules in positive ion mode. The current study examined this technology for the analysis of several nonpolar organic, organometallic, and ionic compounds in positive ion mode, as well as a fluorinated compound and various acids in negative ion mode. NALDI data are compared and contrasted with MALDI data for the same compounds, and the higher sensitivity of NALDI is highlighted by the successful characterization of two porphyrins for a sample amount of 10 amol per spot.

The development of poly(dendrimer)s for advanced processing

A norbornenyl-based homopolymer that has a dendronised iridium(III) complex attached to every monomer unit has been synthesized. The dendronised iridium(III) complex is comprised of three facially arranged 2-phenylpyridyl ligands. Two of the ligands bear first generation biphenyl-based dendrons with 2-ethylhexyloxy surface groups attached and the third ligand is attached to the polymer backbone via a benzyloxy ester. The polymer was formed by ring opening metathesis using the Grubbs III catalyst and was found to have an Mp of 130 kDa by MALDI-TOF mass spectrometry. At a concentration of 25 mg cm−3 the polymer solution had a viscosity of 1.09 mPa s, which was 34% higher than a solution containing a dendrimer of same weight per volume. The dendrimer had the same core, dendrons, and surface groups but differed from the polymer in that it had dendrons attached to three of the ligands rather than the two of the polymer. The solution photoluminescence quantum yield (PLQY) of the poly(dendrimer) was found to be 57%, indicating that intra-polymer chromophore interactions were not leading to strong quenching of the luminescence. However, in the solid-state the PLQY dropped significantly, indicating that inter-polymer chromophore interactions were significant. The presence of the dendrons allowed the simple blending of the polymer with 4,4′-bis(N-carbazolyl)-2,2′-biphenyl (CBP), and the blended film had a PLQY of 50%. Simple bilayer devices with a blended emissive layer and an electron injection and transport layer had an external quantum efficiency of 6.2% at a brightness of 100 cd m−2, showing that poly(dendrimer)s are a promising class of OLED material.

Characterisation of organometallic and coordination compounds by solvent-free matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry.

Insoluble or low solubility organometallic and coordination compounds have been characterised by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry, with solvent-free sample preparation being the key step toward successful analysis.

The role of fullerenes in the environmental stability of polymer:fullerene solar cells

Environmental stability is a common challenge for the commercialisation of low cost, encapsulation-free organic opto-electronic devices. Understanding the role of materials degradation is the key to address this challenge, but most such studies have been limited to conjugated polymers. Here we quantitatively study the role of the common fullerene derivative PCBM in limiting the stability of benchmark organic solar cells, showing that a minor fraction (<1%) of photo-oxidised PCBM, induced by short exposure to either solar or ambient laboratory lighting conditions in air, consistent with typical processing and operating conditions, is sufficient to compromise device performance severely. We identify the effects of photo-oxidation of PCBM on its chemical structure, and connect this to specific changes in its electronic structure, which significantly alter the electron transport and recombination kinetics. The effect of photo-oxidation on device current–voltage characteristics, electron mobility and density of states could all be explained with the same model of photoinduced defects acting as trap states. Our results demonstrate that the photochemical instability of PCBM and chemically similar fullerenes remains a barrier for the commercialisation of organic opto-electronic devices.

Carbohydrate globules: molecular asterisk-cored dendrimers for carbohydrate presentation

A convergent synthesis of a first generation dendrimer with biphenyl-based dendrons and a hexaphenylbenzene core is reported. Suzuki coupling of six first generation biphenyl-dendrons with the rigid hexakis(4-iodophenyl)benzene core furnished the title asterisk-cored dendrimer in 60% yield. Twelve copies of β-(1→6)-linked glucosamine-based oligosaccharides were then efficiently coupled with the acetylenyl surface groups of the dendrimer via a Huisgen 1,3-dipolar cycloaddition reaction to give a series of multivalent carbohydrate constructs that mimic the globular nodules of polysaccharide intercellular adhesin (PIA) produced by Staphylococcus aureus.

Accurate mass measurement by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. I. Measurement of positive radical ions using porphyrin standard reference materials: Accurate mass MALDI of positive radical ions using porphyrins

A method for the accurate mass measurement of positive radical ions by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is described. Initial use of a conjugated oligomeric calibration material was rejected in favour of a series of meso-tetraalkyl/tetraalkylaryl-functionalised porphyrins, from which the two calibrants required for a particular accurate mass measurement were chosen. While all measurements of monoisotopic species were within +/-5 ppm, and the method was rigorously validated using chemometrics, mean values of five measurements were used for extra confidence in the generation of potential elemental formulae. Potential difficulties encountered when measuring compounds containing multi-isotopic elements are discussed, where the monoisotopic peak is no longer the lowest mass peak, and a simple mass-correction solution can be applied. The method requires no significant expertise to implement, but care and attention is required to obtain valid measurements. The method is operationally simple and will prove useful to the analytical chemistry community.

Novel soluble thieno[3,2-b]thiophene fused porphyrazine

The synthesis of the first soluble thieno[3,2-b]thiophene based porphyrazine (ZnTTPz) is reported from the cyclisation of 2,3-dicyano-5-octylthieno[3,2-b]thiophene. ZnTTPz can be considered the all thiophene analogue of naphthalocyanine. ZnTTPz exhibits a red-shifted absorption in solution and thin film, as well as a reduced band gap in comparison to the thiophene analogue due to an increased conjugation length. Films of ZnTTPz processed from solution exhibit p-type semiconducting behaviour in field-effect transistors with low hysteresis and reasonable charge carrier mobility.

Accurate mass measurement by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry. II. Measurement of negative radical ions using porphyrin and fullerene standard reference materials

A method for the accurate mass measurement of negative radical ions by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) is described. This is an extension to our previously described method for the accurate mass measurement of positive radical ions (Griffiths NW, Wyatt MF, Kean SD, Graham AE, Stein BK, Brenton AG. Rapid Commun. Mass Spectrom. 2010; 24: 1629). The porphyrin standard reference materials (SRMs) developed for positive mode measurements cannot be observed in negative ion mode, so fullerene and fluorinated porphyrin compounds were identified as effective SRMs. The method is of immediate practical use for the accurate mass measurement of functionalised fullerenes, for which negative ion MALDI-TOFMS is the principal mass spectrometry characterisation technique. This was demonstrated by the accurate mass measurement of six functionalised C(60) compounds.