Proteomic analysis of the Arabidopsis thaliana cell wall

With the completion of the Arabidopsis genome, many hypothetical proteins have been predicted without any information on their expression, subcellular localisation and function. We have performed proteomic analysis of proteins sequentially extracted from enriched Arabidopsis cell wall fractions and separated by two-dimensional gel electrophoresis (2-DE). The proteins were identified by peptide mass fingerprinting using matrix-assisted laser desorption/ionisation-time of flight (MALDI-TOF) mass spectrometry and genomic database searches. This is part of a targeted exercise to establish the entire Arabidopsis secretome database. We report evidence for new proteins of unknown function whose existence had been predicted from genomic sequences and, furthermore, localise them to the cell wall. In addition, we observed an unexpected presence in the cell wall preparations of proteins whose known biochemical activity has never been associated with this compartment hitherto. We discuss the implications of these findings and present results suggesting a possible involvement of cell wall kinases in plant responses to pathogen attack.     

One‐Dimensional,Cofacial Porphyrin Polymers Formed by Self‐Assembly of meso‐Tetrakis(ERE Donor) Zinc(II) Porphyrins

A series of meso‐tetrakis‐(ERE donor) zinc(II) porphyrins n Zn (ERE donor=4‐R‐3,5‐bis[(E)‐methyl]phenyl; 1 Zn: E=NMe₂, R=Br; 2 Zn: E=NMe₂, R=H; 3 Zn: E=OMe, R=Br; 4 Zn: E=OMe, R=H) have been synthesized in excellent yields. As a result of the combination of a Lewis acidic site and eight Lewis basic sites within one molecule, monomeric molecules of n Zn self‐assemble to form one‐dimensional porphyrin polymers [ n Zn]_∞ in the solid state, as confirmed for 1 Zn and 3 Zn by X‐ray crystallography. The coordination environment around the zinc(II) ions in these polymers is octahedral. They are ligated by four equatorial nitrogen atoms of the porphyrin and two apical E atoms (E=N, O) provided by the EBrE donor groups of adjacent n Zn molecules. Complexes 2 Zn and 4 Zn did not form single crystals, but solid‐state UV/Vis analysis points to the formation of similar structures. Solution UV/Vis and ¹H NMR spectroscopy indicated that interactions between 1 Zn and 2 Zn monomers in the polymers are stronger than between 3 Zn and 4 Zn monomers. Interestingly, they also revealed that the presence of a neighboring bromine atom in the EBrE donor groups has a considerable influence on the coordination properties of the benzylic N or O atoms. The zinc(II) ions of the porphyrins most likely adopt only hexacoordination in the solid state, owing to the unique predisposition of Lewis acidic and basic sites in the n Zn molecules. Several parameters of the aggregates, for example, the interplanar separation between porphyrins and the zinc–zinc distances, change as a function of the coordinating E groups. The high degree of modularity in their synthesis makes these zinc(II) porphyrins an interesting new entry in noncovalent multiporphyrin assemblies.     

Chiral bidentate aminophosphine ligands: synthesis, coordination chemistry and asymmetric catalysis

Chiral aminophosphines Ph2PN(R)(CH2)nN(R)PPh2 1-4 [n= 2, R = CH(CH3)(Ph) 1; n= 3, R = CH(CH2CH3)(Ph) 2, n= 2, R = CH(CH3)(1-naphthyl) 3; n= 2, R = CH(CH3)(C6H11) 4] were synthesized by the reaction of ClPPh2 with the appropriate easily accessible enantiopure amine building blocks. For compounds 1 and 2, the corresponding selenides 5 and 6 were prepared to determine the electronic character of the phosphine moieties. By reaction of 1 with either PdCl2(cod) or PdCl(CH3)(cod) the cis-complexes 7 and 8 were obtained. The molecular structure for complex 7, cis-[PdCl2(1)], was determined by X-ray crystallography. Reaction of PtCl2(cod) with 1 or 2 yielded the corresponding monomeric cis-isomers 9 and 10. The rhodium derivative [RhCl(CO)(1)] (11) was obtained as a mixture of cis and trans-isomers. Preliminary results in the rhodium catalyzed hydroformylation of styrene and vinyl acetate, with ee's up to 51% and high regioselectivities, showed the potential of these chiral aminophosphines for homogeneous catalysis.     

The oxidation of water by cerium(IV) catalysed by nanoparticulate RuO2 on mesoporous silica

Mesoporous silicates are prepared by templating on the hexagonal (H1) mesophase of surfactant bipyridine complexes of ruthenium(II) using a true liquid-crystal templating approach. On calcination, the surfactant template is removed except for the central metal ion that is oxidised, forming nanoparticles of RuO2 that deposit within the pores. RuO2 is a known oxidation catalyst and, despite its anhydrous nature in these silicates, is found to be very active in catalyzing the oxidation of water by acidic CeIV.     

Chemical synthesis of the first lignans to be found in humans and animals

$\text{Trans}$-2,3-$\text{bis}$-(3′-hydroxybenzyl)-butyrolactone (1) and 2,3-$\text{bis}$-(3′-hydroxybenzyl)-butane-1,4-diol (2), recently identified in urine, have been synthesised in racemic form.     

Stereoselective nitrenium ion cyclizations: asymmetric synthesis of the (+)-Kishi lactam and an intermediate for the preparation of fasicularin

The asymmetric synthesis of the (+)-Kishi lactam and an intermediate for the preparation of the marine natural product fasicularin is reported. The keystone of this divergent synthesis is the diastereoselective azaspirocyclization of an N-methoxy γ-arylbutanoamide, which is believed to proceed through the intermediacy of an N-acylnitrenium ion.     

Iron(III) salen-type catalysts for the cross-coupling of aryl Grignards with alkyl halides bearing beta-hydrogens

Iron(III) salen and related complexes are active catalysts for the coupling, under mild and simple reaction conditions, of aryl Grignard reagents with primary and secondary alkyl halide substrates bearing beta-hydrogens.     

Rapid synthesis of pomalidomide-conjugates for the development of protein degrader libraries

Current methods for the preparation of heterobifunctional pomalidomide-conjugates rely on methods that are often low yielding and produce intractable byproducts. Herein we describe our strategy for the reliable and succinct preparation of pomalidomide-linkers which is essential to the formation of these conjugates. We present the preparation of 18 pomalidomide-linkers in high yield compared to current literature methods. Our findings show that secondary amines consistently afford greater yields than their primary counterparts, a trend that we were able to exploit in the synthesis of several new pomalidomide homo-dimers in enhanced yields compared to similar literature syntheses. This trend was further utilised to develop the first one-pot synthesis of JQ1-pomalidomide conjugates in yields up to 62%, providing a method that is suited to rapid preparation of conjugate libraries as is frequently required for the development of new protein degraders.

Current methods for the preparation of heterobifunctional pomalidomide-conjugates rely on methods that are often low yielding and produce intractable byproducts. Herein we describe our strategy for the succinct preparation of pomalidomide-linkers.     

Transport in ceria electrolytes modified with sintering aids: effects on oxygen reduction kinetics

Small (2 mol%) cobalt oxide additions to ceria-gadolinia (CGO) materials considerably improve sinterability, making it possible to obtain ceramics with 95–99% density and sub-micrometre grain sizes at 1,170–1,370 K. The addition of Co causes a significant shift of the electrolytic domain to lower pO₂. This modification to the minor electronic conductivity of the electrolyte material has influence on the cathodic oxygen reduction reaction. The impedance technique is shown to provide information not only about polarisation resistance, but also about the active electrode area from analysis of the current constriction resistance. It is demonstrated that this current constriction resistance can be related to the minor electronic contributions to total conductivity in these materials. A simple imbedded grid approach gives control of the contact area allowing the properties of the electrolyte materials to be studied. A much lower polarisation resistance for the Co-containing CGO electrolyte is observed, which can be clearly attributed to an increased three-phase reaction area in the Co-containing material, as a consequence of elevated p-type conductivity.     

Synthesis, Structure, and Properties of a Model for Galactose Oxidase

An active-site analog of the radical copper enzyme galactose oxidase has been prepared from a synthetic tripod chelate ((2-pyridylmethyl)[(2-hydroxy-3,5-dimethylphenyl)methyl][(2-hydroxy-5-methyl-3-(methylthio)phenyl)methyl]amine, duncamine (dnc)) that binds a single Cu(II) ion through phenolate, thioether-substituted phenolate, and pyridylamine arms. The Cu complex crystallizes as a dinucleated dimer bridged by phenolate oxygens, and the structure has been determined by X-ray crystallography. Addition of pyridine (or other coordinating bases) dissociates the complex into a monomeric derivative that has been characterized spectroscopically (optical absorption and EPR) and electrochemically. The model provides insight into the properties of a mutant form of galactose oxidase which retains the same copper ligand complement as the wild type protein but lacks catalytic activity.