Triazacyclophane (TAC)-scaffolded histidine and aspartic acid residues as mimics of non-heme metalloenzyme active sites

We describe the synthesis and coordination behaviour to copper(II) of two close structural triazacyclophane-based mimics of two often encountered aspartic acid and histidine containing metalloenzyme active sites. Coordination of these mimics to copper(I) and their reaction with molecular oxygen leads to the formation of dimeric bis(μ-hydroxo) dicopper(II) complexes.     

Hard X-ray Spectroscopic Nano-Imaging of Hierarchical Functional Materials at Work

Heterogeneous catalysts often consist of an active metal (oxide) in close contact with a support material and various promoter elements. Although macroscopic properties, such as activity, selectivity and stability, can be assessed with catalyst performance testing, the development of relevant, preferably quantitative structure–performance relationships require the use of advanced characterisation methods. Spectroscopic imaging in the hard X-ray region with nanometer-scale resolution has very recently emerged as a powerful approach to elucidate the hierarchical structure and related chemistry of catalytic solids in action under realistic reaction conditions. This X-ray-based chemical imaging method benefits from the combination of high resolution (∼30 nm) with large X-ray penetration and depth of focus, and the possibility for probing large areas with mosaic imaging. These capabilities make it possible to obtain spatial and temporal information on chemical changes in catalytic solids as well as a wide variety of other functional materials, such as fuel cells and batteries, in their full complexity and integrity. In this concept article we provide details on the method and setup of full-field hard X-ray spectroscopic imaging, illustrate its potential for spatiotemporal chemical imaging by making use of recent showcases, outline the pros and cons of this experimental approach and discuss some future directions for hierarchical functional materials research.     

The discretized flow on domains of attraction: a structural stability result

It is well known that, for stepsize sufficiently small, compactattractors of ordinary differential equations persist underdiscretization. The present paper describes the structure ofthe discrete-time dynamical system obtained via discretizationon A(M_h)\M_h where M_h is the approximate attractor and A(M_h)is its domain of attraction. The existence of a smooth embeddinginto a continuous-time parallelizable flow is proved. The constructioncan be used to define sections for discretizations and can beinterpreted as a justification of the method of modified equations.     

Design and applications of a home-built in situ FT-Raman spectroscopic cell

In the field of heterogeneous catalysis, in situ spectroscopy is one of the topics with growing interest. The characterization of a catalyst under working conditions is essential to identify the catalytic active site and to study the relation between the surface structure of a catalyst and its catalytic performance. For the first time, the design of an in situ spectroscopic cell for FT-Raman is presented and its performance is demonstrated by monitoring the thermal conversion of as synthesized mesoporous titanium and by characterizing the molecular surface structure of the vanadium oxides grafted on MCM-48 after exposure to a probe molecule. The results in both cases indicate that the in situ FT-Raman cell is a promising technique for characterizing the molecular surface structure of catalyst materials.     

Large Ferrierite Crystals as Models for Catalyst Deactivation during Skeletal Isomerisation of Oleic Acid: Evidence for Pore Mouth Catalysis

Large zeolite crystals of ferrierite have been used to study the deactivation, at the single particle level, of the alkyl isomerisation catalysis of oleic acid and elaidic acid by a combination of visible micro‐spectroscopy and fluorescence microscopy (both polarised wide‐field and confocal modes). The large crystals did show the desired activity, albeit only traces of the isomerisation product were obtained and low conversions were achieved compared to commercial ferrierite powders. This limited activity is in line with their lower external non‐basal surface area, supporting the hypothesis of pore mouth catalysis. Further evidence for the latter comes from visible micro‐spectroscopy, which shows that the accumulation of aromatic species is limited to the crystal edges, while fluorescence microscopy strongly suggests the presence of polyenylic carbocations. Light polarisation associated with the spatial resolution of fluorescence microscopy reveals that these carbonaceous deposits are aligned only in the larger 10‐MR channels of ferrierite at all crystal edges. The reaction is hence further limited to these specific pore mouths.     

Palladium-based telomerization of 1,3-butadiene with glycerol using methoxy-functionalized triphenylphosphine ligands

Glycerol is considered a potential renewable building block for the synthesis of existing as well as new chemicals. A promising route is the telomerization of 1,3-butadiene with glycerol leading to C8 chain ethers of glycerol with applications in, for example, surfactant chemistry. Recently, we reported a new set of palladium-based homogeneous catalytic systems for the telomerization of 1,3-butadiene with glycerol and found that palladium complexes bearing methoxy-functionalized triphenylphosphine ligands are highly active catalysts capable of converting crude glycerol without any significant loss of activity. Herein, we present a detailed account of these investigations by reporting on the influence of the butadiene/glycerol ratio, temperature, and reaction time on product selectivity and activity allowing further optimization of catalyst performance. Maximum activity and yield were reached for high 1,3-butadiene/glycerol ratios at a temperature of 90 degrees C, whereas the selectivity for mono- and diethers of glycerol could be optimized by combining high reaction temperatures and short reaction times with low butadiene/glycerol ratios. Variation of the PdII metal precursors and the metal/ligand ratio showed that palladium precursors with halogen ligands gave unsatisfying results, in contrast to precursors with weakly coordinated ligands such as [Pd(OAc)2] and [Pd(acac)2]. [Pd(dba)2], the only Pd0 precursor tested, gave the best results in terms of activity, which illustrates the importance of the ability to form a Pd0 species in the catalytic cycle. Finally, base addition resulted in a shortening of the reaction time and most likely facilitates the formation of a Pd0 species. Based on these results, we were able to realize the first attempts towards a rational ligand design aimed at a high selectivity for mono- and diether formation.