Synthesis,Characterization and Application of New Rhodium Complexes for Indirect Electrochemical Cofactor Regeneration

Electroenzymatic synthesis often suffers from electrochemical reaction steps which proceed slower than the coupled enzyme reaction. For indirect electrochemical cofactor regeneration, we here report two new mediators with superior properties compared to the established rhodium complex (2,2′‐bipyridyl)(pentamethylcyclopentadienyl)rhodium [Cp*Rh(2,2′‐bipyridine)]. After constructing a robotic system for fast and reliable cyclic voltammetry measurements, we screened twelve rhodium complexes with substituted 2,2′‐bipyridine ligands for their reduction potentials and catalytic activity towards the reduction of NADP. Promising complexes were investigated in more detail by cyclic voltammetry and under batch electrolysis conditions. The new complexes Cp*Rh(5,5′‐methyl‐2,2′‐bipyridine) and Cp*Rh(4,4′‐methoxy‐2,2′‐bipyridine) reduced NADP to NADPH three times faster than the established mediator, resulting in volumetric productivities of up to 136 mmol L⁻¹ d⁻¹ and turnover frequencies of up to 113 h⁻¹. This increased reaction rate of these new mediators makes indirect electrochemical approach significantly more competitive to other methods of cofactor regeneration. Abbreviations: ADH=alcohol dehydrogenase; Ag|AgCl=silver|silver chloride reference electrode; bpy=2,2′‐bipyridine; ci=current increase; Cp*=pentamethylcyclopentadienyl; CV=cyclic voltammetry; Ep=peak potential; equiv=equivalent; NADP/NADPH=nicotinamide adenine dinucleotide phosphate oxidised/reduced form.     

The Art of Masonry

Brick masonry is not only a question of building physics, building construction and durability, i.e. sustainability, but has much to do with aesthetics and making sense, which may have been forgotten in modern architecture with its absolute lack of décor. Masonry as an art form has been scarce since the era of brick expressionism. Recently, there have been some exceptions – and thoroughly welcome. The ”Fjordenhus“ in Vejle, Denmark, is an astonishing example.     

Electrodeposition of palladium-dotted nickel nanowire networks as a robust self-supported methanol electrooxidation catalyst

Journal of Materials Science - Mass activity and long-term stability are two major issues in current fuel cell catalyst designs. While supported catalysts normally suffer from poor long-term...     

Toxizitätsreduktion durch (Grundwasser-) Sanierung?

The usage of an automatized and continuously (on-line) working biomonitor for the surveillance of groundwater remediation is presented and the data are compared to different discontinuous acute biotests. The use of an on-line biomonitor at the SAFIRA groundwater remediation testsite showed to be superior to the discontinuous tests. The long-time surveillance of two different remediation techniques revealed a decrease in remediation efficiency of one technique while the other technique -using activated carbon- did not show any reduction in efficiency. The validation of these results with other acute biotests (algae, fishembryo, daphnia and genotoxicity) indicated a complex groundwater contamination which can not be explained by the quantitatively main contaminant monochlorobenzene. It is suggested to use ecotoxicological biotests and knowledge in parallel to the conventional chemical analysis before a remediation strategy is designed. All anthropogenic contaminations (toxic or unwanted) should be identified beforehand such that the developed remediation techniques would be more target-oriented.     

Determination of CFTR densities in erythrocyte plasma membranes using recognition imaging

CFTR (cystic fibrosis transmembrane conductance regulator) is a cAMP-regulated chloride (Cl(-)) channel that plays an important role in salt and fluid movement across epithelia. Cystic fibrosis (CF), the most common genetic disease among Caucasians, is caused by mutations in the gene encoding CFTR. The most predominant mutation, F508del, disturbs CFTR protein trafficking, resulting in a reduced number of CFTR in the plasma membrane. Recent studies indicate that CFTR is not only found in epithelia but also in human erythrocytes. Although considerable attempts have been made to quantify CFTR in cells, conclusions on numbers of CFTR molecules localized in the plasma membrane have been drawn indirectly. AFM has the power to provide the needed information, since both sub-molecular spatial resolution and direct protein recognition via antibody-antigen interaction can be observed. We performed a quantification study of the CFTR copies in erythrocyte membranes at the single molecule level, and compared the difference between healthy donors and CF patients. We detected that the number of CFTR molecules is reduced by 70% in erythrocytes of cystic fibrosis patients.     

Starch Phosphate Hydrogels. Part I: Synthesis by Mono‐phosphorylation and Cross‐linking of Starch

Starch‐based hydrogels were synthesized by cross‐linking monostarch monophosphates (MSMP) with different di‐ and tricarboxylic acids such as succinic, adipic or citric acid. Phosphorylation of starch was performed in a semi‐dry process using a mixture of primary and secondary sodium phosphates. The phosphorus content and degree of substitution of phosphate groups (DS_P) of the resulting MSMP were determined using a photometric method. For structural characterization of starch phosphates ³¹P NMR was used. Investigations showed that MSMP hydrogels were strong water absorbing polymer networks with a free swelling capacity (FSC) of up to 185 g water / g dry hydrogel.     

Submersion injuries in children and adults

Drowning and near drowning remain a common cause of childhood death and disability. Toddlers aged one through four drown in private swimming pools. Submersions greater than 10 minutes and lack of CPR at the scene or the need for greater than 20 minutes of resuscitation portends a poor prognosis. Management of respiratory failure without neurologic impairment has the most successful outcome. Prevention of drowning morbidity is dependent on constant parental supervision, and immediate and expert CPR.