Enhanced Catalytic Activity of Cobalt Porphyrin in CO2 Electroreduction upon Immobilization on Carbon Materials

In a comparative study of the electrocatalytic CO₂ reduction, cobalt meso-tetraphenylporphyrin (CoTPP) is used as a model molecular catalyst under both homogeneous and heterogeneous conditions. In the former case, employing N,N-dimethylformamide as solvent, CoTPP performs poorly as an electrocatalyst giving low product selectivity in a slow reaction at a high overpotential. However, upon straightforward immobilization of CoTPP onto carbon nanotubes, a remarkable enhancement of the electrocatalytic abilities is seen with CO₂ becoming selectively reduced to CO (>90 %) at a low overpotential in aqueous medium. This effect is ascribed to the particular environment created by the aqueous medium at the catalytic site of the immobilized catalyst that facilitates the adsorption and further reaction of CO₂. This work highlights the significance of assessing an immobilized molecular catalyst from more than homogeneous measurements alone.     

An Aldehyde Responsive,Cleavable Linker for Glucose Responsive Insulins

A glucose responsive insulin (GRI) that responds to changes in blood glucose concentrations has remained an elusive goal. Here we describe the development of glucose cleavable linkers based on hydrazone and thiazolidine structures. We developed linkers with low levels of spontaneous hydrolysis but increased level of hydrolysis with rising concentrations of glucose, which demonstrated their glucose responsiveness in vitro. Lipidated hydrazones and thiazolidines were conjugated to the LysB29 side-chain of HI by pH-controlled acylations providing GRIs with glucose responsiveness confirmed in vitro for thiazolidines. Clamp studies showed increased glucose infusion at hyperglycemic conditions for one GRI indicative of a true glucose response. The glucose responsive cleavable linker in these GRIs allow changes in glucose levels to drive the release of active insulin from a circulating depot. We have demonstrated an unprecedented, chemically responsive linker concept for biopharmaceuticals.     

A theoretical study of malonate and formate calcium binding by ab initio techniques

Ab initio calculations at the STO—3G level have been performed on the binding of CA(II) ion to malonate and formate with and without d orbitals in the basis set for the CA(II) ion. The malonate and formate binding results with CA(II) are similar. The addition of d orbitals to CA(II) has little effect on the conformational minimum. The results are qualitatively similar to those from our previous calculations on the Mg²⁺—malonate interaction: a single carboxyl interaction with the metal ion appears to be preferred over a conformation in which two carboxyl groups bind to Ca(II). Moreover, the single carboxyl group interaction with CA(II) appears to be favored over the binding of CA(II) to a single oxygen of a carboxyl group.     

The Remainder in Ruijsenaars’ Asymptotic Expansion of Barnes Double Gamma Function

We show that the remainder in Ruijsenaars’ asymptotic expansion of the logarithm of Barnes double gamma function gives rise to a completely monotone function. Fourier expansions of the multiple Bernoulli polynomials are also obtained. Research supported by the Carlsberg Foundation.     

Optimization of bolt thread stress concentrations

Designs of threaded fasteners are controlled by different standards, and the number of different thread definitions is large. The most commonly used thread is probably the metric ISO thread, and this design is therefore used in the present paper. Thread root design controls the stress concentration factor of threads and therefore indirectly the bolt fatigue life. The root shape is circular, and from shape optimization for minimum stress concentration it is well known that the circular shape is seldom optimal. An axisymmetric Finite Element formulation is used to analyze the bolted connection, and a study is performed to establish the need for contact modeling with regard to finding the correct stress concentration factor. Optimization is performed with a simple parameterization with two design variables. Stress reduction of up to 9% is found in the optimization process, and some similarities are found in the optimized designs leading to the proposal of a new standard. The reductions in the stress are achieved by rather simple changes made to the cutting tool.     

Turbulent boundary layer at the border of geomagnetic trap

A new phenomenon was discovered on the basis of analysis of the Interball project data. A hot plasma flow is thermalized through the formation of “long-operating” vortex streets and local discontinuities and solitons in a distributed region over polar cusps. Plasma percolation through the structured boundary and secondary reconnection of fluctuating magnetic fields in a high-latitude turbulent boundary layer account for the main part of solar wind plasma inflow into the magnetospheric trap. Unlike local shocks, the ion thermalization is accompanied by the generation of coherent Alfvén waves on the scales ranging from ion gyroradius to the radius of curvature of the averaged magnetic field, as well as by the generation of diamagnetic bubbles with a demagnetized heated plasma inside. This “boiling” plasma has a frequency region where the spectrum is different from the Kolmogorov law (with slopes 1.2 and 2.4 instead of 5/3 or 3/2). The fluctuation self-organization in the boundary layer (synchronization of three-wave decays) was observed on certain frequency scales.     

Optical waveguide sensor for on-line monitoring of bacteria

A grating-coupled planar optical waveguide sensor is presented for sensing of bacteria by evanescent waves. The waveguide design results in increased depth of penetration into the sample volume, which makes it suitable for detecting micrometer-sized biological objects. We tested the sensor's performance by monitoring the adhesion of Escherichia coli K12 cells to the sensor surface.     

Second-harmonic generation spectroscopy on?organic?nanofibers

Optical second-harmonic generation upon nanosecond laser irradiation of nanofibers grown from nonsymmetrically functionalized para-quarter-phenylene molecules on mica surfaces is investigated in the spectral region around electronic resonances. Strong multiphoton excited luminescence appears together with the second-harmonic signal in the spectra. It is demonstrated how the two components can be separated by analyzing emission spectra recorded over a broad range of wavelengths around the second-harmonic energy. Spectra of the absolute values of the second-harmonic signals are obtained for three differently functionalized molecules. Together with supplementary measurements of the structure of the nanofiber films this forms the basis for estimation of the second-harmonic susceptibility of the fiber materials. Values of the nonlinear susceptibilities are obtained, which are comparable to those of well-known inorganic nonlinear optical crystals.