Tailoring Spectral and Photochemical Properties of Bioinspired Retinal Mimics by in Silico Engineering

Controlling the spectral tunability and isomerization activity is currently one of the hot topics in the design of photoreversible molecular switches for application in optoelectronic devices. The present work demonstrates how to manipulate the absorption of the retinal protonated Schiff base (rPSB) chromophore over the entire visible range by targeted functionalization of the retinal backbone. Moreover, a correlation between the vertical excitation energy and the profile of the potential energy surface of the bright excited state responsible for the photoreactivity of rPSB is established. This correlation was exploited to rank the functionalized rPSBs into different classes with characteristic photoisomerization activity. Eventually, the synergic effects of functionalization and of external electric fields in the range of a few MV cm⁻¹ were applied to achieve reversable and regioselective control of the photoisomerization propensity of selected rPBS derivatives.     

Electrochemical Magnetic Immunosensors for the Determination of Ceruloplasmin

Electrochemical immunosensors for ceruloplasmin (Cp) are reported for the first time. Two configurations involving magnetic beads (MBs) functionalized with Protein A or Streptavidin for immobilization of Cp antibodies were compared, using competitive immunoassay with synthesized alkaline phosphatase‐Cp conjugate. Upon capturing MBs‐immunoconjugates onto screen‐printed carbon electrodes, quantification of Cp was accomplished by DPV measurement of 1‐naphthol generated after 1‐naphthylphosphate addition. Linear ranges of calibration curves and detection limits were 0.1–1000 µg/mL and 0.040 µg/mL (Protein A‐MBs), and 0.025–20 µg/mL and 0.018 µg/mL (Strept‐MBs). Good results were obtained in the determination of Cp in spiked human serum samples.     

Screening for illicit and medicinal drugs in whole blood using fully automated SPE and ultra‐high‐performance liquid chromatography with TOF‐MS with data‐independent acquisition

A broad forensic screening method for 256 analytes in whole blood based on a fully automated SPE robotic extraction and ultra‐high‐performance liquid chromatography (UHPLC) with TOF‐MS with data‐independent acquisition has been developed. The limit of identification was evaluated for all 256 compounds and 95 of these compounds were validated with regard to matrix effects, extraction recovery, and process efficiency. The limit of identification ranged from 0.001 to 0.1 mg/kg, and the process efficiency exceeded 50% for 73 of the 95 analytes. As an example of application, 1335 forensic traffic cases were analyzed with the presented screening method. Of these, 992 cases (74%) were positive for one or more traffic‐relevant drugs above the Danish legal limits. Commonly abused drugs such as amphetamine, cocaine, and frequent types of benzodiazepines were the major findings. Nineteen less frequently encountered drugs were detected e.g. buprenorphine, butylone, cathine, fentanyl, lysergic acid diethylamide, m‐chlorophenylpiperazine, 3,4‐methylenedioxypyrovalerone, mephedrone, 4‐methylamphetamine, p‐fluoroamphetamine, and p‐methoxy‐N‐methylamphetamine. In conclusion, using UHPLC–TOF‐MS screening with data‐independent acquisition resulted in the detection of common drugs of abuse as well as new designer drugs and more rarely occurring drugs. Thus, TOF‐MS screening of blood samples constitutes a practical way for screening traffic cases, with the exception of δ‐9‐tetrahydrocannabinol, which should be handled in a separate method.     

Evolution of harmonic maps on manifolds flat at infinity

The aim of this article is to prove a global existence result with small data for the heat flow for harmonic maps from a manifold flat at infinity into a compact manifold. By flat at infinity we mean that the growth rate of the volumes of the balls on the manifold is the same as in the flat space. This is true for any manifold for small enough radius, but is in general not true when the radius of the ball grows. So prescribing such a growth rate also at infinity selects a class of manifolds on which our result holds. In this setting estimates are available for the heat kernel and its gradient on the base manifold. From such estimates it is easy to get L ^p −L ^q bounds for the heat kernel. A contraction principle argument then yields a local existence result in a suitable Sobolev space and a global existence result for small data.     

First year mathematics undergraduates’ settled images of tangent line

This study concerns 182 first year mathematics undergraduates’ perspectives on the tangent line of function graph in the light of a previous study on Year 12 pupils’ perspectives. The aim was the investigation of tangency images that settle after undergraduates’ distancing from the notion for a few months and after their participation in university admission examination. To this end we related the performances of the undergraduates and the pupils in the same questions of a questionnaire; we classified the undergraduates in distinct groups through Latent Class Analysis; and, we examined this classification according to the Analytical Local, Geometrical Global and Intermediate Local perspectives on tangency we had identified among pupils. The findings suggest that more undergraduates than pupils demonstrated intermediate perspectives on tangency. Also, the undergraduates’ settled images were influenced by persistent images about tangency and their prior experience in the context of preparation for and participation in the examination.     

Coulomb drag, magnetoresistance, and spin-current injection in magnetic multilayers

We study the effect of spin Coulomb drag on the magnetoresistance and the spin-current injection efficiency of a layered structure consisting of a nonmagnetic semiconductor sandwiched between two ferromagnetic electrodes of spin polarization p. The calculations are done within the framework of the drift-diffusion theory, which we generalize to include the spin trans-conductivity σ_↑↓. We find that for p close to 100% the spin drag enhances the magnetoresistance, while for smaller values of p it reduces it. A new approach to the measurement of σ_↑↓ is suggested.     

Production of “in house” reference materials for ELISA screening of bovine urine and liver samples for clenbuterol

Clenbuterol screening of bovines is done by analysis of urine, for monitoring living animals, and liver, for monitoring animals after slaughter. ELISA has generally been used as the main method for these purposes. Nevertheless, in Europe, methods must be validated according to Commission Decision (EC) 657/2007 criteria, i.e. by use of reference materials. Production of “in house” reference materials is a possibility, but the homogeneity, storage temperature, and period of stability of these materials must be investigated in the laboratory itself. This paper reports GC–MS evaluation of an “in-house”-produced batch of aliquots of bovine urine and liver, fortified with 10.0 ng/ml and 10.0 ng/g clenbuterol, respectively, and stored at ?20 °C and at ?60 °C. For urine stored for 20 weeks at ?20 °C and at 60 °C the stability of clenbuterol was proved at the 95% confidence level. For liver, however, it was demonstrated at the same confidence level that clenbuterol was highly unstable during storage for 20 weeks at either of the temperatures studied.     

Photoaddition to DNA by Nonintercalated Chlorpromazine Molecules

Chlorpromazine (CPZ) forms photoadducts with DNA and photosensitizes DNA strand breaks. These reactions may be responsible for the reported photomutagenicity of CPZ and for the well-known cutaneous and ocular phototoxicity associated with this drug. We have investigated whether CPZ molecules that are intercalated between base pairs in double-stranded (ds) DNA are the absorbing species for the photoaddition reaction. Quenching of CPZ fluorescence by ds-DNA gave nonlinear Stern-Volmer plots, indicating that more than one type of complex is formed. Linear dichroism spectra of CPZ in the presence of ds-DNA showed a minimum at 345 nm, indicating that the absorption maxima of intercalation complex(es) are red-shifted compared to the absorption maximum of free CPZ at 307 nm. The sum of the absorption of all CPZ complexes with ds-DNA, obtained from dialysis experiments, was broadened and maximized at about 315 nm, indicating that complexes not involving intercalation dominate the absorption spectrum at X < 350 nm. The wavelength dependence for covalent binding of CPZ to DNA was determined by irradiating ³H-CPZ in the presence of ds-DNA at 310, 322, 334, 346, 358 and 370 nm. The resulting spectrum correlated closely with the absorption spectrum of nonintercalated CPZ rather than with the spectrum of intercalated CPZ, indicating that the latter species is not the chromophore for the photoaddition reaction.