Shapes of semiflexible polymer rings

The shape of semiflexible polymer rings is studied over their whole range of flexibility. Investigating the joint distribution of asphericity and the nature of asphericity as well as their respective averages, we find two distinct shape regimes depending on the flexibility of the polymer. For a small perimeter to persistence length the fluctuating rings exhibit only planar, elliptical configurations. At higher flexibilities three-dimensional, crumpled structures arise. Analytic calculations confirm the qualitative behavior of the averaged shape parameters and the elliptical shape in the stiff regime.     

Spatial extent of random laser modes

We have experimentally studied the distribution of the spatial extent of modes and the crossover from essentially single-mode to distinctly multimode behavior inside a porous gallium phosphide random laser. This system serves as a paragon for random lasers due to its exemplary high index contrast. In the multimode regime, we observed mode competition. We have measured the distribution of spectral mode spacings in our emission spectra and found level repulsion that is well described by the Gaussian orthogonal ensemble of random-matrix theory.     

Increased Water Reduction Efficiency of Polyelectrolyte‐Bound Trimetallic [Ru,Rh,Ru] Photocatalysts in Air‐Saturated Aqueous Solutions

The groundbreaking use of polyelectrolytes to increase the efficiency of supramolecular photocatalysts in solar H₂ production schemes under aqueous aerobic conditions is reported. Supramolecular photocatalysts of the architecture [{(TL)₂Ru(BL)}₂RhX₂]⁵⁺ (BL=bridging ligand, TL=terminal ligand, X=halide) demonstrate high efficiencies in deoxygenated organic solvents but do not function in air‐saturated aqueous solution because of the quenching of the metal‐to‐ligand charge‐transfer (MLCT) excited state under these conditions. The new photocatalytic system incorporates poly(4‐styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)₂Ru(dpp)}₂RhCl₂]⁵⁺ (bpy=2,2′‐bipyridine, dpp=2,3‐bis(2‐pyridyl)pyrazine). PSS has a profound impact on the photocatalyst efficiency, increasing H₂ production over three times that of deoxygenated aqueous solutions alone. H₂ photocatalysis proceeds even under aerobic conditions for PSS‐containing solutions, an exciting consequence for solar hydrogen‐production research.     

Antiphytopathogenic activity of Psoralea glandulosa (Fabaceae) against Botrytis cinerea and Phytophthora cinnamomi

The resinous exudate, three meroterpenes, namely bakuchiol (1), 3-hydroxybakuchiol (2), 12-hydroxyisobakuchiol (3), and one furanocoumarin, psoralen (4), were isolated from the leaves of culen (Psoralea glandulosa). In addition to these, two semi-synthetic derivatives, bakuchiol acetate (5) and bakuchiol methyl eter (6), were obtained from 1, and were subsequently evaluated in vitro for the inhibitory effect of resin and compounds on the mycelial growth of Botrytis cinerea Pers.: Fr. and Phytophthora cinnamomi Rands. The resinous exudate inhibited the mycelial growth of both the pathogens, while bakuchiol (1) exhibited an inhibitory effect on the mycelial growth of B. cinerea up to 94% at a concentration of 150 mg/L and psoralen (4) reduced the mycelial growth of P. cinnamomi up to 80% at a concentration of 150 mg/L. These compounds have the ability of blocking the development of mycelial growth and may be used as a potential biopesticide in the agricultural sector once the in vivo test results have been validated.     

Study of the distribution of actinides in human tissues using synchrotron radiation micro X-ray fluorescence spectrometry

This study aims at evaluating the capabilities of synchrotron radiation micro X-ray fluorescence spectrometry (SR micro-XRF) for qualitative and semi-quantitative elemental mapping of the distribution of actinides in human tissues originating from individuals with documented occupational exposure. The investigated lymph node tissues were provided by the United States Transuranium and Uranium Registries (USTUR) and were analyzed following appropriate sample pre-treatment. Semi-quantitative results were obtained via calibration by external standards and demonstrated that the uranium concentration level in the detected actinide hot spots reaches more than 100 μg/g. For the plutonium hot spots, concentration levels up to 31 μg/g were found. As illustrated by this case study on these unique samples, SR micro-XRF has a high potential for this type of elemental bio-imaging owing to its high sensitivity, high spatial resolution, and non-destructive character.

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Graphical Abstract SR micro-XRF study of the distribution of actinitides in human tissues. Left Location of the U-contaminated tissue sample in the human body. Middle U distribution derived from the high resolution SR micro-XRF scan on the tissue sample, indication of five U hot spots. Right Detail of the point measurement spectrum of U hot spot 3, intense U-L_α fluorescence peak located at 13.6 keV.

     

Extreme red shifted SERS nanotags

Surfaced enhanced Raman scattering (SERS) nanotags operating with 1280 nm excitation were constructed from reporter molecules selected from a library of 14 chalcogenopyrylium dyes containing phenyl, 2-thienyl, and 2-selenophenyl substituents and a surface of hollow gold nanoshells (HGNs). These 1280 SERS nanotags are unique as they have multiple chalcogen atoms available which allow them to adsorb strongly onto the gold surface of the HGN thus producing exceptional SERS signals at this long excitation wavelength. Picomolar limits of detection (LOD) were observed and individual reporters of the library were identified by principal component analysis and classified according to their unique structure and SERS spectra.     

High resolution mass spectrometry based profiling of diet-related deoxyribonucleic acid adducts

Exposure of DNA to endo- and exogenous DNA binding chemicals can result in the formation of DNA adducts and is believed to be the first step in chemically induced carcinogenesis. DNA adductomics is a relatively new field of research which studies the formation of known and unknown DNA adducts in DNA due to exposure to genotoxic chemicals. In this study, a new UHPLC-HRMS(/MS)-based DNA adduct detection method was developed and validated. Four targeted DNA adducts, which all have been linked to dietary genotoxicity, were included in the described method; O⁶-methylguanine (O⁶-MeG), O⁶-carboxymethylguanine (O⁶-CMG), pyrimidopurinone (M1G) and methylhydroxypropanoguanine (CroG). As a supplementary tool for DNA adductomics, a DNA adduct database, which currently contains 123 different diet-related DNA adducts, was constructed. By means of the newly developed method and database, all 4 targeted DNA adducts and 32 untargeted DNA adducts could be detected in different DNA samples. The obtained results clearly demonstrate the merit of the described method for both targeted and untargeted DNA adduct detection in vitro and in vivo, whilst the diet-related DNA adduct database can distinctly facilitate data interpretation.     

A rugged landscape model for self-organization and emergent leadership in creative problem solving and production groups

The process by which an initially leaderless group differentiates into one containing leadership and secondary role structures was examined using the swallowtail catastrophe model and principles of selforganization. The objectives were to identify the control variables in the process of leadership emergence in creative problem solving groups and production groups. In the first of two experiments, groups of university students (total N = 114) played a creative problem solving game. Participants later rated each other on leadership behavior, styles, and variables related to the process of conversation. A performance quality measure was included also. Control parameters in the swallowtail catastrophe model were identified through a combination of factor analysis and nonlinear regression. Leaders displayed a broad spectrum of behaviors in the general categories of Controlling the Conversation and Creativity in their role-play. In the second experiment, groups of university students (total N = 197) engaged in a laboratory work experiment that had a substantial production goal component. The same system of ratings and modeling strategy was used along with a work production measure. Leaders in the production task emerged to the extent that they exhibited control over both the creative and production aspects of the task, they could keep tension low, and the externally imposed production goals were realistic.     

Responsive microgrooves for the formation of harvestable tissue constructs

Given its biocompatibility, elasticity, and gas permeability, poly(dimethylsiloxane) (PDMS) is widely used to fabricate microgrooves and microfluidic devices for three-dimensional (3D) cell culture studies. However, conformal coating of complex PDMS devices prepared by standard microfabrication techniques with desired chemical functionality is challenging. This study describes the conformal coating of PDMS microgrooves with poly(N-isopropylacrylamide) (PNIPAAm) by using initiated chemical vapor deposition (iCVD). These microgrooves guided the formation of tissue constructs from NIH-3T3 fibroblasts that could be retrieved by the temperature-dependent swelling property and hydrophilicity change of the PNIPAAm. The thickness of swollen PNIPAAm films at 24 °C was approximately 3 times greater than at 37 °C. Furthermore, PNIPAAm-coated microgroove surfaces exhibit increased hydrophilicity at 24 °C (contact angle θ = 30° ± 2) compared to 37 °C (θ = 50° ± 1). Thus PNIPAAm film on the microgrooves exhibits responsive swelling with higher hydrophilicity at room temperature, which could be used to retrieve tissue constructs. The resulting tissue constructs were the same size as the grooves and could be used as modules in tissue fabrication. Given its ability to form and retrieve cell aggregates and its integration with standard microfabrication, PNIPAAm-coated PDMS templates may become useful for 3D cell culture applications in tissue engineering and drug discovery.