Methyl groups as probes for proteins and complexes in in-cell NMR experiments

Studying protein components of large intracellular complexes by in-cell NMR has so far been impossible because the backbone resonances are unobservable due to their slow tumbling rates. We describe a methodology that overcomes this difficulty through selective labeling of methyl groups, which possess more favorable relaxation behavior. Comparison of different in-cell labeling schemes with three different proteins, calmodulin, NmerA, and FKBP, shows that selective labeling with [(13)C]methyl groups on methionine and alanine provides excellent sensitivity with low background levels at very low costs.     

On the swelling behavior of poly(N-Isopropylacrylamide) hydrogels exposed to perfluoroalkyl acids

Per- and polyfluoroalkyl substances (PFAS) have rapidly accumulated in the environment due to their widespread use prior to commercial discussion in the early 21st century, and their slow degradation has magnified concerns of their potential toxicity. Monitoring their distribution is, therefore, necessary to evaluate and control their impact on the health of exposed populations. This investigation evaluates the capability of a simple polymeric detection scheme for PFAS based on crosslinked, thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels. Surveying swelling perturbations induced by several hydrotropes and comparable hydrocarbon analogs, tetraethylammonium perfluorooctane sulfonate (TPFOS) showed a significantly higher swelling ratio on a mass basis (65.5 ± 8.8 at 15°C) than any of the other analytes tested. Combining swelling with the fluorimetric response of a solvachromatic dye, nile red, revealed the fluorosurfactant to initiate observable aggregation (i.e., its critical aggregation concentration) at 0.05 mM and reach saturation (i.e., its charge neutralization concentration) at 0.5 mM. The fluorosurfactant was found to homogeneously distribute throughout the polymer matrix with energy dispersive X-ray spectroscopy, marking the swelling response as a peculiar nexus of fluorinated interfacial positioning and delocalized electrostatic repulsion. Results from the current study hold promise for exploiting the physiochemical response of PNIPAM to assess TPFOS's concentration.     

Optimizing the monomer structure of polyhedral oligomeric silsesquioxane for ion transport in hybrid organic–inorganic block copolymers

Poly(ethylene oxide)-b-polyhedral oligomeric silsesquioxane (PEO–POSS) mixed with lithium bis(trifluoromethanesulfonyl)imide salt is a nanostructured hybrid organic–inorganic block copolymer electrolyte that may enable lithium metal batteries. The synthesis and characteristics of three PEO–POSS block copolymer electrolytes which only differ by their POSS silica cage substituents (ethyl, isobutyl, and isooctyl) is reported. Changing the POSS monomer structure results in differences in both thermodynamics and ion transport. All three neat polymers exhibit lamellar morphologies. Adding salt results in the formation of a disordered window which closes and gives way to lamellae at higher salt concentrations. The width of disordered window decreases with increasing length of the POSS alkyl chain substituent from ethyl to isobutyl and is absent in the isooctyl sample. Rheological measurements demonstrate good mechanical rigidity when compared with similar all-organic block copolymers. While salt diffusion coefficient and current ratio are unaffected by substituent length, ionic conductivity increases as the length of the alkyl chain substituent decreases: the ethyl substituent is optimal for ion transport. This is surprising because conventional wisdom suggests that ion transport occurs primarily in the PEO-rich domains, that is, ion transport should be unaffected by substituent length after accounting for the minor change in conducting phase volume fraction. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 363–371     

The phase behavior of a polymer‐fullerene bulk heterojunction system that contains bimolecular crystals

Polymer:fullerene blends have been widely studied as an inexpensive alternative to traditional silicon solar cells. Some polymer:fullerene blends, such as blends of poly(2,5‐bis(3‐tetradecylthiophen‐2‐yl)thieno[3,2‐b]thiophene (pBTTT) with phenyl‐c71‐butyric acid methyl ester (PC₇₁BM), form bimolecular crystals due to fullerene intercalation between the polymer side chains. Here we present the determination of the eutectic pBTTT:PC₇₁BM phase diagram using differential scanning calorimetry (DSC) and two‐dimensional grazing incidence X‐ray scattering (2D GIXS) with in‐situ thermal annealing. The phase diagram explains why the most efficient pBTTT:PC₇₁BM solar cells have 75–80 wt % PC₇₁BM since these blends lie in the center of the only room‐temperature phase region containing both electron‐conducting (PC₇₁BM) and hole‐conducting (bimolecular crystal) phases. We show that intercalation can be suppressed in 50:50 pBTTT:PC₇₁BM blends by using rapid thermal annealing to heat the blends above the eutectic temperature, which forces PC₇₁BM out of the bimolecular crystal, followed by quick cooling to kinetically trap the pure PC₇₁BM phase. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Aberration correction and its automatic control in scanning electron microscopes

An automatic aberration correction method has been implemented in scanning electron microscopes (SEM). Necessity of the automatic aberration correction is discussed. The procedure of the automatic aberration correction is explained in detail, where deconvolution techniques are used in order to extract probe information from SEM images. Due to the precise digitization and the usage of proper combinations of correction fields, linearity has been found between the amplitude of each aberration and the corresponding field strength. Experimental results are shown which demonstrate that the aberrations are corrected automatically by a linear feedback control method. After the automatic aberration correction, the image quality has been improved drastically.     

A note on Mustaţă's computation of multiplier ideals of hyperplane arrangements

In 2006, M. Mustaţă used jet schemes to compute the multiplier ideals of reduced hyperplane arrangements. We give a simpler proof using a log resolution and generalize to non-reduced arrangements. By applying the idea of wonderful models introduced by De Concini-Procesi in 1995, we also simplify the result. Indeed, Mustaţă's result expresses the multiplier ideal as an intersection, and our result uses (generally) fewer terms in the intersection.

     

Winkelverteilung der Polarisation der Neutronen aus der Reaktion14C(d,n 0)15N bei Deuteronenenergien zwischen 1,3 und 1,9 MeV

Polarization distributions of ground state neutrons emitted from the¹⁴C(d,n ₀)¹⁵N reaction were investigated over the angular range from 15 ° (lab) to 150 ° (lab) at bombarding energies of 1.28, 1.55 and 1.88 MeV. Scattering of neutrons from helium served as polarization analyzer. The experimental results show a large variation with energy of the polarization ranging betweenP(Θ_lab=130 °)=?21% andP(Θ_lab=130 °)=+50% at 1.28 and 1.88 MeV respectively.     

Mass selective separation applied to radioisotopes of cesium

A technique that uses the intrinsic mass‐based separation capability of a quadrupole mass spectrometer has been used to resolve spectral radiometric interference of two isotopes of the same element. In this work the starting sample was a mixture of ¹³⁷Cs and ¹³⁴Cs and was (activity) dominated by ¹³⁷Cs. This methodology separated and ‘implanted’ ¹³⁴Cs that was later quantified for spectral features and activity with traditional radiometric techniques. This work demonstrated a ¹³⁴Cs/¹³⁷Cs activity ratio enhancement of >4 orders of magnitude and complete removal of ¹³⁷Cs spectral features from the implanted target mass (i.e. 134). Copyright © 2016 John Wiley & Sons, Ltd.