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22 records · Page 2

A new method for obtaining model-free viscoelastic material properties from atomic force microscopy experiments using discrete integral transform techniques

Viscoelastic characterization of materials at the micro- and the nanoscale is commonly performed with the aid of force–distance relationships acquired using atomic force microscopy (AFM). The general strategy for existing methods is to fit the observed material behavior to specific viscoelastic models, such as generalized viscoelastic models or power-law rheology models, among others. Here we propose a new method to invert and obtain the viscoelastic properties of a material through the use of the Z-transform, without using a model. We present the rheological viscoelastic relations in their classical derivation and their z-domain correspondence. We illustrate the proposed technique on a model experiment involving a traditional ramp-shaped force–distance AFM curve, demonstrating good agreement between the viscoelastic characteristics extracted from the simulated experiment and the theoretical expectations. We also provide a path for calculating standard viscoelastic responses from the extracted material characteristics. The new technique based on the Z-transform is complementary to previous model-based viscoelastic analyses and can be advantageous with respect to Fourier techniques due to its generality. Additionally, it can handle the unbounded inputs traditionally used to acquire force–distance relationships in AFM, such as ramp functions, in which the cantilever position is displaced linearly with time for a finite period of time.

36 MATERIALS SCIENCE↗

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials

We report the modulation of reactivity of nitrogen dioxide (NO 2 ) in a charged metal–organic framework (MOF) material, MFM-305-CH 3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl - ions in the pores. Uptake of NO 2 into MFM-305-CH 3 leads to reaction between NO 2 and Cl - to give nitrosyl chloride (NOCl) and NO 3 - anions. A high dynamic uptake of 6.58 mmol g -1 at 298 K is observed for MFM-305-CH 3 as measured using a flow of 500 ppm NO 2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g -1 . The binding domains and reactivity of adsorbed NO 2 molecules within MFM-305-CH 3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Noninvasive THz-TDS measurements of plasma bounded and optically shielded by Hall thruster wall material

We experimentally demonstrate the capability of terahertz time-domain spectroscopy (THz-TDS) to noninvasively measure the electron density and collision frequency of plasma bounded and optically shielded by Hall thruster wall material. This paper augments the standard THz-TDS plasma diagnostic theory to account for plasma boundaries, presents THz optical property measurements of three different wall materials (grades M, M26, and HP boron nitride composite), and provides electron density and collision frequency measurements of an inductively coupled plasma bounded and optically shielded by each wall material. We find that the electron density measurement capability is weakly impacted by the boundaries, whereas the electron collision frequency measurement capability is strongly reduced by the boundaries. Here, the bounded plasma electron density trends deviate substantially from those of the unbounded plasma.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Structure and functional determinants of Rad6–Bre1 subunits in the histone H2B ubiquitin-conjugating complex

The conserved complex of the Rad6 E2 ubiquitin-conjugating enzyme and the Bre1 E3 ubiquitin ligase catalyzes histone H2B monoubiquitination (H2Bub1), which regulates chromatin dynamics during transcription and other nuclear processes. Here, we report a crystal structure of Rad6 and the non-RING domain N-terminal region of Bre1, which shows an asymmetric homodimer of Bre1 contacting a conserved loop on the Rad6 ‘backside’. This contact is distant from the Rad6 catalytic site and is the location of mutations that impair telomeric silencing in yeast. Mutational analyses validated the importance of this contact for the Rad6–Bre1 interaction, chromatin-binding dynamics, H2Bub1 formation and gene expression. Moreover, the non-RING N-terminal region of Bre1 is sufficient to confer nucleosome binding ability to Rad6 in vitro. Interestingly, Rad6 P43L protein, an interaction interface mutant and equivalent to a cancer mutation in the human homolog, bound Bre1 5-fold more tightly than native Rad6 in vitro, but showed reduced chromatin association of Bre1 and reduced levels of H2Bub1 in vivo. These surprising observations imply conformational transitions of the Rad6–Bre1 complex during its chromatin-associated functional cycle, and reveal the differential effects of specific disease-relevant mutations on the chromatin-bound and unbound states. Overall, our study provides structural insights into Rad6–Bre1 interaction through a novel interface that is important for their biochemical and biological responses.

59 BASIC BIOLOGICAL SCIENCES↗