ALBERT

Description: Abstract Borates and borosilicates are potential candidates for the design and development of glass formulations with important industrial and technological applications. A major challenge that retards the pace of development of borate/borosilicate based glasses using predictive modeling is the lack of reliable computational models to predict the structure‐property relationships in these glasses over a wide compositional space. A major hindrance in this pursuit has been the complexity of boron‐oxygen bonding due to which it has been difficult to develop adequate B–O interatomic potentials. In this article, we have evaluated the performance of three B–O interatomic potential models recently developed by Bauchy et al [J. Non‐Cryst. Solids, 2018, 498, 294–304], Du et al [J. Am. Ceram. Soc. https://doi.org/10.1111/jace.16082] and Edèn et al [Phys. Chem. Chem. Phys., 2018, 20, 8192–8209] aiming to reproduce the short‐to‐medium range structures of sodium borosilicate glasses in the system 25 Na2O x B2O3 (75 − x) SiO2 (x = 0‐75 mol%). To evaluate the different force fields, we have computed at the density functional theory level the NMR parameters of 11B, 23Na, and 29Si of the models generated with the three potentials and the simulated MAS NMR spectra compared with the experimental counterparts. It was observed that the rigid ionic models proposed by Bauchy and Du can both reliably reproduce the partitioning between BO3 and BO4 species of the investigated glasses, along with the local environment around sodium in the glass structure. However, they do not accurately reproduce the second coordination sphere of silicon ions and the Si–O–T (T = Si, B) and B‐O‐T distribution angles in the investigated compositional space which strongly affect the NMR parameters and final spectral shape. On the other hand, the core‐shell parameterization model proposed by Edén underestimates the fraction of BO4 species of the glass with composition 25Na2O 18.4B2O3 56.6SiO2 but can accurately reproduce the shape of the 11B and 29Si MAS‐NMR spectra of the glasses investigations due to the narrower B–O–T and Si‐O‐T bond angle distributions. Finally, the effect of the number of boron atoms (also distinguishing the BO3 and BO4 units) in the second coordination sphere of the network former cations on the NMR parameters have been evaluated.

Description: Shape-forming techniques which may be useful in producing components for body armor are reviewed. The techniques are classified in three general categories, dry, wet, and plastic. The different shaping techniques are compared based on key parameters including shape limitations, rate of production, cost, and safety. The techniques are evaluated as to their suitability to be used to produce different body armor components such as breast plates, deltoid, shin and knee protection, and helmets. Dry-pressing is the current standard for producing “relatively flat” components such as breast plates, but performance is limited by the inherent problem associated with dry-pressing, namely, the difficulty in producing homogeneous green bodies because of agglomerates in the powder. Plastic processing has the potential to be useful to produce more reliable “flat” components with improved performance due to high shear mixing breaking up agglomerates. Wet (colloidal) processing techniques such as gelcasting and freeze casting may be useful to produce components with high curvature and more complex shape such as helmets. Tiles or segments may be combined to produce shaped components with increased flexibility.

Description: Hydrothermal synthesis has afforded a pair of divalent copper acetate coordination polymers containing either 4,4′-dipyridylamine (dpa) or 4-pyridylisonicotinamide (4-pina), both of which hydrogen-bonding capable central functional groups. X-ray crystallography revealed that both exhibit a 1D chain dimensionality. Use of the kinked tethering ligand dpa produced [Cu(OAc) 2 (dpa)] n ( 1 ), which possesses a simple chain based on dpa linkage of isolated copper ions. On the other hand, employing the straighter amide ligand 4-pina generated {[Cu(OAc) 2 (4-pina)] · 0.5H 2 O} n ( 2 ), which exhibits {Cu 2 O 2 } rhomboid dimers formed through bridging acetate ligands. Weak antiferromagnetic coupling [ g = 1.984(3), J = –3.2(3) cm –1 ] was observed within the axial-equatorial bridged {Cu 2 O 2 } dimers in 2 , with possible ferrimagnetism due to spin canting below 11 K.

Description: The 1,25-dihydroxyvitamin D 3 (1,25D) hormone is derived from vitamin D generated in skin or obtained from the diet, and binds to and activates the vitamin D receptor (VDR) in target tissues including kidney, colon/small intestine, and bone/muscle. We tested resveratrol for its ability to modulate VDR signaling, using vitamin D responsive element (VDRE) and mammalian two-hybrid (M2H) transcriptional system technology. Via VDRE-based assays in kidney, colon and myoblast cells, VDR-mediated transcription was activated by resveratrol, and a cooperative effect on transactivation was observed with resveratrol plus 1,25D. The M2H assay revealed a modest, resveratrol-induced dimerization of VDR with its retinoid X receptor (RXR) heteropartner. Cells treated with both resveratrol and 1,25D displayed synergistic stimulation of VDR-RXR heterodimerization, while resveratrol antagonized rexinoid-mediated RXR-RXR homodimerization. Increased transactivation in response to resveratrol was also observed with a subset of other nuclear receptors and their respective cognate responsive elements. Evaluation of wild-type versus a ligand-binding domain mutant VDR revealed that hormone-responsiveness to 1,25D was severely depressed, while the response to resveratrol was only moderately attenuated. Moreover, radiolabeled 1,25D-displacement assays demonstrated an increase in VDR-bound 1,25D in the presence of resveratrol. Thus, resveratrol may affect VDR and other nuclear receptors indirectly, likely via the ability of resveratrol to: 1) potentiate 1,25D binding to VDR, 2) activate RXR, and/or 3) stimulate SIRT1, an enzyme known to deacetylate nuclear receptors. The results of this study elucidate a possible pathway for crosstalk between two nutritionally derived lipids, vitamin D and resveratrol, both of which converge on VDR signaling. This article is protected by copyright. All rights reserved

Description: The reactivity of particle surfaces can be used as a criterion to group nanoforms (NFs) based on similar potential hazard. Since NFs may partially or completely dissolve over the duration of the assays, with the ions themselves inducing a response, reactivity assays commonly measure the additive reactivity of the particles and ions combined. Here, we determine the concentration of ions released over the course of particle testing, and determine the relative contributions of the released ions to the total reactivity measured. We differentiate three classes of reactivity, defined as being A) dominated by particles, B) additive of particles and ions, or C) dominated by ions. We provide examples for each class by analyzing the NF reactivity of Fe2O3, ZnO, CuO, Ag using the ferric reduction ability of serum (FRAS) assay. Furthermore, another two reactivity tests were performed: Dichlorodihydrofluorescin diacetate (DCFH2‑DA) assay and electron paramagnetic resonance (EPR) spectroscopy. We compare assays and demonstrate that the dose‑response may be almost entirely assigned to ions in one assay (CuO in DCFH2‑DA), but to particles in others (CuO in EPR and FRAS). When considering this data, we conclude that one cannot specify the contribution of ions to NF toxicity for a certain NF, but only for a certain NF in a specific assay, medium and dose. The extent of dissolution depends on the buffer used, particle concentration applied, and duration of exposure. This culminates in the DCFH2‑DA, EPR, FRAS assays being performed under different ion‑to‑particle ratios, and differing in their sensitivity towards reactions induced by either ions or particles. If applied for grouping, read‑across, or other concepts based on the similarity of partially soluble NFs, results on reactivity should only be compared if measured by the same assay, incubation time, and dose range.

Description: The most common bone disease in humans is osteoporosis (OP). Current therapeutics targeting OP have several negative side effects. Bone morphogenetic protein 2 (BMP2) is a potent growth factor that is known to activate both osteoblasts and osteoclasts. It completes these actions through both SMAD-dependent and SMAD-independent signaling. A novel interaction between the BMP type Ia receptor (BMPRIa) and casein kinase II (CK2) was discovered, and several CK2 phosphorylation sites were identified. A corresponding blocking peptide (named CK2.3) was designed to further elucidate the phosphorylation site’s function. Previously, CK2.3 demonstrated an increased osteoblast activity and decreased osteoclast activity in a variety of animal models, cell lines, and isolated human osteoblasts. It is hypothesized that CK2.3 completes these actions through the BMP signaling pathway. Furthermore, it was recently discovered that BMP2 did not elicit an osteogenic response in osteoblasts from patients diagnosed with OP, while CK2.3 did. In this study, we explore where in the BMP pathway the signaling disparity or defect lies in those diagnosed with OP. We found that osteoblasts isolated from patients diagnosed with OP did not activate SMAD or ERK signaling after BMP2 stimulation. When OP osteoblasts were stimulated with BMP2, both BMPRIa and CK2 expression significantly decreased. This indicates a major disparity within the BMP signaling pathway in patients diagnosed with osteoporosis.

Description: Pigments from wood-decay fungi (specifically spalting fungi) have a long history of use in wood art, and have become relevant in modern science due to their longevity and colorfastness. They are presently under investigation as colorants for wood, bamboo, oils, paints and textiles. Major hurdles to their commercialization have been color repeatability (in that the same strain of the same species of fungus may produce different colors over time), and the binding of the pigments to glass storage containers. This is persistent as they do not naturally exist in a loose form. Due to these issues, the ‘standard’ color for each was historically determined not by the amount of pigment, but by the color in a solution of dichloromethane (DCM), using the CIE L*a*b colorspace. This method of standardization severely limited the use of these pigments in industrial applications, as without a dry form, standard methodologies for repeatable color processing into other materials could not be easily implemented. Recent studies have developed a method to crystalize the red pigment from Scytalidium cuboideum (Sacc. & Ellis) Sigler & Kang, producing a highly pure (99%) solid crystal named ‘Dramada’. Herein a method is detailed to compare the molarity of this crystallized pigment to variations in the color, to determine a color saturation curve (by weight) for the pigment from S. cuboideum in DCM and acetone. The molarities for this experiment ranged from 0.024 mM to 19 mM. Each molarity was color read and assigned a CIEL*a*b* value. The results showed that there was a correlation between the molarity and color difference, with the maximum red color occurring between 0.73 mM and 7.3 mM in DCM and between 0.97 mM to 0.73 mM in acetone. Extremely low molarities of pigment produced strong coloration in the solvent, and changes in molarity significantly affected the color of the solution. Having a saturation and color curve for the crystal ‘Dramada’ from S. cuboideum will allow for the reliable production of distinct colors from a known quantity (by weight) of pigment, erasing the final hurdle towards commercial development of the crystallized pigment from S. cuboideum as an industrial dyestuff.

Description: The potential risks of over-the-counter (OTC) medications are often aggravated in vulnerable populations, such as older adults. The elevated patterns of older-adult OTC medication use do not necessarily translate into a greater understanding of these medications or their safety implications. The objective of this study was to assess how older adults’ knowledge, beliefs, and attitudes inform their decision-making regarding OTC use. Situational interviews were conducted in three community pharmacies with 87 older-adult participants to capture how they intended to use an OTC medication. The interviews were transcribed and qualitatively analyzed, generating seven key themes: (1) medication use concerns; (2) following label instructions; (3) wait time until medication effect; (4) responses to medication not working; (5) decision to stop medication; (6) sources of information; and (7) safety implications. This study shows substantial variations in older-adult OTC medication use while providing insight on factors that influence older adults’ appropriate OTC medication use and, in some cases, the potential for harmful effects.