Eu-DOBDC metal–organic frameworks (MOFs) have demonstrated capabilities in the adsorption of acid gases, indicating that other rare earth (RE)-DOBDC MOFs are promising candidates for similar applications. To investigate the entire suite of RE-DOBDC MOFs, density functional theory (DFT) simulations of bulk periodic and cluster structure models were used to predict acid gas adsorption. Cluster models of M­(L)3, L = OOCH–, BDC–, and DOBDC–, were used to calculate binding enthalpies of NO2, SO2, and H2O directly to the metal sites, whereas bulk periodic DFT simulations of RE-DOBDC MOFs investigated the structural effects of the extended MOF framework on acid gas adsorption. From both sets of simulations, the metal center does not exhibit changes in the spin states, indicative of physisorption between the gas molecule and the metal center. However, a comparison of results identified that the presence of structural linkers in periodic DFT simulations increased binding energies between the guest molecule and the MOF over those found by cluster calculations. Additionally, the inclusion of the DOBDC linker in the periodic calculation results in delocalization of the charge between the acid gas and the DOBDC linker. Based on this comprehensive analysis, design of future RE-DOBDC MOFs can exploit differences in binding of the gas molecule with the linker or the metal center.

Soft-Lewis basic complexants that facilitate chemoselective separation of the minor actinides from the lanthanides are critical to the closure of the nuclear fuel cycle. Complexants that modulate covalent orbital interactions with relevant metals of interest can facilitate desired outcomes in liquid−liquid separation, allowing for further transmutative processes that decrease issues related with storage of spent nuclear fuel from energy and weapons production. Synthesis of previously unexplored scaffolds seeks to improve performance over benchmark complexants. In the current work, an intermolecular, thermally initiated, and DBU-assisted [3 + 2] cycloaddition of 3-(6-ethynyl-pyridin-2-yl)-5,6-diphenyl-[1,2,4]triazine dipolarophiles with structurally diverse 4-methylbenzenesulfono-hydrazides afforded 21 yet-to-be reported examples in 42−68% yield and modest regioselectivity for the desired regioisomer. Preparation of requisite starting materials, method definition, dipole and dipolarophile scope, ten-fold scale-up reaction, and downstream functional group interconversion are reported herein.

Purpose: Fluorescently labeled epidermal growth factor receptor (EGFR) antibodies can successfully identify microscopic tumors in multiple in vivo models of human cancers with limited toxicity. This study demonstrates the ability of fluorescently labeled anti-EGFR, cetuximab-IRDye800, to localize to ameloblastoma tumor cells in vitro and in vivo.Material and Methods: EGFR expression in ameloblastoma cells was confirmed by qRT-PCR and immunohistochemistry. Primary ameloblastoma cells were labeled in vitro with cetuximab-IRDye800 or non-specific IgG-IRDye800. An in vivo patient-derived xenograft model of ameloblastoma was developed: tumor tissue from three patients was implanted subcutaneously into immunocompromised mice, animals received intravenous injection of cetuximab-IRDye800 or IgG-IRDye800, and were imaged to detect infrared fluorescence using a LI-COR Pearl imaging

The effect of frustrated Lewis donors on metal selectivity between actinides and lanthanides was studied using a series of novel organic ligands. Structures and thermodynamic energies were predicted in the gas phase, in water, and in butanol using 9-coordinate, explicitly solvated (H2O) Eu, Gd, Am, and Cm in the +III oxidation state as reactants in the formation of complexes with 2-(6-[1,2,4]-triazin-3-yl-pyridin-2-yl)-1H-indole (Core 1), 3-[6-(2H-pyrazol-3-yl)­pyridin-2-yl]-1,2,4-triazine (Core 2), and several derivatives. These complexations were studied using density functional theory (DFT) incorporating scalar relativistic effects on the actinides and lanthanides using a small core pseudopotential and corresponding basis set. A self-consistent reaction field approach was used to model the effect of water and butanol as solvents. Coordination preferences and metal selectivity are predicted for each ligand. Several ligands are predicted to have a high degree of selectivity, particularly when a low ionization potential in the ligand permits charge transfer to Eu­(III), reducing it to Eu­(II) and creating a half-filled f7 shell. Reasonable separation is predicted between Cm­(III) and Gd­(III) with Core 1 ligands, possibly due to ligand donor frustration. This separation is largely absent from Core 2 ligands, which are predicted to lose their frustration due to proton transfer from the 2N to the 3N position of the pyrazole component of the ligands via tautomerization.

Chromatin remodeling, specifically the tissue-specific regulation in mineralized tissues, is an understudied avenue of gene regulation. Here we show that Baf45a and Baf45d, two Baf45 homologs belong to ATPase-dependent SWI/SNF chromatin remodeling complex, preferentially expressed in osteoblasts and odontoblasts compared to Baf45b and Baf45c. Recently, biochemical studies revealed that BAF45A associates with Polybromo-associated BAF (PBAF) complex. However, the BAF45D subunit belongs to the polymorphic canonical BRG1-associated factor (cBAF) complex. Protein profiles of osteoblast and odontoblast differentiation uncovered a significant increase of BAF45A and PBAF subunits during early osteoblast and odontoblast maturation. Chromatin immunoprecipitation sequencing (ChIP-seq) during the bone marrow stromal cells (BMSCs) differentiation showed higher histone H3K9 and H3K27 acetylation modifications in the promoter of Baf45a and Baf45d and increased binding of bone and tooth specific transcription factor RUNX2. Overexpression of Baf45a in osteoblasts activates genes essential for the progression of osteoblast maturation and mineralization. Furthermore, shRNA-mediated knockdown of Baf45a in odontoblasts leads to markedly altered genes responsible for the proliferation, apoptosis, DNA repair, and modest decrease in dentinogenic marker gene expression. Assay for Transposase-Accessible Chromatin sequencing (ATAC-seq) assay in Baf45a knockout osteoblasts revealed a noticeable reduction in chromatin accessibility of osteoblast and odontoblast specific genes, along with transcription factor Atf4 and Klf4. Craniofacial mesenchyme-specific loss of Baf45a modestly reduced the mineralization of the tooth and mandibular bone. These findings indicated that BAF45A-dependent mineralized tissue-specific chromatin remodeling through PBAF-RUNX2 crosstalk results in transcriptional activation is critical for early differentiation and matrix maturation of mineralized tissues.