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As of the writing of this paper, lower bounds are not a staple of quantum chemistry computations and for good reason. All previous attempts at applying lower bound theory to Coulombic systems led to lower bounds whose quality was inferior to the Ritz upper bounds so that their added value was minimal. Even our recent improvements upon Temple's lower bound theory were limited to Lanczos basis sets and these are not available to atoms and molecules due to the Coulomb singularity. In the present paper, we overcome these problems by deriving a rather simple eigenvalue equation whose roots, under appropriate conditions, give lower bounds which are competitive with the Ritz upper bounds. The input for the theory is the Ritz eigenvalues and their variances; there is no need to compute the full matrix of the squared Hamiltonian. Along the way, we present a Cauchy-Schwartz inequality which underlies many aspects of lower bound theory. RMC-4550 We also show that within the matrix Hamiltonian theory used here, the methods of Lehmann and our recent self-consistent lower bound theory (J. Chem. Phys. 2020, 115, 244110) are identical. Examples include implementation to the hydrogen and helium atoms.There is a critical need for the establishment of an engineered model of the vocal fold epithelium that can be used to gain understanding of its role in vocal fold health, disease, and facilitate the development of new treatment options. Toward this goal, we isolated primary vocal fold epithelial cells (VFECs) from healthy porcine larynxes and used them within passage 3. Culture-expanded VFECs expressed the suprabasal epithelial marker cytokeratin 13 and intercellular junctional proteins occludin, E-cadherin, and zonula occludens-1. To establish the engineered model, we cultured VFECs on a hyaluronic acid-derived synthetic basement membrane displaying fibronectin-derived integrin-binding peptide (RGDSP) and/or laminin 111-derived syndecan-binding peptide AG73 (RKRLQVQLSIRT). Our results show that matrix stiffness and composition cooperatively regulate the adhesion, proliferation, and stratification of VFECs. Cells cultured on hydrogels with physiological stiffness (elastic shear modulus, G' = 1828 Pa) adoptedhealth and disease.Thiamine deficiency contributes to several human diseases including Alzheimer's. As its biologically active form, thiamine pyrophosphate (TPP) has been considered as a potential biomarker for Alzheimer's disease (AD) based on several clinical reports that apparently lower blood TPP levels were found in patients with mild cognitive impairment to AD. However, highly sensitive and high-throughput detection of TPP in biological fluids remains an analytical challenge. Here, we report engineering RNA-based sensors to quantitatively measure TPP concentrations in whole blood samples with a detection limit down to a few nM. By fusing a TPP-specific aptamer with the hammerhead ribozyme for in vitro selection, we isolated an allosteric ribozyme with an EC50 value (68 nM) similar to the aptamer's KD value (50 nM) for TPP, which for the first time demonstrates the possibility to maintain the effector binding affinity of the aptamer in such engineered allosteric RNA constructs. Meanwhile, we developed a new blood sample preparation protocol to be compatible with RNA. By coupling the TPP-induced ribozyme cleavage event with isothermal amplification, we achieved fluorescence monitoring of whole blood TPP levels through the "mix-and-read" operation with high-throughput potential. We expect that the engineered TPP-sensing RNAs will facilitate clinical research on AD as well as other thiamine-related diseases.17β-Estradiol (E2) confers neuroprotection in preclinical models of spinal cord injury when administered systemically. The goal of this study was to apply E2 locally to the injured spinal cord for a sustained duration using poly(pro-E2) film biomaterials. Following contusive spinal cord injury in adult male mice, poly(pro-E2) films were implanted subdurally and neuroprotection was assessed using immunohistochemistry 7 days after injury and implantation. In these studies, poly(pro-E2) films modestly improved neuroprotection without affecting the inflammatory response when compared to the injured controls. To increase the E2 dose released, bolus-releasing poly(pro-E2) films were fabricated by incorporating unbound E2 into the poly(pro-E2) films. However, compared to the injured controls, bolus-releasing poly(pro-E2) films did not significantly enhance neuroprotection or limit inflammation at either 7 or 21 days post-injury. Future work will focus on developing poly(pro-E2) biomaterials capable of more precisely releasing therapeutic doses of E2.An in-depth study of the molecular rearrangement of the complex [Au(N9-adeninate)(PTA)] (1), promoted in aqueous solution, is presented. This complex, which has been previously described as forming dimers in its crystalline form, is also demonstrated as being able to assemble into an infinite AuI···AuI chain polymer. The structural motifs are tentatively related to the dramatic modification of the photoemissive properties of 1 in water solution at long times, with the aid of UV-vis and photoluminescence measurements, PGSE-NMR, and theoretical calculations. A subtle equilibrium in favor of aurophilically governed aggregates has been envisaged as the driving force of the molecular rearrangement. Furthermore, 1 has been explored as an additive of the hydrogel of [Au(N9-adeninate)(PMe3)] (2) for a further tuning of its photophysical properties without loss of the gel texture.To quantitatively probe iron intermediate species [Fe(V)/Fe(IV)] in Fe(VI) oxidation, this study systematically investigated the reaction kinetics of Fe(VI) oxidation of 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic)acid (ABTS) at different ratios of [ABTS]0/[Fe(VI)]0 (i.e., >1.0, =1.0, and 1.0, experimental data and model simulation both indicated that the reaction stoichiometric ratio of Fe(VI)/ABTS•+ increased from 1.01.0 to 1.01.2 as [ABTS]0 was increased. Furthermore, the Fe(VI)-ABTS-substrate model was developed to successfully determine reactivity of Fe(V) to different substrates (k = (0.7-1.42) × 106 M-1 s-1). Overall, the improved Fe(VI)-ABTS kinetic model provides a useful tool to quantitatively probe Fe(V)/Fe(IV) behaviors in Fe(VI) oxidation and gains new fundamental insights.
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