Aqueous Sulfate Separation by Crystallization of Sulfate–Water Clusters

An effective approach to sulfate separation from aqueous solutions is based on the crystallization of extended [SO₄(H₂O)₅²⁻]_n sulfate–water clusters with a bis(guanidinium) ligand. The ligand was generated in situ by hydrazone condensation in water, thereby bypassing the need for elaborate syntheses, tedious purifications, and organic solvents. Crystallization of sulfate–water clusters represents an alternative approach to the now established sulfate separation strategies that involve encapsulation of the “naked” anion.     

The Effect of Calcium-Silicate Cements on Reparative Dentinogenesis Following Direct Pulp Capping on Animal Models

Dental pulp vitality is a desideratum for preserving the health and functionality of the tooth. In certain clinical situations that lead to pulp exposure, bioactive agents are used in direct pulp-capping procedures to stimulate the dentin-pulp complex and activate reparative dentinogenesis. Hydraulic calcium-silicate cements, derived from Portland cement, can induce the formation of a new dentin bridge at the interface between the biomaterial and the dental pulp. Odontoblasts are molecularly activated, and, if necessary, undifferentiated stem cells in the dental pulp can differentiate into odontoblasts. An extensive review of literature was conducted on MedLine/PubMed database to evaluate the histological outcomes of direct pulp capping with hydraulic calcium-silicate cements performed on animal models. Overall, irrespective of their physico-chemical properties and the molecular mechanisms involved in pulp healing, the effects of cements on tertiary dentin formation and pulp vitality preservation were positive. Histological examinations showed different degrees of dental pulp inflammatory response and complete/incomplete dentin bridge formation during the pulp healing process at different follow-up periods. Calcium silicate materials have the ability to induce reparative dentinogenesis when applied over exposed pulps, with different behaviors, as related to the animal model used, pulpal inflammatory responses, and quality of dentin bridges.     

Active control of liquid film flows: beyond reduced-order models

Nonlinear Dynamics - The ability to robustly and efficiently control the dynamics of nonlinear systems lies at the heart of many current technological challenges, ranging from drug delivery systems...     

On Some Methods to Derive Necessary and Sufficient Optimality Conditions in Vector Optimization

The aim of this paper is to address new approaches, in separate ways, to necessary and, respectively, sufficient optimality conditions in constrained vector optimization. In this respect, for the necessary optimality conditions that we derive, we use a kind of vectorial penalization technique, while for the sufficient optimality conditions we make use of an appropriate scalarization method. In both cases, the approaches couple a basic technique (of penalization or scalarization, respectively) with several results in variational analysis and optimization obtained by the authors in the last years. These combinations allow us to arrive to optimality conditions which are, in terms of assumptions made, new.     

Proximal-gradient algorithms for fractional programming

In this paper, we propose two proximal-gradient algorithms for fractional programming problems in real Hilbert spaces, where the numerator is a proper, convex and lower semicontinuous function and the denominator is a smooth function, either concave or convex. In the iterative schemes, we perform a proximal step with respect to the nonsmooth numerator and a gradient step with respect to the smooth denominator. The algorithm in case of a concave denominator has the particularity that it generates sequences which approach both the (global) optimal solutions set and the optimal objective value of the underlying fractional programming problem. In case of a convex denominator the numerical scheme approaches the set of critical points of the objective function, provided the latter satisfies the Kurdyka-?ojasiewicz property.     

Vectorial penalization for generalized functional constrained problems

In this paper we use a double penalization procedure in order to reduce a set-valued optimization problem with functional constraints to an unconstrained one. The penalization results are given in several cases: for weak and strong solutions, in global and local settings, and considering two kinds of epigraphical mappings of the set-valued map that defines the constraints. Then necessary and sufficient conditions are obtained separately in terms of Bouligand derivatives of the objective and constraint mappings.     

Conformational Effects of Regioisomeric Substitution on the Catalytic Activity of Copper/Calix[8]arene C−S Coupling

Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C_2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,5 ), while substitution of positions 1 and 4 produces the C_s-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L^1,4 ) described herein. [ Cu(L^1,4)I ] was synthesized from L^1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L^1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L^1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L^1,4 regioisomer undergoes a deformation that does not occur with L^1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L^1,4 − H) (CH₃CN)₂] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework.     

Anisotropy resolved multidimensional emission spectroscopy (ARMES): A new tool for protein analysis

Structural analysis of proteins using the emission of intrinsic fluorophores is complicated by spectral overlap. Anisotropy resolved multidimensional emission spectroscopy (ARMES) overcame the overlap problem by the use of anisotropy, with chemometric analysis, to better resolve emission from different fluorophores. Total synchronous fluorescence scan (TSFS) provided information about all the fluorophores that contributed to emission while anisotropy provided information about the environment of each fluorophore. Here the utility of ARMES was demonstrated via study of the chemical and thermal denaturation of human serum albumin (HSA).     

Integration of an Equilibrium System in an Enhanced Theory of Bending of Elastic Plates

The complete integral of the system of partial differential equations governing the equilibrium bending of elastic plates with transverse shear deformation and transverse normal strain is constructed by means of complex variable methods. The process helps to elucidate the physical meaning of certain analytic constraints imposed on the asymptotic behavior of the solutions and shows that in the case of an infinite plate, any analytic solution has finite energy if and only if the bending and twisting moments, the transverse shear force, the displacements in vertical planes, and two other characteristic quantities vanish at infinity. An example is discussed to illustrate the theory.