Paradigms and Paradoxes: Fractional and Other Non-integer Charges in Chemistry—an Understanding of Aromaticity

Structural Chemistry - In the current study, the energetics of fractionally (and indeed arbitrary non-integer) charged species is explicitly discussed for the enhanced understanding of aromaticity...     

Imprisoned lightning: charge transport in trehalose-derived sugar glasses

Trehalose is a naturally occurring disaccharide noted for its ability to preserve the biological function of proteins and cell membranes during periods of stress—such as water deprivation or extreme temperature—by stabilizing the conformations of the macromolecules within a glassy matrix. This phenomenon makes use of the propensity for trehalose to interact strongly with protein functional groups and solvent water molecules via hydrogen bonding. Previously, it has been shown that trehalose sugar glasses also support long-range charge transport in oxidation-reduction reactions occurring between spatially separated donors and acceptors. Here, through the use of bulk Arrhenius DC-conductivity measurements, we infer that this anomalously high carrier mobility is due to proton hopping along a hydrogen bonding network formed by sorbed “water wires,” a process known as the Grotthuss mechanism. Additionally, we find that the apparent activation energy of the conductivity depends non-monotonically on the bias voltage. The possibility is raised for novel photovoltaic devices based on the entrapment of photosynthetic proteins within these glasses.     

Influence of the Degree of Deacetylation of Chitosan and BMP-2 Concentration on Biocompatibility and Osteogenic Properties of BMP-2/PLA Granule-Loaded Chitosan/β-Glycerophosphate Hydrogels

Compositions based on chitosan/β-glycerophosphate hydrogels with highly porous polylactide granules can be used to obtain moldable bone graft materials that have osteoinductive and osteoconductive properties. To eliminate the influence of such characteristics as chain length, degree of purification, and molecular weight on a designed material, the one-stock chitosan sample was reacetylated to degrees of deacetylation (DD%) of 19.5, 39, 49, 55, and 56. A study of the chitosan/β-glycerophosphate hydrogel with chitosan of a reduced DD% showed that a low degree of deacetylation increased the MSCs (multipotent stromal cells) viability rate in vitro and reduced the leukocyte infiltration in subcutaneous implantation to Wistar rats in vivo. The addition of 12 wt% polylactide granules resulted in optimal composite mechanical and moldable properties, and increased the modulus of elasticity of the hydrogel-based material by approximately 100 times. Excessive filling of the material with PLA (polylactide) granules (more than 20%) led to material destruction at a ~10% strain. Osteoinductive and osteoconductive properties of the chitosan hydrogel-based material with reacetylated chitosan (39 DD%) and highly porous polylactide granules impregnated with BMP-2 (bone morphogenetic protein-2) have been demonstrated in models of orthotopic and ectopic bone formation. When implanted into a critical-size calvarial defect in rats, the optimal concentration of BMP-2 was 10 μg/mL: bone tissue areas filled the entire material’s thickness. Implantation of the material with 50 μg/mL BMP-2 was accompanied with excessive growth of bone tissue and material displacement beyond the defect. Significant osteoinductive and osteoconductive properties of the material with 10 μg/mL of BMP-2 were also shown in subcutaneous implantation.     

Effect of intramolecular crosslinker properties on the mechanochemical fragmentation of covalently folded polymers

The mechanochemical stability of polymers in solution is enhanced if the chains are covalently folded. Under shear forces, the additional bonds absorb mechanical energy and inhibit unfolding, and as a result, slow down fragmentation. However, not all crosslinkers are equal in terms of their properties (length, strength, etc.). In order to understand the role of these added bonds in the polymers' stability under mechanical stress, a thorough study compares the rate of mechanochemistry on single-chain polymer nanoparticles which have been folded with crosslinkers with different lengths, strengths, positioning, and valencies. The usage of bonds with different mechanical strengths in the crosslinkers was found to be the most powerful way to change the mechanochemical fragmentation rate. In addition, positioning and valency also play significant role in the mechanical stabilization mechanism. © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 © 2020 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2020 , 58, 692–703     

Design and experimental validation of a nonlinear controller for underactuated surface vessels

Nonlinear Dynamics - This paper addresses the problem of trajectory tracking control of an underactuated surface vessel moving in a two-dimensional space in the presence of unknown disturbances. In...     

When does every definable nonempty set have a definable element?

The assertion that every definable set has a definable element is equivalent over $\mathsf{ZF}$ to the principle $\mathbf{V}=\mathbf{HOD}$, and indeed, we prove, so is the assertion merely that every Π₂‐definable set has an ordinal‐definable element. Meanwhile, every model of $\mathsf{ZFC}$ has a forcing extension satisfying $\mathbf{V}\ne \mathbf{HOD}$ in which every Σ₂‐definable set has an ordinal‐definable element. Similar results hold for $\mathbf{HOD}(\mathbb{R})$ and $\mathbf{HOD}({\mathrm{Ord}}^{\omega })$ and other natural instances of $\mathbf{HOD}(X)$.     

Interplay of thermochemistry and Structural Chemistry,the journal (volume 29, 2018, issues 3–4) and the discipline

The contents of issues 3 and 4 of Structural Chemistry from the calendar year 2018 are summarized in the present review. A brief thermochemical commentary and recommendations for future research have been added to the summary of each paper.

     

Development and analysis of a malaria transmission mathematical model with seasonal mosquito life-history traits

In this paper, we develop and analyze a malaria model with seasonality of mosquito life-history traits: periodic-mosquitoes per capita birth rate, -mosquitoes death rate, -probability of mosquito to human disease transmission, -probability of human to mosquito disease transmission, and -mosquitoes biting rate. All these parameters are assumed to be time dependent leading to a nonautonomous differential equation system. We provide a global analysis of the model depending on two threshold parameters and (with ). When , then the disease-free stationary state is locally asymptotically stable. In the presence of the human disease-induced mortality, the global stability of the disease-free stationary state is guarantied when . On the contrary, if , the disease persists in the host population in the long term and the model admits at least one positive periodic solution. Moreover, by a numerical simulation, we show that a sub-critical (backward) bifurcation is possible at . Finally, the simulation results are in accordance with the seasonal variation of the reported cases of a malaria-epidemic region in Mpumalanga province in South Africa.