Morphology of adsorbed polymers and solid surface wettability

The adsorption of a polyacrylamide (MW 14600) and two polysaccharides (MW 9260 and 706 x 10(3)) onto model silica surfaces of different hydrophobicities was investigated. In all cases, adsorption adhered to the Freundlich isotherm, reflecting the heterogeneous character of the solid substrates. The latter strongly influenced the character of the adsorbed polymer, with morphologies from chainlike structures to thin films and patches being observed. Surface roughness, polymer type, and molecular weight also play roles in controlling adsorbed polymer morphology. Surface wettability is strongly influenced by the thickness of the adsorbed layer.     

Metric Inequality, Subdifferential Calculus and Applications

In this paper we establish characterizations of Asplund spaces in terms of conditions ensuring the metric inequality and intersection formulae. Then we establish chain rules for the limiting Fréchet subdifferentials. Necessary conditions for constrained optimization problems with non-Lipschitz data are derived.     

Intramolecular,Interrupted Homo-Nazarov Cascade Biscyclizations to Angular (Hetero)Aryl-Fused Polycycles

Herein, a SnCl₄-catalyzed intramolecular, interrupted homo-Nazarov cascade biscyclization to access angular (hetero)aryl-fused polycycles is reported. Subsequent decarboxylation of the readily enolizable products afforded the angular products in up to 71 % yield over two steps, with the trans-diastereomers as the major products. The cyclopropyl homo-Nazarov cyclization precursors were formed using a scalable and modular synthetic route that, ultimately, offers access to 6,6,6-, 6,6,5-, 6,5,6-, 6,6,5,6-, and 6,6,6,5-fused angular polycyclic products. To showcase the rigor and utility of the method, an 8-step total synthesis of (±)-1-oxoferruginol, an antibacterial aromatic abietane diterpenoid, was disclosed.     

Physical Evidence of Stress-Induced Conformational Changes in Polymers

Background

Polymer mechanics and characterization is an active area of research where a keen effort is directed towards gaining a predictive and correlative relationship between the applied loads and the specific conformational motions of the macromolecule chains.

Objective

Therefore, the objective of this research is to introduce the preliminary results based on a novel technique to in situ probe the mechanical properties of polymers using non-invasive, non-destructive, and non-contact terahertz spectroscopy.

Methods

A dielectric elastomer actuator (DEA) structure is used as the loading mechanism to avoid obscuring the beam path of transmission terahertz time-domain spectroscopy. In DEAs, the applied voltage results in mechanical stresses under the active electrode area with far-reaching stretching in the passive area. Finite element analysis is used to model and simulate the DEA to quantify the induced stresses at the observation site over a voltage range spanning from 0 V to 3000 V. Additionally, a novel analysis technique is introduced based on the Hilbert-Huang transform to exploit the time-domain signals of the ultrathin elastomeric film and to defy the limits set forth by the current state-of-the-art analysis techniques.

Results

The computational result shows a nonlinear relationship between the effective stresses and the applied voltage. Analysis of the terahertz time-domain signals shows a shift in the delay times and a decrease in signal peak amplitudes, whereas these characteristics are implicitly related to the change in the index of refraction.

Conclusions

In all, the results evidentially signify the interrelationship between the conformational changes and applied mechanical stress.

     

Implicit multifunction theorems in complete metric spaces

In this paper, we establish some new characterizations of metric regularity of implicit multifunctions in complete metric spaces by using lower semicontinuous envelopes of the distance functions to set-valued mappings. Through these new characterizations it is possible to investigate implicit multifunction theorems based on coderivatives and on contingent derivatives as well as the perturbation stability of implicit multifunctions.     

pH-Sensitive pentablock copolymer nanocapsules as nontoxic and efficient gene carriers

A biodegradable amphiphilic pentablock copolymer PAE‐PCL‐PEG‐PCL‐PAE with a pH‐sensitive unit was synthesized for use as a nontoxic, biodegradable carrier for gene delivery by forming nanocapsules entrapping nucleic acid drugs. The PAE block can interact with plasmid DNA to form polyelectrolyte complexes in an acidic environment. At physiological pH, the PAE blocks are deprotonated and form an insoluble skin, resulting in the formation of nanocapsules that encapsulate plasmid DNA. The surface charges of the nanocapsules became almost neutral at pH = 7.4, and their size ranged from 210 to 280 nm. The nanocapsule maintained most of its transfection efficiency even in the presence of serum. These nanocapsules are therefore potential carriers for systemic gene therapy.

     

Directional Hölder Metric Regularity

This paper studies the first-order behavior of the value function of a parametric optimal control problem with nonconvex cost functions and control constraints. By establishing an abstract result on the Fréchet subdifferential of the value function of a parametric minimization problem, we derive a formula for computing the Fréchet subdifferential of the value function to a parametric optimal control problem. The obtained results improve and extend some previous results.     

Decision making under uncertainty with fuzzy targets

This paper discusses the issue of how to use fuzzy targets in the target-based model for decision making under uncertainty. After introducing a target-based interpretation of the expected value on which it is shown that this model implicitly assumes a neutral behavior on attitude about the target, we examine the issue of using fuzzy targets considering different attitudes about the target selection of the decision maker. We also discuss the problem for situations on which the decision maker’s attitude about target may change according to different states of nature. Especially, it is shown that the target-based approach can provide an unified way for solving the problem of fuzzy decision making with uncertainty about the state of nature and imprecision about payoffs. Several numerical examples are given for illustration of the discussed issues.