A STUDY OF STRUCTURE AND PROPERTY CHANGES OF BIODEGRADABLE POLYGLYCOLIDE AND POLY(GLYCOLIDE-co-LACTIDE)FIBERS DURING PROCESSING AND IN VITRO DEGRADATION*

Structure and properties of bioabsorbable polyglycolide (PGA) and poly(glycolide-co-lactide) (PGA-co-PLA)fibers were investigated during several industrial processing stages and in vitro degradation by means of wide-angle X-raydiffraction (WAXD), dynamic mechanical analysis (DMA) and mechanical property tests. In the orientation stage, the PGAfibers were found to have higher degrees of crystallinity than corresponding PGA-co-PLA samples produced under similarconditions. In the hot-stretching and post-annealing stages, after fibers were braided, PGA samples were found to gain morecrystallinity and higher T_g than PGA-co-PLA samples. The higher crystallinity in PGA fibers resulted in a slower rate ofdegradation. DMA results showed that a great deal of internal stress that was built during orientation and hot-stretchingstages was released in the post-annealing stage for a1l PGA and PGA-co-PLA samples. During earlier stages of in vitrodegradation, both PGA and PGA-co-PLA samples exhibited the typical cleavage-induced crystallization mechanism. Theheat shrinkage in the glass transition area was found to disappear after 6-8 days of degradation for all PGA and PGA-co-PLAsamples, indicating the amorphous portions of the polymers lost orientation after a short period in the buffer solution, mostlikely due to relaxation of the cleaved chains.     

Continuous,on-demand generation and separation of diphenylphosphoryl azide

Diphenylphosphorylazide (DPPA) has been synthesized in microfluidics with near-100% yield in sub-3 minute residence time, affordably, and with a process design that minimizes hazards associated with hydrazoic acid (HN₃) production. A pilot-plant scale continuous process for the on-demand synthesis of diphenylphosphoryl azide (DPPA) that can readily be integrated with subsequent transformations was designed, built, and validated. Using Corning's Low Flow reactor system coupled to a membrane separator and in-line Fourier Transform Infrared (FTIR), DPPA was safely produced at a rate of 1?mol/hr as a 2.0?M anhydrous toluene stream. Continuous FTIR was able to reliably monitor product quality, purity and concentration, showcasing the ease and utility of this continuous flow process for manufacturing common, safe pharmaceutical precursors.     

Stimulus‐Triggered Formation of an Anion–Cation Exciplex in Copper(I) Complexes as a Mechanism for Mechanochromic Phosphorescence

The investigation of the mechanisms of mechanochromic luminescence is of fundamental importance for the development of materials for photonic sensors, data storage, and luminescence switches. The structural origin of this phenomenon in phosphorescent molecular systems is rarely known and thus the formulation of structure–property relationships remains challenging. Changes in the M–M interactions have been proposed as the main mechanism with d¹⁰ coinage metal compounds. Herein, we describe a new mechanism—a mechanically induced reversible formation of a cation–anion exciplex based on Cu–F interactions—that leads to highly efficient mechanochromic phosphorescence and unusual large emission shifts from UV‐blue to yellow for Cu^I complexes. The low‐energy luminescence is thermo‐ and vaporesponsive, thus allowing the generation of white light as well as for recovering the original UV‐blue emission.     

Unprecedented Acid‐Promoted Polymerization and Gelation of Acrylamide: A Serendipitous Discovery

Dilute acid polymerizes degassed, aqueous acrylamide with concomitant gelation, without the need for added free radical initiator or cross‐linking agent. This reaction is accelerated by sonication or UV irradiation, but inhibited by adventitious oxygen or the addition of a free radical inhibitor, suggesting an acid‐accelerated free radical process. The resulting hydrogels are thixotropic in nature and partially disrupted by the addition of chaotropic agents, indicating the importance of hydrogen bonding to the 3D network. This discovery was made while trying to prepare pectin‐polyacrylamide hydrogels. We observed that pectin initiated the gelation of acrylamide, but only if the aqueous pectin samples had a pH lower than ca. 5.     

Boundary Integral Equations for Isotropic Linear Elasticity

This articles first investigates boundary integral operators for the three-dimensional isotropic linear elasticity of a biphasic model with piecewise constant Lamé coefficients in the form of a bounded domain of arbitrary shape surrounded by a background material. In the simple case of a spherical inclusion, the vector spherical harmonics consist of eigenfunctions of the single and double layer boundary operators and we provide their spectra. Further, in the case of many spherical inclusions with isotropic materials, each with its own set of Lamé parameters, we propose an integral equation and a subsequent Galerkin discretization using the vector spherical harmonics and apply the discretization to several numerical test cases.