MS

thesisMany haemorrhagic complications have been attributed to increased intravascular fibrinolytic activity. The degradation products resulting from fibrinolysis have been shown to interfere in fibrin polymerization and have been observed in defective clot formation., Although considerable knowledge has accrued concerning the mechanism of filarinolysis and the resulting products, areas of controversy and intermittent obscurity remain» The study presented herein was conducted to resolve, if possible, existing discrepancies and characterize with certainty intermediate and end proteolytic products, An effort was made to correlate experimental findings with clinical disease states. The products of serial digestion of fibrinogen by plasmin were studied by immunodiffusion, immunoelectrophoresis and gel exclusion. Two products were observed. These products were identified as the D and E fragments, originally reported by Nussenweig et al. (1960). The D fragment was represented by a band located in the beta area of the electrophoretic field. This product was formed early in the digestion process and underwent no further degradation. The second product, a migratory band, probably representing a plasmin susceptible precursor of the E fragment, was initially observed within the locus of the D fragment. However, as digestion progressed the band migrated across the electrophoretic field to the prealbumin area, remaining in this position with exhaustive proteolysis. This band represented the plasmin resistant E fragment end product, Under certain experimental conditions the hydrolysis of fibrinogen into the E fragment may apparently be reversed. Serum samples from 196 hospitalized patients were studied for the presence of fibrinolytic intermediates and end products. Pathologic products were found in 10 of the 196 samples. Of these la samples, 8 contained D fragments, whereas Z samples contained both the D and E fragments. Clinical-pathologic correlation indicates that demonstrable fibrinolytic products were associated with injury to the hepatic, renal and vascular systems. The small molecular weight E fragment was encountered only in instances of renal failure

Pseudodeterminants and perfect square spanning tree counts

The pseudodeterminant $\textrm{pdet}(M)$ of a square matrix is the last nonzero coefficient in its characteristic polynomial; for a nonsingular matrix, this is just the determinant. If $\partial$ is a symmetric or skew-symmetric matrix then $\textrm{pdet}(\partial\partial^t)=\textrm{pdet}(\partial)^2$. Whenever $\partial$ is the $k^{th}$ boundary map of a self-dual CW-complex $X$, this linear-algebraic identity implies that the torsion-weighted generating function for cellular $k$-trees in $X$ is a perfect square. In the case that $X$ is an \emph{antipodally} self-dual CW-sphere of odd dimension, the pseudodeterminant of its $k$th cellular boundary map can be interpreted directly as a torsion-weighted generating function both for $k$-trees and for $(k-1)$-trees, complementing the analogous result for even-dimensional spheres given by the second author. The argument relies on the topological fact that any self-dual even-dimensional CW-ball can be oriented so that its middle boundary map is skew-symmetric.Comment: Final version; minor revisions. To appear in Journal of Combinatoric

Mechanochemical Regulation of a Photochemical Reaction

We introduce the concept of mechanochemically gated photoswitching. Mechanical regulation of a photochemical reaction is exemplified using a newly designed mechanophore based on a cyclopentadiene–maleimide Diels–Alder adduct. Ultrasound-induced mechanical activation of the photochemically inert mechanophore in polymers generates a diarylethene photoswitch via a retro-[4 + 2] cycloaddition reaction that photoisomerizes between colorless and colored states upon exposure to UV and visible light. Control experiments demonstrate the thermal stability of the cyclopentadiene–maleimide adduct and confirm the mechanical origin of the “unlocked” photochromic reactivity. This technology holds promise for applications such as lithography and stress-sensing, enabling the mechanical history of polymeric materials to be recorded and read on-demand

Designing naphthopyran mechanophores with tunable mechanochromic behavior

Mechanochromic molecular force probes conveniently report on stress and strain in polymeric materials through straightforward visual cues. We capitalize on the versatility of the naphthopyran framework to design a series of mechanochromic mechanophores that exhibit highly tunable color and fading kinetics after mechanochemical activation. Structurally diverse naphthopyran crosslinkers are synthesized and covalently incorporated into silicone elastomers, where the mechanochemical ring–opening reactions are achieved under tension to generate the merocyanine dyes. Strategic structural modifications to the naphthopyran mechanophore scaffold produce dramatic differences in the color and thermal electrocyclization behavior of the corresponding merocyanine dyes. The color of the merocyanines varies from orange-yellow to purple upon the introduction of an electron donating pyrrolidine substituent, while the rate of thermal electrocyclization is controlled through electronic and steric factors, enabling access to derivatives that display both fast-fading and persistent coloration after mechanical activation and subsequent stress relaxation. In addition to identifying key structure–property relationships for tuning the behavior of the naphthopyran mechanophore, the modularity of the naphthopyran platform is demonstrated by leveraging blends of structurally distinct mechanophores to create materials with desirable multicolor mechanochromic and complex stimuli-responsive behavior, expanding the scope and accessibility of force-responsive materials for applications such as multimodal sensing

Force-Dependent Multicolor Mechanochromism from a Single Mechanophore

We report a bis-naphthopyran mechanophore that exhibits force-dependent changes in visible absorption. A series of polymers incorporating a chain-centered bis-naphthopyran mechanophore was synthesized and mechanically activated using ultrasonication. By varying the length of the polymer chains, the force delivered to the mechanophore is modulated systematically. We demonstrate that the relative distribution of two distinctly colored merocyanine products is altered predictably with different magnitudes of applied force, resulting in gradient multicolor mechanochromism. The mechanochemical reactivity of bis-naphthopyran is supported by density functional theory calculations and described by a theoretical model that provides insight into the force–color relationship

Mechanochemical Regulation of a Photochemical Reaction

We introduce the concept of mechanochemically gated photoswitching. Mechanical regulation of a photochemical reaction is exemplified using a newly designed mechanophore based on a cyclopentadiene–maleimide Diels–Alder adduct. Ultrasound-induced mechanical activation of the photochemically inert mechanophore in polymers generates a diarylethene photoswitch via a retro-[4 + 2] cycloaddition reaction that photoisomerizes between colorless and colored states upon exposure to UV and visible light. Control experiments demonstrate the thermal stability of the cyclopentadiene–maleimide adduct and confirm the mechanical origin of the “unlocked” photochromic reactivity. This technology holds promise for applications such as lithography and stress-sensing, enabling the mechanical history of polymeric materials to be recorded and read on-demand

Mechanochemically Gated Photoswitching: Expanding the Scope of Polymer Mechanochromism

Mechanophores are molecules that undergo productive, covalent chemical transformations in response to mechanical force. Over the last decade, a variety of mechanochromic mechanophores have been developed that enable the direct visualization of stress in polymers and polymeric materials through changes in color and chemiluminescence. The recent introduction of mechanochemically gated photoswitching extends the repertoire of polymer mechanochromism by decoupling the mechanical activation from the visible response, enabling the mechanical history of polymers to be recorded and read on-demand using light. Here, we discuss advances in mechanochromic mechanophores and present our design of a cyclopentadiene–maleimide Diels–Alder adduct that undergoes a force-induced retro-[4+2] cycloaddition reaction to reveal a latent diarylethene photoswitch. Following mechanical activation, UV light converts the colorless diarylethene molecule into the colored isomer via a 6π-electrocyclic ring-closing reaction. Mechanically gated photoswitching expands on the fruitful developments in mechanochromic polymers and provides a promising platform for further innovation in materials applications including stress sensing, patterning, and information storage