The Group happily welcomes its newest graduate students, Anthony and Brittany! We know you’ll do great things!
The Group warmly welcomes Julia as our newest graduate student! We’re very happy to have you! 🙂
This work was done in collaboration with Prof. Paul Zimmerman and Prof. Allison Roessler, and provides experimental and computational understanding of a recently discovered method for controlling alkene stereochemistry in MF-ROMP.
Congratulations to Dr. Xuejin Yang and Prof. Laura Murphy (2018 Group PhD) on their recent publication in Polymer Chemistry! This work was done in collaboration with Prof. Scott Grayson and Dr. Farihah Haque, and demonstrates …
Congratulations are in order for many group members, as well as our group’s appreciation for the support and encouragement of so many programs. Kyle Chin has been awarded an NSF Graduate Research Fellowship. Rachel Tritt …
Stimuli-responsive materials can enhance the field of three-dimensional (3D) printing by generating objects that change shape in response to external cues. While temperature and pH are common inputs for initiating a response in a 3D-printed object, there are few examples of using a mechanical input to afford a response. Herein, we report a suite of mechanochromic ionic liquid gel inks that can be used to fabricate 3D-printed objects that use a single mechanoactivation event to elicit both a mechanochromic response and an autonomous shape change. Direct-ink write 3D printing was used to deposit ionic liquid gel inks to create multimaterial objects that underwent a predetermined mechanoactivated shape change (mechanomorphic) when the sample was pulled and then released. When spiropyran was incorporated into the inks, the onset of spiropyran isomerization into its purple merocyanine form occurred at strains dependent upon the particular ion gel ink formulation. We suggest that the color onset could be used as a simple indicator for when the strain required to achieve a predetermined change in shape has been reached, potentially serving as real-time visual cue for the user. Such morphing 3D-printed structures with integrated instructions have potential application to areas including stowable structures as well as multiresponsive autonomous components and sensors.
We have achieved breakthroughs for the efficient synthesis of linear polydicyclopentadiene (pDCPD) via photoredox mediated metal-free ring-opening metathesis polymerization (MF-ROMP). Molecular weight control from 1 to 16 kDa can be targeted in a straightforward manner. Assisted by this method, the Tg–Mn dependence of linear pDCPD is investigated and reported for the first time.
We have discovered a new flex-activated mechanophore that releases an N-heterocyclic carbene (NHC) under mechanical load. The mechanophore design is based upon NHC-carbodiimide (NHC-CDI) adducts and demonstrates an important first step toward flex-activated designs capable of further downstream reactivities. Since the flex-activation is non-destructive to the main polymer chains, the material can be subjected to multiple compression cycles to achieve iterative increases in the activation percentage of mechanophores. Two different NHC structures were demonstrated, signifying the potential modularity of the mechanophore design.
Stereochemistry can have profound impact on polymer and materials properties. Unfortunately, straightforward methods for realizing high levels of stereocontrolled polymerizations are often challenging to achieve. In a departure from traditional metal-mediated ring-opening metathesis polymerization (ROMP), we discovered a remarkably simple method for controlling alkene stereochemistry in photoredox mediated metal-free ROMP. Ion-pairing, initiator sterics, and solvation effects each had profound impact on the stereochemistry of polynorbornene (PNB). Simple modifications to the reaction conditions produced PNB with trans alkene content of 25 to >98%. High cis content was obtained from relatively larger counterions, toluene as solvent, low temperatures (-78 °C), and initiators with low Charton values. Conversely, smaller counterions, dichloromethane as solvent, and enol ethers with higher Charton values enabled production of PNB with high trans content. Data from a combined experimental and computational investigation are consistent with the stereocontrolling step of the radical cationic mechanism proceeding under thermodynamic control.
We’d like to warmly welcome Abdullah, Jerry, Ruojia, Yuanzuo, Jacob, Madelyn, and Niko to the team! We’re happy to have you 🙂