Studies of Organic Molecule Recognition by Synthetic Cyclophane Receptors in Aqueous Media

The behaviors of six new cyclophane receptors for organic guest molecules in aqueous media are reported. These new hosts are modifications of more basic parent structures, and the main goal of their examination has been to determine how the modifications affect host selectivity for cationic guests. In particular, we have been interested in determining how additional non-covalent binding interactions can complement the cation-π interactions active in the parent systems. Three types of modifications were made to these systems. Firstly, neutral methoxy and bromine substituents were added to produce four of the six new macrocycles. Secondly, two additional aromatic rings (relative to the parent host) capable of making cation-π interactions with charged guest species were appended. Thirdly, a negatively charged carboxyl group was attached to produce a cavity in which electrostatic interactions should enhance cationic guest binding. ^1H-NMR and circular dichroic techniques were employed to determine the binding affinities of a wide variety of organic guests for the parent and modified structures in aqueous media.

Bromination of the parent host greatly enhances its binding in a general fashion, primarily as the result of hydrophobic interactions. The addition of methoxy groups does not enhance binding, apparently as a result of a collapse of the hosts into a conformation that is not suitable for binding. The appendage of extra aromatic rings enhances the binding of positively charged guests, most likely in response to more complete encapsulation of guest species. The addition of a negatively charged carboxylate enhances the binding to only selective groups of cationic guests. AM1 calculations of the electrostatic potentials of several guests molecules suggests that the enhancements seen with the modified receptor compared to the parent are most likely the result of close contact between regions of highest potential on the guest and the appended carboxylate.

Cosmic Explosions: Observations Of Infant Hydrogen-Free Supernovae Towards An Understanding Of Their Parent Systems

Radiation in the first days of supernova explosions contains rich information about physical properties of the exploding stars. In the past three years, I used the intermediate Palomar Transient Factory to conduct one-day cadence surveys, in order to systematically search for infant supernovae. I show that the one-day cadences in these surveys were strictly controlled, that the realtime image subtraction pipeline managed to deliver transient candidates within ten minutes of images being taken, and that we were able to undertake follow-up observations with a variety of telescopes within hours of transients being discovered. So far iPTF has discovered over a hundred supernovae within a few days of explosions, forty-nine of which were spectroscopically classified within twenty-four hours of discovery.

Our observations of infant Type Ia supernovae provide evidence for both the single-degenerate and double-degenerate progenitor channels. On the one hand, a low-velocity Type Ia supernova iPTF14atg revealed a strong ultraviolet pulse within four days of its explosion. I show that the pulse is consistent with the expected emission produced by collision between the supernova ejecta and a companion star, providing direct evidence for the single degenerate channel. By comparing the distinct early-phase light curves of iPTF14atg to an otherwise similar event iPTF14dpk, I show that the viewing angle dependence of the supernova-companion collision signature is probably responsible to the difference of the early light curves. I also show evidence for a dark period between the supernova explosion and the first light of the radioactively-powered light curve. On the other hand, a peculiar Type Ia supernova iPTF13asv revealed strong near-UV emission and absence of iron in the spectra within the first two weeks of explosion, suggesting a stratified ejecta structure with iron group elements confined to the slow-moving part of the ejecta. With its total ejecta mass estimated to exceed the Chandrasekhar limit, I show that the stratification and large mass of the ejecta favor the double-degenerate channel.

In a separate approach, iPTF found the first progenitor system of a Type Ib supernova iPTF13bvn in the pre-explosion HST archival mages. Independently, I used the early-phase optical observations of this supernova to constrain its progenitor radius to be no larger than several solar radii. I also used its early radio detections to derive a mass loss rate of 3e-5 solar mass per year for the progenitor right before the supernova explosion. These constraints on the physical properties of the iPTF13bvn progenitor provide a comprehensive data set to test Type Ib supernova theories. A recent HST revisit to the iPTF13bvn site two years after the supernova explosion has confirmed the progenitor system.

Moving forward, the next frontier in this area is to extend these single-object analyses to a large sample of infant supernovae. The upcoming Zwicky Transient Facility with its fast survey speed, which is expected to find one infant supernova every night, is well positioned to carry out this task.