Application of mass spectrometry to the study of fluoropolymers. III. Polyperfluorobut-2-yne

Mass spectra of the volatile fractions from polyperfluorobut-2-yne have been obtained. The polymer appears to be thermally stable up to 300°C and molecules containing up to 12 monomer units have been identified. A regular structure is indicated by the mass spectrum which is characterized by unusually intense doubly charged ions. The endgroups are readily identified, and a conjugated polyolefin structure is indicated.     

Non-equilibrium behavior of sticky colloidal particles: beads,clusters and gels

To understand the non-equilibrium behavior of colloidal particles with short-range attraction, we studied salt-induced aggregation of lysozyme. Optical microscopy revealed four regimes: bicontinuous texture, beads, large aggregates, and transient gelation. The interaction of a metastable liquid-liquid binodal and an ergodic to non-ergodic transition boundary inside the equilibrium crystallization region can explain our findings.     

The Kinetics of Ester-Ester Exchange Reactions by Mass Spectrometry

The kinetics of ester-ester exchange reactions between poly(ethy1ene adipate) and poly(trimethy1ene adipate) have been studied by mass spectrometric techniques. Reactions were carried out in the absence of catalyst and solvent. Rate constants for the exchange reaction and corresponding Arrhenius parameters are given.     

When is water not water? Exploring water confined in large reverse micelles using a highly charged inorganic molecular probe

The interior water pool of aerosol OT (AOT) reverse micelles tends toward bulk water properties as the micelle size increases. Thus, deviations from bulk water behavior in large reverse micelles are less expected than in small reverse micelles. Probing the interior water pool of AOT reverse micelles with a highly charged decavanadate (V(10)) oligomer using (51)V NMR spectroscopy shows distinct changes in solute environment. For example, when an acidic stock solution of protonated V(10) is placed in a reverse micelle, the (51)V chemical shifts show that the V(10) is deprotonated consistent with a decreased proton concentration in the intramicellar water pool. Results indicate that a proton gradient exists inside the reverse micelles, leaving the interior neutral while the interfacial region is acidic.     

Application of mass spectrometry to copolymers of ethylene and propylene oxides. II. Kinetic analysis

Molecular-weight distributions derived from mass spectrometric studies of some alkylene oxide copolymers have been used to calculate rate constant ratios for the first eight steps in the polymerization process. Results suggest that there is a significant reduction in reactivity of the growing chains during this initial period.     

Graphene nanoribbon-based supramolecular ensembles with dual-receptor targeting function for targeted photothermal tumor therapy

Triple negative breast cancer (TNBC) is one of the most malignant subtypes of breast cancer. Here, we report the construction of graphene nanoribbon (GNR)-based supramolecular ensembles with dual-receptor (mannose and α_vβ₃ integrin receptors) targeting function, denoted as GNR-Man/PRGD, for targeted photothermal treatment (PTT) of TNBC. The GNR-Man/PRGD ensembles were constructed through the solution-based self-assembly of mannose-grafted GNRs (GNR-Man) with a pyrene-tagged α_vβ₃ integrin ligand (PRGD). Enhanced PTT efficacies were achieved both in vitro and in vivo compared to that of the non-targeting equivalents. Tumor-bearing live mice were administered (tail vein) with GNR-Man/PRGD and then each mice group was subjected to PTT. Remarkably, GNR-Man/PRGD induced complete ablation of the solid tumors, and no tumor regrowth was observed over a period of 15 days. This study demonstrates a new and promising platform for the development of photothermal nanomaterials for targeted tumor therapy.

Dual receptor-targeting supramolecular glycomaterials are constructed based on graphene nanoribbons for the targeted photothermal therapy of triple-negative breast cancer in vivo.     

Dispersion properties of high-contrast grating hollow-core waveguides

We present unique dispersion characteristics of high-contrast grating (HCG) hollow-core waveguides and show that slow light can be facilitated using internal resonances developing inside the waveguide walls. In addition, we show a fast and precise method of inferring the dispersion information from the waveguide angular reflectivity spectrum.     

Coexisting aggregates in mixed aerosol OT and cholesterol microemulsions

Dynamic light scattering and NMR spectroscopic experimental evidence suggest the coexistence of two compositionally different self-assembled particles in solution. The self-assembled particles form in solutions containing water, Aerosol OT (AOT, sodium bis(2-ethylhexyl) sulfosuccinate) surfactant, and cholesterol in cyclohexane. In a similar series of studies carried out in 1-octanol only one aggregate type, that is, reverse micelles, is observed. Dynamic light scattering measurements reveal the presence of two different types of aggregates in the microemulsions formed in cyclohexane, demonstrating the coexistence of two compositionally distinct structures with very similar Gibbs energies. One particle type consists of standard AOT reverse micelles while the second type of particle consists of submicellar aggregates including cholesterol as well as small amounts of AOT and water. In microemulsions employing 1-octanol as the continuous medium, AOT reverse micelles form in a dispersed solution of cholesterol in 1-octanol. Although the size distribution of self-assembled particles is well-known for many different systems, evidence for simultaneous formation of two distinctly sized particles in solution that are chemically different is unprecedented. The ability to form microemulsion solutions that contain coexisting particles may have important applications in drug formulation and administration, particularly as applied to drug delivery using cholesterol as a targeting agent.     

Fast atom bombardment mass spectrometry of butyloxycarbonyl protected (BOC) amino acids

The positive and negative ion mass spectra of a series of BOC-protected amino acids have been obtained using an FAB source. The spectra show characteristic features including a McLafferty type of rearrangement.