Organocatalytic depolymerization of poly(ethylene terephthalate)

We describe the organocatalytic depolymerization of poly(ethylene terephthalate) (PET), using a commercially available guanidine catalyst, 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD). Postconsumer PET beverage bottles were used and processed with 1.0 mol % (0.7 wt %) of TBD and excess amount of ethylene glycol (EG) at 190 °C for 3.5 hours under atmospheric pressure to give bis(2‐hydroxyethyl) terephthalate (BHET) in 78% isolated yield. The catalyst efficiency was comparable to other metal acetate/alkoxide catalysts that are commonly used for depolymerization of PET. The BHET content in the glycolysis product was subject to the reagent loading. This catalyst influenced the rate of the depolymerization as well as the effective process temperature. We also demonstrated the recycling of the catalyst and the excess EG for more than 5 cycles. Computational and experimental studies showed that both TBD and EG activate PET through hydrogen bond formation/activation to facilitate this reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Supercritical fluid extraction strategies of aqueous based matrices

Liquid-liquid extraction employing supercritical carbon dioxide has been developed for removal of polar materials from water.     

A technique for flow-enhanced magnetic resonance angiography of the lower extremities

A two-dimensional, flow-enhanced gradient echo pulse sequence for nuclear magnetic resonance angiography is described. It employs interleaved, presaturated slices to acquire data efficiently on imagers which favor interleaved acquisition over sequential acquisition for multislice imaging. It is useful on any imager when the effective TR is extended to enhance the sensitivity to slow flow. The technique was applied to the region from aortic bifurcation to the iliac bifurcations of three normal volunteers. The right and left common iliac arteries and veins, the separation of the external and internal iliac arteries, and secondary branches were clearly depicted.     

Single-component catalyst/initiators for the organocatalytic ring-opening polymerization of lactide

The synthesis and characterization of a series of primary and secondary alcohol adducts of 1,3-dimesitylimidazolin-2-ylidene is described. These adducts are stable as solids at room temperature, but readily release alcohol and the free carbene in solution. These alcohol adducts function as excellent single-component catalyst/initiators for the ring-opening polymerization of lactide under mild conditions, providing polymers with controlled molecular weights and narrow polydispersities. Multifunctional adducts were used to prepare poly(lactide)s of more complex architectures.     

Effects of hearing loss and spectral shaping on identification and neural response patterns of stop-consonant stimuli

In order to determine the effects of hearing loss and spectral shaping on a dynamic spectral speech cue, behavioral identification and neural response patterns of stop-consonant stimuli varying along the /b-d-g/ place-of-articulation continuum were measured from 11 young adults (mean age = 27 years) and 10 older adults (mean age = 55.2 years) with normal hearing, and compared to those from 10 older adults (mean age = 61.3 years) with mild-to-moderate hearing impairment. Psychometric functions and N1-P2 cortical evoked responses were obtained using consonant-vowel (CV) stimuli with frequency-independent (unshaped) amplification as well as with frequency-dependent (shaped) amplification that enhanced F2 relative to the rest of the stimulus. Results indicated that behavioral identification and neural response patterns of stop-consonant CVs were affected primarily by aging and secondarily by age-related hearing loss. Further, enhancing the audibility of the F2 transition cue with spectrally shaped amplification partially reduced the effects of age-related hearing loss on categorization ability but not neural response patterns of stop-consonant CVs. These findings suggest that aging affects excitatory and inhibitory processes and may contribute to the perceptual differences of dynamic spectral cues seen in older versus young adults. Additionally, age and age-related hearing loss may have separate influences on neural function.     

Organocatalytic living ring-opening polymerization of cyclic carbosiloxanes

[reaction: see text] An organocatalytic route to narrowly dispersed poly(carbosiloxanes) of predictable molecular weight and end group fidelity is described. N-Heterocyclic carbenes (NHC) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) catalyze the ring opening of cyclic carbosiloxanes. The pK(b) of the catalyst is important in preventing adverse transetherification reactions and obtaining well-defined polymers. Mechanistic studies indicate that hydrogen bonding to TBD or the NHC activates alcohols or silanols for ring-opening reactions.     

Conservative methods for the Toda lattice equations

We are concerned with the numerical integration of the Todalattice equations by using different conservative methods. Numericalexperiments suggest that the global error for isospectral schemesdecreases exponentially with time but it is almost constantfor either symplectic or more general integrators. We providea theoretical explanation for these experimental findings.