Surface-enhanced vibrational investigation of adsorbed analgesics

Adsorption properties of acetylsalicylic acid (AA), ibuprofen and acetaminophen deposited from volatile solvents with varying protic/aprotic properties on vacuum-evaporated silver films were characterized using surface-enhanced infrared absorption (SEIRA) and surface-enhanced Raman spectroscopy (SERS). SERS preferentially enhances monolayer Raman shifts, while SEIRA can enhance the infrared absorbance of the monolayer and multilayers. To our best knowledge, this is the first reported study of these molecules using a combination of SERS/SEIRA. SERS revealed that AA and ibuprofen adsorbed ionically in monolayers, independent of the deposition solvents used in the process. SEIRA experiments showed that AA multilayers condensed molecularly using a deposition solvent with polar bonds. However, when an alkane deposition solvent with non-polar bonds such as n-heptane was used, AA adsorbed as acetylsalicylate ions in the first few multilayers, while ibuprofen always adsorbed as the free acid in the multilayer. These ionization trends depend upon the affinity of AA and ibuprofen for the underlying silver film. TPD experiments on silver powders further demonstrated that ibuprofen affinity for silver was less than AA. Furthermore, SEIRA indicated that acetaminophen adsorbed as multilayers of metastable polymorphs using protic or polar aprotic deposition solvents. Protic deposition solvents gave higher quality SERS spectra of an acetaminophen monolayer in comparison to polar aprotic deposition solvents. Such studies could find significant applications in biochemical and nanotechnology processes such as drug delivery, catalysis, and tissue engineering and will contribute to the understanding of the impact and fate of analgesics released into the environment.     

X-ray investigation of the structure of poly(tetramethylene terephthalate)

Poly(tetramethylene terephthalate) (PTMT) undergoes a reversible stress-induced crystal-crystal phase transition. X-ray fiber-diffraction photographs were obtained from the oriented, unstressed (α) phase. Relative intensities were measured from these photographs. These were used to help check the reported structures of the α phase. Structures and observed intensity data from other authors were also utilized. Results show the α phase contains a non-trans, non-gauche bond rotation in the tetramethylene chain and a nonplanar terephthalic acid residue. A tilt of 3.5° between the fiber axis and the c axis was determined in a direction 210° counterclockwise from the b^* axis.     

Infrared studies of the reversible stress-induced crystal-crystal phase transition of poly(tetramethylene terephthalate)

The reversible stress-induced crystal-crystal phase transition of poly(tetramethylene terephthalate) (PTMT) has been studied using infrared spectroscopy. Two spectral regions were used to study this transition: the 900–1000 cm^?1 methylene rocking region and the 1300–1550 cm^?1 methylene bending region. The bands at 917 and 1456 cm^?1 are assigned to the ∝ phase. The bands at 935 and 1388 cm^?1 have components from the α phase and the β phase. Dynamic stretching experiments performed above and below the glass-transition temperature indicated different mechanisms of the phase transition.     

Transient and oscillatory granular shear flow

The forces and particle motion during transient and oscillatory shear of granular material are investigated experimentally. In a shear cell of Taylor-Couette-type we find that how a granular shear flow starts depends strongly on the prior shear direction. If the shear direction is reversed, the material goes through a transient period during which the material compacts, the shear force is small, and the shear band is wide. Three-dimensional confocal imaging of particle rearrangements during shear reversal shows that bulk and surface flows are comparable. Repeated reversals, or oscillations of the shear direction, lead to additional compaction, which can be described by a stretched exponential, similar to compaction induced by tapping.     

Activation barrier scaling and crossover for noise-induced switching in micromechanical parametric oscillators

We explore fluctuation-induced switching in parametrically driven micromechanical torsional oscillators. The oscillators possess one, two, or three stable attractors depending on the modulation frequency. Noise induces transitions between the coexisting attractors. Near the bifurcation points, the activation barriers are found to have a power law dependence on frequency detuning with critical exponents that are in agreement with predicted universal scaling relationships. At large detuning, we observe a crossover to a different power law dependence with an exponent that is device specific.     

Supernarrow spectral peaks near a kinetic phase transition in a driven nonlinear micromechanical oscillator

We measure the spectral densities of fluctuations of an underdamped nonlinear micromechanical oscillator. By applying a sufficiently large periodic excitation, two stable dynamical states are obtained within a particular range of driving frequency. White noise is injected into the excitation, allowing the system to overcome the activation barrier and switch between the two states. While the oscillator predominately resides in one of the two states for most frequencies, a narrow range of frequencies exist where the occupations of the two states are approximately equal. At these frequencies, the oscillator undergoes a kinetic phase transition that resembles the phase transition of thermal equilibrium systems. We observe a supernarrow peak in the spectral densities of fluctuations of the oscillator. This peak is centered at the excitation frequency and arises as a result of noise-induced transitions between the two dynamical states.