High resolution microwave spectroscopy of the isomeric pair vinylcyanoacetylene and cyanovinylacetylene

The carbon chain molecules vinylcyanoacetylene and cyanovinylacetylene have been investigated between 8 and 41 GHz by Fourier transform microwave spectroscopy of a supersonic molecular beam. Owing to the high spectral resolution of the present technique, significantly more accurate rotational and centrifugal distortion constants have been derived for both molecules. In addition, the dipole moments have been calculated at the B3LYP/cc-pVTZ level of theory. Because these carbon chains are similar in structure and composition to known astronomical molecules and because of their high polarity, both species are good candidates for radioastronomical detection.     

A parametric <Emphasis Type="Italic">k</Emphasis>-means algorithm

The k points that optimally represent a distribution (usually in terms of a squared error loss) are called the k principal points. This paper presents a computationally intensive method that automatically determines the principal points of a parametric distribution. Cluster means from the k-means algorithm are nonparametric estimators of principal points. A parametric k-means approach is introduced for estimating principal points by running the k-means algorithm on a very large simulated data set from a distribution whose parameters are estimated using maximum likelihood. Theoretical and simulation results are presented comparing the parametric k-means algorithm to the usual k-means algorithm and an example on determining sizes of gas masks is used to illustrate the parametric k-means algorithm.     

Ultrafast electronic relaxation and coherent vibrational oscillation of strongly coupled gold nanoparticle aggregates

We report the first direct observation of the ultrafast electronic relaxation and coherent vibrational oscillation of strongly interacting gold nanoparticle aggregates measured by femtosecond laser spectroscopy. The electronic relaxation, reflected as a fast decay component with a time constant of 1.5-2.5 ps, becomes faster with decreasing pump power, similar to earlier observations of isolated gold nanoparticles. Surprisingly, periodic oscillations have been observed in the transient absorption/bleach signal and have been attributed to the coherent vibrational excitation of the gold nanoparticle aggregates. The oscillation period has been found to depend on the probe wavelength. As the probe wavelength is varied from 720 to 850 nm, the period changes from 37 to 55 ps. This suggests that the broad extended plasmon band (EPB) contains contributions from gold nanoparticle aggregates with different sizes and/or different fractal structures. Each of the different probe wavelengths therefore interrogates one subset of the aggregates with similar size or structure. Interestingly, the observed oscillation period for a given aggregate size determined by dynamic light scattering is longer than that predicted based on a elastic sphere model. One possible explanation is that the actual size of the aggregates is larger than what was observed from dynamic light scattering. An alternative, perhaps more likely, explanation is that the vibration of the aggregates is "softer" than that of hard spherical gold nanoparticles possibly because the longitudinal speed of sound is lower in the aggregates than in bulk gold. Persistent spectral hole burning was performed and yielded a hole in the nanoparticle aggregate's extended plasmon band, further supporting that the near-IR band is composed of absorption subbands from differently sized/structured aggregates.     

Detection of amines by using the depolymerization of poly(chloroaldehydes)

A detector tube is described in which amine vapors cause decomposition of a chloral-dichloroacetaldehyde copolymer. Detection signal is based on the dissolution of the dye pinacyanole by the liberated chloroacetaldehyde monomers. Of the 77 amines tested, ammonia, allylamine, n-butylamine, isobutylamine, sec-butylamine, cyclohexylamine, diethylamine, dibutylamine, dipropylamine, and piperidine gave strongest tests. The limit of detection of diethylamine is approximately 2 μg. The sensitivity is increased about one order of magnitude if solution techniques are employed. Interferences appear to be few since 71 compounds representing 21 classes of compounds did not give a test.     

The mobile proton in polyalanine peptides

Ion mobility measurements have been performed for protonated polyalanine peptides (A10 + H+, A15 + H+, A20 + H+, A25 + H+, and A15NH2 + H+) as a function of temperature using a new high-temperature drift tube. Peaks due to helices and globules were found at room temperature for all peptides, except for A10 + H+ (where only the globule is present). As the temperature is increased, the helix and globule peaks broaden and merge to give a single narrow peak. This indicates that the two conformations interconvert rapidly at elevated temperatures. The positions of the merged peaks show that A15 + H+ and A15NH2 + H+ spend most of their time as globules when heated, while A20 + H+ and A25 + H+ spend most of their time as helices. The helix/globule transitions are almost certainly accompanied by intramolecular proton transfer, and so, these results suggest that the proton becomes mobile (able to migrate freely along the backbone) at around 450 K. The peptides dissociate as the temperature is increased further to give predominantly the bn(+), b(n-1)(+), b(n-2)(+), ... series of fragment ions. There is a correlation between the ease of fragmentation and the time spent in the helical conformation for the An + H+ peptides. Helix formation promotes dissociation because it pools the proton at the C-terminus where it is required for dissociation to give the observed products. In addition to the helix and globule, an antiparallel helical dimer is observed for the larger peptides. The dimer can be collisionally dissociated by injection into the drift tube at elevated kinetic energies.     

Butanol fermentation research: upstream and downstream manipulations

An overview of advances in acetone-butanol fermentation research is presented with specific reference to the history of acetone-butanol fermentation, genetic manipulation of the butanol-producing Clostridium beijerinckii NCIMB 8052, as well as upstream and downstream processing. Specific reference is made to the development of the hyperamylolytic, hyper-"butanolagenic" C. beijerinckii BA101 strain. Amylolytic enzyme production by C. beijerinckii BA101 was 1.8- and 2.5-fold greater than that of the C. beijerinckii NCIMB 8052 strain grown in starch and glucose, respectively. We confirmed the presence of a phosphoenolpyruvate (PEP)-dependent phosphotransferase system (PTS) associated with cell extracts of C. beijerinckii BA101 by glucose phosphorylation by PEP and ATP-dependent glucose phosphorylation. It was found that C. beijerinckii BA101 was defective in PTS activity and that it compensates for this defect with enhanced glucokinase activity, resulting in an ability to transport and utilize glucose during the solventogenic stage. The principal problem associated with acetone-butanol fermentation by C. beijerinckii or C. acetobutylicum is butanol toxicity/inhibition to the culture. To solve this problem, we have attempted various alternative in situ/online techniques of butanol removal including membrane-based systems such as pervaporation, liquid-liquid extraction, and gas stripping. We found that gas stripping and pervaporation appear to be the most promising of the in situ acetone-butanol fermentation and recovery techniques but, in terms of cost-effective industrial applications, gas stripping appears to be the most promising.     

Carbon-13 Isotopic Species of H2C3, H2C4, and H2C5: High-Resolution Rotational Spectra

The microwave rotational spectra of the carbon-13 isotopic species of H₂C₃, H₂C₄, and H₂C₅ have been observed in a pulsed supersonic molecular beam by Fourier transform microwave spectroscopy. At high resolution all of the rotational lines exhibit hyperfine structure produced by the magnetic interaction between the nuclear spin of ¹³C and the overall rotation of the molecule. The component of the nuclear spin-rotation tensor along the a-inertial axis is large for most isotopic species, especially at the carbene carbon; at this position C_aa is two to three times larger than at other substituted positions along the chain. In contrast to both H₂C₃ and H₂C₃, in H₂C₄C_aa exhibits a pronounced alternation along the carbon chain backbone. Following detection of the five carbon-13 isotopic species and D₂C₅, an experimental structure (r₀) has been determined to high accuracy for H₂C₅.     

High-resolution rotational spectroscopy of the carbon chain anions C3N-, C4H-, and C4D(-)

The rotational spectra of C(3)N(-), C(4)H(-), and C(4)D(-) have been measured at high-spectral resolution by Fourier transform microwave spectroscopy. For both C(3)N(-) and C(4)D(-), hyperfine structure in the lowest-J transitions has been resolved and measured to better than 0.1 ppm. The quadrupole coupling constants eQq for both anions are close to those of the neutral counterparts C(3)N and C(4)D, and that of C(3)N(-) is in good agreement with theoretical calculations. Several properties of these anions, including their linewidths, drift velocities, and abundances, are systematically compared to similar-sized neutral molecules. The production of C(4)H(-) with different hydrocarbon precursor and buffer gases is also discussed.