Radiolysis of Aqueous Solutions of Benzoate Ion: A Radiation Chemistry Experiment for Undergraduates

This investigation describes the chemical effects of ionizing radiation on dilute aqueous solutions of benzoate ion. We have composed an experimental procedure that allows undergraduate chemistry students to identify and to quantitatively determine the amount of the products that are produced. The student investigators determine the absorbed dose that a sample receives when exposed to a ⁶⁰Co source, irradiate dilute aqueous solutions of benzoate ion, and analyze the resulting mixture of hydroxybenzoate ions using high-performance liquid chromatography. The radiolysis of dilute solutions of benzoate ion results in the formation of a mixture of ortho-, meta-, and para-hydroxybenzoate ions that are readily separated on a C₁₈ -Bondapak column. By the use of appropriate calibration curves, the yield (G values) of each of the isomers may be determined and compared.This paper was presented at the 15th Biennial Conference on Chemical Education, Waterloo, Ontario, Canada, August 1998 by N. Zevos and at the 26th Northeast Regional Meeting of the American Chemical Society by Evon Powell.     

6,7‐diaza‐1‐methoxy‐ 5‐methyl‐2, 8‐dioxabicyclo[3.2.1]oct‐6‐ene. An unstable bicyclic precursor of a dioxa carbonyl ylide and carbenes by ylide ring opening

Synthesis of a bicyclic 2,2‐dioxa oxadiazoline (6,7‐diaza‐1‐methoxy‐5‐methyl‐2,8‐dioxabicyclo[3.2.1]oct‐6‐ene) is reported. Its thermolysis at 27°C is about 200 times as fast as the thermolysis of a monocyclic oxadiazoline model system. Presumably, a cyclic dioxa carbonyl ylide is formed initially and the ylide then undergoes a bond scission to afford either a dioxacarbene or a dialkylcarbene or it cyclizes to an oxirane. A small fraction of a dialkylcarbene was trapped as the product of addition to dimethyl acetylenedicarboxylate (DMAD). Computations of the barriers to the loss of N₂ from the oxadiazolines and to the formation of the carbenes from the carbonyl ylide resulting from thermolysis of the bicyclic oxadiazoline are compared to corresponding barriers for a similar monocyclic oxadiazoline. The rate acceleration is accounted for in terms of geometric factors. The complex products from the decomposition of the bicyclic oxadiazoline were not studied. Copyright © 2007 John Wiley & Sons, Ltd.     

Terahertz polarization imaging

We present a new method to measure the polarization state of a terahertz pulse by using a modified electro-optic sampling setup. To illustrate the power of this method, we show two examples in which the knowledge of the polarization of the terahertz pulse is essential for interpreting the results: spectroscopy measurements on polystyrene foam and terahertz images of a plastic coin. Both measurements show a sample-induced rotation of the terahertz electric field vector, which is surprisingly large and is a strong function of frequency. A promising aspect of our setup is the possibility of simultaneously measuring both transversal electric field components.     

Prototype reflectivity analyses of hydrogen storage levels in single-walled carbon nanotubes

A prototype case study is presented that examines the level of hydrogen content in H-SWNTs using the Surface Plasmon Resonance technique. The damping effect and the angular shift in the resonance minimum of an SWNT-gold interface due to the presence of hydrogen is analyzed using a parametric model, which is based on the concept of an effective permittivity. The new approach provides for a non-invasive analysis of the level of hydrogen content in H-SWNTs and is potentially extendable to other carbon-based hydrogen storage materials.     

Dramatic enhancement of third-harmonic generation in three-dimensional photonic crystals

We have observed a dramatic enhancement of third-harmonic generation in 3D polystyrene-air photonic crystals pumped by a near infrared laser beam. As the pump wavelength is tuned, the peak of the enhancement occurs when the third-harmonic wavelength approaches the short-wavelength edge of the band gap. We show that the origin of the enhancement is phase matching provided by the periodic structure of the photonic crystals.     

Characterization and comparison of metal accumulation in two Escherichia coli strains expressing either CopA or MntA, heavy metal-transporting bacterial P-type adenosine triphosphatases

MntA from Lactobacillus plantarum and copA from Enterococcus hirae both encode membrane proteins that are members of the P-type family of adenosine triphosphatases (ATPases). Both transporters act as metal importers to take up nutritionally required substrates; MntA translocates Mn(II) and CopA translocates Cu(I). Both ATPases can also translocate secondary substrates, Cd(II) and Ag(I), respectively. Although functionally and sequentially similar, these ATPases differ in several key residues and in their membrane topologies. The bioaccumulation properties of these two proteins were examined by coexpressing the transporters with overexpressed metallothionein in Escherichia coli cells, a system that has previously shown high levels of substrate-specific uptake. Both strains exhibited rapid metal accumulation, both saturated at around 50 μM metal, and both displayed temperature-sensitive uptake. However, the transporters responded differently when external conditions were varied; MntA displayed increased sensitivity to ionic strength, while CopA was more pH sensitive and more inhibited by chelating agents. The differences in accumulation are likely owing to structural differences in the transmembrane region of these two ATPases.     

Ultrasonic absorption in polymer gel dosimeters

Ultrasonic absorption in polymer gel dosimeters was investigated. An ultrasonic interferometer was used to study the frequency (f) dependence of the absorption coefficient (alpha) in a polyacrylamide gel dosimeter (PAG) in the frequency range 5-20 MHz. The frequency dependence of ultrasonic absorption deviated from that of an ideal viscous fluid. The presence of relaxation mechanisms was evidenced by the frequency dependence of alpha/f(2) and the dispersion in ultrasonic velocity. It was concluded that absorption in polymer gel dosimeters is due to a number of relaxation processes which may include polymer-solvent interactions as well as relaxation due to motion of polymer side groups.The dependence of ultrasonic absorption on absorbed dose and formulation was also investigated in polymer gel dosimeters as a function of pH and chemical composition. Changes in dosimeter pH and chemical composition resulted in a variation in ultrasonic dose response curves. The observed dependence on pH was considered to be due to pH induced modifications in the radiation yield while changes in chemical composition resulted in differences in polymerisation kinetics.     

Observation of ultraslow light propagation in a ruby crystal at room temperature

We have observed slow light propagation with a group velocity as low as 57.5+/-0.5 m/s at room temperature in a ruby crystal. A quantum coherence effect, coherent population oscillations, produces a very narrow spectral "hole" in the homogeneously broadened absorption profile of ruby. The resulting rapid spectral variation of the refractive index leads to a large value of the group index. We observe slow light propagation both for Gaussian-shaped light pulses and for amplitude modulated optical beams in a system that is much simpler than those previously used for generating slow light.     

Inert site in a protein zinc cluster: isotope exchange by high resolution mass spectrometry

Using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry, we show that one Zn2+ ion in the Zn4 cluster of cyanobacterial metallothionein is inert to exchange with 67Zn2+. We suggest that this is zinc in site A, which together with the surrounding alpha and beta secondary structure forms a zinc-finger fold.     

High-Resolution Laser Spectroscopy of YbCl: The A(2)Pi-X(2)Sigma(+) Transition

The A(2)Pi-X(2)Sigma(+) transition of (174)Yb(35)Cl and (172)Yb(35)Cl has been rotationally analyzed for the first time. Doppler-limited laser excitation spectroscopy with selective detection of fluorescence was used to obtain spectra of the 0-0 and 1-0 bands with a measurement accuracy of approximately 0.0035 cm(-1). Resolved fluorescence was used to record the 0-1, 0-2, and 0-3 bands and to unequivocally assign the rotational numbering, N, to the laser excitation spectra. In total, over 1300 line positions have been measured and assigned for each of the two isotopomers and employed in least-squares fits of molecular parameters. The principal results for the A(2)Pi state are A(e) = 1491.494(2) cm(-1) and R(e) = 2.4433(1) ?, and for the X(2)Sigma(+) state, R(e) = 2.4883(2) ? and gamma(e) = 4.59(2) x 10(-3) cm(-1). The interaction between the X(2)Sigma(+) and A(2)Pi states has been investigated and is shown to be the main contributor to the spin-rotation splitting in the ground state. Copyright 2000 Academic Press.