Real-time airborne radiation analysis and collection (RTARAC) searching for airborne species characteristic to nuclear proliferation

An effective means of detecting airborne radioactive aerosol plumes has been developed and tested on aircraft platforms. The Real-Time Airborne Radiation Analysis and Collection (RTARAC) system was mounted in the wing pod of a Navy P-3 where it sampled 20 cubic meters of air per minute on each of eleven sequentially advanced filters. A 140% intrinsic gemanium detector counted radioactive particles collected on the 15 cm circular filters in real-time. Gamma-energy spectrum and near real-time analysis of the sample were displayed on a laptop computer.     

Quantum chemical modeling for 157 nm photolithography

In its continuing quest for smaller length scales, the electronics industry plans to introduce 157 nm as the next lithographic wavelength. Accordingly, there is a pressing need to develop photoresists that are more transparent, and pellicles that are both more transparent and more durable. With the advent and popularization of time-dependent density functional theory (TD-DFT), we now have a practical quantum chemical method for calculating excitation energies and transition moments in the vacuum ultraviolet (VUV) which can greatly assist in the scouting of highly transparent materials. We have performed TD-DFT calculations for a broad variety of fluorinated molecules and we will report calculated VUV photoabsorption spectra for a large family of model fluorohexanes. These calculations, which span a range from 1-fluorohexane to CH₃CF₂CF₂CF₂CF₂CH₃, illustrate some of the principles one may use to design low absorption polymeric materials.     

Photocontrol of DNA binding specificity of a miniature engrailed homeodomain

Control of DNA binding of HDH-3, a 18-residue polypeptide based on the recognition helix of the Q50K engrailed homeodomain, has been achieved. HDH-3 was linked to an azobenzene cross-linker through two cysteine residues in an i, i + 11 spacing. For the thermodynamically stable trans configuration of the cross-linker, the dark-adapted peptide (dad-HDH-3) adopted a mainly alpha-helical structure as judged by circular dichroism (CD) spectroscopy. After irradiation with light of 360 nm, the helical content of the peptide (irrad-HDH-3) was reduced significantly and the CD spectrum of the irradiated peptide resembled that of the largely unstructured, unalkylated peptide. Despite lacking helices-1 and -2 and the N-terminal arm of Q50K engrailed, dad-HDH-3 bound to its natural DNA target sequence TAATCC (QRE) with high affinity (K(D) = 7.5 +/- 1.3 nM). The binding affinity for the mutant DNA sequence, TAATTA (ERE), was reduced significantly (K(D) = 140 +/- 11 nM). Unlike irrad-HDH-3, which like the unalkylated parent peptide displayed only marginal DNA binding specificity, dad-HDH-3 specified base pairs 5 and 6 of QRE with an accuracy rivaling that of the intact wild-type Q50K engrailed homeodomain, making dad-HDH-3 the most specific designed DNA binding miniature homeodomain reported to date. Moreover, DNA binding affinity and specificity of HDH-3 could be controlled externally by irradiation with light.     

Controlling the DNA binding specificity of bHLH proteins through intramolecular interactions

Reversible control of the conformation of proteins was employed to probe the relationship between flexibility and specificity of the basic helix-loop-helix protein MyoD. A fusion protein (apaMyoD) was designed where the basic DNA binding helix of MyoD was stablized by an amino-terminal extension with a sequence derived from the bee venom peptide apamin. The disulfide-stabilized helix from apamin served as a nucleus for a helix that extended for a further ten residues, thereby holding apaMyoD's DNA recognition helix in a predominantly alpha-helical conformation. The thermal stability of the DNA complexes of apaMyoD was increased by 13 degrees C relative to MyoD-bHLH. Measurements of the fluorescence anisotropy change on DNA binding indicated that apaMyoD bound to E-box-containing DNA sequences with enhanced affinity relative to MyoD-bHLH. Consequently, the DNA binding specificity of apaMyoD was increased 10-fold.     

Absolute rate constants for some hydrogen atom abstraction reactions by a primary fluoroalkyl radical in water

A combination of laser flash photolysis and competitive kinetic methods have been used to measure the absolute bimolecular rate constants for hydrogen atom abstraction in water from a variety of organic substrates including alcohols, ethers, and carboxylic acids by the perfluoroalkyl radical, *CF(2)CF(2)OCF(2)CF(2)SO(3)(-) Na(+). Comparison, where possible, of these rate constants with those previously measured for analogous reactions in the non-polar organic solvent, 1,3-bis(trifluoromethyl)benzene (J. Am. Chem. Soc, 1999, 121, 7335) show that the alcohols react 2-5 times more rapidly in the water solvent and that the ethers react at the same rate in both solvents. A transition state for hydrogen abstraction that is more reminiscent of an "intimate ion pair" than a "solvent separated ion pair" is invoked to explain these modest solvent effects.     

On the existence of SH3, SeH3, and TeH3: Discrepancies between all-electron and pseudopotential calculations

Ab initio calculations using both pseudopotential and double and triple-ζ all-electron basis sets, with and without electron correlation (MP2, QCISD), have been performed on the λ⁴-sulfanyl (SH₃), λ⁴-selanyl (SeH₃), and λ⁴-tellanyl (TeH₃) radicals. All-electron basis sets of double-ζ quality predict that SH₃ and SeH₃ correspond to transition states on their respective potential energy surfaces. In contrast, the pseudopotentials of Hay and Wadt predict that SH₃ and SeH₃ correspond to local minima at the QCISD level of theory while the pseudopotentials of Christiansen and Stevens predict transition states. By comparison, TeH₃ proved to be a local minimum at all levels of theory. Interestingly, when a very large (triple-ζ) all-electron basis set was used, SH₃ proved to be a transition state; however, in this instance the potential energy surface was found to be much flatter than in the case for which a double-ζ basis set was used, suggesting that further improvements in the basis set may lead to a local minimum. Further improvements in the all-electron selenium basis also led to a local minimum for SeH₃ at the QCISD level of theory. © 1995 by John Wiley & Sons, Inc.     

One‐Step Ring Opening Metathesis Block‐Like Copolymers and their Compositional Analysis by a Novel Retardation Technique

Using a one‐step synthetic route for block copolymers avoids the repeated addition of monomers to the polymerization mixture, which can easily lead to contamination and, therefore, to the unwanted termination of chain growth. For this purpose, monomers ( M1 – M5 ) with different steric hindrances and different propagation rates are explored. Copolymerization of M1 (propagating rapidly) with M2 (propagating slowly), M1 with M3 (propagating extremely slowly) and M4 (propagating rapidly) with M5 (propagating slowly) yielded diblock‐like copolymers using Grubbs’ first ( G1 ) or third generation catalyst ( G3 ). The monomer consumption was followed by ¹H NMR spectroscopy, which revealed vastly different reactivity ratios for M1 and M2 . In the case of M1 and M3 , we observed the highest difference in reactivity ratios (r₁=324 and r₂=0.003) ever reported for a copolymerization method. A triblock‐like copolymer was also synthesized using G3 by first allowing the consumption of the mixture of M1 and M2 and then adding M1 again. In addition, in order to measure the fast reaction rates of the G3 catalyst with M1 , we report a novel retardation technique based on an unusual reversible G3 Fischer‐carbene to G3 benzylidene/alkylidene transformation.     

Arithmetic on superelliptic curves

This paper is concerned with algorithms for computing in the divisor class group of a nonsingular plane curve of the form which has only one point at infinity. Divisors are represented as ideals, and an ideal reduction algorithm based on lattice reduction is given. We obtain a unique representative for each divisor class and the algorithms for addition and reduction of divisors run in polynomial time. An algorithm is also given for solving the discrete logarithm problem when the curve is defined over a finite field.

     

A model for the biosynthesis of indole alkaloids by cell suspensions ofCatharanthus roseus G. Don

The kinetics of alkaloid formation in a plant cell culture ofCatharanthus roseus G. Don are shown to follow the differential equations:P ₁(t) = aX(t - Δt) - (b + c)P₁(t)P ₂(t) = bP₁(t) - cP₂(t) Where X, P₁, and P₂ are measures of the cell dry weight, intracellular ajmalicine, and serpentine, respectively. From the parameter estimates, it is evident that carry over of kinetin to the second-stage from the first-stage growth medium can have a major effect on alkaloid biosynthesis. This effect appears to be connected with the inhibition of the oxidation of ajmalicine to serpentine.