An analogue of adenine that forms an "A:T" base pair of comparable stability to G:C

The heterocyclic base 7-aminopropargyl-7-deaza-2,6-diaminopurine (D) has been incorporated into oligodeoxynucleotides. D:T has similar thermodynamic stability to G:C and is a stable analogue of A:T.     

Thermochemistry of aqueous hydroxyl radical from advances in photoacoustic calorimetry and ab initio continuum solvation theory

Photoacoustic signals from dilute ( approximately 30 mM) solutions of H2O2 were measured over the temperature range from 10 to 45 degrees C to obtain the reaction enthalpy and volume change for H2O2(aq) --> 2 OH(aq) from which we ultimately determined DeltafG degrees , DeltafH degrees and partial molal volume, v degrees , of OH (aq). We find DeltarH = 46.8 +/- 1.4 kcal/mol, which is 4 kcal/mol smaller than the gas-phase bond energy, and DeltaVr = 6.5 +/- 0.4 mL/mol. The v degrees for OH in water is 14.4 +/- 0.4 mL/ml: smaller than the v degrees of water. Using ab intio continuum theory, the hydration free energy is calculated to be -3.9 +/- 0.3 kcal/mol (for standard states in number density concentration units) by a novel approach devised to capture in the definition of the solute cavity the strength and specific interactions of the solute with a water solvent molecule. The shape of the cavity is defined by "rolling" a three-dimensional electron density isocontour of water on the ab initio water-OH minimum interaction surface. The value of the contour is selected to reproduce the volume of OH in water. We obtain for OH(aq): DeltafH degrees = -0.2 +/- 1.4 and DeltafG degrees = 5.8 +/- 0.4 kcal/mol that are in agreement with literature values. The results provide confidence in the pulsed PAC technique for measuring aqueous thermochemistry of radicals and open the way to obtaining thermochemistry for most radicals that can be formed by reaction of OH with aqueous substrates while advancing the field of continuum solvation theory toward ab initio-defined solute cavities.     

Synthesis, structure, and properties of chromium(III) sulfates

Reactions between CrO₃ and 50- are studied at temperatures up to the boiling point of the acid. Depending on the H₂SO₄ concentration and synthesis temperature, Cr₂(SO₄)₃, CrH(SO₄)₂, (H₃O)[Cr(SO₄)₂], Cr₂(SO₄)₃·H₂SO₄·4H₂O (gross formula), and (H₅O₂)[Cr(H₂O)₂(SO₄)₂], are obtained as identified reaction products in addition to the incompletely characterized chromic-sulfuric acid. The Cr^III-based sulfates are characterized by X-ray powder diffraction, thermogravimetric, and magnetic susceptibility measurements. The nuclear and magnetic structures of Cr₂(SO₄)₃ at are determined, the structure type of (H₃O)[Cr(SO₄)₂] is established, and the crystal structure of (H₅O₂)[Cr(H₂O)₂(SO₄)₂] is firmly stipulated. Magnetic susceptibility data suggest that the samples of CrH(SO₄)₂ are in a micro-crystalline rather than in an amorphous state. All Cr^III-based sulfates synthesized in this study appear to undergo paramagnetic-to-antiferromagnetic transitions at around .     

Clustered bottlenecks in mRNA translation and protein synthesis

Using a model based on the totally asymmetric exclusion process, we investigate the effects of slow codons along messenger RNA. Ribosome density profiles near neighboring clusters of slow codons interact, enhancing suppression of ribosome throughput when such bottlenecks are closely spaced. Increasing the slow codon cluster size beyond approximately 3-4 codons does not significantly reduce the ribosome current. Our results are verified by both extensive Monte Carlo simulations and numerical calculation, and provide a biologically motivated explanation for the experimentally observed clustering of low-usage codons.     

Charge-transfer states in strongly coupled phthalocyanine fullerene ensembles

Fluorescence and transient absorption measurements show that in strongly coupled ZnPc-C60 and H2Pc-C60 dyads charge-separated states are formed; large -delta GCR degree and small lambda assist in stabilising ZnPc(.+)-C60.-/H2Pc(.+)-C60.-.     

Chiral self-discrimination in a M3L2 subphthalocyanine cage

A tris(3-pyridyl)-substituted C3 symmetric subphthalocyanine (SubPc) was dimerized into a M3L2 cage in the presence of a stoichiometric amount of (en)Pd(NO3)2. NMR studies demonstrated the recognition event to be accompanied by chiral self-discrimination between the two enantiomers of the SubPc. Moreover, the specificity is such that only one of four possible isomers was detected in solution.     

Chemiluminescence determination of carbofuran and promecarb by flow injection analysis using two photochemical reactions

A flow injection-chemiluminescent method for the determination of carbofuran and promecarb is proposed. The assay was based on the on-line conversion of the pesticides into methylamine by irradiation with UV light. The methylamine generated was subsequently reacted with tris(2,2'-bipyridine)ruthenium(III), which was generated through the on-line photo-oxidation of tris(2,2'-bipyridine)ruthenium(II) with peroxydisulfate. The emitted light showed a linear relationship with the concentration of the pesticide over the ranges 0.22-11.2 microg ml(-1) for carbofuran and 0.41-16.6 microg ml(-1) for promecarb. The repeatability was 1.6% expressed as relative standard deviation (n = 10) and the reproducibility, studied on five different days, was 2%. The sample throughput was 200 injections per h. The reliability of the method for routine analysis of these pesticides in water, soil and grains is demonstrated.     

A Comparative Study of the Determination of Ferrofluid Particle Size by Means of Rotational Brownian Motion and Translational Brownian Motion

Two methods, the Toroidal Technique and the Forced Rayleigh Scattering (FRS) method, were used in the determination of the size of magnetic particles and their aggregates in magnetic fluids. The toroidal technique was used in the determination of the complex, frequency dependent magnetic susceptibility, x(w)=x'(w) - ix"(w) of magnetic fluids consisting of two colloidal suspensions of cobalt ferrite in hexadecene and a colloidal suspension of magnetite in isopar m with corresponding saturation magnetisation of 45.5 mT, 20 mT and 90 mT, respectively. Plots of the susceptibility components against frequency f over the range 10 Hz to 1 MHz, are shown to have approximate Debye-type profiles with the presence of relaxation components being indicated by the frequency, f _max, of the maximum of the loss-peak in the x"(w) profiles. The FRS method (the interference of two intense laser beams in the thin film of magnetic fluid) was used to create the periodical structure of needle like clusters of magnetic particles. This creation is caused by a thermodiffusion effect known as the Soret effect. The obtained structures are indicative of as a self diffraction effect of the used primary laser beams. The relaxation phenomena arising from the switching off of the laser interference field is discussed in terms of a spectrum of relaxation times. This spectrum is proportional to the hydrodynamic particle size distribution. Corresponding calculations of particle hydrodynamic radius obtained by both mentioned methods indicate the presence of aggregates of magnetic particles.     

An endoscopic imaging system for turbine engine pressure sensitive paint measurements

A fiber-optic endoscopic imaging system for mapping the surface pressure of turbine engine parts coated with pressure sensitive paint has been developed. Fluorescence intensity measurements collected from a ruthenium bathophenanthroline pressure sensitive paint sample under different pressure and temperature settings are presented. Moreover, a simple analysis for the errors resulting from the shift in the pressure sensitive paint fluorescence intensity due to temperature artifacts is given.     

The hypertoric intersection cohomology ring

We present a functorial computation of the equivariant intersection cohomology of a hypertoric variety, and endow it with a natural ring structure. When the hyperplane arrangement associated with the hypertoric variety is unimodular, we show that this ring structure is induced by a ring structure on the equivariant intersection cohomology sheaf in the equivariant derived category. The computation is given in terms of a localization functor which takes equivariant sheaves on a sufficiently nice stratified space to sheaves on a poset. T. Braden’s research was supported in part by NSF grant DMS-0201823. N. Proudfoot’s research was supported in part by an NSF Postdoctoral Research Fellowship and NSF grant DMS-0738335.