Self-assembly of phosphate fluorosurfactants in carbon dioxide

Anionic phosphodiester surfactants, possessing either two fluorinated chains (F/F) or one hydrocarbon chain and one fluorinated chain (H/F), were synthesized and evaluated for solubility and self-assembly in liquid and supercritical carbon dioxide. Several surfactants, of both F/F and H/F types and having varied counterions, were found to be capable of solubilizing water-in-CO2 (W/C), via the formation of microemulsions, expanding upon the family of phosphate fluorosurfactants already found to stabilize W/C microemulsions. Small-angle neutron scatteringwas used to directly characterize the microemulsion particles at varied temperatures, pressures, and water loadings, revealing behavior consistent with previous results on W/C microemulsions.     

CU(II) SENSITIZES pBR322 PLASMID DNA TO INACTIVATION BY UV-B(280–315 nm)

Abstract— Copper(II), in the presence of UV-B radiation(280–315 nm), can generate single-strand breaks in the sugar-phosphate backbone of pBR322 plasmid DNA. A low level of single-strand backbone breaks occurs in the presence of Cu(II) alone, but UV-B irradiation increases the rate by the more than 100-fold. Concomitant with the damage to the DNA backbone is a loss of transforming activity. Oxygen is required for generation of the single-strand breaks but not for the loss of transforming activity. A DNA glycosylase (Fpg), which participates in the repair of certain DNA nitrogenous base damage, does not repair plasmid DNA damaged by Cu(II). The hydroxyl radical scavenging compound DMSO is only somewhat effective at protecting the physical and biological properties of the DNA. These results with Cu(II) are compared to those obtained previously with pBR322 plasmid DNA in the presence of Fe(III) and UV-A.     

Level-spacing distributions and the Airy kernel

Scaling level-spacing distribution functions in the bulk of the spectrum in random matrix models ofN×N hermitian matrices and then going to the limitN leads to the Fredholm determinant of thesine kernel sin(x–y)/(x–y). Similarly a scaling limit at the edge of the spectrum leads to theAiry kernel [Ai(x)Ai(y)–Ai(x)Ai(y)]/(x–y). In this paper we derive analogues for this Airy kernel of the following properties of the sine kernel: the completely integrable system of P.D.E.'s found by Jimbo, Miwa, Môri, and Sato; the expression, in the case of a single interval, of the Fredholm determinant in terms of a Painlevé transcendent; the existence of a commuting differential operator; and the fact that this operator can be used in the derivation of asymptotics, for generaln, of the probability that an interval contains preciselyn eigenvalues.     

On orthogonal and symplectic matrix ensembles

The focus of this paper is on the probability,E (O;J), that a setJ consisting of a finite union of intervals contains no eigenvalues for the finiteN Gaussian Orthogonal (=1) and Gaussian Symplectic (=4) Ensembles and their respective scaling limits both in the bulk and at the edge of the spectrum. We show how these probabilities can be expressed in terms of quantities arising in the corresponding unitary (=2) ensembles. Our most explicit new results concern the distribution of the largest eigenvalue in each of these ensembles. In the edge scaling limit we show that these largest eigenvalue distributions are given in terms of a particular Painlevé II function.     

Fluorescent properties of oligonucleotide-conjugated thiazole orange probes

The fluorescence properties of thiazole orange, linked via a (1) hydrophobic alkyl or a (2) hydrophilic ethylene glycol chain to the central internucleotidic phosphate group of a pentadeca-2'-deoxyriboadenylate (dA15), are evaluated. Linkage at the phosphate group yields two stereoisomers, S-isomer of the phosphorus chiral center (Sp) and R-isomer of the phosphorus chiral center (Rp); these are studied separately. The character of the linkage chain and the chirality of the internucleotidic phosphate linkage site influence the fluorescent properties of these thiazole orange-oligonucleotide conjugates (TO-probes). Quantum yields of fluorescence (phifl) of between 0.04 and 0.07 were determined for the single-stranded conjugates. The fluorescence yield increased by up to five times upon hybridization with the complementary sequence (d5'[CACT15CAC3']); (phifl values of between 0.06-0.35 were determined for the double-stranded conjugates. The phifl value (0.17) of thiazole orange, 1-(N,N'-trimethylaminopropyl)-4-[3-methyl-2,3-dihydro-(benzo-1,3-thiazole)-2-methylidene]-quinolinium iodide (TO-Pro 1) in the presence of the oligonucleotide duplex (TO-Pro 1: dA15.d5'[CACT15CAC3'] (1:1)) is much less than that for some of the hybrids of the conjugates. Our studies, using steady-state and time-resolved fluorescence experiments, show that a number of discrete fluorescent association species between the thiazole orange and the helix are formed. Time-resolved studies on the four double-stranded TO-probes revealed that the fluorescent oligonucleotide-thiazole orange complexes are common, only the distribution of the species varies with the character of the chain and the chirality at the internucleotidic phosphate site. Those TO-probes in which the isomeric structure of the phosphate-chain linkage is Rp, and therefore such that the fluorophore is directed toward the minor groove, have higher phifl values than the Sp isomer. Of the systems studied, thiazole orange linked by an alkyl chain to the internucleotidic phosphate (Rp isomer) has the highest phifl and the greatest fraction of the longest-lived fluorescent thiazole orange species (in the hybrid form).     

The Mitsunobu Reaction: Origin,Mechanism, Improvements,and Applications

The Mitsunobu reaction is a widely used and versatile method for the dehydrative oxidation–reduction condensation of an acid/pronucleophile usually with a primary or secondary alcohol that requires the combination of a reducing phosphine reagent together with an oxidizing azo reagent. The utility of this reaction stems from the fact that it is generally highly stereoselective and occurs with inversion of the stereochemical configuration of the alcohol starting material. Furthermore, as carboxylic acids, phenols, imides, sulfonamides, and other compounds can be used as the acid/pronucleophile, this reaction is useful for the preparation of a wide variety of functional groups. This Focus Review of the Mitsunobu reaction summarizes its origins, the current understanding of its mechanism, and recent improvements and applications.     

Molecular structure retention relationships in comprehensive two-dimensional gas chromatography

Comprehensive two-dimensional gas chromatography (GC x GC) offers new opportunities to develop relationships between molecular structure and retentions in the two dimensional (2D) separation space defined by the GC x GC retention in each dimension. Whereas single dimension GC provides only one retention property for a solute, and hence the specific relationship between retention and chemical property is not readily apparent or derivable, the 2D presentation of compounds in GC x GC provides a subtle and exquisite correlation of chemical property and retention unlike any other GC experiment. The 'orthogonality' of the two separation dimensions is intimately related to the manner in which different separation mechanisms, available through use of two dissimilar phases, are accessible to the different chemical compounds or classes in a sample mixture, and indeed the specific chemical classes present in the sample. The GC x GC experiment now permits various processes such as chemical decompositions, molecular interconversions, various non-linear chromatography effects, and processes such as slow reversible interactions that may arise with stationary phases or in the injector or column couplings, to be identified and further investigated. Here, we briefly review implementation of the GC x GC method, consider the molecular selectivity of GC x GC, and highlight a selection of molecular processes that can be probed by using GC x GC.     

Characterization of plutonium contamination at the former nuclear weapons testing range,at Maralinga in South Australia

Re-suspension studies on soils contaminated with plutonium during nuclear weapons tests were performed by use of a mechanical dust-raising apparatus. Airborne dust was analyzed in terms of mass and²⁴¹Am activities for particle sizes less than 7 m. The AMAD was determined as 4.8 to 6 m, for re-suspended soil. Also, surface soil was characterized in the laboratory by means of sieving and microparticle classification, yielding mass and²⁴¹Am activity distributions with respect to size. Data indicate the granularity of plutonium contamination at both major and minor trial sites. Depth profile analyses for undisturbed, areas demonstrate that most (74% on average) of the americium and plutonium activity is found in the top 10 mm of soil. Plutonium and americium activities were found to be enhanced in the inhalable fraction over their values, in the total soil, and the enhancement factors were similar in re-suspended dust and surface soil. Observed enhancement factors ranged from 3.7 to 32.5.     

The role of proficiency testing in the detection and resolution of calibration bias in the LeadCare® blood lead analyzer; limitations of peer-group assessment

Following implementation of the CLIA ‘88 laboratory regulations, the primary role of proficiency testing (external quality assessment, PT) in the U.S. has been widely viewed as one of assuring regulatory compliance. PT can also be an effective tool for detecting widespread analytical problems, subject to limitations based on the method of PT assigned value determination. A recent case study describes the role of two PT programs in detecting and resolving a calibration bias in the LeadCare blood lead analyzer, and illustrates the limitations of peer-group target determination in fulfilling that PT role.     

Moments of wishart distribution

Moments of central and noncentral Wishart distributions are obtained by differentiating their characteristic functions applying matrix derivative techniques, using a special operator which takes into account the symmetry of the matrices. As a special case, higher moments of the multivariate normal distribution are obtained, arranged automatically in a square matrix form