A characterization based on the equidistribution of the first two spacings of record values

Summary For a sequence {X _n:n=0, 1, 2,...} of i.i.d. discrete random variables let X ₀ denote the zeroeth record value and X _L(1), the first record value. It is shown that X ₀ and X _L(1) –X ₀ are identically distributed if and only if X ₀ has the geometric distribution over the lattice k :k=1, 2,... for some >0.     

Preconcentration of trace metals on Amberlite XAD-4 resin coated with dithiocarbamates and determination by inductively coupled plasma-atomic emission spectrometry in saline matrices

Preconcentration of Cd(II), Cu(II), Mn(II), Ni(II), Pb(II) and Zn(II) in saline matrices on Amberlite XAD-4 resins coated with ammonium pyrrolidine dithiocarbamate (APDC) and piperidine dithiocarbamate (pipDTC) and subsequent determination by inductively coupled plasma atomic emission spectrometry were studied. Parameters such as effect of pH, effect of HNO(3) concentration on elution of metals from resin were studied. The results show that Amberlite XAD-4 coated with APDC was more efficient in the recovery of metal ions compared with Amberlite XAD-4 coated with pipDTC, in the concentration range of 0.1-200 mug l(-1), for 1 g of Amberlite XAD-4 coated resin. The detection limits for Cd(II), Cu(II), Mn(II), Ni(II), Pb(II), Zn(II) are 0.1, 0.4, 0.3, 0.4, 0.6, 0.5 mug l(-1), respectively, for resin coated with APDC and 0.7, 1.0, 0.8, 0.9, 1.7 and 1.2 mug l(-1) for resin coated with pipDTC. The effect of diverse ions on the determination of aforesaid metals was studied. The method was applied for the determination of trace metal ions in artificial sea water and natural water samples. The results were compared with extraction AAS method.     

Matrix-assisted laser desorption/ionization time-of-flight analysis of Bacillus spores using a 2.94 microm infrared laser

The performance of infrared (2.94 microm) and ultraviolet (337 nm) lasers were compared for analysis of purified spores of B. subtilis, B. cereus and B. globigii on a four-inch end-cap reflectron time-of-flight instrument. Infrared matrix-assisted laser desorption/ionization (IR-MALDI) mass spectra of these microorganisms displayed a larger number of biomarker peaks above m/z 4000, compared with UV-MALDI. Biomarker peaks were observed at higher m/z values with the IR laser.     

Neuron-based microarray sensors for environmental sensing

We present a novel sensing scheme for detecting the effects of unburned fossil fuels by integrating microarray technology and dielectrophoresis to develop single-neuron arrays. These arrays have the capability to sense and identify the two fuels, at parts per billion (ppb) concentrations, as well to determine the associated physiological changes at the single-cell level. Identification is achieved through frequency domain analysis of the measured changes to the extracellular electrical activity due to the effect of the fossil fuels. This yields unique electrical identifiers known as "signature patterns". Simultaneous optical visualization to the physiological changes is obtained by specific fluorescent staining. The correlation between the signature patterns and the cellular biological behavior establishes the veracity of this identification technique.     

Phosphorus-based p-tert-butylcalix[5]arene ligands

New calix[5]arene trivalent phosphorus derivatives have been synthesized which should be excellent ligands with which to study and control the interaction of a ligand atom with a metal. The larger cavity of the calix[5]arene (compared to calix[4]arene) provides a good balance between constraint and flexibility. Treatment of p-tert-butylcalix[5]arene with 2 equiv of either tris(dimethylamino)phosphine or dichlorophenylphosphine inserts two RP moieties into the calix[5]arene framework to give calix[5](PR)2(OH) (1, R = Me2N; 2, R = Ph). Further treatment of 1 with 4 equiv of HCl gives calix[5](PCl)2(OH) (3). Heating a solution of the monophosphorus compound calix[5](PNMe2)(OH)3 (4) releases dimethylamine to yield both monomeric calix[5](P)(OH)2 (6) and dimeric [calix[5](P)(OH)2](2) (7), the latter having a tubelike geometry. X-ray crystallographic studies confirm the structures and show that 1 and 2 have approximate cone conformations while 3 has an approximate 1,2-alternate conformation. The orientations of the phosphorus lone pairs and oxygen atoms in all derivatives provide a framework for both soft and hard ligand interactions within the calix[5]arene.     

Photochemistry of bicyclo[2.2.2]oct-7-ene-2,5-diones and the corresponding 5-hydroxyimino and 5-methylene derivatives

Synthesis and photochemistry of several title compounds 1-3 containing multiple chromophoric systems are described. The Diels-Alder reactions of 2,6,6-trimethylcyclohexa-2,4-dienone (5) with acetylenes 6a-d provided the adducts 7a-d, which upon hydrolysis furnished the desired bicyclo[2.2.2]octenediones 1a-d. Oximes 2a-d were prepared from diones 1a-d by treatment with hydroxylamine hydrochloride in pyridine. 5-Methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d were obtained via chemoselective Wittig reaction of the corresponding diones 1a-d. Bicyclo[2.2.2]octenediones 1a-c underwent chemoselective oxa-di-pi-methane rearrangement under sensitized conditions and suffered formal ketene extrusion upon direct irradiation. Direct irradiation of 1d afforded 11d via formal ketene extrusion but under sensitization it remained unchanged. Oximes 2a-d suffered ketene extrusion upon direct irradiation and E/Z isomerization under sensitized conditions. On the other hand, 5-methylenebicyclo[2.2.2]oct-7-en-2-ones 3a-d generally underwent 1,3-acyl shift. The plausible courses of all these photochemical processes are discussed.     

Solvent water tapes in two hydrates of μ‐oxo‐bis­[bis­(2,2′‐bipyridine‐κ2N,N′)(sulfato‐κO)iron(III)]

The title compound, [Fe₂O(SO₄)₂(C₁₀H₈N₂)₄], crystallizes as two different hydrates, viz. 11H₂O, (I), and 15H₂O, (II). The complex is binuclear, in which the two Fe^III atoms are coordinated in an octa­hedral geometry to four N atoms from the two bipyridine ligands, to one O atom from the sulfate ion and to an oxide ion on a twofold axis, which acts as a bridge between the symmetry‐related units. The Fe⋯Fe separation is 3.556 (4) Å and the Fe—O—Fe angle is 161.6 (2)° in (I); the corresponding values are 3.544 (1) Å and 165.8 (2)° in (II). In (II), one of the O atoms of the sulfate ion is disordered over two positions. In both compounds, the solvent water mol­ecules form slightly different one‐dimensional hydrogen‐bonded networks which pass along the c axis of the unit cell. In (I), three solvent water mol­ecules and, in (II), one solvent water mol­ecule, are situated on the twofold axis. In both (I) and (II), the central O atom of the metal complex lies on a twofold axis.     

Ligand location and biochemical productivity of silica-based immunoaffinity adsorbents.

Ligand location within particles, detected by immunogold labelling, was shown to influence the biochemical productivity of a silica-based solid phase, Sorbsil C-500, using a model ligand-biomolecule system (immobilised human immunoglobulin G-anti-human immunoglobulin G monoclonal antibody). The distribution of the ligand was in turn affected by the initial ligand challenge used to prepare the immunoadsorbents. Maximal productivity was achieved with adsorbents prepared with an initial challenge of about 3 mg human immunoglobulin G per ml: the ligand in these cases was shown to be more uniformally distributed within the adsorbent particles than adsorbents, exhibiting low productivity, prepared with either low (1 mg/ml) or high (9 mg/ml) concentrations of human immunoglobulin G. The ligand in the latter was restricted to the periphery of the particles.     

Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.     

Estimation of 90Sr in reprocessed uranium oxide samples

Summary A method has been developed for the estimation of ⁹⁰Sr in reprocessed uranium oxide samples obtained from the Purex processing of natural uranium spent fuel discharged from the research reactor. The method employs a combination of precipitation and solvent extraction procedure to eliminate other beta-impurities prior to resorting to the estimation of ⁹⁰Sr by beta-counting. ¹⁰⁶Ru was eliminated by volatalizing with perchloric acid, uranium was removed by carrier precipitation with strontium as sulphate. The sulphate precipitate was converted to carbonate and dissolved in nitric acid. ²³⁴Th and ²³⁴Pa were eliminated by synergistic solvent extraction using tri-n-butyl phosphate and thenoyl trifluoroacetone extractant mixture in xylene. An iron scavenging step was included to remove any residual impurities. Finally, strontium is precipitated as SrC₂O₄^. H₂O. The separated ⁹⁰Sr activity was followed to check the equilibrium growth of ⁹⁰Y.