Tests of ordered hypotheses in linkage in heredity

The asymptotic null distribution of the likelihood ratio test for two cases of ordered hypotheses in a particular genetic model is considered. A simple iterative process is proposed in order to get the restricted estimates. It is shown that both tests have asymptotically a chi-bar squared distribution and the same size. A simulation study is also conducted in order to compare the usual unrestricted test with the corresponding one of ordered hypotheses. Finally, the results are extended to some special cases.     

Proper holomorphic maps between Reinhardt domains and strictly pseudoconvex domains

LetR be a Reinhardt domain andD a bounded simply connected strictly pseudoconvex domain withC ^∞ boundary. We prove that any proper holomorphic mapF:R →D is, up to biholomorphism ofD, of the form \((z_1^{d_1 } , z_2^{d_2 } , \ldots , z_n^{d_n } )\) withd ₁,d ₂,…,d _n ∈ IN.     

4,5-Dihydroisoxazole and 4,5-dihydro-1,2,4-oxadiazole derivatives from cycloaddition reactions of nitrile oxides to alkyl N-(diphenylmethylene)-α,β-dehydroamino acids

The alkyl N-(diphenylmethylene)-α,β-dehydroamino acids 1 have been submitted to 1,3-dipolar cycloadditions with nitrile oxides. The reactivity of these compounds depends on the type and on the stereochemistry of the β-substituents. With the unsubstituted terms 1a,b the reaction occurs on the C,C double bond, providing a good method for the synthesis of the 4,5-dihydroisoxazole derivatives 3a,b,c and for the gem-functionalized 4,5-dihydroisoxazoles amino carboxylic ester 5. The β-substituted compounds 1c,d,e , inert to 1,1-dimethylethylnitrile oxide, undergo the reaction to the N,C double bond, thus giving with 2a,b the 4,5-dihydro-1,2,4-oxadiazole derivatives 4. All the reactions occur with high site- and regioselectivity.     

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)₂bpy]²⁺) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)₂bpy]²⁺ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)₂bpy]²⁺. The UV‐vis spectrophotometric results indicate that the [Ru(phend)₂bpy]²⁺ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)₂bpy]²⁺ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.     

An electroactive nickel containing polymeric film obtained by electrochemical reduction of an aryl-nickel derivative

The electrochemical reduction of [Ni(PPh₃)₂(p-C₆H₄Br)Br] in acetonitrile results in a polymeric coating of a nickel-containing poly-p-phenylene, formulated as [-Ni(p-C₆H₄)_n-] (n=6?7) on the basis of elemental analysis, IR, UV, MS and ESCA measurements. This coating is found to undergo a two-electron reversible reduction and a one-electron reversible oxidation with a large potential window (3.6 V), without the polymeric film being destroyed. Moreover, the polymer obtained is shown to be electroactive towards dissolved reactants via permeation or mediated electron transfer, depending on the molecular size of the electroactive species employed.     

Cathodic behaviour of nickel(II) in acetonitrile in the presence of carbon monoxide and substituted phosphines

Summary The reduction of nickel perchlorate in the presence of carbon monoxide and substituted phosphines or diphosphines has been studied in acetonitrile by cyclic voltammetry. The results show that only mono- and bis-carbonylphosphinenickel(O) complexes are formed, while no evidence for the formation of carbonyl-nickel(I) and -nickel(II) species was obtained. Although the oxidation processes are not reversible, a good correlation between the anodic peak potentials relative to nickel(O) complexes and the -donor--acceptor abilities of the phosphines employed was observed.     

A simple procedure for the chromatographic analysis of nanoliter samples

A simple method for the analysis of nanoliter droplets is proposed, which is profitable when larger samples cannot be collected as, for instance, in the case of several biological fluids and particularly in clinical chemistry. A glass capillary associated to a micromanipulator is used to collect submicroliter volumes which are partially transferred into transparent polymeric tubings with known internal diameters (120–178 μm), where the volumes sampled are measured by meniscus collimations with a collimator microscope at suitable magnification. Both ends of these tubings are preliminarily equipped with ferrules and fittings, so as to make them suitable for connection as the loop to a conventional high-pressure injection valve. The reliability of this procedure has been tested for the analysis of Na⁺, K⁺ and Ca²⁺ present in minute synthetic standard samples (10–200 nL) by a conventional ion-chromatographic instrumentation. Relative standard deviations in peak area measurements (5–6%) are discussed in terms of the whole approximation affecting volume measurements, which depends on both the inconstancy of the inner diameter of the polymeric tubings employed and the uncertainty characterizing meniscus collimations. The proposed procedure can be easily extended to the determination of any organic or inorganic species present in very small samples, provided that their detection can be achieved by any chromatographic approach or, more generally, by flow injection analysis. Received: 16 June 1997 / Revised: 12 August 1997 / Accepted: 14 August 1997     

Evaluation of new selective molecularly imprinted polymers prepared by precipitation polymerisation for the extraction of phenylurea herbicides

Three different molecularly imprinted polymers (MIPs) have been prepared by precipitation polymerisation using linuron (LIN) or isoproturon (IPN) (phenylurea herbicides) as templates and methacrylic acid (MAA) or trifluormethacrylic acid (TFMAA) as functional monomers. The ability of the different polymers to selectively rebind not only the template but also other phenylurea herbicides has been evaluated. In parallel, the influence of the different templates and functional monomers used during polymers synthesis on the performance of the obtained MIPs was also studied through different rebinding experiments. The experimental binding isotherms were fitted to the Langmuir-Freundlich isotherm allowing to describe the kind of binding sites present in the imprinted polymers under study. It was concluded that TFMAA-based polymer using IPN as template presents the best properties to be used as a selective sorbent for the extraction of phenylurea herbicides.     

Electroanalytical sensors for nonconducting media based on electrodes supported on perfluorinated ion-exchange membranes

Electroanalytical sensors, suitable for the analysis and monitoring of electroactive analytes present in gaseous phase or low-conductive liquid media, and based on electrodes in close contact with perfluorinated ion-exchange polymers are reviewed. The basic operative mechanism of these sensors, in which ion-exchange polymers act as solid polymer electrolytes (SPE's), is thoroughly discussed, while stressing the fundamental reasons why their behavior differs from that of conventional membrane electrodes. The procedures for preparing composite working electrodes by coating one side of ion-exchange membranes with stable porous films of conductive materials are described, along with the most common strategies followed to assemble this type of sensors. Useful examples of measurements in electrolyte-free media of inorganic and organic electroactive species of interest mainly for environmental analysis are given. Future prospects for the development of these sensors are also discussed.