Structural rearrangements and magic numbers in reactions between pyridine-containing water clusters and ammonia

Molecular cluster ions H(+)(H(2)O)(n), H(+)(pyridine)(H(2)O)(n), H(+)(pyridine)(2)(H(2)O)(n), and H(+)(NH(3))(pyridine)(H(2)O)(n) (n = 16-27) and their reactions with ammonia have been studied experimentally using a quadrupole-time-of-flight mass spectrometer. Abundance spectra, evaporation spectra, and reaction branching ratios display magic numbers for H(+)(NH(3))(pyridine)(H(2)O)(n) and H(+)(NH(3))(pyridine)(2)(H(2)O)(n) at n = 18, 20, and 27. The reactions between H(+)(pyridine)(m)(H(2)O)(n) and ammonia all seem to involve intracluster proton transfer to ammonia, thus giving clusters of high stability as evident from the loss of several water molecules from the reacting cluster. The pattern of the observed magic numbers suggest that H(+)(NH(3))(pyridine)(H(2)O)(n) have structures consisting of a NH(4)(+)(H(2)O)(n) core with the pyridine molecule hydrogen-bonded to the surface of the core. This is consistent with the results of high-level ab initio calculations of small protonated pyridine/ammonia/water clusters.     

Analysis of kinetic isotope effects for nonadiabatic reactions

Factors influencing the rates of quantum mechanical particle transfer reactions in many-body systems are discussed. The investigations are carried out on a simple model for a proton transfer reaction that captures generic features seen in more realistic models of condensed phase systems. The model involves a bistable quantum oscillator coupled to a one-dimensional double-well reaction coordinate, which is in turn coupled to a bath of harmonic oscillators. Reactive-flux correlation functions that involve quantum-classical Liouville dynamics for chemical species operators and quantum equilibrium sampling are used to estimate the reaction rates. Approximate analytical expressions for the quantum equilibrium structure are derived. Reaction rates are shown to be influenced significantly by both the quantum equilibrium structure and nonadiabatic dynamics. Nonadiabatic dynamical effects are found to play the major role in determining the magnitude of the kinetic isotope effect for the model transfer reaction.     

Detection of the pesticide compound 1080 (sodium monofluoroacetate) using fluorine-19 nuclear magnetic resonance spectroscopy

Fluorine-19 nuclear magnetic resonance (19F NMR) spectroscopic measurements were used to determine the chemical nature and amounts of organofluorine in dosed meat baits. Earlier work implied that sodium monofluoroacetate (compound 1080) in meat baits was broken down into other organofluorine compounds such as fluorocitrate. No chemical evidence was found for such compounds. Only monofluoroacetate was detected in the prepared 1080 bait samples. Once the baits have aged, aqueous extraction fails to recover all the added 1080. Analysis using 19F NMR confirmed that the 1080 present in the aqueous extracts of the bait is recovered by Kramer's liquid chromatography method. It was shown here that the aqueous extracts do not recover all the 1080 in the meat bait.     

Sensitive Determination of 17β-Estradiol using a Magneto Sensor Based on Magnetic Molecularly Imprinted Polymer

The analysis of 17β-estradiol with high sensitivity and selectivity is extremely relevant to control the impacts that this compound can cause on health and the environment. Thus, we describe the development and application of a magneto carbon paste electrode based on magnetic molecularly imprinted polymer (MCPE-MMIP) for determination of 17β-estradiol. The analyte adsorbed on the MMIP was immobilized on the electrode surface by magnetic capture. The morphological and structural characterization of the obtained MMIP suggests that the material was effectively synthesized. MCPE-MMIP showed an improvement in the sensitivity for 17β-estradiol detection when compared to electrode configurations in the absence of this material. The optimum conditions (0.10 mol L⁻¹ phosphate buffer pH 7.0) were reached by differential pulse adsorptive stripping voltammetry (DPAdSV), in which the method presented linearity ranged from 0.06 to 175 μmol L⁻¹ with limits of detection and quantification of 0.02 and 0.06 μmol L⁻¹, respectively. The proposed sensor was applied effectively in the analysis of 17β-estradiol in river water and raw milk samples, exhibiting excellent recovery values (between 96.20 and 104 %), which were confirmed by HPLC analysis.     

Evidence for an unstable Bi(II) radical from Bi-O bond homolysis. Implications in the rate-determining step of the SOHIO process

The reaction of BiCl(3) with the lithium salt of o-di-tert-butylphenol under nitrogen forms organic oxidation products rather than the expected Bi(OAr)(3) complex, and bismuth disproportionation products. Likewise, the decomposition of Bi(III) aryloxides Bi(O-2,6-(i)Pr(2)C(6)H(3))(3) and ClBi(O-2,4,6-(t)Bu(3)C(6)H(2))(3) leads to corresponding organic oxidation products. These reactions can be explained by Bi-O bond homolysis to form unstable Bi(II) radicals, analogous to a fundamental step suggested to intervene in the SOHIO process.     

Computer simulation of interactions between liquid crystal molecules and polymer surfaces I. Alignment of nematic and smectic A phases

Results are presented from computer simulations of liquid crystal molecules in contact with polymeric surfaces. These form part of a study of the complex alignment interactions which operate in liquid crystal displays. The liquid crystal molecules considered are 4-n-pentyl-4'-cyanobiphenyl (5CB) and 4-n-octyl-4'-cyanobiphenyl (8CB); the polymeric surfaces simulated were crystalline polyethylene, polypropylene, poly(vinyl alcohol) and Nylon 6. Additional simulations were performed using graphite as a substrate. Polyethylene, poly(vinyl alcohol) and Nylon 6 were all found to induce orientation of the 5CB and 8CB molecules parallel to the polymer chain axes, as would be expected from experimental studies. On the other hand, polypropylene induces many different orientations with no clear preference for either. No evidence was found for the alignment of 8CB molecules on graphite substrates, in disagreement both with experimental findings and the results from previous simulations. The nature of the alignment interactions and possible reasons for the observed discrepancies are discussed.     

Dipodal fluorescent chemosensor for Cu and resultant complex as a chemosensor for iodide

A dipodal receptor was synthesized by condensation of isophthalaldehyde and p-toluenesulfonylhydrazide. The receptor was found to be selective for Cu²⁺ recognition in CH₃CN. The resultant Cu²⁺ receptor complex selectively recognized iodide through cation displacement assay in a CH₃CN/H₂O (8:2, v/v) solvent system.     

Electrochemical Characterization of Stainless Steel as a New Electrode Material in a Medical Device for the Diagnosis of Sudomotor Dysfunction

An electrochemical sensor detects the risk of diabetes and prediabetes; low potentials are applied to nickel electrodes and electrical responses are measured. Although the contact of nickel with skin is short, the risk of allergical reactions cannot be discarded. SS 304L, with lower Ni content, was tested in carbonate buffer solutions containing chloride, lactate and urea to investigate its sensitivity to different parameters in sweat and compare it to nickel. The results show that SS 304L is a suitable material for the assessment of sudomotor dysfunction due to its high capacity to detect the deviation in Cl^? concentration. Sensitivity of SS 304L to Cl^? is much higher than for nickel.     

Voltammetric Detection of a Specific DNA Sequence of Avian Influenza Virus H5N1 Using HS‐ssDNA Probe Deposited onto Gold Electrode

The working principle of a genosensor is based on the mechanism of ion‐channel mimetic sensors. The analytical signals generated upon hybridization processes were recorded by a redox active marker [Fe(CN)₆]^3?/4? present in the sample solution using voltammetric techniques. The developed genosensor was suitable for determination of 20‐mer complementary oligonucleotide sequence, and also of the PCR products containing the complementary 20‐mer sequence in various positions, with detection limits in the 10 pM range. The noncomplementary 20‐mer oligonucleotide sequence as well as the PCR product without complementary region generated very weak response. The good discrimination of the position of the complementary part in the PCR products was observed.     

Ionic liquids as reagents and solvents in conjunction with microwave heating: rapid synthesis of alkyl halides from alcohols and nitriles from aryl halides

We show that using ionic liquids as reagents in conjunction with microwave heating it is possible to prepare primary alkyl halides from the corresponding alcohols rapidly. Using ionic liquids as solvents in conjunction with microwave heating it is possible to prepare aryl nitriles from the corresponding aryl bromides or iodides. The scope and limitations of using microwave-promotion as a tool in these reactions is discussed.