EQUILIBRIA INVOLVING COBALT(II) HALIDES AND PHOSPHINE OXIDES I. A SPECTROPHOTOMETRIC STUDY OF THE COBALT(II) CHLORIDE — TRIPHENYLPHOSPHINE OXIDE SYSTEM IN ACETONE MEDIUM

Abstract

The CoCl₂-triphenylphosphine oxide system was studied in anhydrous acetone medium, at 25.00 · 0.05 ° C, by spectrophotometry. It was found that the system comprises at least three complex species, whose over-all stability constants are: β₁ = (1.40 · 0.10) · 10⁴ M^?1, β₂ = (6.77 · 0.95) · 10⁶ M^?2, β₃ = (1.77 · 0.40) · 10⁹ M^?3. The composition of the system as well as the values of the stability constants of the complex species are in a marked disagreement with the literature data. The compatibility between the experimental data and the results obtained in the present work was confirmed by different methods.     

A structured packed-bed reactor designed for exothermic hydrogenation of acetone

Fixed-bed reactors randomly packed with catalysts have many disadvantages that may adversely affect the desired chemical reaction.The increasingly used monolithic reactor,in contrast,has many operational advantages;however,for a kinetically-controlled reaction,it does not contain sufficient catalyst to sustain the reaction.To address the problems associated with both randomly packed-bed reactor and the monolithic reactor,a structured packed-bed reactor was proposed and mathematical models were built for randomly packed-bed reactor and structured packed-bed reactor.Their respective performances were compared when applied to the exothermic reaction of the isopropanol-acetone-hydrogen chemical heat pump system.The results showed that the structured packed-bed reactor performed better in terms of pressure drop and heat transfer capacity,and had a lower radial temperature gradient,indicating that this reactor had a higher effective heat conductivity.Isopropanol on the catalyst particle surfaces was more concentrated near the tube wall because a wall effect existed in the boundary layer around the particle-wall contact points.     

Effect of acetone accumulation on structure and dynamics of lipid membranes studied by molecular dynamics simulations

The modulation of the properties and function of cell membranes by small volatile substances is important for many biomedical applications. Despite available experimental results, molecular mechanisms of action of inhalants and organic solvents, such as acetone, on lipid membranes remain not well understood. To gain a better understanding of how acetone interacts with membranes, we have performed a series of molecular dynamics (MD) simulations of a POPC bilayer in aqueous solution in the presence of acetone, whose concentration was varied from 2.8 to 11.2 mol%. The MD simulations of passive distribution of acetone between a bulk water phase and a lipid bilayer show that acetone favors partitioning into the water-free region of the bilayer, located near the carbonyl groups of the phospholipids and at the beginning of the hydrocarbon core of the lipid membrane. Using MD umbrella sampling, we found that the permeability barrier of ∼0.5 kcal/mol exists for acetone partitioning into the membrane. In addition, a Gibbs free energy profile of the acetone penetration across a bilayer demonstrates a favorable potential energy well of −3.6 kcal/mol, located at 15–16 Å from the bilayer center. The analysis of the structural and dynamics properties of the model membrane revealed that the POPC bilayer can tolerate the presence of acetone in the concentration range of 2.8–5.6 mol%. The accumulation of the higher acetone concentration of 11.2 mol% results, however, in drastic disordering of phospholipid packing and the increase in the membrane fluidity. The acetone molecules push the lipid heads apart and, hence, act as spacers in the headgroup region. This effect leads to the increase in the average headgroup area per molecule. In addition, the acyl tail region of the membrane also becomes less dense. We suggest, therefore, that the molecular mechanism of acetone action on the phospholipid bilayer has many common features with the effects of short chain alcohols, DMSO, and chloroform.     

Highly sensitive breath sensor based on sonochemically synthesized cobalt-doped zinc oxide spherical beads

In this study, we introduce cobalt (Co)-doped zinc oxide (ZnO) spherical beads (SBs), synthesized using a sonochemical process, and their utilization for an acetone sensor that can be applied to an exhalation diagnostic device. The sonochemically synthezied Co-doped ZnO SBs were polycrystalline phases with sizes of several hundred nanometers formed by the aggregation of ZnO nanocrystals. As the Co doping concentration increased, the amount of substitutionally doped Co²⁺ in the ZnO nanocrystals increased, and we observed that the fraction of Co³⁺ in the Co-doped ZnO SBs increased while the fraction of oxygen vacancies decreased. At an optimal Co-doping concentration of 2 wt%, the sensor operating temperature decreased from 300 to 250 °C, response to 1 ppm acetone improved from 3.3 to 7.9, and minimum acetone detection concentration was measured at 43 ppb (response, 1.75). These enhancements are attributed to the catalytic role of Co³⁺ in acetone oxidation. Finally, a sensor fabricated using 2 wt% Co-doped ZnO SBs was installed in a commercially available exhalation diagnostic device to successfully measure the concentration of acetone in 1 ml of exhaled air from a healthy adult, returning a value of 0.44 ppm.     

A Potentiometric Method for Determination of Oxidized Ketone Bodies in Milk

Following the decarboxylation of acetoacetic acid by heating and the separation of acetone from milk matrix by steam distillation, acetone was allowed to react with bromine in the presence of nitric acid, causing the formation of bromoacetone and bromide; the latter was then quantified by means of a suitable ion-selective electrode applying the calibration principle. Based on checking reproducibility and on comparative analyses performed by a widely accepted photometric method, the potentiometric method developed was found to be adequate for the determination of the oxidized ketone bodies.     

溴代1-己基-3-甲基咪唑离子液体与丙酮的相互作用

运用核磁共振氢谱和碳谱手段,研究了室温离了液体溴代1-己基-3-甲基咪唑([C6mim]Br)在不同浓度的离子液体/丙酮混合体系中的1H和13C化学位移．实验结果表明,离了液体[C6mim]Br的阴离子与丙酮甲基上的氢原子相互作用并形成了氢键．量子化学计算结果与核磁共振实验结果一致．     

Theoretical study on the mechanism of the reaction acetone + OH: channels towards the formation of methanol

Two possible pathways for the acetone + OH reaction towards the formation of methanol have been examined theoretically. Our results show that both channels are characterized by a substantial activation barrier and reject the possibility of a significant CH₃CO + CH₃OH channel. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanochemistry: An efficient method of solvent-free synthesis of 3-amino-2,4-dicarbonitrile-5-methylbiphenyls

3-Amino-2,4-dicarbonitrile-5-methylbiphenyls are synthesized by a three-component reaction of aromatic aldehydes, malononitrile, and acetone in the presence of catalytic NaOMe under grindstone method. The yields are excellent; the procedure is simple, efficient, and environmentally benign; and all the reactions go to completion within 2–3 min.     

Use of ion mobility spectroscopy with an ultraviolet ionization source as a vanguard screening system for the detection and determination of acetone in urine as a biomarker for cow and human diseases

An ion mobility spectrometer equipped with an ultraviolet lamp was used for the qualitative and quantitative determination of acetone in urine samples. This analyte can be used as a biomarker for some fat metabolism-related diseases in humans and cows. Samples require no pretreatment other than warming at 80 °C for 5 min, after which an N₂ stream is used to drive volatile analytes to the ion mobility spectrometer. The precision of the ensuing method, expressed as relative standard deviation (%RSD), is better in all cases than 6.7% for peak height and calculated at three levels of concentration. The analyte concentration range studied was from 5 to 80 mg L⁻¹, its limit of detection in the aqueous matrix 3 mg L⁻¹ and recoveries from spiked urine samples 109 ± 3%. The calculated reduced mobility for acetone in the urine samples, 1.75 ± 0.04 cm² V⁻¹ s⁻¹, was similar to previously reported values. Also, the results were consistent with those provided by test strips used for reference. The proposed method provides a new vanguard screening system for determining acetone in urine samples.