Arsenic determination by ICP-QMS with octopole collision/reaction cell. Overcome of matrix effects under vented and pressurized cell conditions

The determination of arsenic by inductively coupled plasma mass spectrometry (ICP-MS) in natural waters with high sodium and chloride content has been investigated. The instrument used is equipped with an octopole collision/reaction cell to overcome spectroscopic interferences. Thus, the optimization of collision/reaction gas flow rates is required when using a pressurized cell. A mixture of 2.9 mL min⁻¹ of H₂ and 0.5 mL min⁻¹ of He has been found to be suitable for the removal of ⁴⁰Ar³⁵Cl⁺ interference.The effect of the introduction of small amounts of alcohol has also been studied in this work under both vented and pressurized cell conditions. It has been observed that the presence of 4% (v/v) of ethanol or methanol results in an increase in arsenic sensitivity. Moreover, under vented cell conditions the addition of alcohol also decreases the formation of polyatomic interference. However, this decrease is not observed under pressurized cell conditions.Different elements have been studied as possible internal standards for arsenic determination in presence of high amounts of sodium. Good results have been obtained for rhodium and yttrium under both vented and pressurized cell conditions. Although the presence of alcohol in the sample matrix also affects their behaviour, rhodium and yttrium are still the most suitable elements to correct for these matrix effects.Different experimental conditions have been compared for arsenic determination in spiked, certified and natural waters with high sodium and chloride content. The best results have been obtained under pressurized cell conditions, in the presence of ethanol and using rhodium as internal standard.     

Preparation and characterization of bilayer carbon/polymer membranes

The objective of the present research work was to develop a membrane with a high H₂O/alcohol selectivity for pervaporation and for use in direct alcohol fuel cells. Sulfonated poly (ether ether ketone) (SPEEK) was coated with a thin continuous carbon molecular sieve (CMS) layer. The membranes obtained had 180- and 400-nm thick CMS layers that led to a clear reduction of alcohol crossover. The water/alcohol selectivity increased with the size of the alcohol molecules as follows: methanol < ethanol < n-propanol < iso-propanol. A water/n-propanol selectivity of up to 34,000 was obtained, confirming the molecular sieving effect. The system was tested in a direct methanol fuel cell using standard electrodes, and demonstrated a better performance than with plain membranes. In a later stage Pt was introduced in the CMS layer during the preparation of the membrane electrode assemblies, this had the advantage that the CMS layer not only acted as an alcohol barrier but also as a catalyst support.     

Osmium (VI) catalyzed chemoselective oxidation of allylic and benzylic alcohols

A mild and highly chemoselective approach to oxidation of allylic, electron rich/deficient benzylic, and heterocyclic alcohols employing catalytic quantities of K₂[OsO₂(OH)₄] (3 mol %) and chloramine-T (50 mol %) is described. The protocol offers short reaction times (25 min–2 h), controlled oxidation, and tolerance to a variety of substrates. A systematic mechanistic study based on the LC-ESI-MS/MS reveals the presence of imidotriooxoosmium species which further reacts with alcohol to give the oxidized product.     

Continuous system with microwave irradiation to obtain alkyl benzoates

In this study, a continuous linear alcohol derivatization is developed. Reaction of alcohol group (ROH) with benzoyl chloride (BC) is carried out in an on-line system with UV detection. All reaction conditions, as flow rate (FR), ROH/BC molar ratio, wavelength, temperature, microwave (MW) irradiation and reaction coil size (internal diameter and length) were optimized. 0.5 mL min⁻¹, 2.49 [BC]/[ROH], 230 nm, 60 °C or medium power (225 W) when MW irradiation was used and a reactor coil of 159 μL (0.5 mm × 810 mm) were the optimum conditions. The on-line system with microwave irradiation was more efficient than the one with a water bath heating. The developed system reduces analysis time consumption, reagent amounts and this system was used to evaluate the composition of commercial samples of alcohols polyethoxylated (surfactants).     

HClO4-supported on silica gel: a mild and efficient catalyst for Hosomi-Sakurai reaction

Perchloric acid supported on silica gel was found to be an efficient catalyst (2 mol %) for the Hosomi-Sakurai allylation of numerous aldehydes with allyltrimethylsilane in the presence of benzyl alcohol. This method was also effective for the allylation of secondary alcohols under mild experimental conditions.     

Liquid–liquid phase behaviour,liquid–liquid density,and interfacial tension of multicomponent systems at 298 K

Experimental liquid–liquid phase diagrams are presented for the multicomponent systems isooctane–benzene–(80 mass% methanol + 20 mass% water)–5 mass% isobutyl alcohol (2-methyl-1-propanol) and isooctane–benzene–(80 mass% methanol + 20 mass% water)–15 mass% isobutyl alcohol, at 298.15 K. The density and interfacial tension of conjugate phases of concentration located in the isothermal binodal have been determined at 298.15 K for the partially miscible systems: isooctane–benzene–methanol, isooctane–benzene–(80 mass% methanol + 20 mass% water), isooctane–benzene–(80 mass% methanol + 20 mass% water)–5 mass% isobutyl alcohol, and isooctane–benzene–(80 mass% methanol + 20 mass% water)–15 mass% isobutyl alcohol. The experimental tie-line data define the binodal or coexistence curve of the two studied multicomponent systems and depending on the initial isobutyl alcohol concentration the liquid–liquid phase diagram is either of type II, with low alcohol concentration, or type I, with high concentration of alcohol, which is a clear indication that the solubility of the partially miscible systems is greatly enhanced via the co-solvency phenomenon. It is observed that both the density of each conjugate phase and the interfacial tension of each tie-line are valuable indicators of the degree of solubility of the multicomponent systems. Furthermore the experimental tie-lines data were correlated with the NRTL and UNIQUAC solution models with satisfactory quantitative results.     

UV-vis spectrophotometric method for the quantitation of all the components of Italian general denaturant and its application to check the conformity of alcohol samples

A simple, fast and relatively inexpensive spectrophotometric method for the identification and the quantification of the individual components of the Italian general denaturant in alcohol samples is proposed.In particular, it is shown that bitrex (a quaternary ammonium salt), whose UV spectrum is completely masked by those of the other denaturant components, can be identified using its reaction with disulphine blue VN-150 (an anionic dye indicator), which leads to the formation of an intensely colored ion-association complex (mole ratio 1:1), easily extractable in chloroform. As far as the quantitative detection is involved, it is however necessary to shake the chloroform phase in the presence of 1 mol L⁻¹ NaClO₄ aqueous solution because of the fast adsorption of the ion pair on the walls of the glass cell. Perchlorate anion, due to mass action, substitutes the anionic dye indicator in the association complex: as a consequence, disulphine blue passes to the aqueous phase, where its absorbance at λ = 640 nm is measured. On the other hand, C.I. Reactive Red 24 dye is easily identifiable from the visible spectrum of the product without any further pretreatment: its concentration can be determined measuring the absorbance at λ = 542 nm. Thiophene, being significantly more concentrated than the other components, can be identified from the UV spectrum of a 1:100 diluted solution of the alcohol sample and quantitatively determined measuring the absorbance at λ = 230 nm. Lastly, methyl ethyl ketone (MEK) can be identified from the UV spectrum of a 1:5 diluted solution of the alcohol sample and quantitatively determined measuring the absorbance at λ = 273 nm. However, more accurate results can be obtained using a multiwavelength analysis in the range 220-250 and 250-310 nm for the determination of thiophene and MEK, respectively.Validation on standard denatured alcohol samples has proven the method to be both accurate and sufficiently precise (within- and between-days repeatability <5%) to be applied to the analysis of real commercial samples.     

Spectrofluorimetric study of the β-cyclodextrin-dapsone-linear alcohol supramolecular system and determination of dapsone

Dapsone (DDS) forms a 1:1 supramolecular complex with β-cyclodextrin (β-CD) both in the absence and presence of linear alcohols. The apparent association constants (K_app) were measured using a steady-state fluorescence method. K_app decreases linearly with an increasing number of carbon atoms in the chain of the alcohol. We attribute this to a competition between dapsone and linear alcohol for the β-CD hydrophobic cavity as detailed analysis of K_app as a function of the concentration of alcohol suggests that the interactions in the β-CD-dapsone-linear alcohol system do not result in the formation of ternary supramolecular complex. Quenching the fluorescence of dapsone with NaI shows that the β-CD cavity acts as a shield against contact between dapsone and this aqueous phase quencher, while addition of alcohols inhibits this protective effect. This again suggests that alcohols occupy the space within the β-CD cavity with the result that dapsone molecules are forced to reside in the aqueous environment. Based on the significant enhancement of the fluorescence intensity of dapsone produced through complex formation, a spectrofluorimetric method for the determination of dapsone in bulk aqueous solution in the presence of β-CD is developed. The linear relationship between the fluorescence intensity and dapsone concentration was obtained in the range of 3.39 to 1.50×10³ ng ml⁻¹, with a correlation coefficient (r) of 0.9998. The detection limit was 1.02 ng ml⁻¹. There was no interference from the excipients normally used in tablet formulations. The application of the present method to the determination of dapsone in tablets and human plasma gave satisfactory results and was compared with the pharmacopoeia method.     

Behavior of 10-(perfluorohexyl)-decanol, a partially fluorinated analog of hexadecanol, at the air-water interface

10-(Perfluorohexyl)-decanol is a partially fluorinated analog of hexadecanol, an important detergent alcohol. With a melting point of T=48.82 °C and a melting enthalpy of ΔH=53.96 J/g, the intermolecular interactions of the fluorinated alcohol are weaker compared to hexadecanol (T=52.67 °C, ΔH=244.41 J/g). The behavior of this fluorinated alcohol at the air-water interface was studied on five different subphases, namely, water, NaCl (150 mM), CaCl₂ (2 mM), HCl (pH=2.0), and urea (0.5 M). Similar to other partially fluorinated amphiphiles, the compression isotherms of the fluorinated alcohol on all subphases are more expanded compared to the hydrocarbon alcohol with a limiting area of 32-36 Å² per molecule and a temperature-dependent phase transition at 5.6-8.2 mN/m (37 °C, compression rate of 10 mm/min). The dependence of the compression isotherms of 10-(perfluorohexyl)-decanol on subphase composition and temperature follows the trends reported for tetra- and hexadecanol. In particular, a shift to smaller molecular areas with increasing temperatures was observed on all five subphases. The shift to smaller molecular areas on urea indicates that in the case of 10-(perfluorohexyl)-decanol the effect is largely due to a loss of material from the air-water interface during compression of the monolayers. However, a squeezing-out of water molecules from the hydration sphere of the polar headgroup may still occur but can not be unambiguously proven.     

A novel Prins-alkynylation reaction for the synthesis of 4-phenacyl tetrahydropyrans

Aldehyde, homoallylic alcohol, and alkyne undergo smooth Prins-type cyclization in the presence of BF₃·OEt₂/CuCl (10 mol % each) in dichloromethane under mild reaction conditions to afford 4-phenacyl tetrahydropyran derivatives in good yields. This method is highly stereoselective, affording cis-tetrahydropyrans exclusively. The salient features of this method are high conversions, mild reaction conditions, short reaction times, high selectivity, and operational simplicity.     

Photochemical and thermal behaviours of poly(vinyl alcohol)/graphite oxide composites

The properties of poly(vinyl alcohol)/graphite oxide (PVAL/GO) composites were investigated during UV irradiation using a mercury lamp (λ = 254 nm). The course of photochemical reactions was monitored by FTIR and UV-vis absorption spectroscopies as well as by estimation of insoluble gel amount formed during crosslinking. Changes in average molecular weights resulting from main chain scission in PVAL were measured by gel permeation chromatography. Composite microstructure was characterized by scanning electron microscopy and X-ray diffraction. The thermal behaviour of composites was determined by a thermogravimetric analysis. It was found that 0.1-5.0% GO addition to polymer bulk slightly hampers photooxidative degradation of PVAL. Thermal degradation in PVAL composites starts at somewhat lower temperatures in the presence of GO but this trend is changed in UV-irradiated samples.     

Tris(trimethylsilylmethyl)alane: an aldehyde selective peterson methylenation reagent

Tris(trimethylsilylmethyl)alane (TTMA) is a rapid, efficient, and highly aldehyde-selective trimethylsilylmethylating reagent. A solid lithium halide complex of the reagent, TTMA · 3LiBr (TTMAs), is particularly effective in this transformation to the Peterson alcohol intermediate.     

InBr3-catalyzed stereoselective synthesis of 3,4-disubstituted hexahydro-1H-furo[3,4-c]pyran derivatives

An ?,δ-unsaturated alcohol tethered with a hydroxyl group, that is, (E)-2-styrylbutane-1,4-diol (1) undergoes a smooth bicyclization with various aldehydes in the presence of 10 mol % InBr₃ and at 0 °C to afford a novel series of hexahydro-1H-furo[3,4-c]pyran derivatives in good yields with high diastereoselectivity.     

Iron-catalyzed one-pot synthesis of benzimidazoles from 2-nitroanilines and benzylic alcohols

The iron-catalyzed heterocyclizations from 2-nitroanilines and benzylic alcohols to form benzimidazoles using hydrogen transfer reaction were investigated in this study. In the presence of dppf in toluene at 150 °C, various benzimidazoles were obtained in moderate to good yields within 24 h. The reaction was proposed to proceed via a cascade of alcohol oxidation, nitro reduction, condensation, and dehydrogenation.     

Performance of amperometric alcohol electrodes prepared by plasma polymerization technique

A single-layer alcohol electrode was prepared by plasma polymerization technique. Ethylenediamine was used to incorporate amino groups on tract-etched polycarbonate membranes in glow discharge reactor. In order to determine the plasma polymerization parameters (discharged power, monomer flow rate, exposure time) on membrane permeability, hydrogen peroxide was used as tracer. The single-layer alcohol electrode that was produced by 0.6% (w/v) of alcohol oxidase (AOx) solution on the polycarbonate membrane, which was modified at 30 W, 20 ml/min monomer flow rate and 15 min exposure time, was selected for optimum performance. Sensitivity, linearity and response time of that particular layer were 5.6 nA/mM, 2 mM and 50 s, respectively. The performance of the amperometric alcohol electrode was tested on commercial alcoholic beverages.     

Remarkable effect of hydrogen-bonding interaction on stereospecificity in the radical polymerization of N-vinylacetamide

Radical polymerization of N-vinylacetamide (NVA) in toluene at low temperatures was investigated. It was found that the addition of Lewis bases or alcohol compounds significantly influenced stereospecificity in NVA polymerization. For example, syndiotacticity increased from 25% to 34% by adding tri-n-butyl phosphate at −40 °C. Mono-alcohol compounds increased heterotacticity and heterotactic poly(NVA) with mr triad content of 58% was obtained at −40 °C in the presence of 1,1,1,3,3,3-hexafluoro-2-propanol. Furthermore, isotactic poly(NVA) with mm triad = 49% was obtained at −60 °C in the presence of diethyl l-tartrate. The NMR analysis demonstrated that complex formation between NVA monomer and the added agents, through hydrogen-bonding interaction, played an important role to induce the stereospecificity.     

Chromium-catalyzed pinacol coupling of benzaldehyde in water

The pinacol coupling of benzaldehyde (0.25 M or 1.25 M) in water was catalyzed by 5-25 mol % CrCl₂ in the presence of Zn-dust or Al-dust at 20 °C or 60 °C. In all cases at most 50% of the pinacol coupling product, 1,2-diphenyl-1,2-ethanediol, was obtained with the major product, benzyl alcohol, being formed by a competitive 2e⁻ reduction of the carbonyl. The dl- to meso-diastereoselectivity of the pinacol products ranged from 0.6:1 to nearly 1:1.     

Mild and facile procedure for clay-catalyzed acetonide protection and deprotection of N(Boc)-amino alcohols and protection of 1,2-diols

The application of clay as a catalyst for acetonide protection of N(Boc)-amino alcohols and 1,2-diols to obtain good to excellent yields of the acetonide derivatives is described. Acetonide deprotection to obtain the parent amino alcohol was carried out using a similar catalyst in the presence of methanol as solvent. The reaction takes place at room temperature within 2 h to give the parent amino alcohol in quantitative yield keeping the N(Boc) group intact.     

Determination of cadmium in alcohol fuel using Moringa oleifera seeds as a biosorbent in an on-line system coupled to FAAS

In this study a new method for determination of cadmium in alcohol fuel using Moringa oleifera seeds as a biosorbent in an on-line preconcentration system coupled to flame atomic absorption spectrometry (FAAS) was developed. Flow and chemical variables of the proposed system were optimized through multivariate designs. The limit of detection for cadmium was 5.50 μg L⁻¹ and the precision was below 2.3% (35.0 μg L⁻¹, n = 9). The analytical curve was linear from 5 to 150 μg L⁻¹, with a correlation coefficient of 0.9993. The developed method was successfully applied to spiked alcohol fuel, and accuracy was assessed through recovery tests, with recovery ranging from 97.50 to 100%.     

Application of hydroxy sodalite films as novel water selective membranes

Supported hydroxy sodalite (H-SOD) membranes were prepared on α-alumina disks using direct hydrothermal synthesis at 413 K for 3.5 h. The continuity of the membranes was verified using single gas permeation of He and N₂ at ambient conditions. The membranes were impermeable to N₂ and He, which validated absence of defects in the membrane structure. The membranes were used in dewatering several organic alcohol/water mixtures (organic alcohol being: methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, and 2-pentanol). The influence of feed temperature (303–473 K), feed concentration (0–100 mol% alcohol in the feed), and absolute feed pressure (1.6–2.4 MPa) on the water flux were analyzed. The absolute feed pressure had no effect on the water permeance. The membrane exhibited a water/alcohol separation factor larger than 10⁶ and showed excellent thermal, mechanical, and operation stability in continuously dehydrating a water/ethanol mixture (72 mol% water) by pervaporation at 473 K and 2.2 MPa for 125 h. The normalized water flux correlated well with the water feed concentration for the primary alcohols. Below 40 mol% water in mixtures with secondary alcohols the water flux was three orders of magnitude lower. The water mobility through the membrane had an activation energy of ∼15 kJ/mol.