Surface acidity/basicity and catalytic activity of ternary oxides of Al, Ce and Dy

The surface acidity and basicity of ternary oxides of AI, Ce and Dy have been determined using a set of Hammett indicators. The data have been correlated with the catalytic activity of these oxides towards the liquid phase reduction of cyclohexanone in 2-propanol. The reaction is favoured by the higher basicity of the ternary oxide.

Surface acidity/basicity and catalytic activity of mixed oxides of Zr, La and Al

The surface acidity/basicity of binary oxides of Zr and La and the ternary oxides of Zr, La and Al are reported. The data have been correlated with their catalytic activity towards liquid phase reduction of cyclohexanone.

Acidity, basicity and catalytic activity of La−Zn mixed oxides

Surface acidity/Basicity of mixed oxides of La and Zn activated at three different temperatures were determined. The data have been correlated with the catalytic activity for liquid phase reduction of cyclohexanone in isopropanol.

Lewis acidity of rare earth exchanged zeolites

The Lewis acidity of yttrium and dysprosium exchanged zeolite Y and ZSM-5 has been determined by titration method using Hammett indicators. The acidity of the Y form increases with increase in concentration of the rare earth cation in the Y zeolite. It is independent of the amount of the rare earth ion for ZSM-5. The data have been correlated with the activity of these zeolites for the esterification of butanol using acetic acid.

Quantifying uncertainty in critical loads: (B) acidity mass balance critical loads on a sensitive site

This paper reports an uncertainty analysis of critical loads for acid deposition for a site in southern England, using the Steady State Mass Balance Model. The uncertainty bounds, distribution type and correlation structure for each of the 18 input parameters was considered explicitly, and overall uncertainty estimated by Monte Carlo methods. Estimates of deposition uncertainty were made from measured data and an atmospheric dispersion model, and hence the uncertainty in exceedance could also be calculated. The uncertainties of the calculated critical loads were generally much lower than those of the input parameters due to a "compensation of errors" mechanism - coefficients of variation ranged from 13% for CLmaxN to 37% for CL(A). With 1990 deposition, the probability that the critical load was exceeded was > 0.99; to reduce this probability to 0.50, a 63% reduction in deposition is required; to 0.05, an 82% reduction. With 1997 deposition, which was lower than that in 1990, exceedance probabilities declined and uncertainties in exceedance narrowed as deposition uncertainty had less effect. The parameters contributing most to the uncertainty in critical loads were weathering rates, base cation uptake rates, and choice of critical chemical value, indicating possible research priorities. However, the different critical load parameters were to some extent sensitive to different input parameters. The application of such probabilistic results to environmental regulation is discussed.

The influence of organic acids in relation to acid deposition in controlling the acidity of soil and stream waters on a seasonal basis

Much uncertainty still exists regarding the relative importance of organic acids in relation to acid deposition in controlling the acidity of soil and surface waters. This paper contributes to this debate by presenting analysis of seasonal variations in atmospheric deposition, soil solution and stream water chemistry for two UK headwater catchments with contrasting soils. Acid neutralising capacity (ANC), dissolved organic carbon (DOC) concentrations and the Na:Cl ratio of soil and stream waters displayed strong seasonal patterns with little seasonal variation observed in soil water pH. These patterns, plus the strong relationships between ANC, Cl and DOC, suggest that cation exchange and seasonal changes in the production of DOC and seasalt deposition are driving a shift in the proportion of acidity attributable to strong acid anions, from atmospheric deposition, during winter to predominantly organic acids in summer.

Prediction of coagulation properties, titratable acidity and pH of bovine milk using mid-infrared spectroscopy

This study investigated the potential application of mid-infrared spectroscopy (MIR 4,000–900 cm−1) for the determination of milk coagulation properties (MCP), titratable acidity (TA), and pH in Brown Swiss milk samples (n = 1,064). Because MCP directly influence the efficiency of the cheese-making process, there is strong industrial interest in developing a rapid method for their assessment. Currently, the determination of MCP involves time-consuming laboratory-based measurements, and it is not feasible to carry out these measurements on the large numbers of milk samples associated with milk recording programs. Mid-infrared spectroscopy is an objective and nondestructive technique providing rapid real-time analysis of food compositional and quality parameters. Analysis of milk rennet coagulation time (RCT, min), curd firmness (a30, mm), TA (SH°/50 mL; SH° = Soxhlet-Henkel degree), and pH was carried out, and MIR data were recorded over the spectral range of 4,000 to 900 cm−1. Models were developed by partial least squares regression using untreated and pretreated spectra. The MCP, TA, and pH prediction models were improved by using the combined spectral ranges of 1,600 to 900 cm−1, 3,040 to 1,700 cm−1, and 4,000 to 3,470 cm−1. The root mean square errors of cross-validation for the developed models were 2.36 min (RCT, range 24.9 min), 6.86 mm (a30, range 58 mm), 0.25 SH°/50 mL (TA, range 3.58 SH°/50 mL), and 0.07 (pH, range 1.15). The most successfully predicted attributes were TA, RCT, and pH. The model for the prediction of TA provided approximate prediction (R2 = 0.66), whereas the predictive models developed for RCT and pH could discriminate between high and low values (R2 = 0.59 to 0.62). It was concluded that, although the models require further development to improve their accuracy before their application in industry, MIR spectroscopy has potential application for the assessment of RCT, TA, and pH during routine milk analysis in the dairy industry. The implementation of such models could be a means of improving MCP through phenotypic-based selection programs and to amend milk payment systems to incorporate MCP into their payment criteria.

Acidity controls on dissolved organic carbon mobility in organic soils

Dissolved organic carbon (DOC) concentrations in surface waters have increased across much of Europe and North America, with implications for the terrestrial carbon balance, aquatic ecosystem functioning, water treatment costs and human health. Over the past decade, many hypotheses have been put forward to explain this phenomenon, from changing climate and land-management to eutrophication and acid deposition. Resolution of this debate has been hindered by a reliance on correlative analyses of time-series data, and a lack of robust experimental testing of proposed mechanisms. In a four-year, four-site replicated field experiment involving both acidifying and de-acidifying treatments, we tested the hypothesis that DOC leaching was previously suppressed by high levels of soil acidity in peat and organo-mineral soils, and therefore that observed DOC increases a consequence of decreasing soil acidity. We observed a consistent, positive relationship between DOC and acidity change at all sites. Responses were described by similar hyperbolic relationships between standardised changes in DOC and hydrogen ion concentrations at all sites, suggesting potentially general applicability. These relationships explained a substantial proportion of observed changes in peak DOC concentrations in nearby monitoring streams, and application to a UK-wide upland soil pH dataset suggests that recovery from acidification alone could have led to soil solution DOC increases in the range 46-126% by habitat type since 1978. Our findings raise the possibility that changing soil acidity may have wider impacts on ecosystem carbon balances. Decreasing sulphur deposition may be accelerating terrestrial carbon loss, and returning surface waters to a natural, high-DOC condition.

Thiol and Sulfenic Acid Oxidation of AhpE, the One-Cysteine Peroxiredoxin from Mycobacterium tuberculosis: Kinetics, Acidity Constants, and Conformational Dynamics

Drug resistance and virulence of Mycobacterium tuberculosis are partially related to the pathogen`s antioxidant systems. Peroxide detoxification in this bacterium is achieved by the heme-containing catalase peroxidase and different two-cysteine peroxiredoxins. M. tuberculosis genome also codifies for a putative one-cysteine peroxiredoxin, alkyl hydroperoxide reductase E (MtAhpE). Its expression was previously demonstrated at a transcriptional level, and the crystallographic structure of the recombinant protein was resolved under reduced and oxidized states. Herein, we report that the conformation of MtAhpE changed depending on its single cysteine redox state, as reflected by different tryptophan fluorescence properties and changes in quaternary structure. Dynamics of fluorescence changes, complemented by competition kinetic assays, were used to perform protein functional studies. MtAhE reduced peroxynitrite 2 orders of magnitude faster than hydrogen peroxide (1.9 x 10(7) M(-1) s(-1) vs 8.2 x 10(4) M(-1) s(-1) at pH 7.4 and 25 degrees C, respectively). The latter also caused cysteine overoxidation to sulfinic acid, but at much slower rate constant (40 M(-1) s(-1)). The pK(a) of the thiol in the reduced enzyme was 5.2, more than one unit lower than that of the sulfenic acid in the oxidized enzyme. The pH profile of hydrogen peroxide-mediated thiol and sulfenic acid oxidations indicated thiolate and sulfenate as the reacting species. The formation of sulfenic acid as well as the catalytic peroxidase activity of MtAhpE was demonstrated using the artificial reducing substrate thionitrobenzoate. Taken together, our results indicate that MtAhpE is a relevant component in the antioxidant repertoire of M. tuberculosis probably involved in peroxide and specially peroxynitrite detoxification.

New insights on the Lewis acidity of diorganolead(IV) compounds: Diphenyllead(IV) complexes with N,O,S-chelating ligands

The reactions of PbPh2(OAC)(2) with alkylglyoxylate thiosemicarbazones (HRGTSC, R = Et, Bu) afforded complexes of the type [PbPh2(GTSC)] center dot H2O, [PbPh2(RGTSC)(2)] and [PbPh2Cl(BUGTSC)]. The structures of HRGTSC (R = Me, Et, Bu), [PbPh2(OAc)(RGTSC)](R = Me, Et, Bu), [PbPh2Cl(BuGTSC)] and [PbPh2(GTSC)] center dot H2O have been studied by X-ray diffraction. [PbPh2(OAc)(RGTSC)] and [PbPh2(GTSC)] center dot H2O have [PbC2NO3S] kernels and the coordination sphere of the metal is pentagonal bipyramidal. [PbPh2Cl(BuGTSC)] has a [PbC2NOSCI] kernel and the coordination geometry around lead is pentagonal bipyramidal with one vacant site. Analysis of the bond distances in [PbPh2(GTSC)] center dot H2O suggests a significant affinity between diphenyllead(IV) and carboxylate donor groups, supporting a borderline acidic character for this organometallic cation. H-1 and C-13 NMR spectra in DMSO-d(6) suggest the partial dissociation of the acetate in [PbPh2(OAc)(RGTSC)] solutions and indicate some differences in the coordination mode of the two RGTSC(-) ligands in [PbPh2(RGTSC)(2)] complexes. (C) 2007 Elsevier Ltd. All rights reserved.

Olfactory perception threshold assessment of volatile acidity in Madeira wines

Madeira wine is a fortified wine with impact in the Madeira Island’s economy. Similarly to other wines, its acidity should be well controlled in order to ensure Madeira wine quality, mostly the volatile acidity. Due to Madeira wine complex flavour, it is crucial to get a better knowledge about the volatile acidity impact in its features, namely determine the perception limit of acetic acid and ethyl acetate, as both are the main contributors for volatile acidity. Firstly, the olfactory perception threshold of volatile acidity was assessed by a trained and an untrained panel, using 5 and 10 years-old Sercial and Malvasia wines. Moreover, the current work also presents the evolution of organic acids, acetic acid and ethyl acetate during 540 days of ageing of Madeira wines (Malvasia, Bual, Verdelho and Sercial), comparing the same wines aged by both traditional ageing processes: canteiro and estufagem. Other wine samples, aged in wood casks (canteiro) for at least 5 years, were also evaluated. HS-SPME followed by GC-MS analysis was used to determine ethyl acetate concentration and IEC-HPLC-DAD was used for the organic acids determination, including acetic acid. The results indicated that acetic acid and ethyl acetate olfactory perception threshold depends essentially on wine’s age. Concerning acetic acid, the untrained panel was in average 5.45 g/L (5 years-old) and 6.22 g/L (10 years-old). Training the expert panel to recognize acetic acid odour, the values decreased for 1.44 g/L (5 years-old) and 1.87 g/L (10 years-old), but still remained higher than the established volatile acidity legal limits. Ethyl acetate threshold was similar for both panels (in average 327.97 mg/L). Both compounds tend to increase exponentially with age, being more evident in sweet wines. Organic acids in young Madeira wines depend mostly on the nature of grape varieties, but this difference is minimized with wine ageing.

Preliminary Study of the Gastric Acidity in Thoroughbred Horses at Rest after Enteral Administration of Esomeprazole Magnesium (Nexium)

The regulation of gastric secretion is of crucial importance to the equilibrium of the gastroenteric system. Despite the large number of factors involved in the causes of peptic illnesses, pH = 4 is considered the threshold between physiologic and deleterious effects of stomach acid secretion. With the aim of maintaining pH greater than 4, proton-pump inhibitors, such as esomeprazole magnesium (NEXIUM), have shown excellent results in the control of acid secretion. Aimed at examining the action of this drug in the control of pH levels of gastric secretion in thoroughbreds, a single dose of 40 or 80 mg of esomeprazole magnesium was administered daily, and pH was determined serially for 5 consecutive days. The results obtained corroborated the efficacy of esomeprazole magnesium in the control of gastric pH at both doses tested, with 100% of the mean pH being greater than 5. Moreover, no statistical difference was noted between the two doses tested.

Correction of soil acidity in the subsurface of an oxisol with sandy loam texture under no-tillage

No Rio Grande do Sul (RS), muitas áreas sob plantio direto apresentam elevada saturação por Al e baixa saturação por bases na camada de 0,10-0,20 m (subsuperfície), e isso pode diminuir a produção de grãos de culturas anuais. O objetivo do presente trabalho foi avaliar se a ocorrência de alta saturação por Al e baixa saturação por bases em subsuperfície (0,10-0,20 m), no plantio direto, pode representar um ambiente restritivo para a produção de culturas, bem como avaliar os modos de incorporação de calcário na correção da acidez do solo em subsuperfície. Para isso, foi realizado um experimento com os cultivos de soja (2005/ 2006), milho (2006/2007), trigo (2007) e soja (2007/2008), em um Latossolo Vermelho distrófico típico (Empresa Brasileira de Pesquisa Agropecuária (EMBRAPA), 2006) de textura franco arenosa, há quatro anos sob plantio direto, no município de Tupanciretã (RS). Os seis tratamentos foram: sem revolvimento com ou sem calcário; lavração com ou sem calcário; e escarificação com ou sem calcário. Aos 24 meses após a aplicação dos tratamentos e nas camadas de 0-0,05, 0,05-0,10, 0,10-0,15, 0,15-0,20 e 0,20-0,30 m, foram avaliados os valores de pH-H2O, saturação por Al e por bases. Avaliou-se a produtividade de soja (2005/2006), milho (2006/2007), trigo (2007) e soja (2007/2008). A acidez do solo em subsuperfície não alterou a produtividade das culturas quando as propriedades de acidez na camada de 0-0,10 m estavam em níveis em que não se recomenda a aplicação de calcário, segundo a CQFSRS/SC (2004). A incorporação de calcário com aração foi o modo mais eficiente de corrigir a acidez em profundidade.

Microhardness change of enamel due to bleaching with in-office bleaching gels of different acidity

Objective. The aim of this study was to assess the enamel microhardness treated with three in-office bleaching agents, containing 35% hydrogen peroxide with different acidity. Materials and methods. Bovine incisors were divided into three groups that received the following bleaching agents: Whiteness HP, Total Bleach and Opalescence Xtra. Three gel applications/10-min each, totaling 30-min of bleaching treatment, were made on the teeth and activated with a blue LED (1000 mW/470 nm) combined to a LASER (120 mW/795 nm) device (Easy Bleach-Clean Line). Vickers hardness (VH) was evaluated at baseline and after the bleaching procedure. The values of Hardness loss [HNL] (% reduction) were calculated. The two-sample t-test was used for comparison of the HNL of the three bleaching products (5% level of significance). Results. The Opalescence Xtra, which had the lowest pH value (pH = 4.30), showed a significant increase of HNL when compared with Total Bleach bleaching agent, which had the highest pH value (pH = 6.62). Conclusions. The 35% hydrogen peroxide bleaching agents resulted in a reduction in surface enamel microhardness and bleaching with the most acid agent resulted in a significant enamel hardness loss compared to the less acid agent (4.30 vs 6.62). Strategies proposed to reduce the enamel loss after bleaching treatment may include the use of daily fluoride therapy, mouth rinsing (fluoride, milk and sodium bicarbonate solution), fluoride/bicarbonate dentifrices without abrasives, do not toothbrush immediately after bleaching, fluorides and calcium add to bleaching agents.