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.

Atributos químicos do solo decorrentes da aplicação em superfície de calcário e gesso em sistema plantio direto recém-implantado

Há interesse em implantar o sistema plantio direto em áreas anteriormente cultivadas no sistema convencional ou sob pastagem, corrigindo a acidez com calagem superficial após a implantação do sistema. Essa prática pode ser possível desde que não haja impedimento físico do solo ao crescimento radicular. Nesse sentido, o gesso é uma alternativa para diminuição da atividade do Al3+ e aumento da saturação por bases (V), principalmente Ca2+, nas camadas do subsolo, podendo ser utilizado como produto complementar ao calcário. Este trabalho objetivou avaliar as alterações dos atributos químicos do solo (pH CaCl2, H + Al, Al3+, Ca2+, Mg2+, S-SO4(2-), V e teor de micronutrientes catiônicos) decorrentes da aplicação de calcário e de gesso agrícola em superfície em sistema plantio direto recém-implantado em região de inverno seco. O experimento foi conduzido em um Latossolo Vermelho distroférrico de Botucatu (SP). O delineamento experimental foi em blocos casualizados com parcelas subdivididas e quatro repetições. As parcelas foram constituídas por quatro doses de calcário dolomítico com PRNT de 71,2 % (0, 1.100, 2.700 e 4.300 kg ha-1), visando elevar a saturação por bases a 50, 70 e 90 %, respectivamente. As subparcelas foram constituídas pelas doses de gesso agrícola de 0 e 2.100 kg ha-1. Amostras de terra foram coletadas nas profundidades de 0-0,05, 0,05-0,10, 0,10-0,20, 0,20-0,40, 0,40-0,60 e 0-0,20 m, aos três, seis, 12 e 18 meses da aplicação dos produtos. A aplicação superficial de calcário diminuiu a acidez e elevou os teores de Ca e Mg trocável, principalmente nas camadas superficiais do solo. A aplicação de gesso agrícola aumentou os teores de Ca trocável e S-SO4(2-), e diminuiu os teores de Al no solo, contribuindo para que os efeitos da calagem superficial nas características químicas do solo alcançassem, de forma mais rápida, as camadas do subsolo. Os valores de saturação por bases obtidos na profundidade de 0-0,20 m com a calagem foram menores do que os estimados pelo método da elevação da saturação por bases, principalmente nas maiores doses, mesmo com a aplicação de gesso agrícola. A calagem em superfície não alterou os teores de micronutrientes na camada de 0-0,20 m de profundidade.

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.

CORREÇÃO da ACIDEZ do SOLO E DESENVOLVIMENTO do SISTEMA RADICULAR do AMENDOIM em FUNÇÃO da CALAGEM

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Liming in the transition to no-till under a wheat-soybean rotation

Soil and subsoil aluminium toxicity has been one of the main limiting factors for soybean and wheat yields in tropical soils. Usually liming is the most effective way to deal with soil acidity and Al toxicity, but in no-till systems the soil is not disturbed making it impossible to incorporate lime in the arable layer, and lime has been usually applied on the soil surface. In this paper soybean and wheat responses to lime applied on the soil surface and/or incorporated in the soil arable layer were evaluated during the transition from conventional tillage to a no-till system. The experiment was conducted for 3 years in Parana, Brazil, using a wheat-soybean rotation. Lime rates ranging from 0.0 to 9.0 t ha(-1) were incorporated down to 20 cm and 4.5 t ha(-1) were spread or not on the soil surface. Soil samples were taken down to 60 cm, 39 months after the first lime application. Soil chemical characteristics were affected by lime application down to 60 cm deep in the profile. Soybean responded to lime irrespective of application method, but the highest accumulated yield was obtained when lime was incorporated into the arable layer. For wheat, the more sensitive the cultivar, the greater was the response to lime. During the introduction of a no-till system, lime must be incorporated into the arable layer when the wheat cultivar is Al-sensitive. (C) 2007 Elsevier B.V. All rights reserved.

Sources of atmospheric acidity in an agricultural-industrial region of São Paulo State, Brazil

[1] Surface-based measurements of atmospheric formic acid (HCOOH), acetic acid (CH3COOH), sulfur dioxide (SO2), hydrogen chloride (HCl), and nitric acid (HNO3) were made in central São Paulo State, Brazil, between April 1999 and March 2000. Mean concentrations were 9.0 ppb (HCOOH), 1.3 ppb (CH3COOH), 4.9 ppb (SO2), 0.3 ppb (HCl), and 0.5 ppb (HNO3). Concentrations in sugar cane burning plumes were 1160-4230 ppb (HCOOH), 360-1750 ppb (CH3COOH), 10-630 ppb (SO2), 4-210 ppb (HCl), and 14-90 ppb (HNO3). Higher ambient concentrations of SO2, HCl and HNO3 were measured during the burning season (May-November). Concentrations of SO2 and HCl increased during the evening, and of HCOOH and CH3COOH were lowest in the morning, with peak levels in the afternoon. Ratios obtained between different species showed either nighttime maxima (SO2/HCOOH, SO2/CH3COOH, SO2/HNO3, CH3COOH/HNO3, SO2/HCl and HCOOH/HNO3), daytime maxima (HCOOH/HCl, CH3COOH/HCl and HNO3/HCl), or no clear trends (HCOOH/CH3COOH). Correlation analysis showed that SO2 and HCl were primary emissions from biomass burning and road transport; HCOOH, HNO3 and CH3COOH were products of photochemistry; HCOOH and CH3COOH were emitted directly during combustion as well as from biogenic sources. Biomass burning affected atmospheric acidity on a regional scale, while vehicular emissions had greater impact in urban and adjacent areas. Atmospheric ammonia levels were insufficient to neutralize atmospheric acidity, which was mainly removed by deposition to the surface.

Determination of olive oil acidity by CE

In this work, a CE method for the determination of olive oil acidity was proposed. The method was based on an ethanolic extraction (at 60 degrees C) of the oil long-chain free fatty acids (LC-FFAs) components followed by CE determination in pH 6.86 phosphate buffer at 15 mmol/L concentration containing 4 mmol/L sodium dodecylbenzenesulfonate (SDBS), 10 mmol/L polyoxyethylene 23 lauryl ether (Brij 35((R))), 2% v/v 1-octanol and 45% v/v ACN under indirect UV detection at 224 nm. Although this electrolyte promoted baseline separation of myristic acid (C14:0) (internal standard (IS)) and olive oil major components (palmitic acid (C16:0), oleic acid (C18:1c) and linoleic acid (C18:2cc)) in less than 8 min, after a few injections, the electropherogram profiles were severely altered (peak broadening, migration time shifts, etc.) and the current increased substantially. An adsorption study was conducted revealing that the dissolution of the capillary external polyimide coating during the electrophoretic run caused the detrimental effect. After removal of the capillary tip coating, ten consecutive injections could be performed without any disturbances and this simple procedure was, therefore, implemented during quantitative purposes. The reliability of the proposed method was further investigated by the determination of acidity of an extra virgin olive oil sample in comparison to the established methodology (AOCS method Ca 5a40, alkaline volumetric titration (AVT)). No statistical differences were found within 95% confidence level. A % acidity of 0.39 +/- 0.02 was found for the olive oil sample under consideration.