Effect of sugar on anthocyanin degradation and water mobility in a roselle anthocyanin model system using 17O NMR

The purpose of this study was to try to elucidate the relationship between anthocyanin degradation and water mobility using (17)O NMR. A model system containing anthocyanin from roselles with different sugar concentrations (20, 40, 60%) was used to compare the effect of sugar (sucrose and honey) on the kinetics of anthocyanin degradation and water mobility after heating. Data on the anthocyanin degradation index (DI), half-life of anthocyanin, and activation energy of anthocyanin degradation showed that sucrose was a good anthocyanin protector, especially at high concentration. However, honey led to a severe anthocyanin degradation after its concentration reached 40% or it was heated to temperatures >50 degrees C. Spin-spin relaxation rates (R(2)) of water using (17)O NMR were further used to monitor the water mobility in two sugar systems to explain the differences in browning under the same concentration and water activity. R(2) in sucrose was significantly higher than that in honey after the concentration reached 40%. Apparently, increasing the ability to bind with water molecules favored the stability of anthocyanin in sucrose solution.     

Molecular water motions of skim milk powder solutions during acidification studied by 17O and 1H nuclear magnetic resonance and rheology

The molecular motion of water was studied in glucono-δ-lactone-acidified skim milk powder (SMP) solutions with various pH values and dry matter contents. NMR relaxometry measurements revealed that lowering the pH in SMP solutions affected 17O and 1H T2 relaxation rates almost identically. Consequently, the present study indicates that the proteins present in the samples do not affect the 1H relaxation behavior markedly, even at relatively high SMP concentrations (15-25%). Comparison of rheological measurements and NMR measurements suggested that the collapse of κ-casein during acidification could contribute to the initial decrease in 17O and 1H relaxation rate in the pH range between 6.6 and 5.5 for 15% SMP and in the pH range between 6.6 and 5.9 for 25% SMP. However, below pH 5.5 the viscosity and 17O and 1H NMR relaxation rates did not correlate, revealing that the aggregation of casein micelles, which increases viscosity below pH 5.5, does not involve major repartitioning of water.     

Mobility and distribution of water in cassava and potato starches by 1H and 2H NMR

Mobility and distribution of water in cassava (rainy and drought crops) and potato starches were studied by solid state and NMR relaxometry as a function of H(2)O and D(2)O contents ranging from 0 to 44% (dry basis). Measurements of relative mobility derived from (2)H solid state NMR were based on relative area and line shape analysis. The narrow peak (mobile component) started to show at 5% and increased with increasing D(2)O content. This increase in mobile fraction was accompanied by a line narrowing. The mobile fractions of deuterons reached a >98% level above 15% D(2)O, which is well below the water holding capacity of starch ( approximately 27%) and the previously assigned "glassy-rubbery transition point" (24.3%; Jouppila, K.; Roos, Y. H. The physical state of amorphous corn starch and its impact on crystallization. Carbohydr. Polym. 1997, 32, 95-104). This reconfirms the liquidlike nature of water in the so-called glassy state of starch granules. The plasticization effect of water on starch chains was observed at 14-17% for cassava and potato starches as indicated by the T(1) minimum. This, however, did not seem to relate to the difference observed in swelling among the starches studied.     

Water (H2 15O) flow in rice is regulated by the concentration of nutrients as monitored by positron multi-probe system (PMPS)

Using H₂ ¹⁵O as a tracer, the effect of the nutrient concentration on the water flow at the discrimination center (DC) of rice was monitored using a positron multi-probe system (PMPS). The maximum velocity of the water flow was achieved by the use of 20× Kasugai's culture solution. The addition of 0.01 to 0.1% NaCl gradually decreased the velocity. In intact plants, the ionic strength of essential elements in the xylem sap may be effective in decreasing the xylem resistance, resulting in the increase of the water flow in the xylem.     

H2O2 Accumulation in Sunflower Leaves as a Consequence of Iron Deprivation

Abstract

The present work aimed at evaluating in sunflower leaves: the relationship between Fe‐deficiency and the possible accumulation of H₂O₂; the activity of some extracellular enzymatic and non‐enzymatic systems involved in H₂O₂ production and scavenging. Iron‐deficient leaves exhibited a significant H₂O₂ accumulation, monitored at extracellular level by electron microscopy analysis. Such an increase in H₂O₂ level could derive from the significant decrease in extracellular ascorbate peroxidase (APX) activity, accompanied by a lower APX protein content detected by immuno‐electrophoresis. Also, extracellular ascorbic acid content was significantly affected by Fe‐deficiency, implying a reduced capacity for H₂O₂ scavenging. The contribute of peroxidases (PODs) involved in lignification process in keeping H₂O₂ levels under the toxic threshold was dependent on their subcellular location: the activity of covalently‐bound (CB) isoforms being increased while that of ionically‐bound (IB) ones decreased. NAD(P)H oxidation activity, known to produce H₂O₂, was found to decrease in apoplastic fluid and IB fraction and to slightly increase in the CB fraction. In conclusion, H₂O₂ accumulation observed in Fe‐deficient sunflower leaves seems to be mostly due to a reduced scavenging capacity of ASA, APX, and PODs, although the possibility of increased H₂O₂ production cannot be excluded.     

Slow recrystallization of tripalmitoylglycerol from MCT oil observed by 2H NMR

The crystallization and recrystallization of fats have a significant impact on the properties and quality of many food products. While crystallization has been the subject of a number of studies using pure triacylglycerols (TAG), recrystallization in similarly pure systems is rarely studied. In this work, perdeuterated tripalmitoylglycerol ( (2)H-PPP) was dissolved in medium chain triacylglycerol oil (MCT) to yield a saturated solution. The solution was heated to cause partial melting of the solid and dissolution of the molten fraction of (2)H-PPP in MCT and was then cooled to the original temperature to induce recrystallization from the supersaturated solution. (2)H NMR was used to monitor the disappearance of (2)H-PPP from the solution and showed that recrystallization occurred in two steps. The first step was rapid, taking place over a few minutes, and accounted for more than two-thirds of the total recrystallization. The second step was much slower, taking place over a remarkably long timescale of hours to days. It is proposed that dissolution occurs from all parts of the crystals, leaving an etched and pitted surface. The first step of crystallization is the infilling of these pits, while the second step is the continued growth on the smoothed crystal faces.     

Evaluation of antiradical capacity by H2O2-hemin-induced luminol chemiluminescence

This paper describes a screening method for antioxidant potential determination based on luminol/hemin/hydrogen peroxide chemiluminescence. The emission depletion, caused by an antiradical compound added during the chemiluminescence decay, is proportional to the number of reactive species trapped. Therefore, the difference between the areas of the emission decay curves, obtained in the absence and in the presence of the potential antioxidant, is a measure for the antiradical capacity of the sample. The technique has been applied to measure the antiradical capacity of pure compounds and complex mixtures from natural origin, providing reliable results that indicate the method's feasibility.     

Soil micro- and mesopores studied by N2 adsorption and Xe NMR of adsorbed xenon

N₂ adsorption (77 K) was combined with ¹²⁹Xe nuclear magnetic resonance spectroscopy of adsorbed xenon to characterise soil meso- (2–50 nm) and microporosity (<2 nm). Materials from the Alh and Bt horizons of a Luvisol, the Go horizon of a Gleysol and the Bvs horizon of a Podzol were analysed. Additionally, we examined samples obtained by mixing of H₂O₂-treated soil fractions with organic soil material (“soil + organic matter” samples). N₂- specific surface areas (S_BET) and micropore volumes (V_micro) and areas (S_micro) were markedly affected by the presence of iron oxides in soils. Their removal with dithionite-citrate-bicarbonate (DCB) treatment was accompanied by a significant decrease in S_BET and almost complete disappearance of the micropores. The organic carbon (OC) content decreased by 10–35% after the DCB-procedure showing that a certain proportion of the soil organic matter was extracted together with iron oxides. This may point to a close association between carbon compounds and iron oxides, possibly by incorporation of low molecular weight organic compounds into the phase of iron oxides. Such interactions are expected to contribute to the stabilisation of organic carbon in soils. Indeed, as compared to the top horizon (Alh of Luvisol), a higher proportion of organic matter was co-extracted with iron oxides from the subsurface horizons (Bt of Luvisol, Go of Gleysol) characterised by higher amounts of organic carbon resisting oxidation with H₂O₂. Examination of the mixed “soil + organic matter” samples supports that after addition, organic molecules occupy micropores (evidenced by N₂ adsorption) and narrower mesopores of the mineral matter (evidenced by ¹²⁹Xe NMR).     

H(2)O(2)-mediated pigment decay in strawberry as a model system for studying color alterations in processed plant foods.

Phenolic and pigment (anthocyanin) stability in processing-ripe strawberries in response to aging under mildly oxidizing conditions, provoked by exogenous application of H(2)O(2), has been studied to design a simplified model system to study color alterations (pigment decay) that occur in strawberry-derived foods during processing and storage. The results showed that phenolic metabolism in strawberry slices during aging under mildly oxidizing conditions may be either oxidative (independent of exogenous H(2)O(2)) or peroxidative (dependent on exogenous H(2)O(2)), and that feeding strawberry slices with H(2)O(2) stimulates the oxidative phenomena which take place in their absence, such as the processes of anthocyanin and catechin degradation. The results also showed that because both (+)-catechin and anthocyanin levels in strawberry slices fall as H(2)O(2) increases, both p-hydroxybenzoic acid and brown polymeric compounds are formed. Comparison of these results with controls in the absence of H(2)O(2) suggests that peroxidase may play an important role in catechin consumption and in anthocyanin degradation and brown polymer formation during the aging of strawberry slices under mildly oxidizing conditions.     

Cross-polarization/magic angle spinning NMR to study glucose mobility in a model intermediate-moisture food system

Theories for the chemical stability of foods cite the role of moisture content or water activity in reactant mobility, though mobility has been variously defined. One theory, based on plasticization by moisture, is limited by a lack of research directly linking the mobility of a matrix to the mobility and reactivity of small solute molecules in foods. A cross-polarization/magic angle spinning technique was developed to study glucose rotational mobility in the solid state over a range of water activities and in matrixes with different glass transition temperatures. Data analysis stressed the significance of separating molecular mobility from relaxation time. Results showed that, in a caseinate matrix, compared to a control, adding glycerol yielded the highest glucose mobility and lowest glass transition temperature (T(g)), while adding sorbitol also increased mobility and lowered T(g). Consequently, plasticization by either moisture or these humectants increases the mobility of small solute molecules such as glucose.     

小麦叶片CO2/H2O交换参数对不同供水条件的响应

在大田不同供水条件下,于小麦孕穗期和灌浆期对小麦叶片气体交换参数的日变化进行了连续测定,结果表明,小麦叶片光合速度,气孔导度,蒸腾速度,以及叶肉细胞间隙ＣＯ２浓度均有较明显的日变化。不同供水条件下,Ｐｎ的日变化趋势不同,充分供水时为典型的双峰曲线,中午有明显的“午休”现象;当非充分供水时,Ｐｎ午休现象明显,且持续时间长,第二高峰表现不明显。     

Effect of gamma-sterilization and autoclaving on soil organic matter structure as studied by solid state NMR, UV and fluorescence spectroscopy

Sterilized soil is often used, for example in degradation studies, sorption experiments, microbiological tests and plant test systems, to distinguish between microbial processes and abiotic reactions. The most commonly used technique for sterilization is autoclaving of the soil. Another technique is irradiation with high‐level gamma radiation (γ‐radiation). One major drawback of sterilization procedures is the possible alteration of the structure of soil components, for example the organic matter. A change in the chemical structure of the soil organic matter can cause different reactions in the above‐mentioned experiments and hence interfere with the aim of clearly distinguishing between biotic and abiotic processes. Two soils (Gleyic Cambisol and Orthic Luvisol) were sterilized by two γ‐irradiation procedures (4 kGy hour^?1 for 9 hours and 1.3 kGy hour^?1 for 27 hours) and repeated autoclaving at 121°C. Gentle physical aggregate fractionation of the sterilized soils revealed a decrease in the aggregation of the soil, which was reflected in an increase of the clay fraction. Subsequent analysis of the aqueous phase revealed much more dissolved organic matter (DOM) in the γ‐sterilized and autoclaved soils than in the untreated soils. Ultraviolet (UV) and fluorescence spectra of the DOM showed a decrease in the aromaticity and polycondensation of the dissolved organic carbon (DOC). ¹³C cross‐polarization/magic‐angle spinning nuclear magnetic resonance (¹³C‐CP/MAS NMR) spectra of the unfractionated soils and their respective soil fractions before and after sterilization showed that the most important change occurred in the carbohydrate and N‐alkyl region, the main components of microorganisms. In general, the impact of the sterilization method was stronger for autoclaving. The γ‐sterilized soils and fractions displayed both fewer and smaller changes in the soil organic matter.     

Inactivation of Escherichia coli O157:H7 and Salmonella Typhimurium in manure-amended soils studied in outdoor lysimeters

The inactivation of Escherichia coli O157:H7 (CCUG 44857) and Salmonella enterica serovar Typhimurium was investigated in two agricultural soils (sandy loam and silty clay) amended with poultry manure, cattle manure slurry or human urine. The study was performed in soil lysimeters placed outdoors, and was repeated over two consecutive years. The amendments, inoculated with E. coli O157:H7 and Salmonella Typhimurium, were mixed with soil on the top of the lysimeters. Samples were collected from the top 5-cm layer of each lysimeter at regular intervals, and the inactivation was monitored over 6 months, by the plate spread method and by enrichment. The inactivation was modelled by fitting a non-linear model to the data, and pathogen reduction times were calculated (90 and 99% reduction). The results showed that the inactivation of E. coli O157:H7 and Salmonella Typhimurium varied depending on the manure type used and its carbon content. The longest inactivation time occurred in samples amended with poultry manure, in which both E. coli O157:H7 and Salmonella Typhimurium were detected up to day 90 with the spread plate method. The most rapid inactivation for both pathogens occurred in soil amended with urine. However, low amounts of culturable E. coli O157:H7 and Salmonella Typhimurium were detected by enrichment throughout the study period (180 days), regardless of manure type.     

Effect of Hydroxypropylation on Retrogradation and Water Dynamics in Wheat Starch Gels Using 1H NMR

The water dynamics in gels made from native wheat starch, control (alkali‐treated) starch, and hydroxypropylated starch were studied using ¹H NMR relaxometry. Transverse relaxation studies showed that at least two domains of water exist in the starch gel, one with a T₂ of 0.5–8 msec and one with a T₂ at 8–200 msec. For starch gels held at 5°C for up to 15 days, the peak T₂ of both regions decreased with time for gels made from native starch, but not for those made from hydroxypropylated starch. Changes in integrated signal in each region suggests that water migrates out of the lower T₂ domain during retrogradation. Gels made from isolated amylose had a single, relatively mobile water domain, with T₂ dependent on gel concentration. This fraction did not change during storage at 5°C. Granule‐rich gels showed two water domains, one with a T₂ range similar to that for amylose gels, which varied over time and were thermally reversible. During storage, most significant changes occurred in the relatively low T₂ region associated with granule remnants. These studies show that, in addition to changes in starch during retrogradation, water dynamics are also affected by recrystallization and chemical modification of starch molecules.     

H2O2/NaOH改性玉米秸秆制备石油吸附剂的实验研究

本文采用H2O2/NaOH对玉米秸秆（RCS）进行改性来制备可吸附石油的生物质吸附剂（HNCS）。通过模拟实验,比较了不同改性时间的HNCS吸油量,发现改性14h的吸油量最大,达14.08g·g-1,而改性前RCS仅为4.33g·g-1,改性使得吸油量提高了325%,且吸油速率更快。通过扫描电子显微镜（SEM）、比表面积/孔隙度分析仪和傅里叶红外光谱仪（FT-IR）,对改性前后样品结构进行表征,同时采用洗涤剂法和硫酸法对纤维素、半纤维素、木质素含量进行测定,结果发现：改性后的HNCS表面更加粗糙,且出现大量的吸附孔隙,比表面积为7.14m·2g-1,表面亲水性官能团减少,纤维素含量增加而木质素含量减少。这说明吸油量和吸油速率受到吸附剂表面官能团、比表面积和孔隙/间隙的影响。     

Photodegradation of metolachlor applying UV and UV/H2O2

Metolachlor is one of the most widely used herbicides in the world for controlling weeds. It has been detected in both ground and surface waters in the United States, and there are rising concerns in regard to its health risks and in developing effective treatment processes for its removal from water. Degradation of metolachlor via ultraviolet (UV) photolysis and an UV/hydrogen peroxide advanced oxidation process (AOP) was studied. The quantum yield of metolachlor at 254 nm was found to be 0.302 +/- 0.001 mol E-1 through direct UV photolysis in the range of pH 6-8. The second-order rate constant of the reaction between metolachlor and hydroxyl radical was determined to be 9.07 (+/-0.21) x 10(9) M-1 s-1 by using a competition kinetics model that utilized nitrobenzene as a reference compound. In addition, these parameters were successfully applied in modeling the kinetics of elimination of metolachlor using an UV/H2O2 process in both laboratory and natural waters. The formation of several photolysis byproducts was identified using gas chromatography/mass spectrometry, and a scheme for the metolachlor photodegradation pathway is proposed.     

Effect of temperature and glassy states on the molecular mobility of solutes in frozen tuna muscle as studied by electron spin resonance spectroscopy with spin probe detection

The mobility of solutes in frozen food systems (tuna muscle, sarcoplasmic protein fraction of tuna muscle, and carbohydrate-water) has been studied using the temperature dependence of the shape of electron spin resonance (ESR) spectra of the spin probe 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPOL). The spin probe was incorporated into the tuna meat from an aqueous solution of TEMPOL or by contact with a layer of TEMPOL crystals. The melting/freezing of freeze-concentrated solutes in frozen tuna meat was observed to take place over a range of temperatures from -25 to -10 degrees C. Lower temperatures gave ESR powder spectra due to the decreased mobility of the spin probe, and the temperature dependence of the mobility of the spin probe did not show abrupt changes at the glass transition temperatures of the systems. The mobility of nonglass forming solutes is concluded to be decoupled from the glass forming components. Similar behavior was also observed for TEMPOL in frozen, aqueous carbohydrate systems. The temperature dependence of the mobility of TEMPOL in the frozen systems was analyzed using the Arrhenius equation, and the logarithm of the Arrhenius preexponential factor tau(a) was found to be linearly correlated with the activation energy for all of the tuna and carbohydrate samples, indicating a common molecular mechanism for the observed mobility of TEMPOL in all of the systems. The linear correlation also suggests that the observed mobility of TEMPOL in the frozen aqueous systems is dominated by enthalpy-entropy compensation effects, where the mobility of TEMPOL is thermodynamically strongly coupled to the closest surrounding molecules.     

Cation Exchange,Specific Surface and Absorbed H2O Molecules

There is a direct relation between the cation exchange capacity of soil particles and their specific surfaces. With the exception of strongly weathered soils like terra rossas, latosols, etc., with large amounts of inactive sesquihydroxides, the average surface occupied by one cation is about 70 Ų. Hygroscopic water absorbed by the soil particles is composed of H₂O molecules bonded the surface as a monolayer and of a varying number of H₂O molecules bonded to the cations, the kind of cation determining their number. Heat of wetting and specific surface are directly related. For Na⁺ saturated montmorillonite samples 150 ergs/cm² is found. The H₂O molecules of the monolayer on the surface of the soil particles have an O? H stretching vibrationband at 3220 cm^?1. This corresponds with an O? H … O distance of 2.77 Å which is almost the same as that of H₂O molecules in ice = 2.76 Å (H₂O molecules in water = 2.86 Å).     

水分胁迫对玉米根系AsA-GSH循环及H2O2含量的影响

以"鲁玉14"、"掖单13"2个不同抗旱性玉米品种为材料,研究不同浓度聚乙二醇-6000(PEG-6000)处理下根系抗坏血酸-谷胱甘肽(AsA-GSH)循环中关键酶和抗氧化剂的变化及其对过氧化氢(H2O2)含量的影响结果表明,谷胱甘肽还原酶(GR)、抗坏血酸过氧化物酶(APX)活性及谷胱甘肽(GSH)含量变化为当聚乙二醇溶液浓度低于100g/kg时,随水分胁迫的增强而上升,当聚乙二醇溶液浓度高于150g/kg时,随水分胁迫的增强而下降.抗坏血酸(AsA)含量随水分胁迫的增加而持续下降,H2O2含量随水分胁迫的加剧而增加.聚乙二醇溶液浓度为150～250g/kg处理下H2O2含量的增加与抗氧化酶活性、抗氧化剂含量的下降呈显著正相关.2品种比较,抗旱性强的品种具有较强的抗氧化能力.     

Antioxidant activity of tomato products as studied by model reactions using xanthine oxidase, myeloperoxidase, and copper-induced lipid peroxidation

The antioxidant content and activity of commercial tomato products differing in variety and processing were studied. Two procedures for extracting hydrophilic and lipophilic antioxidants, namely, two-step 0.1 M phosphate buffer (pH 3.0 and 7.4) extraction and tetrahydrofuran extraction followed by petroleum ether fractionation, were developed. Carotenoids (lycopene, beta-carotene, and lutein) and ascorbic acid were analyzed by HPLC with spectrophotometric and electrochemical detectors, respectively. Total phenolics were determined by using the Folin-Ciocalteu reagent. The antioxidant activity was studied by the following three model systems: (a) the xanthine oxidase (XOD)/xanthine system, which generates superoxide radical and hydrogen peroxide; (b) the myeloperoxidase (MPO)/NaCl/H(2)O(2) system, which produces hypochloric acid; and (c) the linoleic acid/CuSO(4) system, which promotes lipid peroxidation. Results showed that the hydrophilic and lipophilic fractions of all tomato products were able to affect model reactions, whatever reactive oxygen species and catalysts were used to drive oxidation. In the XOD/xanthine system both the hydrophilic and lipophilic fractions displayed an inhibitory activity. The hydrophilic fractions were more effective (I(50) ranging from 680 to 3200 microg, dry weight) than the lipophilic fractions (I(50) ranging from 4000 to 7750 microg, dry weight). In the MPO/NaCl/H(2)O(2) system the hydrophilic fractions inhibited oxidation (I(50) ranging from 2300 to 2900 microg, dry weight), whereas the lipophilic fractions had a lower inhibitory effect at the same concentration. Conversely, in the copper-catalyzed lipid peroxidation only the lipophilic fractions were effective (I(50) ranging from 1030 to 2100 microg, dry weight), whereas the hydrophilic fractions had a pro-oxidant effect in the same concentration range. The extent of inhibition varied according to the tomato sample in the superoxide and hydrogen peroxide generating system and in lipid peroxidation, but was substantially the same in the HClO generating system. Fresh tomato varieties differed considerably in the antioxidant activities of their hydrophilic and lipophilic fractions. Processed tomatoes showed a significantly lower antioxidant activity than fresh tomatoes in their hydrophilic fractions but had a high antioxidant activity in their lipophilic fractions. Because the oxidative reactions produced by the above-mentioned model systems are also involved in the pathogenesis of several chronic diseases, the antioxidant activity of tomato fractions might be related to their in vivo activity. Hence, these measurements may be used for optimizing tomato technologies.