Formation of 2,5-dimethyl-4-hydroxy-3(2H)-furanone through methylglyoxal: a Maillard reaction intermediate

The caramel-like aroma compound, 2,5-dimethyl-4-hydroxy-3(2H)-furanone (DMHF) was quantified and verified by HPLC and GC-MS in the Maillard reaction based on methylglyoxal (MG). The reaction was performed in the 0.5 M phosphate buffer by heating MG with or without either glycine or cysteine at 120 degrees C for 1 h. MG alone or MG with cysteine could produce increased level of DMHF with pH increased, whereas MG with glycine had contrary trend. Experiments using a 1:1 mixture of [(13)C6]glucose and [(12)C6]glucose indicate that in the presence of glycine or cysteine, glucose skeleton kept intact during DMHF formation since a 1:1 mixture of [(13)C6]DMHF and [(12)C6]DMHF was formed. Acetylformoin was detected in the glucose with amino acid reaction system as a precursor of DMHF, while in the MG reaction systems, acetylformoin could not be identified. It is suggested different pathways of DMHF formation via MG and glucose.     

基于SERS的三种食源性致病菌的快速检测

为了探究表面增强拉曼光谱(SERS)法在大肠杆菌(ATCC 25922)、肠炎沙门氏菌(CICC 21540)和单核增生李斯特菌(CICC 10982)快速检测中的可行性,本研究利用两步生长法制备银包金纳米颗粒(Au@Ag NPs)作为增强基底,研究Au@Ag NPs分别与3种致病菌偶联后的拉曼增强效果和稳定性,并对3...     

贵州喀斯特人工草地土壤水分空间异质性对放牧强度的响应

采用地统计学方法研究贵州南部人工草地不同放牧强度(零牧、中牧和重牧)下浅层土壤剖面(0—10,10—20,20—30cm)水分的空间异质性及其影响因素。结果表明:喀斯特人工草地土壤水分的平均值与变异系数均呈现出明显的放牧强度变化与剖面变化规律;在不同放牧强度下,0—10cm和10—20cm土壤剖面含水量均表现为NGHGMG,20—30cm土层土壤含水量为NGMGHG,变异系数均呈中等变异(10%CV100%),平均含水量处于中等水平时土壤水分变异性较高;土壤水分的Moran’s I自相关分析表明,不同放牧强度下不同土层草地土壤水分均具有较强的空间自相关性,且空间自相关性主要受放牧影响;土壤水分半方差分析表明,不同放牧强度下不同土层草地土壤水分空间分布特征模型为指数模型、球状模型或高斯模型,表明其均为聚集分布;不同放牧强度C/(C0+C)值在0.500~0.817之间,表明土壤水分表现出中等或很强的空间自相关性;不同放牧强度土壤水分变程在2.77~15.61m范围内变化(零牧,2.53~12.82m;中牧,2.77~15.61m;重牧,14.03~18.79m),说明影响土壤水分的生态过程随放牧强度变化在不同尺度上起作用;Kriging maps直观地反映和验证了草地土壤水分的空间变化规律,与Moran’s I和半方差函数分析的结果相吻合。综合分析发现,在小尺度内,重牧是地势平坦的喀斯特人工草地表层土壤水分空间变异的主要影响因素。     

基于SERS技术的基底增强效应对比及食源性芽孢快速检测

为了实现食源性芽孢的快速识别,该研究利用表面增强拉曼光谱技术,以产气荚膜梭菌芽孢(C.perfringens spores)、艰难梭菌芽孢(C.difficile spores)和生孢梭菌芽孢(C.sporogenes spores)为研究对象,将3种不同纳米溶胶材料Au NPs、Ag NPs和Au@AgNPs作为表面增强拉曼散射(Surface-enhanced Raman scattering,SERS)基底对食源性芽孢的增强效应进行对比,确定较佳增强效果的纳米材料,进一步开展基于较优纳米溶胶材料为基底的SERS技术对不同种属食源性芽孢的光谱解析及快速识别研究。结果表明,Au@Ag NPs对食源性芽孢的SERS增强效果最较好,其增强因子达3.49×10⁴,且光谱特异性和重现性良好。经拉曼光谱解析,Ca²⁺-DPA的拉曼峰是三种食源性芽孢的共有标志特征峰,拉曼振动峰在1 017、1 440和1 570 cm^-1波段显示且峰强度不同。C.perfringens芽孢在740、787、821、1 203、1 308和1 62...     

Validation study of gas chromatographic determination of pentachlorophenol in animal liver

A validation study was conducted of a gas chromatographic procedure for the determination of pentachlorophenol (PCP) in chicken, pork, and beef liver. Five analysts representing 5 laboratories analyzed randomly numbered blind duplicates at 3 fortified tissue concentrations and one incurred tissue on 2 consecutive days. The PCP concentrations ranged from approximately 40 to 400 parts per billion (ppb). All data were reported to 3 significant figures in ppb. The coefficients of variation for repeatability were between 2.8 and 8.5%, except for the beef liver, at a mean value of 80 ppb PCP, where the CV was 11.3%. The CVs for reproducibility were in the range of 9.7-16.5% with little significant difference by species. The CV asymptotically approached 10% as the PCP level increased.     

Residue analysis of glyphosate and its principal metabolite in certain cereals, oilseeds, and pulses by liquid chromatography and postcolumn fluorescence detection.

A postcolumn liquid chromatographic method to determine the extractable residues of glyphosate (GLYPH) and its principal metabolite, (aminomethyl)phosphonic acid (AMPA), in various cereals and beans is described. The finely ground sample is extracted with a mixture of chloroform and water, and the resulting aqueous layer is passed through a cation exchange column. The eluate is adjusted to pH 7-10 and passed through an anion exchange column. The second column is eluted with 0.3M HCl solution and the resulting acidic eluate is analyzed with liquid chromatography coupled with postcolumn fluorescence detection. The mean recoveries for GLYPH in barley, canola, dry pea, flax, soybean, wheat, and white bean ranged from 90.0 to 98.1%, with coefficients of variation (CV) from 2.9 to 10.0% and limits of detection (LOD) from 0.07 to 0.14 ppm. Similarly, mean recoveries for AMPA in the same crops ranged from 87.4 to 98.9%, with CV from 4.6 to 7.7 and LOD from 0.05 to 0.12 ppm. Using this method, an analyst can routinely analyze 6 samples per 1.5 days. The advantages of this procedure are discussed.     

农药残留的表面增强拉曼光谱快速检测技术研究现状与展望

果蔬农药残留危害人类健康,施药后,农药分布于其表皮和内部组织,果蔬表面农药绝对残留量低、不均匀,直接光谱检测表征难,而表面增强拉曼散射(surface-enhanced Raman scattering,SERS)技术具有分子级检测精度,可以有效扩增信号,在实现微量物质检测方面优势明显。为此,论文综述了国内外表面增强拉曼散射技术的研究现状,特别是详细介绍了通过设计合理的表面增强拉曼基底结构,实现农药残留信号增强的主要技术手段和表面增强拉曼光谱信号分析方法。在此基础上,指出农药残留的表面增强拉曼检测技术研究中的前沿热点问题,探讨并展望了表面增强拉曼技术在农药残留快速检测方面的发展趋势。基于表面增强拉曼的农药高灵敏度、快速检测表征技术,将在农药违禁使用和农药残留超标监管中有广阔应用前景。     

The simultaneous determination of muramic acid and glucosamine in soil by high-performance liquid chromatography with precolumn fluorescence derivatization

Summary The optimal release and quantitative estimation of muramic acid and glucosamine were studied simultaneously in soil samples. The effect of hydrolysis conditions, HCl concentration, hydrolysis time, the ratio of soil dry weight to acid, and the recovery of reference substances were investigated. Derivatization of the fluorogenic reagent o-phthalaldehyde, in the presence of 2-mercaptoethanol with the residue of a soil hydrolysate, was achieved by optimizing the relative amounts of o-phthalaldehyde to hydrolysate in the reaction mixture, the pH of both, and the incubation period. A linear relationship was found between the fluorescence response and the concentration of the test substances. The muramic acid, as well as the glucosamine (o-phthalaldehyde) derivatives gave single peaks, and complete separation from interfering substances at the picomol level was achieved in a short time (3 h preparation and 30 min for chromatography) by using high-performance liquid chromatography.     

表面增强拉曼光谱快速检测生鲜肉中的瘦肉精

为了快速检测生鲜肉中的瘦肉精,该研究利用表面增强拉曼光谱技术,以沙丁胺醇为检测目标物,建立了一种快速检测肌肉组织和肝脏中瘦肉精含量的方法。在碱性环境下利用乙酸乙酯对样品中沙丁胺醇进行提取,采用Savitzky-Golay 5点平滑法和自适应迭代重加权惩罚最小二乘法消除光谱噪声以及荧光背景对分析建模的影响。为检测方法的重复性,对50个相同沙丁胺醇质量分数(1 mg/kg)的肌肉组织样品进行信号采集,对沙丁胺醇特征峰强度进行分析,621、814、1 253、1 489、1 609 cm~(-1) 5个特征峰强度的相对标准偏差(RSD)为6.54%、6.07%、8.65%、7.44%、6.81%,说明该方法具有较好的重复性。建立沙丁胺醇标准溶液的预测模型,沙丁胺醇浓度与其特征峰强度相关性较好,决定系数R~2为0.968。对肌肉组织和肝脏中沙丁胺醇含量进行检测,检测范围分别为0.01~5和0.02~5 mg/kg,检出限分别为0.01和0.02 mg/kg,其含量与预测实测值决定系数为0.912和0.921。研究表明,该方法可以实现肌肉组织和肝脏中沙丁胺醇含量的定量预测。     

Absorption and urinary excretion of quercetin,rutin, and alphaG-rutin,a water soluble flavonoid,in rats

Quercetin, rutin, alphaG-rutin (a water soluble flavonoid), and a mixture of rutin and alphaG-rutin were administered to rats by a single gastric intubation, and their absorption and urinary excretion were examined. The plasma and 24 h urinary levels of aglycons (quercetin and tamarixetin/isorhamnetin) were measured by HPLC after deconjugation with beta-glucuronidase/sulfatase treatment. alphaG-rutin was absorbed more rapidly than quercetin or rutin, and the plasma concentrations of quercetin and tamarixetin/isorhamnetin reached the highest peak level 30 min after dosing. Quercetin, rutin, and the mixture of rutin and alphaG-rutin showed the first peak level 8 h, 8 h, and 30 min after dosing, respectively. The area under the concentration-time curve (AUC) for quercetin in rats administered alphaG-rutin was approximately 4.5- and 2-fold higher than those in rats administered quercetin and rutin, respectively, and was almost the same as that in rats administered a mixture of rutin and alphaG-rutin. The highest 24 h urinary excretion was observed in alphaG-rutin-administered rats. These results suggest that alphaG-rutin is absorbed more efficiently than either quercetin or rutin and that a high plasma concentration can be maintained by supplying rutin and alphaG-rutin in combination.     

表面增强拉曼光谱检测脐橙果皮混合农药残留

为了研究果皮农药残留快速检测方法。该文以脐橙为例,混合农药(亚胺硫磷和乐果)为研究对象,选用银纳米线作为增强基底,利用共焦显微拉曼光谱仪对农药残留进行检测。通过表面增强拉曼光谱(surface enhanced Raman scattering,SERS)技术,采集脐橙表皮混合农药残留的SERS光谱。对混合农药定性分析,银纳米线对2种农药都有较好的增强效果。对采集的光谱进行预处理后,建立模型,进行定量分析,研究结果表明,经过二阶微分预处理后光谱数据结合偏最小二乘法(partial least squares,PLS)得到的模型预测效果最好,预测相关系数(R_p)为0.954,其预测均方根误差(root-mean-square prediction error,RMSEP)为4.822 mg/L。挑选两种农药特征峰的特征波段,混合农药中亚胺硫磷的特征波段经多元散射校正(multiplicative scatter correction,MSC)处理后,建模效果较好,其中R_p为0.898,RMSEP为6.621 mg/L;混合农药中乐果的特征波段经基线校正处理后,建模效果较好,其中R_p为0.911,RMSEP为7.369 mg/L。研究结果表明SERS技术是一种快速、可靠的检测混合农药残留的方法。     

基于增强拉曼光谱的苹果中啶虫脒农药残留的无损定量分析

为了快速准确检测苹果的农药残留,该研究基于表面增强拉曼光谱技术,以新烟碱类农药啶虫脒作为研究对象,建立了一种快速准确检测苹果农药残留含量的方法。为了改善表面增强剂对定量检测的检测精度和稳定性,在pH值为6.5的弱酸性条件下向银溶胶中加入稳定剂聚丙烯酸钠和团聚剂NaCl。采用了卡尔曼平滑（Rauch-Tung-Striebel,RTS）与非对称重加权惩罚最小二乘法（asymmetrically reweighted Penalized Least Squares,arPLS）结合扩展乘性散射校正（Extended Multiplicative Signal Correction,EMSC）来消除噪声和荧光信号对模型的影响。为了检测方法的重复性,对30个相同啶虫脒含量（20 mg/kg）的苹果进行了拉曼信号采集,并对627 cm-1,835 cm-1和1 107 cm-1 3个特征峰强度进行分析,其相对标准偏差（rRelative sStandard dDeviation,RSD）分别为6.14%,6.83%,6.99%,说明该方法具有较好的重复性。采集含有梯度浓度啶虫脒的苹果（0.012 mg/kg～10.830 mg/kg）的信号时,最低检测限为0.035 mg/kg,远低于国家规定的标准0.8 mg/kg。建立的苹果中啶虫脒农药残留偏最小二乘回归（Partial Least Squares Regression,PLSR）预测模型效果较好,检测范围在0.082～3.830 mg/kg,预测相关系数（Rrediction coefficient,Rp）为0.974,预测集均方根误差（Root Mean Square Errors of prediction,RMSEp）为0.044 1 mg/kg,校正相关系数（Correlation coefficient,Rc）为0.986,校正集均方根误差（Root Mean Square Errors of calibration,RMSEc）为0.036 9 mg/kg。研究表明,该方法可以对苹果中残留的啶虫脒农药进行准确的定量预测。     

Determination of molybdenum in soil test extracts with potassium iodide plus hydrogen peroxide reaction

Abstract

The potassium iodide and hydrogen peroxide reaction (KI+H₂O₂) is catalyzed by molybdate. Our objective was to use this reaction to determine molybdenum (Mo) in Mehlich 1 (1:10) soil test extracts. A 350‐nm wavelength and 10‐minute reaction time were selected for the determination and absorbance was linear for 0.0 to 0.15 mg L^‐1 Mo. Ten samples of a LEd‐Iturama soil were extracted with Mehlich 1 and Mo determined. These extracts were also mixed and Mo determined on 10 aliquots of the mixture. Molybdenum concentration in the soil had a coefficient of variation (CV) of 23.5%, whereas that for the mixture was 3.95%. The low CV for the mixture indicates good precision for this method. The higher CV for the individual extracts indicates that most of the variation comes from the extraction phase of individual samples. To show the practical utility of the method, Mo maximum adsorption capacities (MoMAC) of 16 soils, primarily Oxisols, from Minas Gerais, Brazil were determined. The MoMAC varied from 0.15 to 2.02 mg g^‐1 and there were good correlations between MoMAC and soil clay content as well as between MoMAC and soil organic carbon content. From our experience, use of the KI+H₂O₂ reaction is a practical method of determining Mo in Mehlich 1 soil test extracts.     

Honey as a protective agent against lipid oxidation in ground turkey.

Lipid oxidation is a major deteriorative factor in meats. Sources of natural antioxidants that are as effective as commercially available antioxidants are desired. The objective of this research was to investigate honey as an inhibitor of lipid oxidation in ground poultry. The antioxidant content of different varieties of honey was investigated spectrophotometrically and honey's effectiveness in reducing oxidation of ground poultry determined by monitoring thiobarbituric acid reactive substances (TBARS). Buckwheat honey had the highest antioxidant content and acacia honey the lowest. Honeys of different floral sources differed in their protection against lipid oxidation. Buckwheat honey (5%, w/w) reduced TBARS approximately 70%, whereas acacia honey reduced TBARS approximately 34% at 3 days of storage at 4 degrees C. In comparison to butylated hydroxytoluene and tocopherol (0.02% of total fat), honey (at 5% of the weight of the meat) was much more effective at preventing oxidation. Honey has great potential as an antioxidant source and may result in greater acceptability of meat products and prevent negative health implications of oxidized meats.     

Fate of mucilage cell wall polysaccharides during coffee fermentation.

Effects of a 20-h fermentation on cell wall polysaccharides from the mucilage of pulped coffee beans were examined and compared to those of unfermented beans, on alcohol insoluble residues (AIRs), their hot-water-soluble crude pectic substances (PECTs), and their hot-water-insoluble residues (RESs). Yields and compositions were very similar: AIRs, which consisted of approximately 30% highly methylated pectic substances, approximately 9% cellulose, and approximately 15% neutral noncellulosic polysaccharides, exhibited no apparent degradation. However, PECTs from fermented beans were shown to have undergone a slight reduction of their intrinsic viscosity and weight-average molecular weight by capillary viscosimetry and high-performance size-exclusion chromatography. After fermentation, hot-water-insoluble pectic substances of RES exhibited partial de-esterification. Removal of coffee bean mucilage by natural fermentation seems to result from a restricted pectolysis, the mechanism of which remains to be elucidated.     

Physical Properties of Extruded Wheat Starch-Additive Mixtures

The effects of the addition of fatty acids, monoglycerides (MG), and wheat germ oil (WGO) on the level of crystallinity and the crystalline structure of extrusion-cooked wheat starch have been studied using twin-screw extruders. Measurements of water solubility and water absorption indices were made on the extrudates, together with specific mechanical energy (SME) consumption and die pressure for the extruder. MG and the fatty acids added to a level of 4% caused an increase in V_hydrate type crystallinity. WGO addition to a level of 8% caused no change in crystallinity, although the E_hydrate type was favored at lower moisture contents. All additives caused a decrease in SME and an increase or maximum in die pressure. WGO behaved differently than MG and fatty acids in that its addition caused the water solubility index and expansion to increase, as previously observed for other oils added to flours.     

Liquid chromatographic determination of morantel tartrate in cattle feed

A liquid chromatographic (LC) method is proposed for measuring 0.485-0.970% morantel tartrate in cattle feeds. The drug is leached from feed, diluted, separated from interfering substances on a silica column, and measured in the effluent stream by 313 nm spectrophotometric detection. Two potential degradation products, i.e., cis-isomer of morantel tartrate and N-(3-methylaminopropyl)-trans-3-(3-methyl-2-thienyl)acrylamide, and a related anthelmintic, i.e., pyrantel tartrate, do not interfere. Average recovery of drug from liquid spiked samples and laboratory blends was 98-100% with a maximum coefficient of variation (CV) of 2.3%. Results for pelleted and crumbled commercial scale feeds ranged from 94 to 102% of label claim, with a maximum CV of 1.5%.     

Rapid liquid chromatographic determination of dimetridazole and ipronidazole in swine feed

A simple and rapid method is described for the determination of dimetridazole (DMZ) and ipronidazole (IPR) in swine feeds at various levels (0.11-110 ppm). The drugs are released from feed by prewetting with a buffer, followed by extraction with either methanol or methylene chloride, depending on the drug level; if necessary, an acid-base cleanup is used before the liquid chromatographic analysis. The analytes are separated on a C18 column and monitored at 320 nm for detection and quantitation. Recoveries of DMZ from several feed formulations averaged 108% at the 92.8 ppm level with a standard deviation (SD) of 4.00% and a coefficient of variation (CV) of 3.70%, 101% at the 11.2 ppm level with an SD of 11.9% and a CV of 11.8%, and 100% at the 0.112 ppm level with an SD of 9.27% and a CV of 9.25%. Recoveries of IPR averaged 77.1% at the 12.9 ppm level with an SD of 1.75% and a CV of 2.27%; IPR recoveries averaged 35.2% at the 0.129 ppm level with an SD of 3.39% and a CV of 9.63%.     

Influence of Salinity and Acidity on Bioavailability of Sludge-Borne Heavy Metals. A Case Study of Bangkok Municipal Sludge

This study was conducted to assess the potential of Bangkoksewage sludge for amendment of saline and acidic soil withrespect to heavy metal mobilization. Experiments were carriedout at six levels of salinity (with electrical conductivityvalues of 2, 4, 8, 19, 31 and 42 dS m^-1) and two levels ofacidity (with pH values of 5 and 6). A pure sludge sample was used as a control system. Subsamples were collected andanalyzed for total and bioavailable heavy metals. Three sets ofsoil-sludge mixture were prepared using different weight ratio(1:1, 4:1 and 10:1) to simulate the conditions in the field withsludge-amended soil. Samples of soil-sludge mixture were incubated for 4 weeks to stabilize organic substances. Themobility and concentration of bioavailable heavy metal invarying soil-sludge mixture ratio with different electricalconductivity (EC) values were evaluated with the use of DTPA(diethylenetriamine pentaacetric acid) extraction techniques.Pure saline soil sample from Sakhon Nakhon (North-eastern partof Thailand) was used of salt-heavy metal interactions on thegermination percentage in soil mixed with sludge and to screencrops or varieties for their tolerances to soil salinity. Seventypes of seeds – mung bean, corn, soybean, tomato, stringbean, sunflower and marigol – were planted in each of the threesoil-sludge mixtures (1:1, 4:1 and 10:1) with different salinitylevels. Seedlings were monitored by counting the number of seeds thatare germinated and seed germination percentage can be used as anindicator for the level of salinity unsuitable for plant growth.     

Rapid determination of ractopamine in swine urine using surface-enhanced Raman spectroscopy

Ractopamine is approved for use in swine to improve carcass leanness in the United States, but banned in the European Union and China because ractopamine residue may pose health risks. This study investigated the possibility of applying surface-enhanced Raman spectroscopy (SERS) for analysis of ractopamine in swine urine. Ractopamine (0.1-10 μg mL(-1)) was added to urine samples collected from 20 swine to prepare a total of 240 samples. A simple centrifugation, a liquid-liquid extraction (LLE) method, and a more complicated method involving liquid-liquid extraction and solid-phase extraction (LLE-SPE) were used to extract ractopamine from urine samples. Principal component analysis (PCA) and partial least-squares (PLS) regression were used for spectral data analyses. Although no satisfactory result was obtained with the centrifugation method, ractopamine could be detected at levels of 0.8 and 0.4 μg mL(-1) with the LLE and LLE-SPE extraction methods, respectively. The R2 of the PLS model of actual ractopamine values versus predicted values was 0.74 for the LLE method and 0.73 for the LLE-SPE method. The SERS method with simple sample preparation has great potential for rapid analysis of ractopamine in swine urine.