Relationship Between Biogenic Amines and Free Amino Acid Contents of Wines and Musts from Alentejo (Portugal)

The concentration of biogenic amines and free amino acids was studied in 102 Portuguese wines and 18 musts from Alentejo demarcated (D.O.C.) regions. Most wines were commercial, except for 38 monovarietals obtained by micro vinification. Musts from the varieties used to produce the latter wines were also studied. Both biogenic amines and free amino acids were analyzed by HPLC using fluorescence detection for their o-phthalaldehyde/fluorenylmethyl chloroformate (OPA/FMOC) derivatives. The most significant amines (average 10.8 mg/L for histamine+tyramine in red, and 7.4 mg/L for white wines) were found to be present at low levels and, although no important relationship between each individual biogenic amine could be obtained, the total amine content depends significantly on the assimilable amino acid content in wine.     

污水中溶解游离氨基酸和结合氨基酸测定方法研究

采用邻苯二甲醛作为柱前衍生化试剂，结合反相高效液相色谱，对污水中溶解游离氨基酸（dissolvedfreeami．nOacid，DFAA）进行定性和定量分析，探讨了污水样品有无前处理对DFAA分析的影响，并采用气相酸水解方法对污水中总溶解氨基酸（dissolvedtotalaminoacid，DTAA）进行了分析。结果表明，污水经过pH调节和N，流清洗后，可以明显去除氨和挥发性胺的干扰，色谱峰更加清晰；前处理后的水样经RP—HPLC分析，能够快速检测出14种氨基酸，各氨基酸在一定线性范围内呈现良好的线性关系，相应的线性相关系数（R^2）均大于0．99，加标回收率为92％～102％。污水处理厂进水和出水中氨基酸主要以溶解结合氨基酸（dissolvedcombinedaminoacid，DCAA）为主，与进水相比，出水中DFAA含量减少了0．22μmol／L，DTAA由5．68μmol／L降至3．08μmol／L。     

Responses of free amino acids in rice seedlings during cyanide metabolism

Responses of free amino acids to botanical assimilation of free cyanide were investigated. Young rice seedlings (Oryza sativa L. cv. XZX 45) were grown in nutrient solution amended with free cyanide (KCN). Cyanide was analyzed in solution as well as in plant materials to estimate the phyto-assimilation potential. Free amino acids in different parts of plants were also measured to determine metabolic responses to KCN exposure. Phyto-assimilation of KCN was obvious, and the rates were positively correlated to the concentration supplied. Although changes in total amino acid content in plant materials were negligible during KCN metabolism (p?>?0.05), responses of different amino acids to KCN treatments were quite different. All treatments with KCN increased the content of proline (Pro) and isoleucine (Ile) in roots significantly compared with control (p?<?0.05), while changes of aspartic acid, lysine, and histidine in roots were more evident at higher KCN treatments (p?<?0.05). Results indicate that the content of Pro, Ile, and tyrosine showed pronounced increase in shoots of rice seedlings exposed to KCN at 1.44 mg CN/L or higher (p?<?0.05). Other amino acids slightly changed in all plant materials exposed to KCN (p?>?0.05). Results indicate that specific amino acids in rice seedlings showed positive response to non-toxic concentrations of exogenous KCN. These findings could provide additional insights into the inducible mechanisms underlying the involvement of amino acids in KCN metabolism.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 +/- 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Validation and global uncertainty of a gas chromatographic with mass spectrometry method for fenamidone analysis in grapes and wines

Fenamidone is an imidazolinone fungicide recently introduced in viticulture practices. This work reports the validation and assessment of global uncertainty of a gas chromatographic with mass spectrometry method to analyze fenamidone in grapes and wines. This method consists in a simple and fast liquid-liquid extraction step followed by chromatographic determination. Limits of detection for fenamidone in grapes and wines were, respectively, 0.05 mg/kg and 0.06 mg/L, precision was below 9.4% and average recovery was 89 ± 5%. In the concentration range from 0.05 to 1.00 mg/kg (or mg/L) of fenamidone, global uncertainty calculated following the EURACHEM/CITAC rules, and also by the Horwitz function, was below 25%. The EURACHEM/CITAC global uncertainty budget used gave lower estimates than those obtained from the Horwitz function.     

Synthesis and pesticidal activity of new N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines

A series of novel N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were synthesized as potential new agents to control pests. Their structures were confirmed on the basis of IR, NMR and elemental analyses. Six new N-alkyl-N-[1-(2-hydroxyphenyl) ethyl]amines were prepared by reduction of corresponding Schiff bases using sodium borohydride in 80–87 % yields. These compounds were tested for their antifungal activity against two pathogenic fungi viz., Rhizoctonia bataticola ITCC 0482 and Sclerotium rolfsii ITCC 5226 and for insecticidal activity against insects of stored grain pest Callosobruchus analis. Fungicidal bioassay revealed that compound N-Decyl-N-[1-(2-hydroxyphenyl)ethyl]amine, was highly effective against R. bataticola (ED₅₀ 6.86 mg L^?1) which was comparable with that of commercial fungicide hexaconazole (ED₅₀ 6.35 mg L^?1). Also compounds N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine, N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine and N-Nonyl-N-[1-(2-hydroxyphenyl)ethyl]amine displayed promising fungitoxicity against same pathogen. However, compound N-Heptyl-N-[1-(2-hydroxyphenyl)ethyl]amine was also found to be effective against S. rolfsii (ED₅₀ 4.92 mg L^?1 as against 1.27 mg L^?1 for hexaconazole). Compound N-Hexyl-N-[1-(2-hydroxyphenyl)ethyl]amine was most effective as insecticide followed by compound N-Octyl-N-[1-(2-hydroxyphenyl)ethyl]amine. LC₅₀ values for these compounds were 155.0 and 275.0 mg L^?1 respectively as against 36.70 mg L^?1 for commercial insecticide dichlorovos. The results obtained from bioassays indicate that this class of compounds can be utilized for the design of new substances endowed with pesticidal activities.     

树脂吸附法处理氯霉素中间体DL-氨基物合成废水

研究了树脂吸附法处理氯霉素生产中产生的DL 1 对硝基苯基 2 氨基 1 ,3 丙二醇 (DL 氨基物 )碱解废水的工艺。结果表明 ,NG 1 0 0超高交联吸附树脂对废水中DL 氨基物具有较好的吸附性能。在试验条件下 ,废水CODCr为 72 0 0mg/L ,DL 氨基物含量为 2 86 5mg/L ,批处理 1 7BV时 ,平均出水CODCr降至 89 3mg/L ,CODCr去除率 >98% ;出水中DL 氨基物未检出 ,去除率近 1 0 0 %。树脂经稀酸脱附处理后 ,再生性能良好 ,高浓脱附液可直接回用于氯霉素生产酸性水解工艺中 ,使回收物得到有效利用     

ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site

An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ～33% of the PM_1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional groups than the urban source.     

Chemical and enzymatic interactions of Direct Black 38 and Direct Brown 1 on release of carcinogenic amines

Release of amine products from azo compounds is of considerable interest, since most of the metabolized amine products have toxic and carcinogenic characters. Moreover, most of the azo dyes are extensively used as coloring agents in inks, textiles, leathers, food and pharmaceutical industries. The present study emphasis on the quantification and comparison of amines released from water soluble dyes by (i) extra cellular protein (ECP) of Streptomyces sp. SS07 and by (ii) chemical methods. It has been observed that both the methods release considerable quantities of similar type of amine products. Release of amine compounds by ECP and chemical reduction in acid and alkaline sweat medium from a leather garment sample was also assessed. ECP (0.7852 mg protein/mg of ECP) releases benzidine and 4-amino biphenyl from Direct Black 38 and Direct Brown 1 as stable products at pH 9.2 and at 37 degrees C for a contact period of 24 h. On comparison with chemical reduction, it was observed that about 5-20% increase in the release of amine products by ECP was observed. However, more than 60% of amine products were released by chemical method from leather garment samples than direct treatment with ECP.     

Influence of several fungicides on the antioxidant activity of red wines (var. Monastrell)

The antioxidant activity of wines obtained from grapes treated with six fungicides (famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl, quinoxyfen and trifloxystrobin) was investigated. Two field trials in triplicate were carried out for each formulation of the fungicide at the recommended dose of the manufacturer. The first trial was carried out under good agricultural practices (GAP), following the recommended pre-harvest interval, and the second one under critical agricultural practices (CAP) that involves treating the same field just before the harvest. The residue levels were determined by gas and liquid chromatography coupled to mass detectors (GC-MS and LC-MS). The antioxidant activity was determined in the wines obtained from the thirteen trials including one control, six from treated grapes obeying the pre-harvest interval, and six from grapes treated at the day of harvest or at most unfavorable conditions. Elimination of 40–100% of the initial fungicide residues present in grapes was observed during the wine-making process. It can be inferred from the results that the use of these fungicides did not produce any decrease of the antioxidant activity in the wines (7.19 ± 0.22 mmol Trolox/L for the blank wine versus a range of 6.45 ± 0.82 mmol Trolox/L to 10.06 ± 0.59 mmol Trolox/L for the treated wines) at the pre-harvest interval and most unfavorable conditions. Nevertheless, the presence of famoxadone, kresoxim-methyl and quinoxyfen increased the antioxidant activity and this was directly related to their residue levels in the grapes. Also, the wine phenolic composition was altered in variable intensity by the presence of the fungicide residues.     

Contents of free amino acids in needles of Norway Spruce trees in relation to novel forest decline. Studies on trees from a site in the northern Black Forest

The free amino acid content in needles of Norway spruce trees (about 45-year-old) was determined by means of HPLC. The studied trees have been growing at a forestry site in the Black Forest which is characterized by a high impact of ozone and magnesium deficiency. Measurements were carried out on visibly healthy and on damaged trees on several dates during two vegetation periods and during the course of a day. The amino acids occurring at the highest concentrations were glutamate, arginine, aspartate, and glutamine. The typical seasonal changes in the content of free amino acids, with their minimum during summer, were disturbed in the needles of the damaged trees. Particularly in summer and autumn the damaged trees showed increased levels of total amino acids and of most single amino acids. During the course of a day, the needles of the damaged trees showed a reduced amplitude in diurnal variations with the absolute level almost always higher in comparison to that of the undamaged trees. The results suggest that a shift in protein turnover towards enhanced degradation has taken place.     

高硬度富锶地下水的软化沉淀-超滤膜联用工艺

针对一种高硬度富锶地下水,分别采用石灰和石灰-碳酸钠两种方法,利用药剂软化/超滤膜工艺对其进行软化处理,同时考察了药剂投量对出水锶含量的影响。结果表明,采用石灰软化/超滤膜法,Ca(OH)2最佳投加量为270 mg/L时,出水总硬度(以CaCO3计)由287.12 mg/L降低到96.44 mg/L,硬度去除率为66.41%,出水锶含量也由原水中的0.37 mg/L下降为0.21 mg/L;而采用石灰-碳酸钠软化/超滤膜法,Ca(OH)2和Na2CO3最佳投加量分别为270 mg/L、160mg/L时,出水总硬度降低到60.34 mg/L,硬度去除率达78.98%,锶含量仅为0.02 mg/L。2种处理方法出水总硬度均达到预期目标,石灰软化/超滤膜法可使出水锶含量满足富锶水的要求,而石灰-碳酸钠软化/超滤膜法则造成了对人体有益微量元素锶的大量损失。     

纳米TiO2/EP光催化降解罗丹明B废水的研究

通过溶胶-凝胶法制备出可漂浮于水面的膨胀珍珠岩(EP)负载型TiO2,研究其在水中对罗丹明B(RB)的去除效果、吸附降解动力学以及最佳工艺条件,并研究其多次回收再生后的降解效果。结果表明,浸渍3次的负载型TiO2光催化活性最高,回收5次后活性变化很小,降解率下降不到8%;光催化剂用量为0.2 g,20 mL初始浓度为10 mg/L和15mg/L RB溶液光照6 h后降解率分别达98%和74%。在实验浓度范围内,该光催化反应可用一级反应动力学方程描述。     

鸡粪堆肥水溶性有机物转化特性研究

采用离子色谱和三维荧光光谱,分别对鸡粪堆肥不同阶段水溶性有机物(DOM)中典型小分子有机酸、磷酸和荧光有机物进行了研究。分析显示,所研究的7种酸(乙酸、琥珀酸、苹果酸、草酸、柠檬酸、酒石酸及磷酸)中,苹果酸的含量最高(1 000 mg/L),草酸的浓度最低(3 mg/L),琥珀酸和柠檬酸未检测到。随着堆肥的进行,各种酸的含量先上升而后下降,堆肥结束降至最低;堆肥过程样品所有荧光峰强度之和与COD达到显著相关(R=0.917,P0.05),类蛋白荧光峰强度与总荧光峰强度的比值不断降低,而类富里酸荧光峰强度与总荧光峰强度的比值不断上升。结果表明,堆肥过程小分子有机酸主要出现在堆肥中期;类蛋白荧光强度或类富里酸荧光强度与总荧光强度之比可以有效表征堆肥腐熟过程。     

沼泽红假单胞菌W12对活性黑5的厌氧脱色和降解作用

从处理印染废水的厌氧移动床生物膜反应器（moving bed biofilm reactor, MBBR）中分离到一株具有高效脱色活性的沼泽红假单胞菌W12。经实验确定W12对活性黑5（reactive black 5，RB5）脱色的适宜条件为：pH＜10；有光照；谷氨酸盐或乳酸盐作为碳源，当乳酸钠为碳源时浓度应＞500 mg/L；盐度不超过5％；RB5浓度不大于700 mg/L。紫外可见光谱扫描结果表明，RB5的脱色和降解过程生成芳香胺类化合物，这些中间产物可进一步降解。此外发现，RB5诱导生成的胞外代谢物能提高W12的脱色活性。     

Organic acids in continental background aerosols

With a newly developed method aerosol samples from three distinctly different continental sites were analyzed: an urban site (Vienna), a savanna site in South Africa (Nylsvley Nature Reserve, NNR) and a free tropospheric continental background site (Sonnblick Observatory, SBO). In all samples a range of monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) has been identified and quantified. The three most abundant MCAs in Vienna were the C18, C16 and C14 acids with concentrations of 66, 45 and 36 ng m^-3, respectively. At the mid tropospheric background site (SBO) the three most abundant MCAs were the C18, C16 and C12 acid. For the DCAs at all three sites oxalic, malonic and succinic acid were the dominant compounds. For some individual compounds an information about the sources could be obtained. For example the determined unsaturated MCAs in South Africa appear to result from biogenic sources whereas in Vienna those acids are considered to be derived from combustion processes. Oxalic and glyoxalic acid appear to have a free tropospheric air chemical source. The relative high amounts at SBO in comparison to Vienna can only be explained by secondary formation of oxalic acid in the atmosphere.     

Stress reactions in Vitis vinifera L. following soil application of the herbicide flumioxazin

In order to evaluate the stress effects of flumioxazin (fmx) on grapevine, a non-target plant (Vitis vinifera L.), physiological parameters such as carbohydrate content, water status or nitrogenous metabolites were investigated on fruiting cuttings and plants grown in vineyard. In the leaves of cuttings, the soil-applied herbicide induced stress manifestations including a decrease of the dry weight percentage and the soluble carbohydrate content during the first week after treatment. Thereafter, a decrease of the osmotic potential was observed, as well as a decrease of total protein content and a parallel accumulation of free amino acids, including proline. Altogether, these results suggest that soil-applied fmx induced a stress in grapevines, leading to leaf proteolysis. However, this stress was partially recovered 3 weeks after herbicide application, suggesting that the cuttings were capable to adapt to the fmx exposure. In the vineyard, the flumioxazin effects were still significant 5 months after the treatment, particularly in the CH cv. They included a decrease of the leaf dry weight percentage and soluble carbohydrate content, as well as an increase of the osmotic potential. The decrease of leaf soluble carbohydrates may have dramatic consequences for the berry growth and the reserve constitution. Moreover, treated plants were characterized by a decrease of the free amino acid content and an accumulation of ammonium, while the protein level did not significantly increase, suggesting a degradation of amino acids. The alteration of carbon and nitrogen status after herbicide treatment may affect the grapevine vigour in a long term.     

MBR-NF截留液中腐植酸的纳滤分离浓缩特性

MBR-NF截留液是一类难处理的高浓度有机废水,其所含有机物几乎都是腐植酸,可考虑资源利用。实验室内采用纳滤对其所含腐植酸进行分离浓缩。引入分离因子来表征纳滤的分离效果。实验结果表明,分离因子(SF)与体积浓缩倍数(CF)有很好的线性关系,浓缩倍数为5时,截留液中有机碳浓度为9 413 mg/L,重金属浓度处于mg/L水平,分离因子达到2.76,表明纳滤可有效地将MBR-NF截留液中的腐植酸与无机盐分离,并进行浓缩。     

Norway spruce and spruce shoot aphid as indicators of traffic pollution

Two-year-old Norway spruce (Picea abies (L.) Karst) seedlings were exposed to traffic emissions along roadsides with three different traffic densities and speed limits; highway, street and a quiet local road. The responses of the exposed seedlings as a host plant and those of spruce shoot aphid (Cinara pilicornis Hartig) were studied. The concentrations of soluble N and free amino acids, defence chemicals (total phenolics, monoterpenes) were analysed, and aphid growth and reproduction were studied. Along the highway, street and at the local road control site, the atmospheric concentrations of black carbon (BC) and oxides of N (NO(x)) were measured for 1 week during the experiment. The BC data indicate deposition of organic particulate compounds along the highway and street. The NO(x) concentrations along the highway and street showed great diurnal variation, but the average NO(x) concentrations were relatively low. Thus, no changes in N metabolism or growth of the exposed Norway spruce seedlings were found. Along the street, the concentrations of many individual free amino acids, such as proline, as well as total amino acid concentrations, were lower than at the associated control site. Correspondingly, there was also no increase in spruce shoot aphid mean relative growth rate. The aphid reproduction, however, increased along the highway and is suggested to be due to more conducive microclimatic conditions at the exposure site or lack of natural enemies. No changes in defence chemicals (total phenolics, monoterpenes) in relation to the traffic exposure were found. Instead, the microclimatic conditions (temperature, solar irradiation) seemed to affect the concentration of total phenolics.     

Influence of ozone air pollution on plant-herbivore interactions. Part 1: Biochemical changes in ornamental milkweed (Asclepias curassavica L.; asclepiadaceae) induced by ozone

A series of fumigation experiments was conducted with bloodflower (Asclepias curassavica L.) in continuous-flow stirred reactors (CSTRs) to elucidate the effects of ozone on foliar concentrations of several primary and secondary plant metabolites relevant to herbivores. Plants 8 weeks of age were subjected to different ozone levels ranging from 0 to 134 nl liter(-1) for exposure periods up to 16 days. Leaves were analyzed for concentration of soluble carbohydrates, starch, free amino acids, soluble protein, total phenolics, and total cardenolides. Significant interactions between the linear effects of ozone concentration and exposure time were found for soluble carbohydrates, amino acids, cardenolides and phenolics. No significant treatment effects could be observed on foliar starch and protein concentration. The metabolic responses of plants to fumigation appeared to be altered by overall plant nutrition. It is possible that the metabolic changes observed in the host plant represent important changes in nutritional quality to insects.