Polycyclic aromatic hydrocarbons (PAH) in chocolate on the German market

Benzo[a]anthracene (BaA), chrysene (CHR), cyclopenta[c,d]pyrene (CPP), 5-methylchrysene (5MC), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[j]fluGoranthene (BjF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DhA), indeno[1,2,3-cd]pyrene (IcP), benzo[g,h,i]perylene (BgP), dibenzo[a,l]pyrene (DlP), dibenzo[a,e]pyrene (DeP), dibenzo[a,i]pyrene (DiP) and dibenzo[a,h]pyrene (DhP), the 15 SCFPAH, assessed to be relevant as well as benzo[c]fluorene (BcL) recommended by the European Food Safety Authority (EFSA), were analysed in different types of chocolate. The sample preparation included accelerated solvent extraction (ASE), size exclusion chromatography (SEC) and solid phase chromatography using small silica gel columns. The individual PAH were separated by gas chromatography using a VF-17ms GC column and detected by high resolution mass spectrometry (HRMS). The investigation of 40 samples of various types of chocolate with different cocoa contents resulted in a median benzo[a]pyrene (BaP) content of 0.22 μg/kg. Furthermore, the results showed a linear correlation between the content of BaP and the sum content of the 16 priority PAH. Therefore, the analysis of BaP as a leading substance seems to be suitable to estimate the PAH contamination in chocolate.     

NNK和B[a]P在卷烟烟气基质中的联合致突变性

以苯并[a]芘(B[a]P)、甲基亚硝胺吡啶基丁酮(NNK)为目标化合物,设置卷烟烟气冷凝物(CSC)的浓度为0(CK),0.005,0.010,0.015,0.020 mg/mL;NNK的浓度为0(CK),0.005,0.010,0.020,0.040 mg/mL;B[a]P的浓度为0(CK),0.00025,0.00050,0.00075,0.00100 mg/mL,研究了NNK,B[a]P和CSC的联合致突变性。结果表明:①CSC,NNK和B[a]P均可诱导鼠伤寒沙门氏菌TA98,TA100发生突变,且剂量-效应明显。②B[a]P与CSC联合呈相加作用;B[a]P与NNK联合高剂量呈弱相加作用;CSC与NNK联合低剂量呈弱相加作用。③在不同情况下,三者联合作用致TA98呈弱相加作用。综上,NNK和B[a]P在卷烟烟气基质中的联合致突变性呈现量效、时效和先后作用顺序的复杂性。     

Structural determination of subsidiary colors in commercial Food Green No. 3 (fast green FCF, FD & C Green No. 3).

HPLC analysis revealed that eight subsidiary colors existed in commercial Food Green No. 3 (fast green FCF, FD & C Green No. 3). Among them, four subsidiary colors C, F, G, and H were isolated by using preparative HPLC and their structures were determined by MS and NMR. They were the disodium salt of 2-[[4-[N-ethyl-N-(3- sulfophenylmethyl)amino]phenyl][4-[N-ethyl-N-(4- sulfophenylmethyl)amino]phenyl]methylio]-4-hydroxybenzenesulfonic acid (abbreviated as m,p-G-3), the sodium salt of 2-[[(4-N-ethylamino)phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)amino]-phenyl]methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(EA) (m-EBASA)], the sodium salt of 2-[[(4-N-diethylamino)phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)amino]phenyl]-methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(di-EA) (m-EBASA)], and the sodium salt of 2-[[4-[N-ethyl-N-(phenylmethyl)amino]phenyl][4-[N-ethyl-N-(3- sulfophenylmethyl)-amino]phenyl]methylio]-4-hydroxybenzenesulfonic acid [abbreviated as HSBA-(EBA)(m-EBASA)], respectively. HSBA-(di-EA) (m-EBASA) was a subsidiary color newly found in commercial Food Green No. 3.     

Secondary organic aerosol production from terpene ozonolysis. 2. Effect of NOx concentration

We report secondary organic aerosol (SOA) yields from the ozonolysis of alpha-pinene in the presence of NO and NO2. Experimental conditions are characterized by the [VOC]0/ [NOx]0 ratio (ppbC/ppb), which varies from approximately 1 to approximately 300. SOA yield is constant for [VOC]0/[NOx]0 > approximately 15 and decreases dramatically (by more than a factor of 4) as [VOC]0/[NOx]0 decreases. Aerosol production is completely suppressed in the presence of NO for [VOC]0/[NOx]0 < or = 4.5. Fouriertransform IR analysis of filter samples reveals that nitrate-containing species contribute significantly to the total aerosol mass at low [VOC]0/[NOx]0. Yield reduction is a result of the formation of a more volatile product distribution as [VOC]0/[NOx]0 decreases; we propose that the change in the product distribution is driven by changes in the gas-phase chemistry as NOx concentration increases. We also present two-product model parameters to describe aerosol production from the alpha-pinene/0/NOx system under both high- and low-NOx conditions.     

Kinetic resolution of an indan derivative using Bacillus sp. SUI-12: synthesis of a key intermediate of the melatonin receptor agonist TAK-375

The chiral indan derivative (S)-2 (2-[(8S)-1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-yl]ethyl-amine) was synthesized by enzyme-catalyzed asymmetric hydrolysis of the racemic acetamide 1 (N-[2-(1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-yl)ethyl]acetamide). The reaction was carried out using Bacillus sp. SUI-12 screened for the ability to hydrolyze 1 to give (S)-2 with high enantioselectivity. In a scaled-up experiment, a low reaction rate was observed. However, by changing the culture medium and the reaction conditions, it became possible to run the reaction to 40% conversion on a 10-g or more scale, obtaining (S)-2 at >;99% enantiomeric excess (ee). The (S)-2 obtained was available for the synthesis of the melatonin receptor agonist TAK-375 (N-[2-[(8S)-1,6,7,8-tetrahydro-2H-indeno[5,4-b]furan-8-yl]ethyl]propanamide).     

miRNA影响苯并[a]芘诱发毒性的机制研究进展

苯并[a]芘（B[a]P）作为多环芳烃类化合物（PAHs）中毒性最大的一种强致癌物,广泛存在于高温加工食品中。大量流行病学研究表明,B[a]P与许多疾病的发生发展密切相关。微小RNA（miRNA）是短的（17–25个核苷酸）非编码RNA,通过mRNA降解或翻译抑制负调控特定的靶基因。miRNA在B[a]P诱发致癌性、生殖毒性、神经毒性等过程中发挥重要作用。本文根据现有的研究发现,对miRNA在B[a]P毒性过程中的作用机制作一综述,旨在深入揭示B[a]P的毒理机制并为其疾病预防和食品安全控制提供新的研究方向和思路。     

[C] Milk, urine and faeces excretion kinetics in lactating goats after an oral administration of [C]polycyclic aromatic hydrocarbons

The aim of this work was to characterize phenanthrene, pyrene, benzo(a)pyrene and TCDD transfer to milk, urine and faeces in lactating goats after a single oral ingestion (2.5 10⁶ Bq) of [¹⁴C]phenanthrene, [¹⁴C]pyrene, [¹⁴C]benzo[a]pyrene or [¹⁴C]2,3,7,8-TCDD.

Seven hours after [¹⁴C] PAHs oral ingestion, a radioactivity peak was detected in plasma for all compounds studied. Regarding excretion routes, three specific types of behaviour were noticed: 2,3,7,8-TCDD was mainly excreted in milk (7.8%) and a large part of radioactivity ingested remained in the organism (71.2%). Phenanthrene and pyrene presented a similar behaviour, with a low milk transfer (1.6% and 1.9%, respectively) and a high excretion through urine (40.4% and 11.4%, respectively) suggesting their metabolization. Benzo[a]pyrene was poorly absorbed (88% of the ingested part of this compound was detected in faeces) and radioactivity due to benzo[a]pyrene was not significantly detected in milk (0.2%).     

Effects of volatile fatty acids on propionate metabolism and gluconeogenesis in caprine hepatocytes

Isolated caprine hepatocytes were incubated with fatty acids of various chain lengths. Short-chain fatty acids effects on rates of gluconeogenesis and oxidation from [2-14C]propionate were determined. Additions of glucose (2.5 mM) had no effect on hepatic [2-14C]propionate metabolism in the presence and absence of amino acids. A complete mixture of amino acids increased label incorporation from [2-14C]propionate into [14C]glucose by 22%. Butyrate inhibited [2-14C]propionate metabolism and increased the apparent Michaelis constant for [2-14C]propionate incorporation into [14C]glucose from 2.4 +/- 1.5 to 5.6 +/- .9 mM. Butyrate's effects on propionate were similar in the presence and absence of L-carnitine (1 mM). Isobutyrate, 2-methylbutyrate, and valerate (1.25 mM) had no effect on [14C]glucose production but decreased 14CO2 production to 57, 61, and 54% of the control [2-14C]propionate (1.25 mM). This inhibition on 14CO2 production was not competitive. Isovalerate had no effect on either [2-14C]propionate incorporation into glucose or CO2. An increase in ratio of [14C]glucose to 14CO2 from [2-14C]propionate demonstrated that short-chain fatty acids other than butyrate do not inhibit gluconeogenesis from propionate. In addition, fatty acids that generate a net synthesis of intracellular oxaloacetate may partition propionate carbons toward gluconeogenic rather than oxidative pathways in goat hepatocytes.     

Automobile tires--a potential source of highly carcinogenic dibenzopyrenes to the environment

Eight tires were analyzed for 15 high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAH), using pressurized fluid extraction. The variability of the PAH concentrations determined between different tires was large; a factor of 22.6 between the lowest and the highest. The relative abundance of the analytes was quite similar regardless of tire. Almost all (92.3%) of the total extractable PAH content was attributed to five PAHs: benzo[ghi]perylene, coronene, indeno[1,2,3-cd]pyrene, benzo[e]pyrene, and benzo[a]pyrene. The difference in the measured PAH content between summer and winter tires varied substantially across manufacturers, making estimates of total vehicle fleet emissions very uncertain. However, when comparing different types of tires from the same manufacturer they had significantly (p = 0.05) different PAH content. Previously, there have been no data available for carcinogenic dibenzopyrene isomers in automobile tires. In this study, the four dibenzopyrene isomers dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene constituted <2% of the sum of the 15 analyzed HMW PAHs. These findings show that automobile tires may be a potential previously unknown source of carcinogenic dibenzopyrenes to the environment.     

Polycyclic aromatic hydrocarbons (PAH) in chocolate on the German market

Benzo[a]anthracene (BaA), chrysene (CHR), cyclopenta[c,d]pyrene (CPP), 5-methylchrysene (5MC), benzo[b]fluoranthene (BbF), benzo[k]fluoranthene (BkF), benzo[j]fluGoranthene (BjF), benzo[a]pyrene (BaP), dibenzo[a,h]anthracene (DhA), indeno[1,2,3-cd]pyrene (IcP), benzo[g,h,i]perylene (BgP), dibenzo[a,l]pyrene (DlP), dibenzo[a,e]pyrene (DeP), dibenzo[a,i]pyrene (DiP) and dibenzo[a,h]pyrene (DhP), the 15 SCFPAH, assessed to be relevant as well as benzo[c]fluorene (BcL) recommended by the European Food Safety Authority (EFSA), were analysed in different types of chocolate. The sample preparation included accelerated solvent extraction (ASE), size exclusion chromatography (SEC) and solid phase chromatography using small silica gel columns. The individual PAH were separated by gas chromatography using a VF-17ms GC column and detected by high resolution mass spectrometry (HRMS). The investigation of 40 samples of various types of chocolate with different cocoa contents resulted in a median benzo[a]pyrene (BaP) content of 0.22 μg/kg. Furthermore, the results showed a linear correlation between the content of BaP and the sum content of the 16 priority PAH. Therefore, the analysis of BaP as a leading substance seems to be suitable to estimate the PAH contamination in chocolate.

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Zusammenfassung:  Für Bestimmung der 15+1 von der EU als priorit?r eingestuften PAK in verschiedenen Schokoladen wurde eine Analysenmethode bestehend aus beschleunigter L?sungsmittelextraktion (ASE), Gelpermeationschromatographie (GPC) und Nachreinigung an einer Minikieselgels?ule verwendet. Die Identifizierung und Quantifizierung der einzelnen Verbindungen erfolgte nach gaschromatographischer Trennung mit dem hochaufl?senden Massenspektrometer unter Verwendung einer VF-17ms GC-S?ule. Die Untersuchung von 40 Schokoladenproben mit verschiedenen Kakaogehalten erbrachte im Median einen Gehalt an Benzo[a]pyren (BaP) von 0,22 μg/kg. Es zeigte sich weiterhin eine enge Korrelation des BaP-Gehalts vom Gesamtgehalt der 15+1 EU-PAK. über die Leitsubstanz BAP l?sst sich somit der Gesamtgehalt der 15+1 EU-PAK durch die alleinige Bestimmung von BaP in Schokolade absch?tzen.

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Received: February 10, 2009; accepted: February 25, 2009.     

Analysis of an Acid Hydrolysate of a Low-Substituted Hydroxypropyl Starch

The major components, besides glucose, of an acid hydrolysate of a low-substituted hydroxypropyl starch (DS 0.07) were identified by proton magnetic resonance (PMR) analysis of their peracetates as 6-0-[2-(RS)-hydroxypropyl]-D-glucopyranose, 2-0-[2-(RS)-hydroxypropyl]-D-glucopyranose, 1,2-0-[2,1-(R)-propylene]-α-D-glucopyranose, 1,2-0-[2,1-(S)-propylene]-α-D-glucopyranose, and 1,2-0-[2,1-(R)-propylene]-α-D-glucofuranose. The analytical data indicated that in the product examined over 80% of the hydroxypropyl groups were attached to C-2 of the glucose moiety and about 7% to C-6.     

Influence of infrared final cooking on polycyclic aromatic hydrocarbon formation in ohmically pre-cooked beef meatballs

Effects of infrared cooking on polycyclic aromatic hydrocarbon (PAH) formation in ohmically pre-cooked beef meatballs were investigated. Samples were pre-cooked in a specially designed-continuous type ohmic cooking at a voltage gradient of 15.26 V/cm for 92 s. Infrared cooking was applied as a final cooking method at different combinations of heat fluxes (3.706, 5.678, 8.475 kW/m²), application distances (10.5, 13.5, 16.5 cm) and application durations (4, 8, 12 min). PAHs were analyzed by using high performance liquid chromatography (HPLC) equipped with a fluorescence detector. The total PAH levels were detected to be between 4.47 and 64 μg/kg. Benzo[a] pyrene (B[a]P) and PAH4 (sum of B[a]P, chrysene (Chr), benzo[a]anthracene (B[a]A) and benzo[b]fluoranthene (B[b]F)) levels detected in meatballs were below the EC limits. Ohmic pre-cooking followed by infrared cooking may be regarded as a safe cooking procedure of meatballs from a PAH contamination point of view.     

[PSI] and [URE3] as yeast prions

[URE3] is a non-Mendelian genetic element that mimics recessive mutations in the chromosomal URE2 gene making cells derepressed for nitrogen catabolic enzymes. [PSI] is a non-Mendelian enhancer of readthrough of translational termination similar in its effects to some mutations in the chromosomal SUP35 gene. Three lines of evidence led to the proposal⁷⁵ that both [URE3] and [PSI] are prions, infectious proteins analogous to the scrapie agent mediating transmissible spongiform encephalopathies of mammals. (1) Both [PSI] and [URE3] are reversibly curable. (2) [PSI] propagation requires SUP35 and [URE3] propagation requires URE2 with recessive chromosomal mutants having the same phenotypes as the presence of the respective dominant non-Mendelian element. (3) Overproduction of Sup35p and Ure2p increases the frequency of cells acquiring [PSI] or [URE3], respectively.     

Oxidation of ferrocyanide by birnessite

The Fe-CN complexes ferrocyanide, [FeII(CN)6]4-, and ferricyanide, [FeIII(CN)6]3-, which are contaminants in soil and groundwater, form a redox couple, [FeII(CN)6]4- <==> [FeIII(CN)6]3- + e-, E(H) = 356 mV. We studied the oxidation of [FeII(CN)6]4- by birnessite, delta-MnIVO2, in batch experiments as influenced by [FeII(CN)6]4- concentration, pH, and reaction time. Additionally, stopped-flow experiments were carried out at five temperatures (10-30 degrees C) and four pH values (pH 4.1-5.3). In the batch experiments, [FeII(CN)6]4- was completely oxidized to [FeIII(CN)6]3-, and oxidation did neither depend on time for t > 2 min, nor on concentration (0.12-0.47 mM), nor on pH (pH 3.3-9.9). Lasting adsorption of Fe-CN complexes on the birnessite surface or precipitation of manganese ferricyanide were not detected. Manganous ions resulting from the reductive dissolution of birnessite did not precipitate as manganese oxide because an identical decrease of Mn solution concentrations was observed under air and under a N2 atmosphere. Two processes were detected by the stopped-flow experiments. The first rapid one with an activation energy of approximately 60 kJ mol(-1) was attributed to short-term adsorption and simultaneous oxidation of [FeII(CN)6]4- on the birnessite surface. The second slower process with an activation energy of approximately 20 kJ mol(-1) was attributed most probably to diffusion of the reaction product Mn2+ into the interior of the birnessite, which creates fresh reaction sites at the outer surface.     

冷冻除脂-气相色谱-串联质谱法检测食用植物油中30 种多环芳烃

建立冷冻除脂--气相色谱-串联质谱检测食用植物油中30?种多环芳烃（polycyclic aromatic hydrocarbons,PAH）的方法。选用6?种氘标记PAH为内标,样品经乙腈--丙酮溶液（4∶1,V/V）于离心管中涡旋提取,10?000?r/min离心5?min,－80?℃对油脂冷冻固化,倾出提取液,再经减压浓缩和氮气吹干,以二氯甲烷复溶,气相色谱--串联质谱多反应监测方式进行检测。结果表明,在相应质量浓度范围内30?种PAH均有良好线性（R2＞0.998）,检出限为0.10～1.83?μg/kg,定量限为0.35～6.11?μg/kg,在5、20?μg/kg和50?μg/kg添加水平下的回收率为67.77%～119.28%,相对标准偏差为1.18%～12.47%。采用本方法对市售11?类38?个食用植物油样品的检测显示,萘、1-甲基萘、2--甲基萘、联苯、2,6--二甲基萘、苊烯、苊、2,3,6--三甲基萘、芴、二苯并噻吩、菲、蒽、1-甲基菲、荧蒽、芘、环戊烯[c,d]芘、苯并[a]蒽、屈、苯并[b]荧蒽、苯并[k]荧蒽、苯并[e]芘和苯并[a]芘的检出率均为100%;5--甲基屈、苝、茚并[1,2,3--c,d]芘、二苯并[a,h]蒽、苯并[g,h,i]苝和二苯并[a,l]芘的检出率分别为86.84%、63.16%、81.58%、21.05%、81.58%和26.32%;二苯并[a,e]芘和二苯并[a,h]芘未检出;PAH总量为92.56～905.16?μg/kg,其中苯并[a]芘含量为1.94～7.40?μg/kg,依据食品安全标准限量,PAH处于较安全水平。     

Polycyclic aromatic hydrocarbons in food samples collected in Barcelona, Spain

This study reports on the concentrations of eight polycyclic aromatic hydrocarbons (PAHs) in food samples collected in the city of Barcelona (Catalonia, Spain) from 2003 to 2004. Food samples included meat products, fish (fresh and smoked), other seafood (cephalopods, crustaceans, and bivalves), vegetable oil, and tea. Concentrations of benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, benzo[alpha]pyrene, benzo[e]pyrene, dibenz[a,h]anthracene, and indeno[1,2,3-c,d]pyrene were determined by reversed-phase high-performance liquid chromatography with fluorescence detection. PAHs were detected in most tea samples (94%), which had the highest concentration of total PAHs (mean concentration of 59 microg/kg). Other food groups with a high presence of PAHs were bivalves (present in 34% of the samples; mean value of 2.7 microg/kg) and meat products (present in 13% of the samples; mean value of 1.7 microg/kg). The PAHs detected most frequently were benzo[e]pyrene and benzo[b]fluoranthene. No sample had levels above current regulation standards. Nevertheless, the frequent presence of PAHs in bivalves, tea samples, and meat products, together with the fact that dietary sources are the main exposure to these carcinogenic compounds, suggests the need for some monitoring scheme to follow up on these trends.     

Nationwide survey of salmonella prevalence in environmental dust from layer farms in Japan

A nationwide survey was conducted to determine Salmonella prevalence in airborne dust from layer farms. Of the 4,090 layer farms in Japan, 203 were surveyed and 48 (23.6%) of these were positive for Salmonella. Salmonella isolation rates were higher in the eastern (24.3%), central (25.6%), western (23.9%), and southern (27.5%) prefectures than they were in the northern (13.3%) prefecture. We recovered 380 Salmonella isolates and identified 34 different Salmonella serovars. Salmonella Infantis was the most prevalent serovar (42 [11.1%] of 380), followed by Salmonella Agona (39 [10.3%] of 380), Salmonella Mbandaka (37 [9.7%] of 380), Salmonella Cerro (32 [8.4%] of 380), Salmonella Thompson (29 [7.6%] of 380), and Salmonella Braenderup (27 [7.1%] of 380). Of the 380 isolates, 273 (71.8%) were resistant to more than one antibiotic. Salmonella Infantis (41 [97.6%] of 42), Salmonella Agona (38 [97.4%] of 39), and Salmonella Mbandaka (34 [91.9%] of 37) showed the highest resistance rates. We found 18 different resistance patterns and the most common (179 [47.1%] of 273) was resistant to dihydrostreptomycin. One of the 13 Salmonella Hadar isolates was resistant to eight antibiotics. To investigate characteristics of Salmonella Agona, Salmonella Infantis, and Salmonella Mbandaka isolates across different prefectures, we performed pulsed-field gel electrophoresis by using XbaI and BlnI. The Salmonella Agona and Salmonella Mbandaka dendrograms were grouped into seven clusters, with 80 and 70% similarity, respectively. Because the Salmonella Infantis dendrogram showed low similarity, there is a possibility of genetic diffusion of this serovar across Japan. This report is the first to describe Salmonella contamination in airborne dust from layer farms in Japan. Our findings should be useful for future Salmonella infection monitoring and control.     

PTV-GC/MS-SIM法检测卷烟烟气中的B[a]P

采用程序升温汽化(programmed temperature vaporization,PTV)大体积进样与气相色谱-质谱选择离子扫描模式(GC/MS-SIM)联用,检测了卷烟主流烟气中苯并[a]芘(benzo[a]pyrene B[a]P),优化了PTV-GC/MS-SIM检测卷烟烟气B[a]P的参数。样品经反相C18固相萃取柱(solid-phase extraction,SPE)纯化后的洗脱液不再需要浓缩,直接应用PTV技术进样,提高了洗脱液的利用率,缩短了分析时间,提高了GC/MS-SIM检测卷烟烟气B[a]P的灵敏度。