Perfluorooctanoic Acid and Perfluorooctane Sulfonate in Human Milk: First Survey from Lebanon.

Human milk is the primary source of nutrition for infants in their first year of life. Its potential contamination with perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), a group of toxic man-made chemicals, is a health concern that may threatens infants' health. Our study aims to assess the levels of PFOA and PFOS in the breast milk of Lebanese lactating mothers and the maternal factors associated with their presence. High-performance liquid chromatography (HPLC) coupled with a Micromass Quattro micro API triple quadrupole mass spectrometer was used to detect the level of contamination in 57 collected human milk samples. PFOA and PFOS were present in 82.5% and 85.7% of the samples, respectively, while PFOA levels ranged between 120 and 247 pg/mL with a median of 147 pg/mL, and those of PFOS ranged between 12 and 86 pg/mL with a median of 27.5 pg/mL. The median contamination for PFOA exceeded the threshold set by the European Food Safety Authority (EFSA) (60 pg/mL); however, that of PFOS was below the threshold (73 pg/mL). The consumption of bread, pasta, meat, and chicken more than twice per week and that of white tubers and roots at least once per week was significantly associated with higher levels of PFOA (p < 0.05). No significant association was found between maternal age, BMI, parity, level of education, place of residence, source of water used, and smoking with the levels of PFOA and PFOS in the human milk. Additionally, the consumption of cereals at least twice per week was significantly associated with higher levels of PFOS. These findings call for actions to improve the local environmental and agricultural practices, and the regulations and standards for inspecting imported food. It is important to highlight that the benefits of breastfeeding outweigh the reported contamination with PFOS and PFOA in our study.

Persistent Organic Pollutants in Human Milk: Exposure Levels and Determinants among Lactating Mothers in Lebanon.

ABSTRACT: Exposure of newborns to persistent organic pollutants (POPs) is a public health concern. The objective of this study was to assess the prevalence of POPs in human milk collected from lactating mothers in Lebanon and to investigate the sociodemographic, nutritional, and other lifestyle determinants. Fifty-four breast milk samples were collected as per World Health Organization guidelines. A survey was used to assess the anthropometric and demographic characteristics of participants. Dietary habits were evaluated based on a semiquantitative food frequency questionnaire. Organochlorine pesticides and polychlorinated biphenyls were measured in milk samples with liquid-liquid extraction and gas chromatography. Among the screened POPs, dichlorodiphenyldichloroethylene (DDE) was the only POP detected in breast milk samples and was found in only 17.9% of the samples, with a mean (SD) of 11.6 (5.0) µg/L and a range of 5.7 to 21.4 µg/L. Prepregnancy body mass index and age were positively associated with DDE contamination in breast milk. Women who consumed cereals at least two times per week had detectable DDE contamination in their breast milk. Consumption of potatoes and beans at least once per week was also associated with DDE contamination. Our study is the first to assess the presence of POPs in breast milk in Lebanon. The benefits of breastfeeding compensate for the low prevalence of DDE in the breast milk. Our findings highlight the high need to implement monitoring policies, good agricultural practices, and education programs for breastfeeding mothers.

Selective and sensitive turn on fluorescence cyanide recognition in aqueous medium based on Zn(II)-hydrazone metal complex chemosensor.

Detection and quantification of the cyanide ion (CN- ) has attracted considerable attention because of its extreme toxicity. A novel Zn(II)-complex, applicable as a fluorescent chemosensor for CN- recognition, was synthesized in excellent yields from the reaction of zinc sulfate with the novel hydrazone: 3-(amino-9H-purin-yl)-N'-(hydroxybenzylidene) propanehydrazide. The structures of the hydrazone (L) and the zinc-hydrazone complex (L.Zn) were characterized by ultraviolet-visible spectrophotometry, Fourier-transform infrared spectrometry, mass spectrometry, proton- and carbon-13-nuclear magnetic resonance. The sensing performance of the proposed chemosensors, L and L.Zn, towards common ions was investigated via naked-eye studies as well as absorption and emission spectral analysis. Hydrazone (L) efficiently functioned as a fluorescence sensor for aluminum ions (Al3+ ) and zinc ions (Zn2+ ) with large binding constants, and exhibited colorimetric and fluorometric responses for several basic anions: OH- , CO3 2- , HCO3 - , HSO3 - , CH3 COO- and CN- . However, L.Zn showed quick, sensitive and specific enhancement of fluorescence intensity towards CN- anion, and a linear relationship was observed as the concentration of CN- varied from 1 to 14 µM. The detection limit was determined to be 0.14 µM, which is lower than the 1.9 µM maximum value recommended by the World Health Organization for drinking water. The practical performance of the sensor was successfully demonstrated using various environmental water samples spiked with cyanide ion.

An assessment of the occurrence and nutritional factors associated with aflatoxin M1, ochratoxin A, and zearalenone in the breast milk of nursing mothers in Hamadan, Iran.

This research investigated the occurrence of aflatoxin M1 (AFM1), ochratoxin A (OTA), and zearalenone (ZEN) in human milk samples in the Hamadan city, Iran. The study was carried out using the milk of nursing mothers from ten governmental health care centers. Mycotoxin content of ninety milk samples measured using enzyme-linked immunosorbent assay (ELISA). All samples that tested positive for AFM1 with the ELISA test were subsequently analyzed by high-performance liquid chromatography (HPLC). The mean ± SD concentrations of AFM1, determined by ELISA and HPLC were 5.98 ± 1.47 and 4.36 ± 1.23 ng/L, respectively. OTA and ZEN levels were below the detection limit (<5 ng/L) in all samples. None of the contaminated samples exceeded the regulation limit set by the European Commission (25 ng/L) for AFM1 in infant formula. We found a significant correlation between the AFM1 concentration in breast milk and infant age and milk consumption by the nursing mother (p < 0.05). These findings revealed that infants are susceptible to AFM1 exposure from their mother's milk. The authors recommend that additional research be conducted on the analysis of foodstuff and biological fluids for various mycotoxins.

Determination of Aluminum, Chromium, and Barium Concentrations in Infant Formula Marketed in Lebanon.

ABSTRACT: Infant formula is a major nutritional component for many infants and toddlers. However, the presence of contaminants, such as toxic metals, may pose increased health risks to infants. An investigation of the total concentrations of the metals aluminum (Al), barium (Ba), and chromium (Cr) in infant formulae marketed in Lebanon was performed. Powdered dairy and nondairy infant formula samples were collected from all commercially available brands (n = 39) in the Lebanese market on two production dates (78 samples in total) and analyzed for these three metals with inductively coupled plasma mass spectrometry. All brands contained detectable concentrations of Al and Ba, Cr was detected in 95% of brands. Mean (±standard deviation) concentrations of the metals were estimated as 1.54 ± 1.43 (Al), 0.256 ± 0.593 (Ba), and 0.168 ± 0.143 (Cr) (µg/g). The concentration ranges in the powdered formula were 0.080 to 7.93 (Al), 0.038 to 5.35 (Ba), and 0.041 to 0.348 (Cr) µg/g. A significant difference in the mean concentrations of Al, Ba, and Cr for the two production dates of a single brand was observed in 92, 59, and 83% of samples, respectively. The mean concentration of Al in the soy-based formula was significantly higher than that of aluminum in milk-based and corn-based formulas (P = 0.018). Cr concentrations in the continuation special formulations were significantly higher than those in the beginner formulations (P = 0.008). Our study provides the first publicly available information on metal contamination in infant formulas in Lebanon and reveals the need for frequent monitoring and surveillance of these products intended for infant consumption.

GC-MS analysis of polycyclic aromatic hydrocarbons in bottled olive oil marketed in Lebanon.

Lebanon has witnessed elevated levels of pollution over the last few years due to increased waste incineration, emissions from vehicles and electricity generators, and mass demonstrations involving the burning of tires. The resultant generation of polycyclic aromatic hydrocarbons (PAHs) from the incomplete combustion of organic materials present in these sources may contaminate various foods including olive oil. Lebanon has a sizeable olive oil industry that is a main pillar of its agricultural sector. In this study, we investigated the occurrence of 16 semi-volatile lipophilic organic pollutants in 25 bottled olive oil brands, marketed in Lebanon, using a solid phase extraction (SPE) method followed by gas chromatography mass spectrometry (GC-MS). PAHs were detected in 60% of brands (41% of samples) where 12% of brands contained traces of probably carcinogenic (Class 2A) compounds and 56% of brands contained traces of possibly carcinogenic (Class 2B) compounds. One brand revealed levels of benzo[a]pyrene of 9.45 µg/kg and 11.9 µg/kg in batches collected over two production dates which are higher than the limit set by the European Commission for benzo[a]pyrene in food (2 µg/kg). The same batches contained a total of 19.3 µg/kg and 26.7 µg/kg of the four PAHs: benzo[a]pyrene, benz[a]anthracene, benzo[b]fluoranthene, and chrysene which also exceeded the limit set by the EC for the combination of these four PAHs in olive oil (10 µg/kg). This study is the first-of-its-kind in Lebanon and emphasizes the need to perform adequate cleanup steps in the manufacturing process in order to reduce the content of carcinogenic PAHs in olive oil.

Determination of Ochratoxin A (OTA), Ochratoxin B (OTB), T-2, and HT-2 Toxins in Wheat Grains, Wheat Flour, and Bread in Lebanon by LC-MS/MS.

Cereals are prone to fungal infection during growth, harvesting, transportation, and/or storage. As a result, cereals such as wheat grains and wheat-derived products may be contaminated with mycotoxins leading to acute and chronic health exposure. The current study investigated the presence of the mycotoxins: ochratoxin A (OTA), ochratoxin B (OTB), T-2, and HT-2 toxins in samples of wheat grains (n = 50), wheat flour (n = 50), and bread (n = 37) from the main mills in Lebanon using LC-MS/MS. Accuracy ranged from 98-100%, recoveries from 93-105%, and intraday and interday precision were 5-7% and 9-12%, respectively. The tested wheat grains, wheat flour, and bread samples did not contain detectable levels of T-2 and HT-2 toxins and OTB. Four wheat flour samples (8% of flour samples) showed positive OTA levels ranging from 0.6-3.4 µg·kg-1 with an arithmetic mean of 1.9 ± 0.2 µg·kg-1. Only one sample contained an OTA concentration greater than the limit set by the European Union (3 µg·kg-1) for wheat-derived products. This study suggests that mycotoxin contamination of wheat grains, wheat flour, and bread in Lebanon is currently not a serious public health concern. However, surveillance strategies and monitoring programs must be routinely implemented to ensure minimal mycotoxin contamination of wheat-based products.

Spectroscopic Evaluation of Novel Adenine/Thymine-Conjugated Naphthalenediimides: Preference of Adenine-Adenine over Thymine-Thymine Intermolecular Hydrogen Bonding in Adenine- and Thymine-Functionalized Naphthalenediimides.

The synthesis and spectroscopic characterization of novel nucleobase (adenine/thymine)-conjugated naphthalenediimides (NDIs), namely, NDI-AA, NDI-TT, and NDI-AT have been successfully achieved. NDI-AA, NDI-TT and NDI-AT have similar absorption in the 300-400 nm region. The effect of solvent on the absorption spectrum indicates aggregation, either through intermolecular π-σ interaction among the main chromophore or through intermolecular hydrogen bonding between adenine and adenine group. Addition of water does not assist hydrogen bond formation between thymine-thymine, rather increasing the polarity of the solvent encourages π-σ interaction among NDI-TTs. No spectral change for NDI-TT with increasing temperature confirms hydrogen bonding is not playing a crucial role in NDI-TT. A fluorescence study on NDI-AA also establishes excimer formation along with ground state aggregation. As the water content in the solvent mixture increases, aggregation of NDI-AA is discouraged due to adenine-adenine hydrogen bonding in accordance with earlier results. At the same time, the NDI-TT emission spectrum does not shift to the blue region and the intensity of the peak around 535 nm increases at the expense of fluorescence in 411 nm. Thus, increasing water content in the solvent mixture facilitates aggregation through π-σ interaction in NDI-TT as thymine-thymine hydrogen bonding is less pronounced.

Analysis of aluminum, minerals and trace elements in the milk samples from lactating mothers in Hamadan, Iran.

The present cross-sectional study is aimed at analyzing the breast milk of lactating mothers in Hamadan, Iran for aluminum and several minerals and trace elements. Ten governmental health care centers were utilized to facilitate collection of breast milk samples. The breast milk samples were collected at 1, 2, 6, 7, and 12 months postpartum from one hundred healthy lactating women, who delivered full-term newborns. Detection of sodium (Na), zinc (Zn), calcium (Ca), iron (Fe), copper (Cu), magnesium (Mg) and aluminum (Al) levels was conducted with the use of Inductively Coupled Plasma Mass Spectrometry (ICP-MS). This method has shown high accuracy, precision, sensitivity, and linearity for the wide range of concentrations. The accumulated data were not normally distributed; thus, the non-parametric Mann-Whitney U test was used in the statistical analysis of the results. Mean concentrations of Fe, Zn, Cu, Ca, Mg, and Na were 0.75, 1.38, 0.35, 255, 34.58, and 155.72 µg/mL, respectively. The mean level of Al, a well-known neurotoxic metal, was determined to be an alarming 0.191 µg/mL. Moreover, 95% of participants contained very harmful concentrations of Al in their milk. This study also revealed Zn deficiency in about 50% of milk samples. Further investigation is needed to elucidate sources of exposure and factors that may influence maternal and fetal exposure to aluminum.

Synthesis and polymerization of 1-(2-diallylaminoethyl)pyrimidines.

We report the preparation and characterization of three pyrimidine-based monomers, specifically: 1-(2-diallylaminoethyl)uracil, 1-(2-diallylaminoethyl)thymine and 1-(2-diallylaminoethyl)cytosine. Monomer synthesis was initiated by reaction of the pyrimidine with ethylene carbonate to form the hydroxyethyl adduct which was subsequently chlorinated to afford the chloroethyl intermediate. Reaction of the chloroethyl derivatives with diallylamine resulted in the desired monomers. We demonstrated a two-fold increase in the overall yield of the three monomers in comparison to reported procedures. The cyclopolymerization and cyclo-copolymerization of 1-(2-diallylaminoethyl)pyrimidine trifluoroacetate salts in water resulted in low-yield homopolymers. In contrast, the neutral 1-(2-diallylaminoethyl)pyrimidines cyclo-copolymerized with sulfur dioxide and V-50 initiator to yield the corresponding copolymers in higher yields ranging from 30 to 60%.

Lead, cadmium and arsenic in human milk and their socio-demographic and lifestyle determinants in Lebanon.

INTRODUCTION: Exposure of newborns to toxic metals is of special interest due to their reported contamination in breast milk and potential harm. The aim of this study was to assess the occurrence and factors associated with lead, cadmium and arsenic contamination in breast milk collected from lactating mothers in Lebanon. METHODS: A total of 74 breast milk samples were collected from primaparas according to guidelines set by the World Health Organization. A survey was administered to determine the demographic and anthropometric characteristics of participating lactating mothers. Dietary habits were assessed using a semi-quantitative food frequency questionnaire. The milk samples were analyzed for the presence of arsenic, cadmium and lead using microwave-assisted digestion and atomic absorption spectrophotometry. RESULTS: Arsenic contamination was found in 63.51% of breast milk samples (mean 2.36 ± 1.95 µg/L) whereas cadmium and lead were detected in 40.54% and 67.61% of samples respectively (means 0.87 ± 1.18 µg/L and 18.18 ± 13.31 µg/L). Regression analysis indicated that arsenic contamination was associated with cereal and fish intake (p = 0.013 and p = 0.042 respectively). Residence near cultivation activities (p = 0.008), smoking status before pregnancy (p = 0.046), potato consumption (p = 0.046) and education level (p = 0.041) were associated with lead contamination. Cadmium contamination was significantly associated with random smoke exposure (p = 0.002). CONCLUSION: Our study is the first in Lebanon to report toxic metal contamination in breast milk. Although estimated weekly infant intake of these metals from breast milk was found to be lower than the limit set by international guidelines, our results highlight the need for developing strategies to protect infants from exposure to these hazardous substances.

Analysis of Aflatoxin M1 in Breast Milk and Its Association with Nutritional and Socioeconomic Status of Lactating Mothers in Lebanon.

Aflatoxin B1 (AFB1) is the most potent of the dietary aflatoxins, and its major metabolite, aflatoxin M1 (AFM1), is frequently found in the breast milk of lactating mothers. The aim of this study was to assess the occurrence and factors associated with AFM1 contamination of breast milk collected from lactating mothers in Lebanon. A total of 111 breast milk samples were collected according to the guidelines set by the World Health Organization. Samples were analyzed with a competitive enzyme-linked immunosorbent assay between December 2015 and November 2016. A survey was used to determine the demographic and anthropometric characteristics of participating lactating mothers. Dietary habits were assessed using a semiquantitative food frequency questionnaire. Mean (±standard deviation) concentration of AFM1 in the breast milk samples was 4.31 ± 1.8 ng/L, and 93.8% of samples contained AFM1 at 0.2 to 7.9 ng/L. The mean concentration of AFM1 was significantly lower (P < 0.05) in fall and winter (4.1 ± 1.9 ng/L) than in spring and summer (5.0 ± 1.7 ng/L). None of the samples exceeded the European Commission regulation limit (25 ng/L) for infant milk replacement formula. AFM1 contamination was significantly associated (P < 0.05) with the daily consumption of white cheeses but not with the consumption of meat or cereal products. No significant association (P > 0.05) was observed between AFM1 concentrations in breast milk and anthropometric sociodemographic factors (age and level of education) or the governorate of residence of the nursing mothers. The mean AFM1 estimated daily intake was found to be 0.69 ng/day/kg of body weight. Although the incidence of AFM1 contamination was low, our first-of-its-kind study highlights the importance of conducting investigations on mycotoxin contamination in breast milk and of developing protection strategies to tackle the exposure of infants to this potent chemical hazard.

Evaluation of gluten in gluten-free-labeled foods and assessment of exposure level to gluten among celiac patients in Lebanon.

The aim of the study was to evaluate gluten contamination in all the gluten-free (GF)-labeled food products sold in Lebanon. Over a 2-year period, a total of 173 food samples collected from 135 brand names were analyzed. Gluten contamination was detected in 33 of 173 (19%) samples, and its content ranged between 2.5 and >80 mg kg-1. In 10 of the 173 samples (6%), the quantity of gluten exceeded the upper limit of 20 mg kg-1. Out of the 10 contaminated products, eight (80%) were locally manufactured. Among these 10 products, eight (80%) were wheat-starch-based foods. Of the 40 brand names tested twice in 2014 and 2015, 15 (38%) showed significantly (p < .05) different gluten content between the 2 years. Using a food frequency questionnaire, exposure level to gluten through the contaminated products was evaluated among 15 celiac patients. Two patients reported consuming these products more than twice per week.

Regioselective formation of interlocked dicarba bridges in naturally occurring cyclic peptide toxins using olefin metathesis.

Bis-dicarba analogues of native dicystine-containing alpha-conotoxin Rg1A, an analgesic peptide isolated from cone snail venom, were constructed on resin using a regioselective metathesis-hydrogenation strategy.

Metathesis assisted synthesis of cyclic peptides.

Installation of reversible, metathesis-active tethers into linear peptide sequences can be used to promote formation of cyclic peptide amides and esters.

Microwave-assisted RCM for the synthesis of carbocyclic peptides.

Microwave irradiation dramatically improves the efficiency of ring closing metathesis (RCM) reactions of resin-attached peptides and the technology is illustrated by the highly selective synthesis of dicarba analogues of alpha-conotoxin IMI.

Controlled synthesis of (S,S)-2,7-diaminosuberic acid: a method for regioselective construction of dicarba analogues of multicystine-containing peptides.

A method to facilitate regioselective formation of multiple dicarba isosteres of cystine is described. A sequence of ruthenium-catalyzed cross metathesis and rhodium-catalyzed hydrogenation of nonproteinaceous allylglycine derivatives has been developed to achieve high-yielding and unambiguous formation of diaminosuberic acid derivatives. Allylglycine derivatives readily undergo ruthenium-catalyzed metathesis and hydrogenation to yield diaminosuberic acid derivatives in near quantitative yield. Under the same experimental conditions, prenylglycine was found to be inert to both Grubbs' and Wilkinson's catalyzed metathesis and hydrogenation, respectively, but was readily activated for metathesis via cross metathesis with Z-butene. Subsequent cross metathesis of the metathesis-formed crotylglycine derivative, followed by hydrogenation, yielded the second diaminosuberic acid derivative in excellent yield.

A one pot, metathesis-hydrogenation sequence for the selective formation of carbon-carbon bonds.

A combination of homogeneous hydrogenation and metathesis reactions allows highly efficient, stepwise chemo- and stereoselective formation of three separate 2,7-diaminosuberic acid derivatives in a single pot without isolation of intermediates.

Cross-metathesis of unsaturated natural oils with 2-butene. High conversion and productive catalyst turnovers.

The cross-metathesis of synthetic and natural triglycerides containing unsaturated fatty acids with 2-butene can be achieved with high conversion and excellent productive turnovers. These reactions are catalysed by second-generation ruthenium-based olefin metathesis catalysts and can be conducted at -5 degrees C in liquid 2-butene.