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We report herein a highly efficient strategy for construction of a bridged oxa-[3.2.1]octane-embedded 5-7-6 tricyclic carbon skeleton through [3 + 2] IMCC (intramolecular [3 + 2] cross-cycloaddition), and the substituents and/or stereochemistries on C-4, C-6, C-7 and C-10 fully match those in the rhamnofolane, tigliane and daphnane diterpenoids. Furthermore, ring-opening of the bridged oxa-[3.2.1]octane via C-O bond cleavage was also successfully achieved., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Perchlorate is a low molecular weight highly soluble anion. It occurs naturally in the environment, primarily near potash deposits and in arid regions. The determination of perchlorate in human milk is of interest in vulnerable populations such as infants and pregnant women. In this study, a sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in human milk samples collected from the Maternal-Infant Research on Environmental Chemicals (MIREC) Study. The limit of detection (LOD) was 0.27 µg·kg -1 for human milk. A total of 439 human milk samples were analysed with measurable levels of perchlorate in most of the milk samples, and the mean value was 7.62 ± 32.7 µg·kg -1 . This project provided important information related to perchlorate levels in human milk collected across Canada and the extent to which pregnant women and their infants may be exposed to perchlorate. A dietary exposure assessment was also conducted in infants based on the measured values in human milk. The mean perchlorate probable daily intakes (PDIs) for infants consuming human milk were 0.31 ± 0.07 μg/kg bw/day for infants under 1 year and 0.17 ± 0.10 μg/kg bw/day for infants between 1 and 3 years old. None of the estimates exceeded the FAO/WHO provisional maximum tolerable daily intake (PMTDI) of 10 μg/kg bw/day.

Bacterial soft rot caused by Dickeya zeae MS1 (Erwinia chrysanthemi) is one of the most devastating banana diseases worldwide. However, knowledge of the development and ecological interactions of D. zeae MS1 biofilm is limited. Here, we visualized the development and architecture of D. zeae MS1 biofilm using confocal laser scanning microscopy, and we evaluated the ability of D. zeae MS1 to form biofilms under different environmental conditions (carbon sources, temperatures, pH levels and mineral elements) using a microtiter plate assay. We found that the development of D. zeae MS1 biofilm could be categorized into four phases and that mature biofilm consisted of a highly organized architecture of both bacterial cells and a self-produced matrix of extracellular polysaccharides. Furthermore, sucrose was the most suitable carbon source for supporting the growth of biofilm cells and that 32 °C and pH 7.0 were the most favorable of the temperatures and pH levels examined. Meanwhile, the addition of Ca 2+ , Fe 2+ , K + and Na + enhanced the formation of biofilm in minimal medium cultures, whereas 2.5 mM Cu 2+ and Mn 2+ was inhibitory. A better understanding of biofilm formation under different environmental parameters will improve our knowledge of the growth kinetics of D. zeae MS1 biofilm.

In order to determine the baseline levels of perchlorate in major brands of baby food, 200 baby food products were collected from retail stores in Ottawa, Canada and analysed for perchlorate in 2010. The seven food groups tested were fruit, juices, vegetables, meat, yogurt, mixed (vegetable mixed with meat) and other (e.g. vegetable mixed with meat and cereal, cheese, egg,). Samples were extracted with a mixture of methanol and 1% acetic acid (4:1, v/v). Determination was conducted by stable isotope dilution ion chromatography tandem mass spectrometry (ID-IC-MS/MS). The complexity of different food matrices required additional method validation. The perchlorate levels in 46 samples were found to be lower than the quantification limit (0.2 ng g -1 ). The perchlorate levels in the other 154 baby food samples were also low; about 96.7% of the baby foods had perchlorate levels less than 10 ng g -1 (ranged from 0.2 to 22.4 ng g -1 , median1.35 ng g -1 ); only 5 samples had perchlorate levels higher than 10 ng g -1 . Dietary exposure to perchlorate from analysed baby food was conservatively estimated to range from 0.007 to 0.121 µg/kg bw/d based on the mean intake for children (1-5 years old).

(-)-Englerin A was synthesized in 20 steps from the commercially available material ( R)-(+)-limonene. In addition, (-)-englerin B, (+)-orientalol E/F and (-)-oxyphyllol were obtained from the intermediate in the route. The key steps include a hydroxyl-directing stereoselective and regioselective intramolecular cyclopropanation and a multi-gram-scale stereoselective formal intramolecular [3 + 2] cross cycloaddition ([3 + 2]-IMCC) of a cyclopropane 1,1-diester with a carbonyl. A precursor of 7,10-diastereoisomer of englerins was also obtained.

A tandem isomerization/intramolecular [3 + 2] cross-cycloaddition (IMCC) of cyclopropane 1,1-diesters with α,β-unsaturated ketones/aldehydes under a cooperative catalysis of photo and Lewis acids has been successfully developed. This supplied a general and efficient strategy for construction of medium-sized carbocyclic (8-, 9-, and 10-membered) skeletons as well as such carbocycle-based bridged oxa-bicyclo[n.2.1] (n = 4-6) skeletons.

A novel Lewis acid catalyzed formal intramolecular [3 + 3] cross-cycloaddition (IMCC) of cyclopropane 1,1-diesters has been successfully developed. This supplies an efficient and conceptually new strategy for construction of bridged bicyclo[2.2.2]octane skeletons. This [3 + 3]IMCC could be run up to gram scale and from easily prepared starting materials. This [3 + 3]IMCC, together with our previously reported [3 + 2]IMCC strategy, can afford either the bicyclo[2.2.2]octane or bicyclo[3.2.1]octane skeletons from the similar starting materials by regulating the substituents on vinyl group.

A triflic acid-catalyzed formal [3 + 2] cycloaddition of cyclopropane 1,1-diesters with nitriles was developed. This reaction was expeditious, and the scope of the substituents in both cyclopropanes and nitriles was broad. This supplies an efficient and practical method for the synthesis of 1-pyrrolines.

Objective: To compare the effectiveness of the traditional center of tibial plateau as the entry point and digital technology in the design of intramedullary tibial nail point positioning method in total knee arthroplasty (TKA)., Methods: Between October 2011 and October 2012, 60 cases undergoing unilateral TKA and meeting the selection criteria were randomly divided into 2 groups: in group A (30 cases), the tibial plateau center as the entry point of tibial intramedullary positioning was used; in group B (30 cases), Mimics 10.01 software to simulate the guide rod point of tibial intramedullary positioning was used. There was no significant difference in gender, age, etiology, disease duration, sides, and preoperative knee range of motion, Hospital for Special Surgery (HSS) score, and Western Ontario and McMaster University Osteoarthritis Index (WOMAC) between 2 groups (P > 0.05). Postoperative X-ray films were taken to measure the tibiofemoral angle and tibial angle; knee range of motion, and HSS and WOMAC scores were used to assess the activity of knee., Results: The entry point of group B was located in front of the center of tibial plateau, which was inconsistent with the traditional entry point. The incision healed by first intention in all patients of 2 groups. The patients were followed up 6 to 12 months (mean, 8.6 months). The X-ray measurement at 1 week after operation showed no significant difference in tibiofemoral angle between 2 groups (t = -6.65, P = 0.72), but the anteroposterior and lateral tibial angles of group A were significantly lower than those of group B (P < 0.05). The knee range of motion, HSS score, and WOMAC score of 2 groups were significantly higher at 3 and 6 months after operation when compared with preoperative values (P < 0.05), and the values at 6 months were significantly increased than those at 3 months after operation (P < 0.05). HSS score and WOMAC score had no significant difference between 2 groups at 3 months after operation (P > 0.05), but the scores of group B were significantly higher than those of group A at 6 months (P < 0.05). The knee range of motion of group B was significantly better than that of group A at 3 months after operation (t = 2.13, P = 0.04), but no significant difference was found between 2 groups at 6 months (t = 0.58, P = 0.56)., Conclusion: Compared with the traditional intramedullary guide rod insertion point positioning, digital individualized design of entry point positioning has the advantages of more accurate lower limb force line, better recovery of knee function, and earlier 90 degrees activities, but the long-term effectiveness needs further observation.

Background: The Maternal-Infant Research on Environmental Chemicals (MIREC) Study was established to obtain Canadian biomonitoring data for pregnant women and their infants, and to examine potential adverse health effects of prenatal exposure to priority environmental chemicals on pregnancy and infant health., Methods: Women were recruited during the first trimester from 10 sites across Canada and were followed through delivery. Questionnaires were administered during pregnancy and post-delivery to collect information on demographics, occupation, life style, medical history, environmental exposures and diet. Information on the pregnancy and the infant was abstracted from medical charts. Maternal blood, urine, hair and breast milk, as well as cord blood and infant meconium, were collected and analysed for an extensive list of environmental biomarkers and nutrients. Additional biospecimens were stored in the study's Biobank. The MIREC Research Platform encompasses the main cohort study, the Biobank and follow-up studies., Results: Of the 8716 women approached at early prenatal clinics, 5108 were eligible and 2001 agreed to participate (39%). MIREC participants tended to smoke less (5.9% vs. 10.5%), be older (mean 32.2 vs. 29.4 years) and have a higher education (62.3% vs. 35.1% with a university degree) than women giving birth in Canada., Conclusions: The MIREC Study, while smaller in number of participants than several of the international cohort studies, has one of the most comprehensive datasets on prenatal exposure to multiple environmental chemicals. The biomonitoring data and biological specimen bank will make this research platform a significant resource for examining potential adverse health effects of prenatal exposure to environmental chemicals., (© 2013 John Wiley & Sons Ltd and Her Majesty the Queen in Right of Canada. Reproduced with the permission of the Minister of Health.)

A highly efficient and convenient method for the synthesis of 1,2,4,5-tetrasubstituted imidazoles from readily accessible 2-azido acrylates and nitrones has been developed. This reaction proceeded under mild conditions without the assistance of any metal, acid, or base.

Catalyzed by N-heterocyclic carbenes (NHCs), domino ring-opening/redox amidation/cyclization reactions of the readily available formylcyclopropane 1,1-diesters with 2-chloro-1H-indole-3-carboaldehydes were reported. This methodology provides an efficient and direct construction of a 6-5-6 tricyclic hydropyrido[1,2-a]indole skeleton, which can be potentially applied for the synthesis of several types of polycyclic indole alkaloids.

The first Friedel-Crafts reaction initiated by the direct generation of a carbocation at the C3 position of MCP 1,1-diesters through distal-bond cleavage was presented. The described method supplied a new synthetic strategy to prepare indene and hydronaphthalene derivatives in moderate to excellent yields under mild conditions.

Children's exposure to arsenic and chromium from playground equipment constructed with chromated copper arsenate (CCA)-treated wood is a potential concern because of children's hand-to-mouth activity. However, there exists no direct measure of Cr levels on the hands of children after playing in such playgrounds. In this study we measured both soluble and total Cr on the hands of 139 children playing in playgrounds, eight of which were constructed with CCA-treated wood and eight of which were not. Children's age and duration of play were recorded. The hands of each child were washed after play with 150 mL deionized water, which was collected in a bag and subsequently underwent analysis of Cr and 20 other elements, using inductively coupled plasma mass spectrometry. Total average Cr on the hands of 63 children who played in CCA playgrounds was 1,112 +/- 1,089 ng (median, 688; range 78-5,875). Total average Cr on the hands of 64 children who played in non-CCA playgrounds was 652 +/- 586 ng (median, 492; range 61-3,377). The difference between the two groups is statistically significant (p < 0.01). Cr levels were highly correlated to both Cu (r = 0.672) and As (r = 0.736) levels in CCA playgrounds (p < or = 0.01), but not non-CCA playgrounds (r = 0.252 and 0.486 for Cu and As, respectively). Principal-component analysis indicates that Cr, Cu, and As are more closely grouped together in CCA than in non-CCA playgrounds. These results suggest that the elevated levels of Cr and As on children's hands are due to direct contact with CCA wood.

Increasing concerns over the use of wood treated with chromated copper arsenate (CCA) in playground structures arise from potential exposure to arsenic of children playing in these playgrounds. Limited data from previous studies analyzing arsenic levels in sand samples collected from CCA playgrounds are inconsistent and cannot be directly translated to the amount of children's exposure to arsenic. The objective of this study was to determine the quantitative amounts of arsenic on the hands of children in contact with CCA-treated wood structures or sand in playgrounds. We compared arsenic levels on the hands of 66 children playing in eight CCA playgrounds with levels of arsenic found on the hands of 64 children playing in another eight playgrounds not constructed with CCA-treated wood. The children's age and duration of playtime were recorded at each playground. After play, children's hands were washed in a bag containing 150 mL of deionized water. Arsenic levels in the hand-washing water were quantified by inductively coupled plasma mass spectrometry. Our results show that the ages of the children sampled and the duration of play in the playgrounds were similar between the groups of CCA and non-CCA playgrounds. The mean amount of water-soluble arsenic on children's hands from CCA playgrounds was 0.50 microg (range, 0.0078-3.5 microg). This was significantly higher (p < 0.001) than the mean amount of water-soluble arsenic on children's hands from non-CCA playgrounds, which was 0.095 microg (range, 0.011-0.41 microg). There was no significant difference in the amount of sand on the children's hands and the concentration of arsenic in the sand between the CCA and non-CCA groups. The higher values of arsenic on the hands of children playing in the CCA playgrounds are probably due to direct contact with CCA-treated wood. Washing hands after play would reduce the levels of potential exposure because most of the arsenic on children's hands was washed off with water. The maximum amount of arsenic on children's hands from the entire group of study participants was < 4 microg, which is lower than the average daily intake of arsenic from water and food.

Arsenic has been used successfully in clinical trials for treating acute promyelocytic leukemia (APL). Although sublethal doses of inorganic arsenic are used, little is known about the pharmacokinetics and metabolism of the high levels of arsenic in APL patients. To fill this important gap, this study describes the speciation of arsenic in urine from four APL patients treated with arsenic. Each patient was injected daily with an arsenite (As(III)) solution that contained 10 mg of As(2)O(3) precursor. Speciation analysis of the patient urine samples collected consecutively for 48 h, encompassing two intravenous injections of arsenic, revealed the presence of monomethylarsonous acid (MMA(III)), dimethylarsinous acid (DMA(III)), monomethylarsonic acid (MMA(V)), and dimethylarsinic acid (DMA(V)). The intermediate methyl arsenic metabolites, MMA(III) and DMA(III), were detected in most urine samples from all of the patients when a preservative, diethyldithiocarbomate, was added to the urine samples to stabilize these trivalent arsenic species. The major arsenic species detected in the urine samples from the patients were As(III), MMA(V), and DMA(V), accounting for >95% of the total arsenic excreted. The relative proportions of As(III), As(V), MMA(V), and DMA(V) in urine samples collected 24 h after the injections of As(III) were 27.6 +/- 6.1, 2.8 +/- 2.0, 22.8 +/- 8.1, and 43.7 +/- 13.3%, respectively. The relatively lower fraction of the methylated arsenic species in these APL patients under arsenic treatment as compared with that from the general population exposed to much lower levels of arsenic suggests that the high levels of As(III) inhibit the methylation of arsenic (inhibits the formation of methyl arsenic metabolites). The arsenic species excreted into the urine accounted for 32-65% of the total arsenic injected. These results suggest that other pathways of excretion, such as through the bile, may play an important role in eliminating (removing) arsenic from the human body when challenged by high levels of As(III).

We report a convenient and simple solution-phase electron-transfer reaction of C(60) with zinc and alpha-bromoacetonitrile, alpha-bromo acetate esters, allyl bromide, benzyl bromide and alpha-bromo ketones in DMF, with which different types of monoalkylated C(60) derivatives can be prepared. When this method is employed with C(70), 2-carbomethoxymethyl-1,2-dihydro[70]fullerene (isomer 5a) is produced as one of the two 1,2-monoalkylated C(70) isomers, together with the first 5,6-monoalkylated C(70) derivative.

A labile rhizosphere soil solution fraction has been recommended to predict the bioavailability of heavy metals and rare earth elements to plants. This method used moist rhizosphere soil in combination with a mixture of 0.01 mol L(-1) of low-molecular-weight organic acids (LMWOAs) as extractant. The extracted soil solutions were fractionated into two colloidal fractions of <0.45 microm (F(3)) and <0.2 microm (F(2)), and one truly dissolved fraction including free metal ions and inorganic and organic complexes (fractionr(0.2 microm, LMWOAs) approximately r(0.45 microm, LMWOAs). In the case of rare earth elements the good correlation was obtained for both the wheat roots and shoots. Generally, the correlation coefficients obtained by LMWAOs were better than that obtained by the first step of BCR method. Therefore, LMWAOs and F(lrss) were strongly recommended to predict the bioavailability of metals in soil pools to plants.

The fulleride dianions C(60)(2-) and C(70)(2-) were generated by deprotonation of the corresponding hydrogenated fullerenes, 1,2-C(60)H(2) and 1,2-C(70)H(2). These anions were prepared in the presence of a variety of alkylating agents, and mono- or dialkylated products were obtained. Alkylation was not successful with sulfonate ester alkylating agents. Deprotonation of monoalkylated compounds, followed by second alkylation with a different alkylating agent, produced heterodialkylated compounds. The monoalkyated material was invariably the 1,2-isomers, while the dialkylated materials were generally 1,4-isomers, although some 1,2-isomer was observed in the C(70) context. The major product from alkylation of C(70)(2-) was the 7,23-isomer 13a, a structure where the alkylation took place near the equator of the fullerene cage, rather than at the more strained carbons near the poles.