Functionalization of gold and silver nanoparticles with diphenyl dichalcogenides probed by surface enhanced Raman scattering

This paper describes a surface-enhanced Raman scattering (SERS) systematic investigation regarding the functionalization of gold (Au) and silver (Ag) nanoparticles with diphenyl dichalcogenides, i.e. diphenyl disulfide, diphenyl diselenide, and diphenyl ditelluride. Our results showed that, in all cases, functionalization took place with the cleavage of the chalcogenchalcogen bond on the surface of the metal. According to our density functional theory calculations, the molecules assumed a tilted orientation with respect to the metal surface for both Au and Ag, in which the angle of the phenyl ring relative to the metallic surface decreased as the mass of the chalcogen atom increased. The detected differences in the ordinary Raman and SERS spectra were assigned to the distinct stretching frequencies of the carbonchalcogen bond and its relative contribution to the ring vibrational modes. In addition, the SERS spectra showed that there was no significant interaction between the phenyl ring and the surface, in agreement with the tilted orientation observed from our density functional theory calculations. The results described herein indicate that diphenyl dichalcogenides can be successfully employed as starting materials for the functionalization of Au nanoparticles with organosulfur, organoselenium, and organotellurium compounds. On the other hand, diphenyl disulfide and diphenyl diselenide could be employed for the functionalization of Ag nanoparticles, while the partial oxidation of the organotellurium unit could be detected on the Ag surface. Copyright (C) 2011 John Wiley & Sons, Ltd.

One-pot synthesis of functionalized beta-amino sulfides/beta-amino selenides via ring opening of cyclic sulfamidates

A number of functionalized beta-amino and gamma-amino sulfides and selenides have been synthesized involving a one-pot process of ring opening of cyclic sulfamidates with `in situ' generated thiolate and selenoate species from diaryl disulfides and diphenyl diselenide using rongalite. A mild and efficient method has been developed for the synthesis of cysteines from serine.

Regioselective Bis-Selenation of Allenes Catalyzed by Palladium Complexes: A Theoretical Study

The reaction mechanism of Pd(O)-catalyzed allene bis-selenation reactions is investigated by using density functional methods. The overall reaction mechanism has been examined. It is found that with the bulkier PMe3 ligand, the rate-determining step is the reductive elimination process, while allene insertion and reductive elimination processes are competitive for the rate-determining step with the PH3 ligand, indicating the importance of the ligand effect. For both cis and trans palladium complexes, allene insertion into the Pd-Se bond of the trans palladium complex using the internal carbon atom attached to the selenyl group is prefer-red among the four pathways of allene insertion processes. The formation of sigma-allyl and pi-allyl palladium complexes is favored over that of the sigma-vinyl palladium species. By using methylallene, the regioselectivity of monosubstituted allene insertion into the Pd-Se bond is analyzed.

Ionothermal, microwave-assisted synthesis of indium(III) selenide

Microcrystalline indium(III) selenide was prepared from a diphenyl diselenide precursor and a range of chloroindate(III) ionic liquids via a microwave-assisted ionothermal route; this is the first report on the use of either microwave irradiation or ionic liquids to prepare this material. The influence of the reaction temperature, dilution with a spectator ionic liquid and variation of the cation and the anion of the ionic liquid on the product morphology and composition were investigated. This resulted in a time-efficient and facile one-pot reaction to produce microcrystalline indium(III) selenide. The product formation in the ionic liquids has been monitored using Raman spectroscopy. The products have been characterised using PXRD, SEM and EDX. Advantages of this new route, such as the ease of solubilisation of all reactants into one phase at high concentration, the negligible vapour pressure irrespective of the reaction temperature, very fast reaction times, ease of potential scale-up and reproducibility are discussed.

Zinc selenide nano- and microspheres via microwave-assisted ionothermal synthesis

Zinc selenide nanospheres were prepared from a diphenyl diselenide precursor and a range of chloro- and bromozincate(II) ionic liquids via a microwave-assisted ionothermal route; this is the first report on the use of microwave irradiation in combination with ionic liquids to prepare this material. The method is a time-efficient and a facile one-pot reaction to produce zinc(II) selenide nanomaterials. The product formation in the ionic liquids has been monitored using Raman spectroscopy. The products have been characterised using PXRD, SEM, EDX, photoluminescence and UV-VIS spectroscopy. Advantages of this new route, such as ease of solubilisation of all reactants into one phase at high concentration, the negligible vapour pressure irrespective of the reaction temperature, very fast reaction times, ease of potential scale-up and reproducibility are discussed.

Ionothermal Syntheses of Nano- and Microstructured Ternary Copper–Indium–Chalcogenides

Ternary compounds of copper indium selenide nano- and microsized materials were prepared through colloidal synthesis using an indium(III) selenide precursor and copper(I) chloride via a microwave-assisted ionothermal route. The indium(III) selenide precursor used in the reaction was formed in situ from a diphenyl diselenide precursor and chloroindate(III) ionic liquids (ILs), also via a microwave-assisted ionothermal route. The crystal structures of three intermediates, namely, CuCl2(OMe)2(H2O)){Cu(PhSeO2)2}n, [CuCl(Se2Ph2)2]n, and [C8mim]3{Cu(I)Cl2Cu(II)OCl8}n, were determined after formation through a ionothermal procedure utilizing metal-containing imidazolium ILs and a selenium precursor with conventional heating. Herein, we compare the use of microwave irradiation over conventional heating with different ILs on the stoichiometry of the resulting products. The influence of the reaction temperature, reaction time, order of addition of reagents, and variation of ILs, which were characterized using PXRD, SEM, and EDX, on the final products was investigated.

Antioxidant effect of functionalized alkyl-organotellurides: a study in vitro

We evaluated the in vitro antioxidant effect of alkyl-organotellurides A-D on lipid peroxidation and protein carbonylation in rat liver homogenates. The thiol oxidase and thiol peroxidase-like activities of compounds were investigated. delta-Aminolevulinic acid dehydratase (delta-ALA-D) activity was determined in rat liver homogenates. Compounds A-D protected against lipid peroxidation induced by Fe(2+)/EDTA and sodium nitroprusside (SNP). According to the confidence limits of the IC(50) values of compounds A-D, the IC(50) values for organotellurides followed the order: C (0.30 mu M) <= B (0.40 mu M) < D (0.68 mu M) < A (2.90 mu M), for Fe(2+)/EDTA, and B (0.21 mu M) <= C (0.33 mu M) < D (0.43 mu M) < A (1.21 mu M) for SNP-induced lipid peroxidation. Compounds A-D reduced protein carbonyl content to control levels. The results demonstrated an inverse correlation between thiol oxidase and delta-ALA-D activities. This study supports an antioxidant effect of organotellurides A-D on rat liver.

A convenient synthetic route for alkynylselenides from alkynyl bromides and diaryl diselenides employing copper(I)/imidazole as novel catalyst system

A mild, convenient, and effective strategy is developed for the synthesis of alkynyl selenides from alkynyl bromides and respective diselenides using Cul/imidazole as a novel catalyst system with Mg as additive. The Procedure affords the title compounds in moderate to good yield (51-89%). The main advantages of the protocol include the use of inexpensive copper catalyst, a novel Cu(I)/imidazole combination, and good yield of the products. (C) 2008 Elsevier Ltd. All rights reserved.

Concentrations of polybrominated diphenyl ethers (PBDEs) in matched samples of human milk, dust and indoor air

Polybrominated diphenyl ethers (PBDEs) are lipophilic, persistent pollutants found worldwide in environmental and human samples. Exposure pathways for PBDEs remain unclear but may include food, air and dust. The aim of this study was to conduct an integrated assessment of PBDE exposure and human body burden using 10 matched samples of human milk, indoor air and dust collected in 2007–2008 in Brisbane, Australia. In addition, temporal analysis was investigated comparing the results of the current study with PBDE concentrations in human milk collected in 2002–2003 from the same region. PBDEs were detected in all matrices and the median concentrations of BDEs -47 and -209 in human milk, air and dust were: 4.2 and 0.3 ng/g lipid; 25 and 7.8 pg/m3; and 56 and 291 ng/g dust, respectively. Significant correlations were observed between the concentrations of BDE-99 in air and human milk (r = 0.661, p = 0.038) and BDE-153 in dust and BDE-183 in human milk (r = 0.697, p = 0.025). These correlations do not suggest causal relationships — there is no hypothesis that can be offered to explain why BDE-153 in dust and BDE-183 in milk are correlated. The fact that so few correlations were found in the data could be a function of the small sample size, or because additional factors, such as sources of exposure not considered or measured in the study, might be important in explaining exposure to PBDEs. There was a slight decrease in PBDE concentrations from 2002–2003 to 2007–2008 but this may be due to sampling and analytical differences. Overall, average PBDE concentrations from these individual samples were similar to results from pooled human milk collected in Brisbane in 2002–2003 indicating that pooling may be an efficient, cost-effective strategy of assessing PBDE concentrations on a population basis. The results of this study were used to estimate an infant's daily PBDE intake via inhalation, dust ingestion and human milk consumption. Differences in PBDE intake of individual congeners from the different matrices were observed. Specifically, as the level of bromination increased, the contribution of PBDE intake decreased via human milk and increased via dust. As the impacts of the ban of the lower brominated (penta- and octa-BDE) products become evident, an increased use of the higher brominated deca-BDE product may result in dust making a greater contribution to infant exposure than it does currently. To better understand human body burden, further research is required into the sources and exposure pathways of PBDEs and metabolic differences influencing an individual's response to exposure. In addition, temporal trend analysis is necessary with continued monitoring of PBDEs in the human population as well as in the suggested exposure matrices of food, dust and air.

Polybrominated diphenyl ether (PBDE) concentrations decrease with age : analysis of pooled human blood serum in the Australian population

Introduction Polybrominated diphenyl ethers (PBDEs) are considered to be a cost effective and efficient way to reduce the possibility of product ignition and inhibit the spread of fire, thereby limiting harm caused by fires. PBDEs are incorporated into a wide variety of manufactured products and are now considered an ubiquitous contaminant found worldwide in biological and environmental samples . In comparison to “traditional” persistent organic pollutants (POPs), the exposure modes of PBDEs in humans are less well defined, although dietary sources, inhalation (air/particulate matter) and dust ingestion have been reported 2-4. Limited investigations of population specific factors such as age or gender and PBDE concentrations report: no conclusive correlation by age in adults ; higher concentrations in children ; similar concentrations in maternal and cord blood ; and no gender differences . After preliminary findings of higher PBDE concentrations in children than in adults in Australia11 we sought to investigate at what age the PBDE concentrations peaked in an effort to focus exposure studies. This investigation involved the collection of blood samples from young age groups and the development of a simple model to predict PBDE concentrations by age in Australia.

Higher accumulation of polybrominated diphenyl ethers in infants than in adults

Pooled serum samples collected from 8132 residents in 2002/03 and 2004/05 were analyzed to assess human polybrominated diphenyl ether (PBDE) concentrations from specified strata of the Australian population. The strata were defined by age (0−4 years, 5−15 years, < 16 years, 16−30 years, 31−45 years, 46−60 years, and >60 years); region; and gender. For both time periods, infants and older children had substantially higher PBDE concentrations than adults. For samples collected in 2004/05, the mean ± standard deviation ΣPBDE (sum of the homologue groups for the mono-, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, and deca-BDEs) concentrations for 0−4 and 5−15 years were 73 ± 7 and 29 ± 7 ng g−1 lipid, respectively, while for all adults >16 years, the mean concentration was lower at 18 ± 5 ng g−1 lipid. A similar trend was observed for the samples collected in 2002/03, with the mean ΣPBDE concentration for children <16 years being 28 ± 8 ng g−1 lipid and for the adults >16 years, 15 ± 5 ng g−1 lipid. No regional or gender specific differences were observed. Measured data were compared with a model that we developed to incorporate the primary known exposure pathways (food, air, dust, breast milk) and clearance (half-life) data. The model was used to predict PBDE concentration trends and indicated that the elevated concentrations in infants were primarily due to maternal transfer and breast milk consumption with inhalation and ingestion of dust making a comparatively lower contribution.

Serum polybrominated diphenyl ethers (PBDE) in pooled serum are higher in children (2-5 years of age) than in infants and adults

Background: Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in many products and have been detected in human samples worldwide. Limited data show that concentrations are elevated in young children. Objectives: We investigated the association between PBDEs and age with an emphasis on young children from Australia in 2006–2007. Methods: We collected human blood serum samples (n = 2,420), which we stratified by age and sex and pooled for analysis of PBDEs. Results: The sum of BDE-47, -99, -100, and -153 concentrations (Σ4PBDE) increased from 0–0.5 years (mean ± SD, 14 ± 3.4 ng/g lipid) to peak at 2.6–3 years (51 ± 36 ng/g lipid; p < 0.001) and then decreased until 31–45 years (9.9 ± 1.6 ng/g lipid). We observed no further significant decrease among ages 31–45, 45–60 (p = 0.964), or > 60 years (p = 0.894). The mean Σ4PBDE concentration in cord blood (24 ± 14 ng/g lipid) did not differ significantly from that in adult serum at ages 15–30 (p = 0.198) or 31–45 years (p = 0.140). We found no temporal trend when we compared the present results with Australian PBDE data from 2002–2005. PBDE concentrations were higher in males than in females; however, this difference reached statistical significance only for BDE-153 (p = 0.05). Conclusions: The observed peak concentration at 2.6–3 years of age is later than the period when breast-feeding is typically ceased. This suggests that in addition to the exposure via human milk, young children have higher exposure to these chemicals and/or a lower capacity to eliminate them. Key words: Australia, children, cord blood, human blood serum, PBDEs, polybrominated diphenyl ethers. Environ Health Perspect 117:1461–1465 (2009). doi:10.1289/ehp.0900596

Polybrominated diphenyl ether (PBDE) concentrations decrease with age : analysis of pooled human blood serum in the Australian population

Introduction Polybrominated diphenyl ethers (PBDEs) are considered to be a cost effective and efficient way to reduce the possibility of product ignition and inhibit the spread of fire, thereby limiting harm caused by fires. PBDEs are incorporated into a wide variety of manufactured products and are now considered an ubiquitous contaminant found worldwide in biological and environmental samples1 . In comparison to “traditional” persistent organic pollutants (POPs), the exposure modes of PBDEs in humans are less well defined, although dietary sources, inhalation (air/particulate matter) and dust ingestion have been reported 2-4. Limited investigations of population specific factors such as age or gender and PBDE concentrations report: no conclusive correlation by age in adults; higher concentrations in children ; similar concentrations in maternal and cord blood; and no gender differences. After preliminary findings of higher PBDE concentrations in children than in adults in Australia11 we sought to investigate at what age the PBDE concentrations peaked in an effort to focus exposure studies. This investigation involved the collection of blood samples from young age groups and the development of a simple model to predict PBDE concentrations by age in Australia.

Assessing exposure to polybrominated diphenyl ethers (PBDEs) for workers in the vicinity of a large recycling facility

Increased levels of polybrominated diphenyl ethers (PBDEs) can occur particularly in dust and soil surrounding facilities that recycle products containing PBDEs. This may be the source of increased exposure for nearby workers and residents. To investigate, we measured PBDE levels in soil, office dust and blood of workers at the closest workplace (i.e. within 100m) to a large automotive shredding and metal recycling facility in Brisbane, Australia. The workplace investigated in this study was independent of the automotive shredding facility and was one of approximately 50 businesses of varying types within a relatively large commercial/industrial area surrounding the recycling facility. Concentrations of PBDEs in soils were at least an order of magnitude greater than background levels in the area. Congener profiles were dominated by larger molecular weight congeners; in particular BDE-209. This reflected the profile in outdoor air samples previously collected at this site. Biomonitoring data from blood serum indicated no differential exposure for workers near the recycling facility compared to a reference group of office workers, also in Brisbane. Unlike air, indoor dust and soil sample profiles, serum samples from both worker groups were dominated by congeners BDE-47, BDE-153, BDE-99, BDE-100 and BDE-183 and was similar to the profile previously reported in the general Australian population. Estimated exposures for workers near the industrial point source suggested indoor workers had significantly higher exposure than outdoor workers due to their exposure to indoor dust rather than soil. However, no relationship was observed between blood PBDE levels and different roles and activity patterns of workers on-site. These comparisons of PBDE levels in serum provide additional insight into the inter-individual variability within Australia. Results also indicate congener patterns in the workplace environment did not match blood profiles of workers. This was attributed to the relatively high background exposures for the general Australian population via dietary intake and the home environment.