Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthe...Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.展开更多
This study was to develop the flame retardant (FR) protective clothing which had multifunction such anti-bacterial, UV cut, FR function with water repellent and water vapor permeable laminating textiles for industrial...This study was to develop the flame retardant (FR) protective clothing which had multifunction such anti-bacterial, UV cut, FR function with water repellent and water vapor permeable laminating textiles for industrial workers. First of all, the FR yarn and FR textiles were developed for this purpose. Second, the comparison analysis between the halogen laminating textiles and halogen-free laminating textiles were tested to figure out the eco-friendly laminating method. Third, the flame retardant ability was compared the halogen laminated textiles to halogen-free laminated textiles. LOI, UV protection ratio, antibiosis after 50 laundry test, water proof pressure, and moisture permeability of developed textiles were tested. GC-HR-TOF-MS was used for analysis of laminating film (halogen and halogen-free). 4.1 wt% TiO2 yarn showed antibacterial function (Pneumococcus & Staphylococcus aureus: 99.9%), UV Protection (UVA: 90.8, UVB: 92.1), and LOI (33.6). The chosen optimal compounding ratio for PU compound of HRF and HFFR were as followed: PU resin 58.3%, DMF (Dimethyl formamide, δ = 12.2) 8.3%, MEK (Methylethylketone) 8.3% and FR (flame retardants) 25.0%. Binder for laminating should not be included over 10% of FRs because of adhesion between textiles and FR laminating film. There were detected phosphorus compounds in the textiles treated by halogenated type flame retardants and halogenated-free type flame retardants. There were not any detected harmful compounds from all textile samples.展开更多
This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts(DBPs) upon chlorination of natural organic matter(NOM) in the presence of iopamidol and bromide(Br^-).Experi...This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts(DBPs) upon chlorination of natural organic matter(NOM) in the presence of iopamidol and bromide(Br^-).Experiments were conducted with low bromide source waters with different NOM characteristics from Northeast Ohio,USA and varied spiked levels of bromide(2-30 μmol/L) and iopamidol(1-5 μmol/L).Iopamidol was found to be a direct precursor to trihalomethane(THM) and haloacetic acid formation,and in the presence of Br^-favored brominated analogs.The concentration and speciation of DBPs formed were impacted by iopamidol and bromide concentrations,as well as the presence of NOM.As iopamidol increased the concentration of iodinated DBPs(iodo-DBPs) and THMs increased.However,as Br^-concentrations increased,the concentrations of nonbrominated iodo-and chloro-DBPs decreased while brominated-DBPs increased.Regardless of the concentration of either iopamidol or bromide,bromochloroiodomethane(CHBrClI) was the most predominant iodo-DBP formed except at the lowest bromide concentration studied.At relevant concentrations of iopamidol(1 μmol/L) and bromide(2 μmol/L),significant quantities of highly toxic iodinated and brominated DBPs were formed.However,the rapid oxidation and incorporation of bromide appear to inhibit iodoDBP formation under conditions relevant to drinking water treatment.展开更多
Disinfection by-products（DBPs） are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown a...Disinfection by-products（DBPs） are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown and were the subject of recent epidemiological studies. However,most bioanalytical methods focus on a select few DBPs. In this study, a new comprehensive bioanalytical method has been developed that can quantify mixtures of organic halogenated compounds, including DBPs, in human urine as total organic chlorine（TOCl）, total organic bromine（TOBr）, and total organic iodine（TOI）. The optimized method consists of urine dilution, adsorption to activated carbon, pyrolysis of activated carbon, absorption of gases in an aqueous solution, and halide analysis with ion chromatography and inductively coupled plasma-mass spectrometry. Spike recoveries for TOCl, TOBr, and TOI measurements ranged between 78% and 99%. Average TOCl, TOBr, and TOI concentrations in five urine samples from volunteers who consumed tap water were 1850, 82, and 21.0 μg/L as X^-, respectively.Volunteers who consumed spring water（control） had TOCl, TOBr, and TOI average concentrations in urine of 1090, 88, and 10.3 μg/L as X^-, respectively. TOCl and TOI in the urine samples from tap water consumers were higher than the control. However, TOBr was slightly lower in tap water urine samples compared to mineral water urine samples, indicating other sources of environmental exposure other than drinking water. A larger sample population that consumes tap water from different cities and mineral water is needed to determine TOCl, TOBr, and TOI exposure from drinking water.展开更多
In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as het...In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene•g-cat–1•h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.展开更多
基金supported by the National Natural Science Foundation of China(21073053,21473049)the Natural Science Foundation of Hebei Province,China(B2016205207)
文摘Four lanthanide coordination complexes, namely, [Ln（2,3-DClBA）3（5,5’-dmebipy）（H2O）]2（Ln=Sm（1）, Eu（2）, Dy（3）, Ho（4））; 2,3-DClBA=2,3-dichlorobenzoate; 5,5’-dmebipy=5,5’-dmethylbipyridine） were synthesized and characterized by elemental analysis, infrared spectroscopy and single crystal X-ray diffraction. Findings indicated that complex 3 was a dinuclear molecule, and the center Dy3＋ was eight-coordinated. Each dinuclear units could be connected by H bond and halogen-halogen interactions. Luminescent property of complex 2 suggested the typical intense emissions of Eu3＋ ions. Thermal analysis showed that the complexes decomposed in three steps： the coordination water was lost firstly then the neutral ligand 5,5’dmebipy was lost and lastly the 2,3-DClBA ligand was lost.
文摘This study was to develop the flame retardant (FR) protective clothing which had multifunction such anti-bacterial, UV cut, FR function with water repellent and water vapor permeable laminating textiles for industrial workers. First of all, the FR yarn and FR textiles were developed for this purpose. Second, the comparison analysis between the halogen laminating textiles and halogen-free laminating textiles were tested to figure out the eco-friendly laminating method. Third, the flame retardant ability was compared the halogen laminated textiles to halogen-free laminated textiles. LOI, UV protection ratio, antibiosis after 50 laundry test, water proof pressure, and moisture permeability of developed textiles were tested. GC-HR-TOF-MS was used for analysis of laminating film (halogen and halogen-free). 4.1 wt% TiO2 yarn showed antibacterial function (Pneumococcus & Staphylococcus aureus: 99.9%), UV Protection (UVA: 90.8, UVB: 92.1), and LOI (33.6). The chosen optimal compounding ratio for PU compound of HRF and HFFR were as followed: PU resin 58.3%, DMF (Dimethyl formamide, δ = 12.2) 8.3%, MEK (Methylethylketone) 8.3% and FR (flame retardants) 25.0%. Binder for laminating should not be included over 10% of FRs because of adhesion between textiles and FR laminating film. There were detected phosphorus compounds in the textiles treated by halogenated type flame retardants and halogenated-free type flame retardants. There were not any detected harmful compounds from all textile samples.
基金supported by the German Research Foundation (Deutsche Forschungsgemeinschaft,DFG,project number TE 533/4-1)the National Science Foundation (NSF,project numbers NSF1124865 and NSF1124844).
文摘This study investigated the speciation of halogen-specific total organic halogen and disinfection byproducts(DBPs) upon chlorination of natural organic matter(NOM) in the presence of iopamidol and bromide(Br^-).Experiments were conducted with low bromide source waters with different NOM characteristics from Northeast Ohio,USA and varied spiked levels of bromide(2-30 μmol/L) and iopamidol(1-5 μmol/L).Iopamidol was found to be a direct precursor to trihalomethane(THM) and haloacetic acid formation,and in the presence of Br^-favored brominated analogs.The concentration and speciation of DBPs formed were impacted by iopamidol and bromide concentrations,as well as the presence of NOM.As iopamidol increased the concentration of iodinated DBPs(iodo-DBPs) and THMs increased.However,as Br^-concentrations increased,the concentrations of nonbrominated iodo-and chloro-DBPs decreased while brominated-DBPs increased.Regardless of the concentration of either iopamidol or bromide,bromochloroiodomethane(CHBrClI) was the most predominant iodo-DBP formed except at the lowest bromide concentration studied.At relevant concentrations of iopamidol(1 μmol/L) and bromide(2 μmol/L),significant quantities of highly toxic iodinated and brominated DBPs were formed.However,the rapid oxidation and incorporation of bromide appear to inhibit iodoDBP formation under conditions relevant to drinking water treatment.
文摘Disinfection by-products（DBPs） are a complex mixture of compounds unintentionally formed as a result of disinfection processes used to treat drinking water. Effects of long-term exposure to DBPs are mostly unknown and were the subject of recent epidemiological studies. However,most bioanalytical methods focus on a select few DBPs. In this study, a new comprehensive bioanalytical method has been developed that can quantify mixtures of organic halogenated compounds, including DBPs, in human urine as total organic chlorine（TOCl）, total organic bromine（TOBr）, and total organic iodine（TOI）. The optimized method consists of urine dilution, adsorption to activated carbon, pyrolysis of activated carbon, absorption of gases in an aqueous solution, and halide analysis with ion chromatography and inductively coupled plasma-mass spectrometry. Spike recoveries for TOCl, TOBr, and TOI measurements ranged between 78% and 99%. Average TOCl, TOBr, and TOI concentrations in five urine samples from volunteers who consumed tap water were 1850, 82, and 21.0 μg/L as X^-, respectively.Volunteers who consumed spring water（control） had TOCl, TOBr, and TOI average concentrations in urine of 1090, 88, and 10.3 μg/L as X^-, respectively. TOCl and TOI in the urine samples from tap water consumers were higher than the control. However, TOBr was slightly lower in tap water urine samples compared to mineral water urine samples, indicating other sources of environmental exposure other than drinking water. A larger sample population that consumes tap water from different cities and mineral water is needed to determine TOCl, TOBr, and TOI exposure from drinking water.
文摘In the practical use for the production of the α-olefins, it is highly desired to develop a novel heterogeneous catalyst system. The metal complexes immobilized into the clay interlayers show a great potential as heterogeneous catalysts due to their excellent processability. In this study, nine types of heterogeneous procatalyst Ln/Ni2+-micas were synthesized via a one-pot preparation method, which includes both the condensation reaction of the ligand derivatives and the intercalation of the ligands into the Ni2+ ion-exchanged fluorotetrasilicic mica interlayer. The ligand structures of the prepared procatalysts were [Ln: R-N = C(Nap)-C(Nap) = N-R] [(Nap = 1,8-naphthdiyl) (L1, R = 2-MePh;L2, R = 2-FPh;L3, R = 2-BrPh;L4, R = 4-MePh;L5, R = 4-FPh;L6, R = 4-BrPh;L7, R = 2,4-F2Ph;L8, R = 2,4-Br2Ph;L9, R = 2,6-F2Ph). At 50℃ and 0.7 MPaethylene pressure, the triisobutylaluminum-activated L1-L6/Ni2+-mica showed a catalytic activity for the ethylene oligo-/polymerization in the range of 334 - 549 g-ethylene•g-cat–1•h–1. A high catalyst activity was obtained when the substituent having a larger steric bulk than that of a methyl substituent was introduced at the ortho-position of the aryl rings. The introduction of the fluorine substituent as a strong electron-withdrawing group to the para-position also increased the catalytic activity. The L2, L4, L5, and L6/Ni2+-micas showed moderate selectivities to oligomers consisting of C4-C20 in the range of 19.9 - 41.6 wt% at 50℃. The calculated Schulz-Flory constants α based on the mole fraction of C12 and C14 were within 0.61 - 0.78.
