Synthesis of hollow silica spheres SBA-16 with large-pore diameter

Hollow silica SBA-16 spheres with cubic ordered mesoporous shells were synthesized by an emulsion-templating method, using Pluronic F127 as a structure-directing agent, tetraethyl orthosilicateas as a silica source and heptane as a cosolvent in the presence of NH₄F. The size of these spheres is in the range of 10 to 30 μm. The shell is about 700 nm thick and consists of large pores, ~ 9 nm in diameter, arranged in a cubic order. After calcination, the spheres maintain their mesoporosity and show a high surface area of 822 m²/g. The formation mechanism of the silica hollow spheres is discussed.     

Screening of human antibiotic substances and determination of weekly mass flows in five sewage treatment plants in Sweden

Twelve antibiotic substances for human use, including trimethoprim and representatives of the fluoroquinolone (FQ), sulfonamide (SA), penicillin (PE), cephalosporin (CE), nitroimidazole (NI), tetracycline (TC), and macrolide (MA) groups, were subjected to a screening study at five Swedish sewage treatment plants (STPs) during one week in 2002 and one week in 2003. The analytes were extracted from raw sewage water, final effluent, and sludge by solid-phase extraction (SPE) or liquid-solid extraction (as appropriate) and then identified and quantified by liquid chromatography/tandem mass spectrometry. The mostfrequently detected antibiotics in the matrices considered in this study were norfloxacin, ofloxacin, ciprofloxacin, trimethoprim, sulfamethoxazole, and doxycycline. The other analytes were only detected in a few samples. Analysis of the weekly mass flows through each STP showed that FQs were partly eliminated from the water during sewage water treatment and the highest amounts of these substances were found in sludge. Sulfamethoxazole and trimethoprim were mainly found in raw sewage water and final effluent, but these substances had balancing mass flows, indicating that they too can withstand sewage water treatment. The mass flow patterns for doxycycline were more complex, with high amounts occurring in sludge in some cases, suggesting thatthe behavior of this analyte may be more strongly influenced by the treatment process and other variables at individual STPs. The environmental load (the sum of the amounts in the final effluent and sludge) normalized to the number of inhabitants in the catchment area of each investigated STP compared with theoretical predictions based on consumption data (in parentheses) showed good correlations: norfloxacin, 0.8 (0.9); ofloxacin, 0.3 (0.2); ciprofloxacin, 1.3 (3.5); sulfamethoxazole, 0.2 (0.4); trimethoprim, 1.1 (1.0); and doxycycline, 0.7 (0.4) mg per person per week. The results show that reasonably accurate predictions of environmental load of these antibiotics can be time-effectively derived from consumption data without additional measurements.     

Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility

Twelve air samples were collected from an electronic recycling facility in Sweden representing three different dust fractions; respirable, total and inhalable dust. Four samples were collected from each fraction. The highest concentration of polybrominated diphenyl ether (PBDE) #209 (ten bromine atoms) was found in the samples from the inhalable dust fraction (ID), which was 10 times higher than for the "total dust" fraction (TD). The concentration ranges were 157.6-208.6; 13.9-16.7; and 2.8-3.3 ng/m3 for inhalable, total and respirable fractions, respectively. The second most abundant PBDE congener was PBDE #183 (seven bromine atoms), followed by the second most abundant substance 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) in all samples. In addition, decabromodiphenyl ethane (DeBDethane) was tentatively identified in five of the samples. Because of the large differences in air concentrations between the three fractions in ID, TD and RD, it is suggested that the inhalable instead of "total dust" fraction should be used to assess air concentrations, in particular for the larger and higher brominated flame retardants (BFRs).     

A robust method to determine the shear strength of cement-based injection grouts in the field

There is no standardised method to directly determine the shear strength of grouts in the field. Determining the shear strength would make it possible to calculate the penetration length of cement-based grouts and hence establish a design of the grouting procedure. By developing a new robust method that consists of a stick sinking in the grout, a direct measurement of the shear strength can be made, using the same set up as the separation test. The sink of the stick depends on the shear force interaction between the grout and the stick, and hence the shear strength of the grout can be determined. To verify the results, the shear strengths obtained with the stick are compared with measurements of the shear strength made with a rotational rheometer in the laboratory. The comparison shows good agreement; hence the stick can be used in the field to determine the yield strength of cement-based grouts.     

Terbutaline enantiomer separation and quantification by complexation and field asymmetric ion mobility spectrometry-tandem mass spectrometry

Recently, we introduced a new approach to chiral separation and analysis of amino acids by chiral complexation and electrospray high-field asymmetric waveform ion mobility spectrometry coupled to mass spectrometry (ESI-FAIMS-MS). In the present work, we extended this approach to the separation of the drug compound terbutaline. Terbutaline enantiomers were complexed with metal ions and an amino acid to form diastereomeric complexes of the type [M(II)(L-Ref)2((+)/(-)-A)-H](+), where M(II) is a divalent metal ion, L-Ref is an amino acid in its L-form, and A is the terbutaline analyte. When metal and reference compound were suitably chosen, these complexes were separable by FAIMS. We also detected and characterized larger clusters that were transmitted at distinct FAIMS compensation voltages (CV), disturbing data analysis by disintegrating after the FAIMS separation and forming complexes of the same composition [M(II)(L-Ref)2((+)/(-)-A)-H](+), thus giving rise to additional peaks in the FAIMS CV spectra. This undesired phenomenon could be largely avoided by adjusting the mass spectrometer skimmer voltages in such a way that said larger clusters remained intact. In the quantitative part of the present work, we achieved a limit of detection of 0.10% (-)-terbutaline in a sample of (+)-terbutaline. The limit of detection and analysis time per sample compared favorably to literature values for chiral terbutaline separation by HPLC and CE.     

Catalytic oxidation of CO over ordered mesoporous platinum

Hexagonal phase mesoporous (H₁Pt) was recently reported to have different catalytic properties compared to conventional platinum catalysts. To further investigate this observation the catalytic activity of H₁Pt/Al₂O₃ for CO oxidation was compared with the activity of a corresponding catalyst prepared from Pt-black (Pt-black/Al₂O₃). The H₁Pt/Al₂O₃ catalyst showed ignition at lower temperatures but extinction at higher temperatures compared to Pt-black/Al₂O₃. These observations were further supported by oxygen step-response experiments at constant temperature, where the H₁Pt/Al₂O₃ catalyst showed ignition at lower oxygen concentrations when starting from a CO poisoned surface and extinction at higher O₂ concentrations when starting from the high-reactive state. Furthermore, adsorption of CO on the catalysts was studied in situ using infrared spectroscopy in absence and presence of oxygen after pre-oxidation and pre-reduction, respectively. At 150 °C the H₁Pt/Al₂O₃ sample showed activity for CO oxidation in the presence of oxygen regardless of pretreatment, whereas Pt-black/Al₂O₃ was inactive due to CO self-poisoning. The differences observed in the low reactive state are suggested to be due to structural differences of the platinum surface in the catalysts resulting in a lower sensitivity of the H₁Pt/Al₂O₃ catalyst towards CO self-poisoning and a higher capacity to activate oxygen, and thus a higher activity for CO oxidation. During the high reactive state, the observed higher sensitivity to the concentration ratio between CO and oxygen, and to the temperature is likely due to less optimal ratio between the sticking coefficients of the reactants on the H₁Pt catalyst and to higher mass-transport limitations in its narrower pores during the initial stage of the extinction.     

Historical trends in mercury sedimentation and mixing in the Strait of Georgia, Canada

Seventeen sediment cores collected in the Strait of Georgia reveal a history of mercury contamination that began in the 1860s and include episodic contamination during World War II and in the late 1960s. Surface sediment mercury concentrations ranged from 60 to 420 ng/g dry weight and the current fluxes to sediments are estimated at 5-181 ng cm(-2) a(-1). In one location in Port Moody Arm, a Hg spill seems to have sufficiently poisoned the sediments to eliminate biomixing for about 20 years. Although the surface concentration of Hg is likely to decrease at all stations in coming years, sites in the industrialized Vancouver Harbor and Port Moody Arm will continue to be sufficiently contaminated to endanger benthic organisms. Variations in sedimentation and mixing rates among sites result in surface sediment Hg concentration patterns that do not reflect accurately the distribution of Hg flux. In particular, the concentration of Hg in sediments near the mouth of the Fraser River is low, despite the high Hg load of that river, because of dilution by other particles. A preliminary Hg budget indicates that most of the Hg enters the Strait of Georgia via the Fraser River (2090 kg a(-1)), and that, while burial in Strait of Georgia sediments is a major sink (1800 kg a(-1)), there may be a significant outflow of Hg through Juan de Fuca Strait (approximately 3400 kg a(-1)).     

Influence of genotype and protein content on the baking quality of hearth bread

The relationships between protein content and quality and the loaf characteristics of hearth breads made from the respective flours were investigated for 20 wheat genotypes, comprising both commercially grown cultivars and advanced breeding lines, grown in 1997 and 1998. In both years the average protein content was increased by increasing the level of nitrogenous fertiliser application, this effect being more pronounced in 1997 than in 1998. Grain samples were milled and evaluated for endosperm hardness, protein content, SDS sedimentation volume, mixing properties and baking quality determined by a hearth bread baking test using optimal mixing and fixed proving time. When producing hearth bread, both the form (height/width) ratio and loaf volume are critical external characteristics. Genotype differences, mainly due to differences in protein quality, were more important for both form ratio and loaf volume than differences in protein content. The dough development time of the Farinograph, operated at high speed (126 rev min^?1), was the best indicator of heart bread baking quality, giving high positive correlations to both the volume (r = 0.89) and form ratio of the loaf (r = 0.90). Climatic differences between the two years, in particular temperature during ripening, also affected the quality parameters studied. Copyright © 2004 Society of Chemical Industry     

CYP2E1 in Alcoholic and Non-Alcoholic Liver Injury. Roles of ROS,Reactive Intermediates and Lipid Overload

CYP2E1 is one of the fifty-seven cytochrome P450 genes in the human genome and is highly conserved. CYP2E1 is a unique P450 enzyme because its heme iron is constitutively in the high spin state, allowing direct reduction of, e.g., dioxygen, causing the formation of a variety of reactive oxygen species and reduction of xenobiotics to toxic products. The CYP2E1 enzyme has been the focus of scientific interest due to (i) its important endogenous function in liver homeostasis, (ii) its ability to activate procarcinogens and to convert certain drugs, e.g., paracetamol and anesthetics, to cytotoxic end products, (iii) its unique ability to effectively reduce dioxygen to radical species causing liver injury, (iv) its capability to reduce compounds, often generating radical intermediates of direct toxic or indirect immunotoxic properties and (v) its contribution to the development of alcoholic liver disease, steatosis and NASH. In this overview, we present the discovery of the enzyme and studies in humans, 3D liver systems and genetically modified mice to disclose its function and clinical relevance. Induction of the CYP2E1 enzyme either by alcohol or high-fat diet leads to increased severity of liver pathology and likelihood to develop ALD and NASH, with subsequent influence on the occurrence of hepatocellular cancer. Thus, fat-dependent induction of the enzyme might provide a link between steatosis and fibrosis in the liver. We conclude that CYP2E1 has many important physiological functions and is a key enzyme for hepatic carcinogenesis, drug toxicity and liver disease.     

Phase behavior, nucleation and optical properties of the binary system isotactic polypropylene/N,N′,N″-tris-isopentyl-1,3,5-benzene-tricarboxamide

The phase behavior of the binary system consisting of isotactic polypropylene (i-PP) and N,N′,N″-tris-isopentyl-1,3,5-benzene-tricarboxamide (1)—a selected member of a class of novel, versatile ‘designer’ nucleating/clarifying agents—was investigated over the entire additive concentration range by means of differential scanning calorimetry (DSC) and optical microscopy. Experimental phase diagrams were constructed from data obtained in melting and crystallization studies, and a simple monotectic is advanced, very similar to the previously studied binary system i-PP/1,3:2,4-bis(3,4-dimethylbenzylidene) sorbitol (DMDBS). In contrast to the latter, the crystallization temperature in the present system i-PP/1 was found to increase to ∼120 °C already at the lowest additive concentration employed and remained constant at further increasing additive concentration. Liquid-liquid phase separation was observed at elevated temperatures for i-PP/1 mixtures comprising more than ∼2 wt% of 1. A study on the optical properties of the i-PP/1 system revealed that the values for haze and clarity of injection-molded plaques progressively decreased and increased, respectively, in the concentration range up to 0.15 wt%. An intermediate region of fairly concentration-independent optical properties was found between 0.15 and 1 wt%, followed by a rapid increase in haze at concentrations exceeding 2 wt%.