A small angle neutron scattering study of the adsorbed asphaltene layer in water-in-hydrocarbon emulsions: structural description related to stability

We have developed a specific protocol to study with SANS measurements, the structure of the interfacial film layer in water-in-oil emulsions stabilized by asphaltene. Using the contrast matching technique available for neutron scattering, we have access to both the composition and the quantity of interface. The results obtained give us a view of the asphaltene aggregates in the interfacial film, which are structured as a monolayer and show a direct correlation between the size of asphaltene aggregates in solution and the thickness of the film layer. The organization of the interface has been studied as a function of several parameters such as the quantity of resins, i.e., the size of aggregates, the pH of the aqueous phase, and the aging time of the emulsions and the consequences of these variations on the macroscopic stability of these emulsions. We show that the key parameter for the stability is the inter-asphaltene aggregate interaction inside the film layer. Changing the attractive/repulsive balance between the aggregates in the film at the microscopic scale, by changing the aggregate's size or the aggregate's ionization, has a direct incidence on the quantity of water recovered after centrifugation: the stronger the attraction between aggregates in the film, the more stable the emulsion is.     

Effect of interfacial interaction on the cross-sectional morphology of tobacco mosaic virus using GISAXS

We have investigated the effect of the interfacial interaction on the cross-sectional morphology of the tobacco mosaic virus (TMV) in solution and on two types of solid substrates, SiOx (polar) on Si(100) and polystyrene film (nonpolar) on Si(100), using small-angle X-ray scattering (SAXS) and grazing incidence small-angle X-ray scattering (GISAXS), respectively. Results reveal that the flexible chains at the outer surface of TMV either expand or contract depending on the nature of the substrate. Although the unfavorable interaction between the TMV and the PS causes a minimal effect, the stronger attractive interaction between the outer protein surface of TMV and the SiOx substrate induces pronounced deformation of its cross-sectional morphology.     

Luminescent biological probes derived from ruthenium(II) estradiol polypyridine complexes

Four luminescent ruthenium(II) polypyridine estradiol complexes [Ru(NwedgeN)2(bpy-estradiol)](PF6)2 (NwedgeN = 2,2'-bipyridine (bpy), 4,7-diphenyl-1,10-phenanthroline (Ph2-phen); bpy-estradiol = 5-(4-(17alpha-ethynylestradiolyl)phenyl)-2,2'-bipyridine (bpy-ph-est), 4-(N-(6-(4-(17alpha-ethynylestradiolyl)benzoylamino)hexyl)aminomethyl)-4'-methyl-2,2'-bipyridine (mbpy-C6-est)) have been designed as new luminescent biological probes. The lipophilicity and photophysical and electrochemical properties of these complexes have been investigated. Upon photoexcitation, all the complexes exhibited intense and long-lived triplet metal-to-ligand charge-transfer (3MLCT) (dpi(Ru) --> pi*(diimine)) emission in fluid solutions at 298 K and in low-temperature glass. The binding of the complexes to estrogen receptor-alpha (ERalpha) has been studied by emission titrations. The Ph2-phen complexes showed emission enhancement and increased lifetimes upon binding to the protein. Additionally, the cytotoxicity of the complexes toward the HeLa cell line has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay and the IC50 values ranged from 83.1 to 166.6 microM (cisplatin showed an IC50 value of 34.3 microM under the same experimental conditions). Furthermore, the cellular uptake of the complexes has been investigated by flow cytometry and laser-scanning confocal microscopy.     

Intramolecular [2 + 2]-photocycloaddition/thermal fragmentation approach toward 5-8-5 ring systems

[reaction: see text]. An intramolecular [2 + 2]-photocycloaddition is used to provide a photoadduct, which upon fragmentation, lactone cleavage, and subsequent Cope rearrangement provides a dicyclopenta[a,d]cyclooctene ring system with substituents in place (e.g., C3 and C11) to access several 5-8-5 diterpene and sesterterpene natural products.     

Capturing aqueous [F]-fluoride with an arylboronic ester for PET: Synthesis and aqueous stability of a fluorescent [F]-labeled aryltrifluoroborate

The aqueous stability of aryltrifluoroborates is of importance to their use in transition metal mediated coupling reactions as well as their potential use in [¹⁸F]-labeled aryltrifluoroborate PET imaging agents. Nevertheless, few studies have fully characterized the solvolysis of fluoride from an aryltrifluoroborate in water. Using [¹⁹F] NMR, fluorescence and [¹⁸F]-labeling techniques, we disclose the composition of an aryltrifluoroborate of exceptional kinetic stability with respect to solvolytic defluoridation. This work not only highlights the potential of using [¹⁸F]-labeled aryltrifluoroborates for PET tracers, but provides a chemical platform and a general approach for evaluating the stability of other aryltrifluoroborates.     

An Automatic Molecular Dispenser of Chloride

The combined activity of the 1.1.1‐cryptand and of a dicopper(II) bistren cryptate complex including chloride makes the Cl^? ion be continuously and slowly delivered to the solution, without any external intervention. The 1.1.1‐cryptand slowly releases OH^? ions, according to a defined kinetics, and each OH^? ion displaces a Cl^? ion from the cryptate. Chloride displacement induces a sharp colour change from bright yellow to aquamarine and can be conveniently monitored spectrophotometrically, even in diluted solutions. The 1.1.1‐cryptand is the motor of a molecular dispenser (the dicopper(II) cryptate) delivering chloride ion automatically, from the inside of the solution.     

Diastereo‐ and Enantioselective Synthesis of Organometallic Bis(helicene)s by a Combination of C?H Activation and Dynamic Isomerization

Homochiral and heterochiral cis‐bis‐cycloplatinated‐[6]helicene derivatives 1 b^{1, 2} , as representative examples of platina[6]helicenes that share a common platinum center, have been prepared. A diastereo‐ and enantioselective synthesis, which combines CH activation and dynamic isomerization from heterochiral structure 1 b² into homochiral structure 1 b¹ , is also described. Overall, this isomerization process results in the transfer of chiral information from one helicene moiety to the other one. The chiroptical properties of homochiral (P)‐ and (M)‐ 1 b¹ were greatly modified upon oxidation into their corresponding (P)‐ and (M)‐diiodo‐Pt^IV complexes ( 5 ). The changes were also analyzed by performing theoretical calculations. C? H activation in the synthesis of organometallic helicenes is further demonstrated by the preparation of cis‐bis‐cycloplatinated‐[8]helicene 1 c .     

Sampling and analysis of volatile organics emitted from wastewater treatment plant and drain system of an industrial science park

Volatile organic compounds (VOCs) were monitored in the different sections of a wastewater treatment plant (WWTP), the outlet of both the WWTP and rainfall water, and the downstream of the WWTP joining the river in the area or vicinity of an industrial science park located in Hsinchu, Taiwan. Levels of VOCs were determined by collecting air samples over several sampling points and analyzed using gas chromatography. Among VOCs identified in the drainage and effluent system in each season, acetone, isopropanol (IPA) and dimethyl sulfide (DMS) were the major emission species and maximum concentrations were 400.4, 22.8 and 641.2 ppbv, respectively. The ambient air and wastewater sample analysis from neighboring wastewater streams identified pollutants being discharged from unaccounted sources other than the industrial park. According to the 24 h semi-continuous monitoring data (27/7/2002-29/7/2002), the total VOC concentration was an average of 93 ppbv (acetone contributed ∼78%) with a dramatic variation during the day and night. The emission rate of measured VOCs estimated using fixed box model projected an average of 2-4 μg m⁻² h⁻¹) during the day and 9-17 μg m⁻² h⁻¹ during the night. In addition, the isopleth maps show that the acetone and DMS emissions influence adversely the nearby residential area located at less than 100 m downwind from the plant. Eventually, based on this study, an on-line monitoring and alerting system could be built for a long-term performance, and with regular information on the varying pollutants over time construction of a green strategy and creation of a sustainable environment can be achieved.     

Measurement of non-methane hydrocarbons in Taipei city and their impact on ozone formation in relation to air quality

Air pollutants data from semi-continuous measurements at multiple sampling sites in Taipei metropolitan area of Taiwan was obtained by collecting air samples in canisters. The hydrocarbon composition was determined by using GC/MS and GC/FID. The air samples were pre-concentrated onto glass beads prior to separation by PLOT and DB-1 columns of GC. The method showed detection limit of <1 ppb and relative standard deviation in the range of 5-30% for different compounds. Aromatic hydrocarbons (toluene, benzene, etc.) and aliphatic hydrocarbons (ethylene, acetylene, propane, etc.) were correlated primarily to determine the source of emission. The estimated hydrocarbons were ranked according to their abundance and photochemical reactivity. The criteria pollutants, ozone and NO₂ were measured by UV-differential optical absorption spectroscopy (UV-DOAS), and were utilized to determine the relative importance of non-methane hydrocarbons (NMHC) and significant contribution of NO₂ in limiting ozone formation. The obtained results suggest that ozone formation in Taipei city is probably limited by the supply of non-methane hydrocarbons. The concentration profile of targeted pollutants was compared to other metropolitan areas to determine air quality and the pollutant sources.