Heteroepitaxial Growth of Calcium Silicate Hydrate on Calcium Germanate Hydrate

The hydration of tricalcium silicate at 25°C was accelerated by seeding with 5 wt% tricalcium germanate. Based on heat evolution, seeding resulted in the elimination of the induction period. However, the shape of the hydration peak remained the same. Because tricalcium germanate hydrates first, the microstructure of the calcium silicate hydrate which subsequently forms is influenced by the calcium germanate hydrate morphology. Calcium silicate hydrate formed in the presence of calcium germanate hydrate exhibits the morphology typical of the latter. Acceleration of hydration and morphological variation indicate heteroepitaxial growth.     

Fluorinated Polyphosphazenes: A Survey

A general survey of fluorinated phosphazene polymers starting from their synthesis in 1965 to recent times is presented. Various types of fluorinated phosphazenes are described depending on the way fluorine atoms are connected to the polyphosphazene skeleton. The characterization, properties and practical utilization of these compounds in different domains are critically discussed.     

The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Production of FAME from acid oil,a by-product of vegetable oil refining

Simple alkyl FA esters have numerous uses, including serving as biodiesel, a fuel for compression ignition (diesel) engines. The use of acid-catalyzed esterification for the synthesis of FAME from acid oil, a by-product of edible vegetable oil refining that is produced from soapstock, was investigated. Soybean acid oil contained 59.3 wt% FFA, 28.0 wt% TAG, 4.4 wt% DAG, and less than 1% MAG. Maximum esterification occurred at 65°C and 26 h reaction at a molar ratio of total FA/methanol/sulfuric acid of 1∶15∶1.5. Residual unreacted species under these conditions, as a fraction of their content in unesterified acid oil, were FFA, 6.6%; TAG, 5.8%; and DAG, 2.6%. This corresponds to estimated concentrations of FFA, 3.2%; TAG, 1.3%; and DAG, 0.2%, on a mass basis, in the ester product. In an alternative approach, the acylglycerol species in soapstock were saponified prior to acidulation. High-acid (HA) acid oil made from this saponified soapstock had an FFA content of 96.2 wt% and no detectable TAG, DAG, or MAG. Optimal esterification conditions for HA acid oil at 65°C were a mole ratio of FFA/methanol/acid of 1∶1.8∶0.17, and 14 h incubation. FAME recovery under these conditions was 89% of theoretical, and the residual unesterified FFA content was approximately 20 mg/g. This was reduced to 3.5 mg/g, below the maximum FFA level allowed for biodiesel, by washing with NaCl, NaHCO₃, and Ca(OH)₂ solutions. Alternatively, by subjecting the unwashed ester layer to a second esterification, the FFA level was reduced to less than 2 mg/g. The acid value of this material exceeded the maximum allowed for biodiesel, but was reduced to an acceptable value by a brief wash with 0.5 N NaOH.     

Optical Properties and London Dispersion Forces of Amorphous Silica Determined by Vacuum Ultraviolet Spectroscopy and Spectroscopic Ellipsometry

Precise and accurate knowledge of the optical properties of amorphous silica is important because of the increasing application of SiO₂ in optical and electrooptical devices, including photolithography masks for semiconductor fabrication, recently as a potential 157 nm mask substrate. The optical properties in the vacuum ultraviolet (VUV) region have been investigated, because they convey detailed information on the electronic structure and interatomic bonding of the material. In this work, we have combined spectroscopic ellipsometry and VUV spectroscopy to directly determine the optical functions of SiO₂ in this range, thereby reducing the uncertainty in the low-energy extrapolation of the data, essential for Kramers–Kronig analysis of VUV reflectance. We report the complex optical properties of SiO₂, over the range of 1.5 to 42 eV, showing improved agreement with theory when contrasted with earlier results. In addition to the features previously reported at 10.4, 11.6, 14.03, and 17.10 eV, new interband transitions have been observed at 21.3 eV along with O 2 s transitions at 32 eV. We found the bulk plasma peak to be 23.7 eV in the energy loss function spectrum. Based on the magnitude of these new results, the Hamaker constant for SiO₂|Vacuum|SiO₂ is 71.6 zJ, which is larger than the previously reported value of 66 zJ.     

1H T2‐NMR monitoring of crosslinked polyolefin aging

This work examines the correlation between the ¹H‐NMR T₂ relaxation constant and the mechanical properties of aged crosslinked polyolefin cable insulation. T₂ experiments on unswollen samples could not differentiate between unaged and highly aged materials; all exhibited ¹H T₂ constants of approximately 0.5 ms. To accentuate the effects of aging, samples were swollen in various solvents. Unaged samples had T₂ values of approximately 15 ms in good solvents. With thermal aging, T₂ values decreased as the ultimate tensile elongation decreased. However, the correlation between T₂ and elongation differed for samples irradiated with high‐energy radiation and for materials aged above versus below the crystalline melting temperature. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2578–2582, 2003     

Identification of a Small‐Molecule Inhibitor of HIV‐1 Assembly that Targets the Phosphatidylinositol (4,5)‐bisphosphate Binding Site of the HIV‐1 Matrix Protein

The development of drug resistance remains a critical problem for current HIV‐1 antiviral therapies, creating a need for new inhibitors of HIV‐1 replication. We previously reported on a novel anti‐HIV‐1 compound, N²‐(phenoxyacetyl)‐N‐[4‐(1‐piperidinylcarbonyl)benzyl]glycinamide ( 14 ), that binds to the highly conserved phosphatidylinositol (4,5)‐bisphosphate (PI(4,5)P₂) binding pocket of the HIV‐1 matrix (MA) protein. In this study, we re‐evaluate the hits from the virtual screen used to identify compound 14 and test them directly in an HIV‐1 replication assay using primary human peripheral blood mononuclear cells. This study resulted in the identification of three new compounds with antiviral activity; 2‐(4‐{[3‐(4‐fluorophenyl)‐1,2,4‐oxadiazol‐5‐yl]methyl})‐1‐piperazinyl)‐N‐(4‐methylphenyl)acetamide ( 7 ), 3‐(2‐ethoxyphenyl)‐5‐[[4‐(4‐nitrophenyl)piperazin‐1‐yl]methyl]‐1,2,4‐oxadiazole ( 17 ), and N‐[4‐ethoxy‐3‐(1‐piperidinylsulfonyl)phenyl]‐2‐(imidazo[2,1‐b][1,3]thiazol‐6‐yl)acetamide ( 18 ), with compound 7 being the most potent of these hits. Mechanistic studies on 7 demonstrated that it directly interacts with and functions through HIV‐1 MA. In accordance with our drug target, compound 7 competes with PI(4,5)P₂ for MA binding and, as a result, diminishes the production of new virus. Mutation of residues within the PI(4,5)P₂ binding site of MA decreased the antiviral effect of compound 7 . Additionally, compound 7 displays a broadly neutralizing anti‐HIV activity, with IC₅₀ values of 7.5–15.6 μM for the group M isolates tested. Taken together, these results point towards a novel chemical probe that can be used to more closely study the biological role of MA and could, through further optimization, lead to a new class of anti‐HIV‐1 therapeutics.     

Carbonaceous Aerosol Sources in Rio de Janeiro

Aerosol carbon concentrations, organic / elemental speciation, and carbon isotopic composition data (¹³C/¹²C ratios and ¹⁴C content) are reported from the second Rio de Janeiro Aerosol Characterization Study (RIO-JACS II), along with supplemental meteorologic and inorganic aerosol data. These data and their diurnal and weekday / weekend variability are used to identify sources of carbonaceous aerosols in the urban Rio air basin. Specifically, contributions from biogenic sources, anthropogenic emissions (principally transportation sources), and sugar cane-derived alcohol-fueled vehicular emissions to aerosol carbon levels in Rio are estimated from measurements of carbon-14, organic and elemental carbon, and ¹³C/¹²C isotopic composition in total aerosol samples collected at two ambient Rio sites and in a heavily traveled tunnel. The major source of elemental (soot) carbon appears to be diesel vehicles, but secondary sources of both biogenic and fossil organic aerosol carbon are indicated.     

Drying of Pastes in Vibro-Fluidized Beds: Effects of the Amplitude and Frequency of Vibration

Abstract

The dimensionless vibration number (Γ) is the parameter most widely applied to quantify the vibration energy of a vibro-fluidized bed. It is defined as a function of the amplitude (A) and of the frequency of vibration (f). Most works in literature present their results as a function of Γ, which is adopted as a single parameter to explain the results on fluid dynamic behavior of vibro-fluidized beds, independent on the magnitudes of A and f. From its definition, however, it is possible to obtain identical values of Γ just by combining different values of A and f, and further studies are necessary for a better analysis of fluid dynamic behavior of vibro-fluidized beds concerning their vibration energy. Therefore, in this work the effects of dimensionless vibration number on the fluid dynamic behavior of a vibro-fluidized bed will be investigated by choosing different combinations of A and f values arranged to provide identical values of Γ. The tests were carried out for dry and wet beds, for values of Γ = 0.0 (fluidized bed), 1.0, 2.0, and 4.0. The results indicate that Γ must be used carefully when applied as the only parameter to characterize the vibration effects in a vibro-fluidized bed since very different fluid dynamic behavior was detected at a fixed Γ at different amplitudes and frequencies.