Rheology and colloidal structure of silver nanoparticles dispersed in diethylene glycol

Rheological behavior of agglomerated silver nanoparticles (~ 40 nm) suspended in diethylene glycol over a wide range of volumetric solids concentrations (? = 0.11–4.38%) was studied. The nanoparticle suspensions generally exhibited a yield pseudoplastic behavior. Bingham plastic, Herschel–Bulkley and Casson models were used to evaluate the shear stress-shear rate dependency. Analyzing the effect of silver concentrations on the yield stress and viscosity of the suspensions followed an exponential form, revealing an increase in the degree of interparticle interactions with increasing solid concentrations. Fractal dimension (D_f) was estimated from the suspension yield stress and ? dependence, and was determined as D_f = 1.51–1.62 for the flocculated nanoparticle suspensions. This suggested that the suspension structure was probably dominated by the diffusion-limited cluster–cluster aggregation (DLCA) due mostly to the strong attractions involved in the interparticle potentials. Maximum solids concentration of the suspensions was determined to be ?_m = 11%.     

How Phosphorous Flame Retardant Additives Affect Benzoxazine-Based Monomer and Polymer Properties

The phosphorous-based flame retardant additives poly(m-phenylene methylphosphonate) (PMP) and resorcinol bis(diphenyl phosphate) (RDP) are reacted with bisphenol F and aniline–based benzoxazine (BF-a). DSC, rheological analysis, FT-IR, and soxhlet extraction reveal the covalent incorporation of both FR additives—initiating phenols in PMP structure as well as free phenols generated via transesterification reaction in the case of RDP. In contrast to PMP, RDP elongates the processing window but decreases the thermo–mechanical properties. Both additives increase the resistance in reactions against small flames with solely a phosphorous loading of 0.3 wt%, resulting in a V-0 rating and an improvement in the OI value by up to 2% for RDP and 4% for PMP. Both FRs reduce the heat release rate but increase the smoke production and the smoke toxicity in the case of RDP.     

A Novel Coenzyme A Analogue in the Anaerobic,Sulfate-Reducing,Marine Bacterium Desulfobacula toluolica Tol2T

Coenzyme A (CoA) thioesters are formed during anabolic and catabolic reactions in every organism. Degradation pathways of growth-supporting substrates in bacteria can be predicted by differential proteogenomic studies. Direct detection of proposed metabolites such as CoA thioesters by high-performance liquid chromatography coupled with high-resolution mass spectrometry can confirm the reaction sequence and demonstrate the activity of these degradation pathways. In the metabolomes of the anaerobic sulfate-reducing bacterium Desulfobacula toluolica Tol2^T grown with different substrates various CoA thioesters, derived from amino acid, fatty acid or alcohol metabolism, have been detected. Additionally, the cell extracts of this bacterium revealed a number of CoA analogues with molecular masses increased by 1 dalton. By comparing the chromatographic and mass spectrometric properties of synthetic reference standards with those of compounds detected in cell extracts of D. toluolica Tol2^T and by performing co-injection experiments, these analogues were identified as inosino-CoAs. These CoA thioesters contain inosine instead of adenosine as the nucleoside. To the best of our knowledge, this finding represents the first detection of naturally occurring inosino-CoA analogues.     

Efficient Stacking on Protein Amide Fragments

The less polar π‐surface of protein amide groups is exposed in many receptor binding sites, either as part of the backbone or in Gln/Asn side chains. Using quantum chemical calculations and Protein Data Bank (PDB) searches on model systems, we investigate the energetics and geometric preferences for the stacking on amide groups of a large number of heteroarenes that are relevant to medicinal chemistry. From this study, we discern that the stacking energy of an aromatic ligand substituent can be improved by: 1) orienting the fragment dipole vector such that it is aligned in an antiparallel fashion with the dipole of the interacting protein amide group, 2) increasing its dipole moment, and 3) decreasing its π‐electron density. These guidelines should be helpful to more rationally exploit this interaction type in future structure‐based drug design.     

Emulsifier and antioxidant properties of by‐products obtained by enzymatic degumming of soybean oil

The enzymes used in degumming, called phospholipases, specifically act on phospholipids without degrading the oil itself. Degumming using a phospholipase C enzyme allows to meet all market specifications while it increases the oil yield. The aim of this study was to evaluate antioxidant and emulsifier properties of the recovered gum (RG) obtained by enzymatic oil degumming process of crude soybean oil subjected to modifications as deoiling (RG deoiled) or ethanol fractionation (RG soluble and insoluble). RG soluble allowed obtaining more stable oil‐in‐water emulsions (30:70 w/w) in comparison with those by‐products assayed at different concentrations (0.1–1.0%). Also, deoiled soybean lecithin (DSL) and RG deoiled had a similar behavior in relation to the kinetic destabilization (% backscattering profiles), despite the different degumming processes used to obtain these samples. The study on induction times (Metrohm Rancimat) showed a significant antioxidant effect (p<0.05) against a refined sunflower oil associated with all the by‐products analyzed. However, RG soluble and DSL showed a strong effect on the oil stability at high concentrations (1000–2000 ppm). These results showed that the deoiled recovered gum and its derivates obtained by ethanol fractionation are a potential alternative for industrial application as additive. Practical applications: The economic benefits of enzymatic degumming process have also been quantified by several oilseed processors. This process allows obtaining a by‐product with a high concentration of different phospholipids. This study intends to increase the commercial value of this recovered gum contributing to the food industry with useful information about their functional properties.     

Distinguishing Between Spherical and Nonspherical Particles by Measuring the Variability in Azimuthal Light Scattering

Azimuthal variabilities in scattering of monochromatic, circularly polarized light by individual spherical and nonspherical particles were measured using the DAWN-A (Wyatt et al. Appl. Opt. 27:2405–2421, 1988) differential light scattering detector. Measured aerosols included polystyrene latex spheres (PSL), quartz, and sodium chloride particles of 0.576, 0.741, 0.966, and 1.250 μm diameter. Signals from eight detectors at different azimuthal angles at a polar angle of 55° showed that variabilities for nonspherical particles significantly exceeded values for the spherical PSL. The probability that a quartz or sodium chloride particle would be incorrectly identified as a sphere are less than about 5% for all sizes investigated.     

Bulk Sediment and Diatom Silica Carbon Isotope Composition from Coastal Marine Sediments off East Antarctica

Organic carbon occluded in diatom silica is assumed to be protected from degradation in the sediment. δ¹³C from diatom carbon (δ¹³C_(diatom)) therefore potentially provides a signal of conditions during diatom growth. However, there have been few studies based on δ¹³C_(diatom). Numerous variables can influence δ¹³C of organic matter in the marine environment (e.g., salinity, light, nutrient and CO₂ availability). Here we compare δ¹³C_(diatom) and δ¹³C_(TOC) from three sediment records from individual marine inlets (Rauer Group, East Antarctica) to (i) investigate deviations between δ¹³C_(diatom) and δ¹³C_(TOC), to (ii) identify biological and environmental controls on δ¹³C_(diatom) and δ¹³C_(TOC), and to (iii) discuss δ¹³C_(diatom) as a proxy for environmental and climate reconstructions. The records show individual δ¹³C_(diatom) and δ¹³C_(TOC) characteristics, which indicates that δ¹³C is not primarily controlled by regional climate or atmospheric CO₂ concentration. Since the inlets vary in water depths offsets in δ¹³C are probably related to differences in water column stratification and mixing, which influences redistribution of nutrients and carbon within each inlet. In our dataset changes in δ¹³C_(diatom) and δ¹³C_(TOC) could not unequivocally be ascribed to changes in diatom species composition, either because the variation in δ¹³C_(diatom) between the observed species is too small or because other environmental controls are more dominant. Records from the Southern Ocean show depleted δ¹³C_(diatom) values (1–4 ‰) during glacial times compared to the Holocene. Although climate variability throughout the Holocene is low compared to glacial/interglacial variability, we find variability in δ¹³C_(diatom), which is in the same order of magnitude. δ¹³C of organic matter produced in the costal marine environment seems to be much more sensitive to environmental changes than open ocean sites and δ¹³C is of strongly local nature.     

Growth of all-carbon horizontally aligned single-walled carbon nanotubes nucleated from fullerene-based structures

All-carbon single-walled carbon nanotubes (SWCNTs) were successfully synthesized, nucleated using a fullerene derivative. A systematic investigation into the initial preparation of C₆₀ fullerenes as growth nucleators for the SWCNTs was conducted. Enhancement in the yield of the produced SWCNT has been achieved with exploring different dispersing media for the fullerenes, the period, and environment of the initial thermal treatment of the fullerenes in addition to the use of different fullerene-based structures. The systematic studies significantly advance our understanding of the growth of the all-carbon catalyst-free single-walled carbon nanotubes. Field-effect transistors were fabricated using the catalyst-free SWCNT and then electrically characterized, showing current capacity as high as the well-studied catalyst-assisted nanotubes.     

Kinetics of Mullite Grain Growth in Alumino Silicate Fibers

Grain growth kinetics of mullite in laboratory-produced and commercial (3M-Nextel 720) alumino silicate fibers was analyzed in the temperature range between 1500° and 1700°C. The lab fibers consist of mullite plus traces of α-alumina, while the phase content of the commercial Nextel 720 fibers is about 60 wt% mullite plus 40 wt%α-alumina. The temperature-induced grain coarsening of mullite follows the empirical law D ^{1/ n} − D ₀^{1/ n} = kt . Two different temperature regimes can be distinguished with respect to the grain growth exponents: above 1600°C the growth exponent is ≈1/3, while below 1600°C the growth exponent of ≈1/12 is exceptionally low. Laboratory-produced and commercial fibers show almost identical mullite grain growth kinetics.