Characterization of char from the pyrolysis of tobacco

Pyrolysis of tobacco was studied in oxidative and nonoxidative (inert) environments at atmospheric pressure and temperatures ranging from 150 to 750 degrees C. The objective was to study the effect of pyrolysis conditions on the characteristics of the solid residue, i.e., char. The char was characterized using cross-polarization (13)C nuclear magnetic resonance (CPMAS NMR), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), the Brunauer-Emmett-Teller (BET) surface area, and the elemental composition. The char yield from pyrolysis (i.e., nonoxidative) decreased sharply with an increase in temperature to ca. 22% (dry, ash-free basis) at high temperatures. In oxidative pyrolysis, i.e., in 5% oxygen, the char was completely oxidized above 600 degrees C. The gaseous product from pyrolysis at high temperatures contained a significant concentration of hydrogen. The surface area of the char was low, with a maximum of 8 m(2)/g at 400 degrees C. SEM analysis indicated that pyrolysis of the tobacco led to a gradual accumulation of inorganic crystals on the exposed surfaces, and some constituents also melted, resulting in the formation of vesicles by evolving gas. NMR analysis showed significant changes in pectin and sugar constituents of the tobacco and breaking of glycosidic bonds of cellulose at 300-500 degrees C before the char became predominantly aromatic at high temperatures. FTIR results showed a continuous decrease in the intensity of the OH stretch with temperature and the aromatic character to be at maximum at 550-650 degrees C. The H/C ratio of the char decreased continuously with temperature, while the O/C ratio became constant above 300 degrees C due to the presence of oxides and carbonates in the char. The results are consistent with the analysis of the evolved gases.     

Antioxidant capacity of oat (Avena sativa L.) extracts. 1. Inhibition of low-density lipoprotein oxidation and oxygen radical absorbance capacity

Milled oat groat pearlings, trichomes, flour, and bran were extracted with methanol and the fractions tested in vitro for antioxidant capacity against low-density lipoprotein (LDL) oxidation and R-phycoerythrin protein oxidation in the oxygen radical absorbance capacity (ORAC) assay. The oxidative reactions were generated by 2,2'-azobis(2-amidinopropane) HCl (AAPH) or Cu(2+) in the LDL assay and by AAPH or Cu(2+) + H(2)O(2) in the ORAC assay and calibrated against a Trolox standard to calculate Trolox equivalents (1 Trolox equivalent = 1 TE = activity of 1 micromol of Trolox). The antioxidant capacity of the oat fractions was generally consistent with a potency rank of pearlings (2.89-8.58 TE/g) > flour (1.00-3.54 TE/g) > trichome (1.74 TE/g) = bran (1.02-1.62 TE/g) in both LDL and ORAC assays regardless of the free radical generator employed. A portion of the oat antioxidant constituents may be heat labile as the greatest activity was found among non-steam-treated pearlings. The contribution of oat tocols from the fractions accounted for <5% of the measured antioxidant capacity. AAPH-initiated oxidation of LDL was inhibited by the oat fractions in a dose-dependent manner, although complete suppression was not achieved with the highest doses tested. In contrast, Cu(2+)-initiated oxidation of LDL stimulated peroxide formation with low oat concentrations but completely inhibited oxidation with higher doses. Thus, oats possess antioxidant capacity most of which is likely derived from polar phenolic compounds in the aleurone.     

A giant sauropod dinosaur from an Upper Cretaceous mangrove deposit in Egypt

We describe a giant titanosaurid sauropod dinosaur discovered in coastal deposits in the Upper Cretaceous Bahariya Formation of Egypt, a unit that has produced three Tyrannosaurus-sized theropods and numerous other vertebrate taxa. Paralititan stromeri is the first tetrapod reported from Bahariya since 1935. Its 1.69-meter-long humerus is longer than that of any known Cretaceous sauropod. The autochthonous scavenged skeleton was preserved in mangrove deposits, raising the possibility that titanosaurids and their predators habitually entered such environments.     

Enantioselective organocatalysis using SOMO activation

The asymmetric alpha-addition of relatively nonpolar hydrocarbon substrates, such as allyl and aryl groups, to aldehydes and ketones remains a largely unsolved problem in organic synthesis, despite the wide potential utility of direct routes to such products. We reasoned that well-established chiral amine catalysis, which activates aldehydes toward electrophile addition by enamine formation, could be expanded to this important reaction class by applying a single-electron oxidant to create a transient radical species from the enamine. We demonstrated the concept of singly occupied molecular orbital (SOMO) activation with a highly selective alpha-allylation of aldehydes, and we here present preliminary results for enantioselective heteroarylations and cyclization/halogenation cascades.