Kinetics of levoglucosan and formaldehyde formation during cellulose pyrolysis process

The mechanisms and kinetics studies of the formation of levoglucosan and formaldehyde from anhydroglucose radical have been carried out theoretically in this paper. The geometries and frequencies of all the stationary points are calculated at the B3LYP/6-31+G(D,P) level based on quantum mechanics, Six elementary reactions are found, and three global reactions are involved. The variational transition-state rate constants for the elementary reactions are calculated within 450-1500 K. The global rate constants for every pathway are evaluated from the sum of the individual elementary reaction rate constants. The first-order Arrhenius expressions for these six elementary reactions and the three pathways are suggested. By comparing with the experimental data, computational methods without tunneling correction give good description for Path1 (the formation of levoglucosan); while methods with tunneling correction (zero-curvature tunneling and small-curvature tunneling correction) give good results for Path2 (the first possibility for the formation of formaldehyde), all the test methods give similar results for Path3 (the second possibility for the formation of formaldehyde), all the modeling results for Path3 are in good agreement with the experimental data, verifying that it is the most possible way for the formation of formaldehyde during cellulose pyrolysis. © 2012 Elsevier Ltd. All rights reserved.

Levoglucosan formation mechanisms during cellulose pyrolysis

Levoglucosan is one important primary product during cellulose pyrolysis either as an intermediate or as a product. Three available mechanisms for levoglucosan formation have been studied theoretically in this paper, which are free-radical mechanism; glucose intermediate mechanism; and levoglucosan chain-end mechanism. All the elementary reactions included in the pathway of every mechanism were investigated; thermal properties including activation energy, Gibbs free energy, and enthalpy for every pathway were also calculated. It was concluded that free-radical mechanism has the highest energy barrier during the three levoglucosan formation mechanisms, glucose intermediate mechanism has lower energy barrier than free-radical mechanism, and levoglucosan chain-end mechanism is the most reasonable pathway because of the lowest energy barrier. By comparing with the activation energy obtained from the experimental results, it was also concluded that levoglucosan chain-end mechanism fits better with the experimental data for the formation of levoglucosan. © 2013 Elsevier B.V. All rights reserved.

Patient survival following arteriovenous fistula formation

PURPOSE: Efforts to promote arteriovenous fistulas (AVFs) have been successful in increasing the prevalence of AVF use as the primary vascular access for haemodialysis (HD). Sustained preference for AVF use may not be the most appropriate vascular access choice for all patient groups. Arteriovenous grafts (AVGs) offer advantages of earlier use and lower primary failure rates compared to AVFs so may be preferable for patients where short-term vascular access is needed. This study was designed to assess comparative mortality in different age groups following AVF formation.

METHODS: A prospective cohort of patients having AVF creation was recruited. Patients were subdivided into three age groups: Group A: lt;50 years; Group B: 50-74 years and Group C: ≥75 years. Survival curves and Cox regression analysis were performed on each of these groups.

RESULTS: One hundred and thirty-four patients (n = 134) were recruited into the study. The prevalence of diabetes increased significantly with age. As expected, mortality was higher in older age groups (log rank (Mantel-Cox) 19.227; p = 0.0001). Mortality rates at 1 year were 0% in group A, 12.5% in group B and 29.1% in group C. Medium-term mortality at 4 years was 7.9% in group A, 39.1% in group B and 54.8% in group C.

CONCLUSIONS: We found a significantly higher mortality rate in patients ≥75 years in comparison to those lt;75 years. The choice of vascular access modality should be tailored to the individual with particular reference to the patient's expected survival.

Stress tolerance and virulence of insect-pathogenic fungi are determined by environmental conditions during conidial formation

The virulence to insects and tolerance to heat and UV-B radiation of conidia of entomopathogenic fungi are greatly influenced by physical, chemical, and nutritional conditions during mycelial growth. This is evidenced, for example, by the stress phenotypes of Metarhizium robertsii produced on various substrates. Conidia from minimal medium (Czapek's medium without sucrose), complex medium, and insect (Lepidoptera and Coleoptera) cadavers had high, moderate, and poor tolerance to UV-B radiation, respectively. Furthermore, conidia from minimal medium germinated faster and had increased heat tolerance and were more virulent to insects than those from complex medium. Low water-activity or alkaline culture conditions also resulted in production of conidia with high tolerance to heat or UV-B radiation. Conidia produced on complex media exhibited lower stress tolerance, whereas those from complex media supplemented with NaCl or KCl (to reduce water activity) were more tolerant to heat and UV-B than those from the unmodified complex medium. Osmotic and nutritive stresses resulted in production of conidia with a robust stress phenotype, but also were associated with low conidial yield. Physical conditions such as growth under illumination, hypoxic conditions, and heat shock before conidial production also induced both higher UV-B and heat tolerance; but conidial production was not decreased. In conclusion, physical and chemical parameters, as well as nutrition source, can induce great variability in conidial tolerance to stress for entomopathogenic fungi. Implications are discussed in relation to the ecology of entomopathogenic fungi in the field, and to their use for biological control. This review will cover recent technologies on improving stress tolerance of entomopathogenic fungi for biological control of insects.

Diagenetic Alterations and Reservoir Quality Evolution of Lower Cretaceous Fluvial Sandstones: Nubian Formation, Sirt Basin, North-Central Libya

Lower Cretaceous meandering and braided fluvial sandstones of the Nubian Formation form some of the most important subsurface reservoir rocks in the Sirt Basin, north-central Libya. Mineralogical, petrographical and geochemical analyses of sandstone samples from well BB6-59, Sarir oilfield, indicate that the meandering fluvial sandstones are fine- to very fine-grained subarkosic arenites (av. Q91F5L4), and that braided fluvial sandstones are medium- to very coarse-grained quartz arenites (av. Q96F3L1). The reservoir qualities of these sandstones were modified during both eodiagenesis (ca. <70oC; <2 km) and mesodiagenesis (ca. >70oC; >2km). Reservoir quality evolution was controlled primarily by the dissolution and kaolinitization of feldspars, micas and mud intraclasts during eodiagenesis, and by the amount and thicknessof grain-coating clays, chemical compaction and quartz overgrowths during mesodiagenesis. However, dissolution and kaolinitization of feldspars, micas and mud intraclasts resulted in the creation of intercrystalline micro- and mouldic macro-porosity and permeability during eodiagenesis, which were more widespread in braided fluvial than in meandering fluvial sandstones. This was because of the greater depositional porosity and permeability in the braided fluvial sandstones which enhanced percolation of meteoric waters. The development of only limited quartz overgrowths in the braided fluvial sandstones, in which quartz grains are coated by thick illite layers, retained high porosity and permeability (12-23 % and 30- 600 mD). By contrast, meandering fluvial sandstones underwent porosity loss as a result of quartz overgrowth development on quartz grains which lack or have thin and incomplete grain-coating illite (2-15 % and 0-0.1mD). Further loss of porosity in the meandering fluvial sandstones occurred as a result of chemical compaction (pressuredissolution) induced by the occurrence of micas along grains contacts. Otherdiagenetic alterations, such as the growth of pyrite, siderite, dolomite/ankerite and albitization, had little impact on reservoir quality. The albitization of feldspars may have had minor positive influence on reservoir quality throughthe creation of intercrystalline micro-porosity between albite crystals.The results of this study show that diagenetic modifications of the braided and meandering fluvial sandstones in the Nubian Formation, and resulting changes in reservoir quality, are closely linked to depositional porosity and permeability. They are also linked to the thickness of grain-coating infiltrated clays, and to variations in detrital composition, particularly the amounts of mud intraclasts, feldspars and mica grains as well as climatic conditions.

Formation of epitaxial BaTiO3/SrTiO3 multilayers grown on Nb-doped SrTiO3 (001) substrates

The formation of epitaxial BaTiO3/SrTiO3 multilayers; is studied in terms of the growth mechanism by investigating surface morphologies, crystalline orientations, microstructures, and structures of the interfaces, as well as by determining the dielectric properties. Under specific conditions, the epitaxial BaTiO3 films follow a layer-then-island (Stranski-Krastanov) mechanism on SrTiO3 (001)-oriented substrates. In view of actual efforts made to grow epitaxial superlattices involving very thin individual layers of BaTiO3 and/or SrTiO3, we have determined that the BaTiO3 films Of up to 6,nm thickness do not show any defects and have a sharp BaTiO3-on-SrTiO3 interface. On the contrary, SrTiO3-on-BaTiO3 interfaces within multilayers are rough, probably due to the different growth mechanisms of the two different materials, or due to a difference in the morphological stability of the growth surfaces caused by different surface energies of BaTiO3 and SrTiO3 and by different mobilities of the Ba and Sr atoms reaching the SrTi3 and BaTiO3 layers, respectively.

Inland shell midden site-formation:Investigation into a late Pleistocene to early Holocene midden from Trang An, Northern Vietnam

Over the course of the past two decades there has been growing research interest in the site formation processes of shell middens. This stands along-side and is being used to inform cultural, dietary and palaeo-environmental reconstructions. Just as midden site formation processes have turned out to be many and varied, however, the kinds of shell-bearing sites that past human communities created are likely to have been no less diverse. Subsuming such sites under a single category - shell middens - normalises that variation and may lead to the misinterpretation of site function. The greater part of research in this field also continues to focus on coastal shell middens; comparatively little attention has been paid to middens containing freshwater and especially terrestrial molluscs from hinterland locations. As a result, much of the current understanding about shell-midden sites carries a spatial as well as a functional bias. This paper hopes to contribute towards discussion on both fronts. It presents a detailed examination of the formation processes that went into the creation of a land snail-dominated late- to post-glacial midden from northern Vietnam, and considers the role that it may have played in the early settlement of this area. The data presented comes from ongoing archaeological excavations at Hang Boi, a cave located in the sub-coastal karstic uplands of Trang An park, in the Vietnamese Province of Ninh Binh. (C) 2010 Elsevier Ltd and INQUA. All rights reserved.