Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.

Anomalous fluorinations of 3-aryl-2-hydroxypropanoic esters by diethylaminosulfur trifluoride (DAST).

Anomalous fluorinations of 3-aryl-2-hydroxypropanoic esters by diethylaminosulfur trifluoride (DAST). Haigh, David; Jefcott, Lee J.; Magee, Katherkine; McNab, Hamish. Dep. Med. chem., SmithKline Beecham Pharmaceuticals, Epsom, UK. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1996), (24), 2895-2900. Publisher: Royal Society of Chemistry, CODEN: JCPRB4 ISSN: 0300-922X. Journal written in English. CAN 126:143928 AN 1997:56534 CAPLUS (Copyright (C) 2009 ACS on SciFinder (R)) Abstract Treatment of 3-aryl-2-hydroxypropanoic esters with diethylaminosulfur trifluoride (DAST) gives considerable amts. of rearranged 2-aryl-3-fluoropropanoic esters, together with the expected products. The extent of rearrangement is dependent on solvent and on the substitution pattern of the aryl ring; the mechanism of rearrangement probably involves anchimeric assistance by the aryl group in the SN1 component of the reaction pathway. Reaction of the isomeric 3-hydroxy-2-phenylpropanoic ester shows much less rearrangement under similar conditions, and an elimination product is also obtained.

Facile biocatalytic reduction of the carbon-carbon double bond of 5-benzylidenethiazolidine-2,4-diones. Synthesis of ( )-5-(4-{2-[methyl(2-pyridyl)amino]ethoxy}benzyl)thiazolidine-2,4-dione (BRL 49653), its (R)-(+)-enantiomer and analogs.

Cantello, Barrier C. C.; Eggleston, Drake S.; Haigh, David; Haltiwanger, R. Curtis; Heath, Catherine M.; Hindley, Richard M.; Jennings, Keith R.; Sime, John T.; Woroniecki, Stefan R. SmithKline Beecham Pharmaceuticals, Surrey, UK. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry (1994), (22), 3319-24. Publisher: Royal Society of Chemistry, CODEN: JCPRB4 ISSN: 0300-922X. Journal written in English. CAN 122:105736 AN 1995:237497 CAPLUS (Copyright (C) 2009 ACS on SciFinder (R)) Abstract A novel biotransformation system for the redn. of carbon-carbon double bonds in 5-benzylidenethiazolidine-2,4-diones to give the corresponding 5-benzylthiazolidine-1,4-diones, using whole cells of red yeasts, is described. These reduced compds., which are recovered in good yield, are of potential use in the treatment of non-insulin dependent diabetes mellitus. The mild reaction conditions developed allow redn. of 5-benzylidenethiazolidine-2,4-diones contg. other functionalities which are not compatible with alternative redn. methods. The biocatalytic redn. is enantioselective and the synthesis of R-(+)-5-(4-{2-[methyl(2-pyridyl)amino]ethoxy}benzyl)thiazolidine-2,4-dione by Rhodotorula rubra CBS 6469 and structure confirmation by X-ray crystallog. is detailed. Optimization of reaction conditions (including immobilization) for these whole cell redn. system is described.

Organometallic hydrogen transfer and dehydrogenation catalysts for the conversion of bio-renewable alcohols

Organometallic hydrogen transfer and dehydrogenation provide straightforward atom efficient routes from alcohols to a variety of chemical products. The potential of these reactions to enable the conversion of biomass to value added chemicals is discussed, with reference to the products that can be prepared from aliphatic alcohols in good isolated yield.

Amination and dehydration of 1,3-propanediol by hydrogen transfer: reactions of a bio-renewable platform chemical

1,3-propanediol was subjected to a range of amination conditions. The N-heterocyclic carbene piano stool complex [Cp*IrCl2(bmim)] was found to be a good catalyst for amination and dehydration in toluene or ionic liquid; product compositions could be tuned by altering the ratio of diol to amine.

Bio-port Free Energy City

In an age of depleting oil reserves and increasing energy demand, humanity faces a stalemate between environmentalism and politics, where crude oil is traded at record highs yet the spotlight on being ‘green’ and sustainable is stronger than ever. A key theme on today’s political agenda is energy independence from foreign nations, and the United Kingdom is bracing itself for nuclear renaissance which is hoped will feed the rapacious centralised system that the UK is structured upon. But what if this centralised system was dissembled, and in its place stood dozens of cities which grow and monopolise from their own energy? Rather than one dominant network, would a series of autonomous city-based energy systems not offer a mutually profitable alternative? Bio-Port is a utopian vision of a ‘Free Energy City’ set in Liverpool, where the old dockyards, redundant space, and the Mersey Estuary have been transformed into bio-productive algae farms. Bio-Port Free Energy City is a utopian ideal, where energy is superfluous; in fact so abundant that meters are obsolete. The city functions as an energy generator and thrives from its own product with minimal impact upon the planet it inhabits. Algaculture is the fundamental energy source, where a matrix of algae reactors swamp the abandoned dockyards; which themselves have been further expanded and reclaimed from the River Mersey. Each year, the algae farm is capable of producing over 200 million gallons of bio-fuel, which in-turn can produce enough electricity to power almost 2 million homes. The metabolism of Free-Energy City is circular and holistic, where the waste products of one process are simply the inputs of a new one. Livestock farming – once traditionally a high-carbon countryside exercise has become urbanised. Cattle are located alongside the algae matrix, and waste gases emitted by farmyards and livestock are largely sequestered by algal blooms or anaerobically converted to natural gas. Bio-Port Free Energy City mitigates the imbalances between ecology and urbanity, and exemplifies an environment where nature and the human machine can function productively and in harmony with one another. According to James Lovelock, our population has grown in number to the point where our presence is perceptibly disabling the planet, but in order to reverse the effects of our humanist flaws, it is vital that new eco-urban utopias are realised.

Dilute phosphoric acid-catalysed hydrolysis of municipal bio-waste wood shavings using autoclave parr reactor system

The visibility of using municipal bio-waste, wood shavings, as a potential feedstock for ethanol production was investigated. Dilute acid hydrolysis of wood shavings with H3PO4 was undertaken in autoclave parr reactor. A combined severity factor (CSF) was used to integrate the effects of hydrolysis times, temperature and acid concentration into a single variable. Xylose concentration reached a maximum value of 17 g/100 g dry mass corresponding to a yield of 100% at the best identified conditions of 2.5 wt.% H3PO4, 175 degrees C and 10 min reaction time corresponding to a CSF of 1.9. However, for glucose, an average yield of 30% was obtained at 5 wt.% H3PO4, 200 degrees C and 10 min. Xylose production increased with increasing temperature and acid concentration, but its transformation to the degradation product furfural was also catalysed by those factors. The maximum furfural formed was 3 g/100 g dry mass, corresponding to the 24% yield. (C) 2011 Elsevier Ltd. All rights reserved.

Arcellacea (Testate Amoebae) as Bio-indicators of Road Salt Contamination in Lakes

Winter deicing operations occur extensively in mid- to high-latitude metropolitan regions around the world and result in a significant reduction in road accidents. Deicing salts can, however, pose a major threat to water quality and aquatic organisms. In this paper we examine the utility of Arcellacea (testate amoebae) for monitoring lakes that have become contaminated by winter deicing salts, particularly sodium chloride. We analysed 50 sediment samples and salt-related water-property variables (chloride concentrations; conductivity) from 15 lakes in the Greater Toronto Area and adjacent areas of southern Ontario, Canada. The sampled lakes included lakes in proximity to major highways and suburban roads, and control lakes in forested settings away from road influences. Samples from the most contaminated lakes, with chloride concentrations in excess of 400 mg/l and conductivities of >800 μS/cm, were dominated by species typically found in brackish and/or inhospitable lake environments and by lower faunal diversities (lowest Shannon Diversity Index values) than samples with lower readings. Q-R-mode cluster analysis and Detrended Correspondence Analysis (DCA) resulted in the recognition of four assemblage groupings. These reflect varying levels of salt contamination in the study lakes, along with other local influences, including nutrient loading. The response to nutrients can, however, be isolated if the planktic eutrophic indicator species Cucurbitella tricuspis is removed from the counts. The findings show that the group have considerable potential for biomonitoring in salt-contaminated lakes, and through application to lake sediment cores, may provide significant insights into long-term benthic community health, which is integral for remedial efforts.

Development and characterization of self-assembling nanoparticles using a bio-inspired amphipathic peptide for gene delivery

The design of a non-viral gene delivery vehicle capable of delivering and releasing a functional nucleic acid cargo intracellularly remains a formidable challenge. For systemic gene therapy to be successful a delivery vehicle is required that protects the nucleic acid cargo from enzymatic degradation, extravasates from the vasculature, traverses the cell membrane, disrupts the endosomal vesicles and unloads the cargo at its destination site, namely the nucleus for the purposes of gene delivery. This manuscript reports the extensive investigation of a novel amphipathic peptide composed of repeating RALA units capable of overcoming the biological barriers to gene delivery both in vitro and in vivo. Our data demonstrates the spontaneous self-assembly of cationic DNA-loaded nanoparticles when the peptide is complexed with pDNA. Nanoparticles were < 100 nm, were stable in the presence of serum and were fusogenic in nature, with increased peptide α-helicity at a lower pH. Nanoparticles proved to be non-cytotoxic, readily traversed the plasma membrane of both cancer and fibroblast cell lines and elicited reporter-gene expression following intravenous delivery in vivo. The results of this study indicate that RALA presents an exciting delivery platform for the systemic delivery of nucleic acid therapeutics.

Combining Bio- and Chemo-catalysis for the Conversion of Bio-Renewable Alcohols

The use of biomass as a source of fuel is on the sharp increase. In parallel with this expansion, new chemical processes and technologies are required to improve efficiency, sustainability, and profitability.
Biocatalytic and chemocatalytic methods can be combined to affect the conversion of bio-alcohols, and convert them to valuable chemical targets in an atom efficient and environmentally benign manor. Fermentation offers a useful first step in biomass conversion, as whole cell biocatalysts can provide sustained activity when fed with crude biomass. Coupling this with homogeneous and/or heterogeneous catalysis enables the preparation of a diverse product range. The transition between biocatalytic and chemocatalytic steps can be assisted by utilising ionic liquids.
Ionic liquids have potential roles in biorefineries that generate alcohols; as an extractant, reaction medium, and catalytic reagent. Underpinning the potential of ionic liquids in this area is: 1. the ability of ionic liquids to solubilize polyols and alcohols; 2. the facility to functionalise ionic liquids and tune properties; 3. the low volatility of ionic liquids.
The FP7 project GRAIL will be highlighted; this project focusses on the utilisation of glycerol formed as a by-product in biodiesel synthesis.

A Microbial Link to Weathering of Postglacial Rocks and Sediments, Mount Viso Area, Western Alps, Demonstrated through Analysis of a Soil/Paleosol Bio/Chronosequence

Understanding the mechanism associated with rates of weathering and evolution of rocks→sediment→soil→paleosol in alpine environments raises questions related to the impact of microbial mediation versus various diverse abiotic chemical/physical processes, even including the overall effect of cosmic impact/airburst during the early stage of weathering in Late Glacial (LG) deposits. This study is of a chronosequence of soils/paleosols, with an age range that spans the post–Little Ice Age (post-LIA; <150 yr), the Little Ice Age (LIA; AD 1500–1850), the middle Neoglacial (∼3 ka)–Younger Dryas (YD; <12.8 ka), and the LG (<15 ka). The goal is to elicit trends in weathering, soil morphogenesis, and related eubacterial population changes over the past 13–15 k.yr. The older LG/YD paleosols in the sequence represent soil morphogenesis that started during the closing stage of Pleistocene glaciation. These are compared with undated soils of midto late Neoglacial age, the youngest of LIA and post-LIA age. All profiles formed in a uniform parentmaterial ofmetabasalt composition and in moraine, rockfall, protalus, and alluvial fan deposits. Elsewhere in Europe,North America, and Asia, the cosmic impact/airburst event at 12.8 ka often produced a distinctive, carbon-rich “black mat” layer that shows evidence of high-temperature melting. At this alpine site, older profiles of similar LG age contain scorched and melted surface sediments that are otherwise similar in composition to the youngest/thinnest profiles developing in the catchment today. Moreover, microbial analysis of the sediments offers new insight into the genesis of these sediments: the C and Cu (u = unweathered) horizons in LG profiles present at 12.8 ka (now Ah/Bw) show bacterial population structures that differ markedly from recent alluvial/protalus sample bacterial populations. We propose here that these differences are, in part, a direct consequence of the age/cosmic impact/weathering processes that have occurred in the chronosequence. Of the several questions that emerge from these sequences, perhaps the most important involve the interaction of biotic-mineral factors, which need to be understood if we are to generally fully appreciate the role played by microbes in rock weathering.