bluuebunny/crossref_metadata_2025_split huggingface dataset:
Industrial Applications of Homogeneous Enantioselective Catalysts
Authors: Blaser Hans‐Ulrich , Hoge Garrett , Pugin Benoît , Spindler Felix 
Published: June 2010

AbstractThis chapter describes the state of the art of the application of homogeneous enantioselective catalysts for the industrial production of chiral fine chemicals. Covered are enantioselective catalytic processes that have been and/or are currently used for the commercial manufacture of chiral compounds and also selected pilot‐ and bench‐scale processes not (yet) used in actual production, together with a few selected feasibility studies. After a short introduction, essential requirements and suitable strategies for the application of homogeneous catalysis in fine chemicals production are discussed. In the subsequent sections, enantioselective catalytic processes are described, organized according to the following reactions and substrate types: hydrogenation of dehydro‐α‐ and ‐β‐amino acid derivatives; simple enamides and enol acetates; itaconic acid derivatives; allylic alcohols and α,β‐unsaturated acids; miscellaneous CC systems; α‐ and β‐functionalized ketones; aromatic ketones; CN bonds; oxidation of sulfides; Sharpless epoxidation and dihydroxylation; Jacobsen epoxidation; isomerization; addition reactions to CC, CO and CN bonds; and opening of oxacycles.
Hydrogenation forCCBond Formation
Authors: Bower John F. , Krische Michael J. 
Published: June 2010

AbstractThe sections in this article areBy‐product‐freeCCCoupling and the Departure from Preformed Organometallic ReagentsHydrogenative Vinylation of Carbonyl Compounds and IminesHydrogenative Allylation of Carbonyl CompoundsHydrogenative Aldol and Mannich AdditionsHydrogenative Acyl Substitution (Reductive Hydroacylation)Hydrogenative CarbocyclizationFuture DirectionsAcknowledgments
Palladacycles in Catalysis
Authors: Dupont Jairton , Flores Fabricio R. 
Published: June 2010

Abstract
Palladium compounds containing a Pd‐C that are stabilized intramolecularly by at least one two‐electron donor group have numerous applications as pre‐catalysts. In particular, these compounds denominated palladacycles possess very attractive properties such as high thermal stability and low air sensitivity and they are ease to handle. These compounds are very active catalyst precursors in Heck coupling, Suzuki coupling, Buchwald–Hartwig amination and related coupling reactions under mild conditions, for instance at room temperature or in water. However, palladacycles serve as precursors to highly active palladium(0) species consist of soluble clusters or colloids, often stabilized by quaternary ammonium salts in highly dilute solutions or highly active low‐coordinate complexes of electron‐rich phosphines or carbenes. Moreover, chiral palladacycles are very important catalysts for enantioselective allylic rearrangements, allylic additions and aldol chemistry, since they act as Pd(II) Lewis acids and no redox process occurs
Homogeneous Catalyst Design for the Synthesis of Aliphatic Polycarbonates and Polyesters
Authors: Coates Geoffrey W. , Jeske Ryan C. 
Published: June 2010

AbstractAliphatic polyesters and polycarbonates are generally biodegradable materials and as a result they have many important uses in agricultural, medical and packaging applications. This chapter focuses on the use of homogeneous catalysts for the synthesis of these environmentally benign polymers.
Zeolites in Catalysis
Authors: Brown Stephen H. 
Published: June 2010

AbstractZeolite catalysts are commonly used tools for the production of fuels and petrochemicals from crude oil and natural gas. The active site in a zeolite catalyst is typically a Brønsted acid. This chapter reviews the mechanisms of acid‐catalyzed reactions of hydrocarbons. When these reactions take place inside the pores of zeolite catalysts, steric constraints influence the product distribution. This is often referred to as shape selectivity. Various types of zeolite shape selectivity are illustrated using important industrial reactions.
Sol–Gel Sulfonic Acid Silicas as Catalysts
Authors: Lee Adam F. , Wilson Karen 
Published: June 2010

Abstract
Silica‐supported sulfonic acids are a class of solid Brønsted acid catalysts that generally comprise organo‐sulfonic acid groups tethered to silica surfaces. Methodologies to prepare organically modified silica have been widely developed in separation science and the techniques for their preparation are well documented. The application of this chemistry to prepare pure Brønsted sulfonic acid functionalized mesoporous silicas has stimulated significant research effort in this area, since these materials are interesting alternatives to commercially available sulfonated polymer resins, such as Amberlyst–15 and Nafion‐H (sulfonated polystyrene and perfluorinated sulfonic acid resins respectively), which suffer from low surface areas and thermal stability. This chapter presents an overview of the preparation of mesostructured silica supported sulfonic acids, their catalytic applications and reviews the approaches taken to tune catalyst performance in organic transformations.
Applications of Environmentally Friendly
Ti
O
2
Photocatalysts in Green Chemistry: Environmental Purification and Clean Energy Production Under Solar Light Irradiation
Authors: Matsuoka Masaya , Anpo Masakazu 
Published: June 2010

Abstract

Recent developments in titanium dioxide‐based photocatalysts are reviewed concerning developments in the highly dispersed TiO
2
photocatalysts prepared on or within zeolites and visible light‐responsive TiO
2
photocatalysts. Special attention is focused on the application of these catalysts in green chemistry, e.g. solar energy conversion and environmental protection. The unique applications of TiO
2
species within zeolites for environmental protection such as reduction of CO
2
and H
2
O and direct decomposition of NO

x

into N
2
and O
2
are discussed, focusing on the relationship between the reactivity and local structures of the TiO
2
species. The preparation of visible light‐responsive TiO
2
photocatalysts by applying ion engineering techniques such as ion implantation and an RF magnetron sputtering deposition method is discussed, with emphasis on its unique reactivity for the separate evolution of H
2
and O
2
from water under sunlight irradiation.
Nanoparticles in Green Catalysis
Authors: Kidwai Mazaahir 
Published: June 2010

AbstractIn recent years, there has been growing interest in the catalytic properties of transition metal nanoparticles. The high surface area‐to‐volume ratio of solid‐supported metal nanoparticles is mainly responsible for their catalytic properties and this can be exploited in many industrially important reactions. Green chemistry and nanotechnology are the tools which can be used simultaneously for the development of the various industrial and biologically active components. Various organic transformations and syntheses were carried out using both methodologies as a synthetic tool, as described in this chapter.
‘Heterogreeneous Chemistry’
Authors: Jacobsen Heiko 
Published: June 2010

Abstract
‘Heterogreeneous Chemistry’ adheres to the philosophy of green chemistry, outlined in the ‘12 Principles of Green Chemistry’, and is intimately linked to heterogeneous catalysis. The concept of ‘Heterogreeneous Chemistry’ is illustrated in catalytic applications relating to uses of renewable feedstocks, in particular biomass. Since solvents play an essential role in green catalysis, ‘heterogreeneous’ aspects of solvents systems are discussed.
Sustainable Heterogeneous Acid Catalysis by Heteropoly Acids
Authors: Kozhevnikov Ivan 
Published: June 2010

AbstractHeterogeneous acid catalysis byheteropoly acids(HPAs) has the potential for substantial economic and green benefits. The aim of this chapter is to discuss the perspectives of acid catalysis by solid HPAs, focusing in particular on several approaches that could help to achieve sustainable catalyst performance. These approaches include developing novel HPA catalysts possessing high thermal stability, modification of HPA catalysts to enhance coke combustion, inhibition of coke formation on HPA catalysts during operation and reactions in supercritical fluids and cascade reactions using multifunctional HPA catalysis.
The Kinetics ofTiO2‐based Solar Cells Sensitized by Metal Complexes
Authors: Fitch Anthony G. , Walker Don , Lewis Nathan S. 
Published: June 2010

AbstractThe sections in this article areIntroductionHistoryDSSCDesignFunction of theDSSCPerformance of aDSSCKinetics ProcessesCharge InjectionRecombination to the DyeRegenerationConclusionAcknowledgment
Automotive Emission Control: Past, Present and Future
Authors: Farrauto Robert J. , Hoke Jeffrey 
Published: June 2010

Abstract

The first automobile catalysts, for gasoline fueled internal combustion engines (IC) were introduced in 1975. They were designed to facilitate the reduction of carbon monoxide (CO) and unburned gasoline derived hydrocarbons (HC). The catalyst had to continue to function with an approximate reduction of 90% (relative to an uncontrolled 1970 vehicle) for 50,000 miles. The automobile industry was skeptical since the success of the catalyst was dependent on the driving and maintenance cycles of the average consumer. Since that time we have seen one of the most successful applications of catalysis for cleaning emissions from IC engines including gasoline, diesel, two and 4 cycle engines, power plants, chemical plants, restaurants, and wide body aircraft to name a few. Today we see the three way catalyst (TWC) as the heart of a closed loop engine control strategy successfully reducing emissions of CO, HC and oxides of nitrogen (NO
x
) to near zero for 150,000 miles. This has clearly been an achievement of epic proportions with a positive impact on the environment and the health of the world.

Now catalytic scientists and engineers are faced with new challenges for controlling diesel engine emissions for trucks, buses and passenger cars. As we approach 2010 Federal Standard emissions of CO, HC, NO
x
and particulates must approach zero levels. The homogeneous charge combustion engine (HCCI) is in development and holds promise for cleaner diesel emissions.

This review provides a brief history of some of the accomplishments in controlling emissions from the gasoline and diesel engines. It also describes alternative technologies under investigation including advanced NO
x
reduction, new engine concepts and the fuel cell as the end game in the hydrogen economy. A common thread for all these technologies is heterogeneous catalysis.
Heterogeneous Catalysis for Hydrogen Production
Authors: Scott Morgan S. , Idriss Hicham 
Published: June 2010

Abstract
Hydrogen is poised as one of the main energy carriers in the future, in particular if ways of making it from renewable sources are made available using reliable technologies. This chapter deals with heterogeneous catalytic systems for making hydrogen from ethanol, a biorenewable source. The two main methods for making hydrogen are discussed: oxidation and reforming. The catalytic role is also discussed in terms of its components with emphasis on noble metals deposited over nanoparticles of cerium oxide, one of the most active catalysts for this reaction.
High‐Throughput Screening of Catalyst Libraries for Emissions Control
Authors: Cypes Stephen , Cizeron Joel , Hagemeyer Alfred , Volpe Anthony 
Published: June 2010

AbstractCatalysis plays a very important role in sustainable and green chemistry applications such as renewable resources for energy and fuels, waste recovery and recycling and low‐ or even zero‐emissions power plants, chemical production sites and vehicles. Emissions control and environmental protection are new challenges that call for novel and far more efficient catalysts to be developed in short time periods. In this chapter, examples of the application of high‐throughput methods to heterogeneously catalyzed green chemistries are discussed. High‐throughput and combinatorial catalysis is ideally suited for the discovery of novel noble metal and mixed metal oxide catalyst formulations for total combustion/volatile organic compound(VOC) removal, emissions control from stationary and mobile sources (NOxabatement, CO oxidation, automotive three‐way catalysis) because simple gas‐phase feeds and product mixes allows for truly parallel detection and very high sample throughputs. Furthermore, these methods are advantageously applicable to multicomponent catalysts (e.g. mixed metal oxides, alloys) for selective oxidation, hydrogenation, dehydrogenation and refining, including desulfurization and denitrification. Additionally, improved fast analytical techniques are making it increasingly possible to perform high‐throughput experimentation on complex real plant or vehicle feeds. This chapter focuses on the primary screening of metal oxides for low‐temperature CO oxidation and VOC combustion using infrared thermography reactors and SCR DeNOxof wafer‐formatted catalyst libraries using scanning mass spectrometry.
Catalytic Conversion of High‐Moisture Biomass to Synthetic Natural Gas in Supercritical Water
Authors: Vogel Frédéric 
Published: June 2010

AbstractMethane produced from waste biomass is a renewable and clean biofuel that can be distributed using the existing natural gas infrastructure. It can be used for heat and power generation and as a transportation fuel. High‐moisture biomass is a relatively untapped resource with a significant energetic potential and attractive costs. However, new technologies are needed for converting high‐moisture biomass efficiently into methane and recovering the nutrients for use as a fertilizer. Gasification of the biomass in a hydrothermal environment is an emerging technology that offers many advantages over gas‐phase conversion processes or anaerobic digestion. Heterogeneous catalysis is the key to a successful hydrothermal gasification process for the synthesis of methane. Only a few metals, including Ru, Ni, Rh and Pt, are useful under these conditions. Pd and Co catalysts might also be suitable but conclusive data are lacking. Alloying is another approach that holds promise to yield active and stable catalysts. The choice of hydrothermally stable supports is limited to some insoluble oxides and carbon. Some of these oxides have not yet been tested as catalyst supports (e.g. Nb2O5, Ta2O5and UO2) and might prove useful. The mechanism for the gasification of the organic compounds to CO and H2is likely to follow a Mars–van‐Krevelen redox cycle with two oxides of the catalytic metal involved. The strongest evidence for such a mechanism was found for RuO2, but specificin situstudies are needed for corroborating this hypothesis and determining the actual oxidation states involved in the mechanism. Deactivation in hydrothermal gasification follows the same modes as in gas‐phase and liquid‐phase catalysis. Coke deposition is not a primary cause of deactivation due to the high partial pressure of water and the high solubility of coke precursors in near‐ and supercritical water. Salts play a crucial role in catalyst deactivation. Sulfate was found to be a strong poison for Ru catalysts, but the actual poison might be sulfide, formed by reduction of the sulfate with hydrogen or organic compounds. Based on this knowledge, a continuous catalytic hydrothermal gasification process is under development at PSI featuring continuous on‐line salt precipitation and removal before the catalytic reactor.
Catalysis with CytochromeP450 Monooxygenases
Authors: Urlacher Vlada B. 
Published: June 2010

AbstractCytochromes P450 belong to the ever‐growing superfamily of heme‐containing monooxygenases with currently more than 7700 gene sequences found in all domains of life. Cytochrome P450 enzymes play a central role in drug metabolism and have been shown to be involved in the biosynthesis of important natural compounds. These enzymes convert a vast range of substrates and catalyze diverse reactions. Their properties have been used for drug development, bioremediation and the synthesis of fine chemicals. Significant progress has been made over the past decade in engineering P450 monooxygenases with widely altered substrate specificities, substantially increased activity and enhanced stability. Furthermore, several approaches for the replacement or regeneration of the cofactor NAD(P)H have been developed, allowing the more cost‐effective use of P450 enzymes. In this chapter, we focus on the recent progress in applying P450 monooxygenases as biocatalysts. The P450 engineering issue will also be discussed.
Biocatalytic Processes Using Ionic Liquids and Supercritical Carbon Dioxide
Authors: Lozano Pedro , De Diego Teresa , Iborra José L. 
Published: June 2010

AbstractBiocatalytic processes based on ionic liquids (ILs) and supercritical carbon dioxide are interesting alternatives to organic solvents for designing clean synthetic chemical processes to obtain pure products directly. In such enzymatic processes, the classical advantages of supercritical carbon dioxide to extract, dissolve and transport chemicals are compromised by the denaturing effect that it has on enzymes. On the other hand, ILs have shown themselves to be excellent non‐aqueous environments for enzyme catalysis. Biphasic systems based on ILs and supercritical carbon dioxide have been proposed as the first approach to integral green bioprocesses in non‐aqueous media, where both the biocatalytic and extraction steps are coupled in an environmentally benign and efficient reaction/separation process.
Thiamine‐Based Enzymes for Biotransformations
Authors: Pohl Martina , Gocke Dörte , Müller Michael 
Published: June 2010

AbstractChiral and prochiral α‐oxyfunctionalized compounds, in particular carboxylic acids, aldehydes, ketones, alcohols, are indispensable building blocks for asymmetric synthesis. 2‐Hydroxy ketones encompassing a chiral and prochiral center are therefore versatile building blocks for organic synthesis, as they can be easily transformed into other functionalities, such as diols, epoxides, amino alcohols and diamines. The review describes the current state of the art concerning thiamine diphosphate‐dependent enzymes, which catalyze the formation of chiral 2‐hydroxy ketones.
Baeyer–Villiger Monooxygenases in Organic Synthesis
Authors: Kirschner Anett , Bornscheuer Uwe T. 
Published: June 2010

AbstractThe sections in this article areIntroductionGeneral Aspects of the Baeyer–Villiger OxidationMechanistic AspectsChemical Versus Enzymatic Baeyer–Villiger OxidationBiochemistry of Baeyer–Villiger MonooxygenasesCatalytic MechanismStructural FeaturesApplication of Baeyer–Villiger Monooxygenases in Organic ChemistryIsolated Enzymes Versus Whole CellsBaeyer–Villiger Monooxygenases Relevant for Synthetic ApplicationsRepresentative Synthetic ApplicationsKinetic Resolutions of Racemic KetonesDesymmetrization of Prochiral KetonesRegiodivergent TransformationsLarge‐Scale ApplicationHeteroatom OxidationProtein EngineeringConclusions and PerspectivesAcknowledgments
Biotransformations and the Pharma Industry
Authors: Meyer Hans‐Peter , Ghisalba Oreste , Leresche James E. 
Published: June 2010

AbstractBiotechnology should focus on areas where organic chemists have a true need. This is less in the area of renewable feedstocks than in the area of ecologically burdened synthetic chemical methods, which should be replaced as soon as possible by biotransformation steps. An analysis of the organic chemical toolbox shows the directions in which the efforts in enzyme screening and improvement must go. The still suboptimally equipped enzymatic toolbox must be filled with readily available enzymes that can be used by organic chemists.
PAHBioremediation by Microbial Communities and Enzymatic Activities
Authors: Andreoni Vincenza , Gianfreda Liliana 
Published: June 2010

AbstractPolycyclic aromatic hydrocarbons (PAHs) are hydrophobic, persistent, ubiquitous pollutants of the environment. The capability for PAH degradation of soil indigenous microorganisms has been investigated in numerous studies. PAH‐degrading bacteria have been found in pristine and contaminated temperate and tropical zone ecosystems, in Arctic and Antarctic soils, in sediments and in the rhizosphere of numerous different plants. A broad range of oxygenases is distributed among the microorganisms growing on PAHs and several groups of genes for the initial PAH oxygenation are now known. Gene sequences encoding for enzymes specific for the initial and ring oxygenase have been used to construct specific probes. The broad biodegradative capabilities evolved by microorganisms towards these compounds and the available tools for monitoring their presence in the environment account for bioremediation‐based strategies with the potential to restore PAH‐contaminated soils. Compost and composting matrices have enormous potential for assisting the bioremediation of PAH‐polluted soils and both techniques have been successfully applied to ameliorate soil contaminated with PAHs. One way to achieve trulyin situbioremediation is by utilizing plants to perform rhizosphere bioremediation. Phytoremediation is of particular interest as a secondary polishing approach for PAH‐contaminated soil previously treated by land farming, augmentation of the soil with selected PAH‐degrading bacteria and growth of plants with plant growth‐promoting rhizobacteria. A different approach, alternative to whole microbial and plant cells, is the use of extracellular enzymes, such as oxidoreductases of fungal origin with known abilities to transform or even to degrade PAHs effectively.
Introduction
Authors: Jessop Philip , Leitner Walter 
Published: June 2010

AbstractThe sections in this article areWhat is a Supercritical Fluid (SCF)?Practical Aspects of Reactions in Supercritical FluidsThe Motivation for Use ofSCFsin Modern Chemical SynthesisThe History and Applications ofSCFsThe Discovery ofSCFsand Their Use as SolventsExtraction and Chromatography inSCFsThe History of Chemical Reactions inSCFsIndustrial Use ofSCFsas Reaction Media
Basic Physical Properties, Phase Behavior and Solubility
Authors: Foster Neil R. , Lucien Frank P. , Mammucari Raffaella 
Published: June 2010

AbstractThe sections in this article areIntroductionBasic Physical Properties of Supercritical FluidsPhase Behavior in High‐Pressure SystemsTypes of Binary Phase DiagramsAsymmetric Binary MixturesFactors Affecting Solubility in Supercritical FluidsThe Supercritical SolventChemical Functionality of the SoluteTemperature and Pressure Effects
Expanded Liquid Phases in Catalysis: Gas‐expanded Liquids and Liquid–Supercritical Fluid Biphasic Systems
Authors: Hintermair Ulrich , Leitner Walter , Jessop Philip 
Published: June 2010

AbstractThe sections in this article areA Practical Classification of Biphasic Systems Consisting of Liquids and Compressed Gases for Multiphase CatalysisPhysical Properties of Expanded Liquid PhasesVolumetric ExpansionDensityViscosityMelting PointInterfacial TensionDiffusivityPolarityGas SolubilityChemisorption of Gases in Liquids and their Use for Synthesis and CatalysisIn SituGeneration of Acids and Temporary Protection StrategiesSwitchable Solvents and Catalyst SystemsUsing Gas‐expanded Liquids for CatalysisMotivation and Potential BenefitsSequential Reaction–Separation ProcessesTunable Precipitation and CrystallizationTunable Phase SeparationsTunable MiscibilityHydrogenation ReactionsCarbonylation ReactionsOxidation ReactionsMiscellaneousWhy Perform Liquid–SCFBiphasic Reactions?By Necessity (Unintentional Immiscibility)To Facilitate Post‐Reaction SeparationTo Facilitate Product/Catalyst Separation in Continuous Flow SystemsTo Stabilize a CatalystTo Remove a Kinetic ProductTo Control the Concentration of Reagent or Product in the Reacting PhaseTo Permit Emulsion PolymerizationTo Create Templated MaterialsBiphasic Liquid–SCFSystemsSolvent SelectionAqueous–SCFBiphasic SystemsIonic Liquid–SCFBiphasic SystemsPolymer–SCFBiphasic SystemsLiquid Product–SCFBiphasic SystemsBiphasic Reactions in EmulsionsWater‐in‐SCFInverse EmulsionsSCF‐in‐Water EmulsionsIonic Liquid‐in‐SCFEmulsionsApplications of Emulsions