Outlook and Conclusion

Yamada, S., and Kunitake, T. (1997) Thin Solid Films, 300, 107. 

Brumen, M., and Moehwald, H. (2004) Phys. Chem. Chem. Phys., 6, 4078. 

Design and Applications (ed. S. Minko), Blackwell Publishing Professional, Ames, lA. p. 229. 

7 Layer-hy-Layer Selj-kssemhled Multilayer Stimuli-Responsive Polymeric Films 

Munoz-Dorado, M., and Rodn guez-Garci a, I. (2008) Chem. 

Another notable early example of heterocycle synthesis via cobalt-mediated C-H activation would be the transformation of Af,Af-diallylanilines into quinoline derivatives reported by Jones and coworkers [6]. The reaction of AfAf-diallylaniline in the presence of a catalytic amount of Co2(CO)g under 

Transition Metal-Catalyzed Heterocycle Synthesis via C—H Activation, First Edition. Edited by Xiao-Feng Wu. 2016 Wiley-VCH Verlag GmbH Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH Co. KGaA. 

While major advances in the area of C-H functionalization have been made with catalysts based on rare and expensive transition metals such as rhodium, palladium, ruthenium, and iridium [7], increasing interest in the sustainability aspect of catalysis has stimulated researchers toward the development of alternative catalysts based on naturally abundant first-row transition metals including cobalt [8]. As such, a growing number of cobalt-catalyzed C-H functionalization reactions, including those for heterocycle synthesis, have been reported over the last several years to date (early 2015) [9]. The purpose of this chapter is to provide an overview of such recent advancements with classification according to the nature of the catalytically active cobalt species involved in the C-H activation event. Besides inner-sphere C-H activation reactions catalyzed by low-valent and high-valent cobalt complexes, nitrene and carbene C-H insertion reactions promoted by cobalt(II)-porphyrin metalloradical catalysts are also discussed. 

Heterocycle Synthesis via Low-Valent Cobalt-Catalyzed C-H Activation 

Since the discovery and development of highly efficient Rh catalysts with chiral diphosphites and phosphine-phosphites in the 1990s, the enantioselectivity of asymmetric hydroformylation has reached the equivalent level to that of asymmetric hydrogenation for several substrates. Nevertheless, there still exist substrates that require even further development of more efficient chiral ligands, catalyst systems, and reaction conditions. Diastereoselective hydroformylation is expected to find many applications in the total synthesis of complex natural products as well as the syntheses of biologically active compounds of medicinal and agrochemical interests in the near future. Advances in asymmetric hydrocarboxylation has been much slower than that of asymmetric hydroformylation in spite of its high potential in the syntheses of fine chemicals. 

The asymmetric catalytic Pauson-Khand reaction met success in the late 1990s. Not only the conventional Co catalyst but also other metal complexes, such as Ti, Rh, and Ir, are applicable to the reaction. Asymmetric hydrocyanation of vinylar-enes is accomplished using Ni complex of chiral diphosphite. Further studies on the scope and limitation are expected. 

Asymmetric addition of small-molecule nucleophiles to carbonyl groups and their derivatives are catalyzed by either Lewis acids or Lewis bases. Carbon dioxide is now a promising building block for as5mimetric organic synthesis. 

Several asymmetric polymerization of small molecules have been reported applying the asymmetric catalysis methodology to polymer synthesis. Unique physical properties due to the mainchain stereoregularity are envisioned. 

Pfaltz, A. In Comprehensive Asymmetric Catalysis, Vol. 1, Chap. 1 Jacobsen, E. Phaltz, A. Yamamoto, H, (Eds.), Springer-Verlag, Berlin, 1999. 

Ink-jet printer heads and digital mirror devices can presently be regarded as the most successful microactuators on the market. From an economic point of view the ink-jet printer head can even be said to be the most successful device of all currently available microsystems. This demonstrates the extraordinary commercial potential of microactuators in an impressive way. 

Microfluidic actuators for controlling fluids have a very high potential of penetrating into new applications outside the printer field. This includes infusion pumps for use in medicine industrial and micromechanical valves for various applications, microdosing of fluids in microarray technology and other applications. 

The market outlook appears to be particularly favomable for microvalves, driven by piezoelectric bending transducers or thermal principles. Such devices are already being produced and sold by several companies. The possible applications of these valves will increase when they can be mass-produced inexpensively and operated with very low power consmnption. Stimulus can be expected particularly from valves with 3/2-way functionahty, to be introduced as pilot valves in many areas of automation. 

Micropumps for transporting and dosing small liquid quantities represent another main group of microfluid actuators. The fact that these pumps are 

Strongly miniaturized micromotors based on electromagnetic forces on the threshold of commercial application, whereas electrostatic micromotors are still in a demonstrator stadium. 

Encinas, A., Keck, )., and Rising, C.F. (2009) Chem. Rev., 109, 3903. Resorcylic Acid Lactones A Pluripotent Scaffold with Therapeutic Potential, S. Barluenga, P.-Y. Dakas, 

Boulifa, E. Moulin, N. Winssinger, (2008), C. R. Chim., 11, 1306-1317. Hsp90 Inhibition with Resorcyclic Acid Lactones (RALs), N. Winssinger, ).-G. Fontaine, S. Barluenga, (2009), Cun. Topic Med. Chem., 9, 1419-1435. 

For a few papers reporting SAR studies, see (a) Napolitano, C., Natoni, B., Santocanale, C., Evensen, L, Lorens, 

Liniger, M., Neuhaus, C., Hoftnann, T., Fransioli-Ignazio, L., Jordi, M., 

Tanaka, I., Ikemori-Kawada, M., Kawakami, Y., Inoue, A., Kawai, T., Kishi, Y., and Wang, Y. (2009) Bioorg. Med. Chem. 

2763 (d) Kennedy, J.W.J. and Hall, D.G. (2003) Angew. Chem., Int. Ed., 42, 4732 (e) For a detailed discussion of changing the electronics of the silicon upon extra coordination to Lewis bases, see  

7 (a) Allyl trichlorosilane is conveniently prepared from allyl chloride, C SiH, CuCl, and (i-Pr)2EtN (or EtsN) in ether at 20°C Kobayashi, S. and Nishio, K. 

13 For the reaction catalyzed by Lewis adds see Fleming, 1. (1991) Allylsilanes, aUylstannanes and related systems, in Comprehensive Organic Synthesis, vol. 2 (eds B.M. Trost and I. Fleming), Pergamon, Oxford, p. 563. 

14 (a) trans-Crotyl trichlorosilane can be synthesized from trans-crotyl chloride, QsSiH, CuQ, and (i-Pr)2EtN in ether at 20°C see Reference [7] and the following Aoki, S., Mikami, K., Terada, M., and Nakai, T. (1993) Tetrahedron, 49, 1783 (b) D Aniello, F Falorni, M Mann, A., and Taddei, M. (1966) Tetrahedron Asymmetry, 7,1217  

15 (a) cis-Crotyl trichlorosilane can be prepared via the 1,4-addition of CljSiH to butadiene, catalyzed by (PhCN)2PdCl2 

Oxocarbons, pseudo-oxocarbons, and squaraines are a very versatile class of compounds, being useful in a wide range of areas, from model compounds to medicinal chemistry. Their role in coordination of metal ions appears to be their most important property. For the coming years, oxocarbons and their derivatives will be very important in crystal engineering. For this application, their impressive ability to provide several different coordination modes is particularly important. 

de Oliveira, L.F.C. (1991) Estudo espec-troscopico de compostos policarbonilicos e de seus compostos de coordenagao. PhD Thesis. Universidade de Sao Paulo, Brazil. 

(1998) J. Chem. Soc., Dalton Trans., 24, 4131-4137 (c) Ucar, I. and Bulut, A. (2005) Acta Crystal-logr. Sect. E, 61, M2730-M2732  

Nichol, G.S., Harrington, R.W., and Clegg, W. (2005) Acta Crystallogr. Sect. 

(a) Klewe, B. (1971) Acta Chem. Scand., 25 (6), 1975- (b) de Oliveira, V.E. (2007). Sintese e caracteriza ao de complexes e esquarainas. Master Dissertation. Universidade Federal de Juiz de Fora, Brazil. 

The Pd-Pb intermetallic catalyst and Au-NiO, nanoparticle catalyst developed and industrialized by Asahi Kasei are both unprecedented and unique aerobic oxidative esterification catalysts. We believe that three production processes - our oxidative esterification method (TEA to C4 isobutene hydrocarbon feedstock) in addition to the alpha process (C2 ethylene hydrocarbon feedstock) and the improved ACH process (C3 propene hydrocarbon to acetone feedstock see Chapter 7 in this book on the cumene-based phenol process) - will be competing for the top position in the global market as the MMA manufacturing method. 

On the other hand, if the oxidative esterification reaction is considered as a general synthetic method for esters, it is quite significant that the Au-NiO, catalyst can almost completely suppress production of the ester by-product derived from oxidation of the alcohol reaction partner. As a general organic synthetic method for esters, it is not controlled by the equilibrium theory, and it is expected to develop as a green manufacturing method that does not require acid or alkali and does not proceed via organic acids. 

(2003) Esterification Methods, Reaction and Applications, Wiley-VCH Verlag GmbH, Weinheim. 

Shiraish, T. and Mouri, Z. (1974) Manufacturing method of x,p-unsaturated acid and its esters. Japanese Patent 49-35322 Al, Apr. 1, 1974, to Sumitomo Chemical Co., Ltd. 

State energy through fluorescence and crosses over efficiently ( isc = 45%) to the triplet state (Ti). The corresponding quantum yields for the branched 21b are F = 15% and isc = 3% [127]. 

Fukui functions support the understanding of biotic and abiotic reactions and degradation processes for small molecules. In conjunction with (bio-)chemical expertise and experience, Fukui functions can also be used to predict reactive behavior. In contrast to other quantum chemical approaches to reactivity, the calculation of Fukui functions does not directly depend on energies for open shell systems, which require a higher level of theory to be of acceptable quality. 

The fundamental weakness of this ligand-based approach, the disregard of any enzyme specihc interactions, may also be viewed as a strength Metabolism is not restricted to oxidation mediated by cytochrome, nor is it restricted to electrophilic attack. Fukui functions lf as well as/ ) may thus help to imderstand in vivo metabolic reactions of unknown enzymatic origin. 

Fukui calculations for Cpd 1 are in line with experimental and theoretical evidence. Development of a combined docking/local reactivity approach could be a less reliable, but significantly cheaper, alternative to QM/MM studies on full reaction paths. 

exciting developments can be expected from conceptual DFT, for example the extension of the theory to excited state Fukui functions , which may be of interest for an abiotic degradahon process of particular interest for agro-chemistry Photodegradation. 

The authors want to thank Thorsten Burger and Svend Matthiessen for their assistance in performing the calculations. 

Within more than a decade, nanoscience and nanotechnology have been greatly developed, resulting in a wide range of techniques, processes, devices, and applications covering various fields such as mechanical, thermal, electrical, optical, energy, medical, and food, as discussed in this chapter from the aspect of polymer nanocomposites. The supplied list is not exhaustive and the treated topics could be considered as representative in this field. 

Despite important progress in understanding the structure-property relationship and in successful experimentation of composite materials and devices, commercial products using polymer composites are still scarce on the market. A number of available commercial utilities taken from company and industry information are recently reviewed [131]. Among these, one can find items such as tennis balls, tennis rackets, tires, automotives, bandage, beverage containers, and so on. Various applications such as OLEDs, dental composites, batteries, and so on can also be added to this list. To explain the limited number of industrial commercialized applications, two facts can be evoked. First, economic competition requires products to be profitable, that is, there should be a high demand for them, and this will 

From the scientific viewpoint, a number of issues are yet to be solved for improving the quality of the material as well as the fabrication process. An important factor to warrant the properties of composites is the quality of the fillers. They should have a well-defined distribution and will therefore need a precise control over the fabrication process. The dispersion of fillers in the polymer matrix should also be carefully performed and controlled for obtaining reliable expected properties. Future developments of nanotechnology should take into account this aspect to simplify the fabrication process by keeping the same material quality. The concept of nanocomposites may be oriented toward a better organization of the structure with ordered or aligned nanofillers, to allow production of high-quality materials at low cost. 

1 Jancar, J., Douglas, J.F., Starr, F.W., Kumar, S.K, Cassagnau, P., Lesser, A.J., Stemstein, S.S., and Buehler, M.J. (2010) Current issues in research on structure-property relationships in polymer nanocomposites. Polymer, 51, 3321-3343. 

2 Eder, D. (2010) Carbon nanotube-inorganic hybrids. Chemical Reviews, 110, 1348-1385. 

Biodegradable shape memory polymers are candidates for the next promising generation of implant materials. The fact that these materials belong to a polymer system allows the adjustment of certain properties in a wide range, e.g. mechanical properties and degradation behaviour. Today, such materials can be synthesized in a kilogram scale. 

It is well established that microreactors and continuous flow synthesis enable reactions to be performed more rapidly, efficiently, and selectively than batch reactions. In addition to traditional solution phase synthesis, microreactor technology has now been demonstrated to effldently enable photochemistry and electrochemistry to be more easily introduced into the methodology available to the synthetic chemist. As illustrated within this chapter, it is also possible to conduct PET radiosynthesis within these systems where a key advantage is that the processing time can be substantially reduced. 

7 Beltuau, V., Noeureuil, P Ratzke, E Skvortsov, A., Gallagher, S Motti, CA and OdgemoHer, M. (2010) Tetrahedron Lett., 

11 Matsubara, H., Hino, Y, and Ryu, I. (2010) Proceedir cfthe 11th International Corference on Microreaction Technology, Kyoto, Japan, pp. 44-45. 

The competitive nature of the pharmaceutical industry and the high costs associated with drug development has created great demands for improvements in the 

Current technologies, implemented in the laboratories, have aheady improved the knowledge basis in early discovery and development however, more is to come. Genomic and in silico techniques, once validated, will be able to provide information economically and with a broader spectrum of detailed information on the mechanism or pathway affected. 

Bolger, B. Agoram, R. Fraczkiewicz and B. Steere in Drug Bioavailability. Estimation of Solubility, Permeability and Bioavailability , H.v.d. Waterbeemd, H. Lennemas and R Artursson (eds), Wiley, Weinheim, 2003. 

R Hammett, Physical Organic Chemistry Reaction Rates, Equilibria, and Mechanisms , McGraw-Hill, New York, 1940. 

Perrin, B. Dempsey andE.P. Serjeant, pKa Prediction for Organic Acids and Bases , Chapman Hall, London and New York, 1981. 

Advanced characterization of the structure, properties and function of the self-assembled precursor can be extrapolated from studies on the more robust crosslinked material, especially in changing or challenging environments, in which the assemblies would not remain intact. The introduction of crosslinks has aided in the maintenance of native conformations as a powerful technique during studies to determine the order and structure of biological assemblies [61, 62], Moreover, the robust characteristics that the crosslinks provide, combined with the ability to define their regioselectivity, are expected to expand the realm of possible applications for nanoscale materials. 

The new connective sites provide the opportunity to destroy or disconnect other regions of the nanostructure without destruction of the entire nanoscale entity. This was demonstrated by the excavation of the core of shell crosslinked polymer micelles, by the removal of the colloid from colloidally templated 

The nonionic template strategy based on hydrogen bonds and to a certain extent on n-n interactions has made catenanes and rotaxanes readily available. The molecular recognition and self-organization process which is responsible for the formation of intertwined and interlocked structures is founded upon the same weak interactions that govern many biological processes. Amide-based catenanes and rotaxanes can thus serve as valuable models for complex molecular recognition patterns in nature. 

The great variety of incorporable building blocks also offers the synthetic chemist many potential structural and functional design possibilities. The insertion of, e.g., photo-responsive elements, groups with further supramolecular derivatization potential, or sulfonamide units which enable subsequent inter- and intramolecular linkage of catenanes and rotaxanes might render good service in the development of molecular switches [64] and devices [65]. 

Amide-linked catenanes and rotaxanes can play a major role in the study of rare forms of chirality, e.g. topological chirality and cycloenantiomerism [60]. Resolution of enantiomeric catenanes, rotaxanes, and pretzelanes has been achieved by HPLC on chiral column materials, but further work must be performed to determine absolute configurations and to realize new chiral skeletons composed of achiral building blocks. Topological asymmetric synthesis still belongs to dreams of the future yet should be kept in mind. 

Much is expected of new slipping procedures performed in the melt. Results with a pure hydrocarbon axle have shown that attractive interactions such as hy- 

Summing up, it can be said that interwoven and interlocked molecules open up enormous possibilities not only to chemists but also to interdisciplinary researchers. Non-ionic templated syntheses and the newly established non-template strategy are powerful tools for further rapid and unprecedented developments in this field. 

In this chapter, we have presented some of the recent developments and applications of ATR FT-IR imaging to pharmaceutical samples, materials development, and biomedical apphcations. The use of both micromode and macromode in ATR FT-IR imaging has been discussed as have relevant examples of transmission 

Along with the development of these approaches, swollen polystyrene- and poly(chloromethylstyrene)-type polymeric precursors were first investigated for the post-erosslinMng proeedure. Followed by the diseovety of functionalized aromatie ben l ehlorides, groundbreaking progress in this field has 

This work was carried out by Marie Hutin, David Schultz, David Gerard, and Sonya Torche, in addition to our collaborators Christopher Cramer, Laura Gagliardi, 

Gerald Bernardinelli, Christoph Schalley, Jerome Lacour, Richard Frantz, Damien Jeannerat, Andre Pinto and Philippe Perrottet. Financial support has been provided by the Walters-Kundert Chairtable trust, the University of Geneva, the Swiss National Science Foundation, the ERA-Chemistry Network, and the Swiss State Secretariat for Education and Research. 

12 Albrecht, M. (2000) Journal of Inclusion Phenomena and Macrocyclic Chemistry, 36, 127-51. Seidel, S.R. and Stang, P.). 

I am indebted to my colleagues, whose names are cited in the references, and who made this research possible. I also thank the Canada Research Chair (Tier I) Foundation, the CFI, NSERC, and the (US) NSF-EPA Joint Program for a Sustainable Environment for their partial support of this research. 

Corey and X. M. Cheng, The Logic of Chemical Synthesis, John Wiley Sons, New York, 1989, pp. 1-91. 

Organic Chemistry, Pearson Education, New Jersey, 4th edn, 2004. 

Fleming, Pericyclic Reactions, Oxford University Press, New York, 1999, pp. 1-89. 

http //www.nobelprize.org/nobel prizes/chemistry/laureates/. 

The resulting semi-quantitative model was used in conjunction with structure-based docking and scoring, 3D-QS AR based affinity and selectivity predictions and in silico ADME models to estimate membrane permeability, solubility, and other key properties for the optimization process in this series. Hence, in this as well as in other series, multiple models can be collectively applied for ranking and prioritizing synthesis candidates and focused virtual libraries during advanced stages of multidimensional compound optimization. 

Hudson BD, Hyde RM, Rahr E et at. (1996) Parameter based methods for compound selection from chemical databases. Quant Struct-Act Relat 15 285-289 Matter H, Schwab W, Barbier D et al. (1999) Quantitative structure-activity relationship of human neutrophil col-lagenase (MMP-8) inhibitors using comparative molecular field and X-ray structure analysis. J Med Chem 42 1908-1920 

Matter H, Schudok M, Schwab W et al. (2002) Tetrahydroisoquinohne-3-carboxylate based matrix-metalloproteinase inhibitors Design, synthesis and structure-activity relationship. Bioorg Med Chem 10 3529-3544 

Matter H, Schudok M (2004) Recent advances in the design of matrix metalloproteinase inhibitors. Curr Opin Drug Disc Dev 7 513-535 

Sadowski J, Rudolph C, Gasteiger J (1992) The generation of 3D models of host-guest complexes. Anal Chim Acta 265 233-241 

Using a combination of several in situ characterization methods to look at working catalysts, and catalytic reactions, from different perspectives, represents a substantial step toward elucidating the chemistry of catalyst materials and associated reaction mechanisms. 

Continuing technological developments and the wide availability of more flexible fiber-optic systems for different spectroscopies offer new possibilities for realizing multitechnique in situ approaches for catalytic research. Several devices for different spectroscopies are already commercially available, although complete systems for reaction monitoring remain comparatively expensive. 

Utilization of setups including X-rays for in situ characterization of catalytic systems requires access to synchrotrons, and is therefore rather restricted to groups with the requisite expertise. To overcome this, more intensive collaboration between catalytic scientists and synchrotron specialists should be encouraged. 

It has to be realized that no universal multitechnique setup exists to address aU problems, as each in situ method has specific technical requirements (e.g.. 

Although the use of multitechnique approaches requires specialist operator knowledge, in particular, concerning the interpretation of the resulting spectroscopic data, the apphcations, and type of information produced should motivate catalyst scientists to apply combined spectroscopic techniques to provide comprehensive insight into catalytic reactions and the catalyst mode of action. 

1) AlN substates with a diameter up to 2 indi are available from Crystal IS, Inc. 70 Cohoes Avenue, Green Island, NY 12183, USA. 

The author is indebted to his coworkers for their vital contributions to this work, particularly, P. Waltereit, Y. J. Sun, A. Trampert, T. Y. Liu, S. Cronenberg, S. Dhar, and H. T. Grahn. Special thanks are due to H.-P. Schonherr for his expert technical assistance. 

Nakamura, A. et al. (1999) Japanese Journal of Applied Physics, Part 2, 38, L914. 

Bykhovski, A., Gelmont, B., and Shur, M. (1993) Journal of Applied Physics, 74, 6734. 

Ishikawa, H., and Jimbo, T. (2003) Journal of Vacuum Science and Technology. B, 21, 888. 

Boronic acid-derived fluorescent chemosensors are unique in that the inter-molecular interaction is a covalent bond, and not hydrogen bonding as is the case for most conventional fluorescent molecular sensors used for the selective reeognition of hydroxyl carboxylic acids. This chapter summarizes the development of the boronic acid-based chiral fluorescent chemosensors over recent years and the enantioselective fluorescent reeognition of chiral a-hydroxyl carboxylic acids analytes in aqueous solutions. The fundamental scaffolds of these chiral sensors include a fluorophore, an arylboronie aeid binding site, and linker between the two units. The systems usually consist of a bis-boronic acid unit, which is required for enantioselective recognition of the chiral a-hydroxyl carboxylic acid analytes. However, mono-boronic acid fluorescent chemosensors have also been developed. All three components of the chiral boronic acid sensors play an important role in determining the 

The catalytic asymmetric CDC reaction of starting materials without prefunctionalization is evidently one of the most direct and powerful methods in organic synthesis. This chapter summarizes and discusses the outstanding achievements that have been made in the past decade in the field of enan-tioselective CDC reactions. Various catalytic systems, including well-defined 

Although high selectivity and reactivity have been obtained, most asymmetric C—H bond functionalization reactions presented here only occur at some 

Based on the notion of sustainable development as a regulative idea outlined above, the link between sustainable development and education can be summarized as follows. Sustainable development is part and parcel of a general educational task, aimed at empowering the young generation to design their conditions of life on a more humane scale. It is based on an educational notion, which focuses on humans self-development and self-determination as they interact with, and reflect on, the world, with others, and with themselves. Education relates to the ability to contribute to the design of society in a reflected and responsible manner in terms of sustainable future development. 

In the context of sustainable development, learning is equivalent to addressing issues of howto sustainably shape the future in concrete fields of action, ie., chemistry and chemistry education. This includes observation, analysis, assessment and design of a given context in creative and cooperative processes. What is addressed and called for specifically are a critical assessment of knowledge in the light of the present-day information overload, the development of self-worth, self-determination and self-reliance, as well as social competencies such as the ability to participate.  

Chemistry dramatically influences everything from the life of the individual to society as a whole. Chemistry curricula and chemistry teacher education should more thoroughly reflect not only the importance of education and sustainable development, but support the development of human identity, which is interrelated with the environment, both individually and collectively, the goal being to allow students to actively learn how to shape society in a positive, sustainable fashion. 

Agenda 21, UNCED, New York, 1992, retrieved from the World Wide Web, December 30, 2012 at http //www.un.org/esa/dsd/agenda21/. 

UNESCO, Education for Sustainable Development. From Rio to Johannesburg Lessons learnt from a decade of commitment, Report presented at the Johannesburg world summit for Sustainable Development, UNESCO, Paris, 2002. 

A wide variety of polymeric membranes with different barrier properties is already available, many of them in various formats and with various dedicated specifications. The ongoing development in the field is very dynamic and focused on further increasing barrier selectivities (if possible at maximum transmembrane fluxes) and/ or improving membrane stability in order to broaden the applicability. This tailoring of membrane performance is done via various routes controlled macro-molecular synthesis (with a focus on functional polymeric architectures), development of advanced polymer blends or mixed-matrix materials, preparation of novel composite membranes and selective surface modification are the most important trends. Advanced functional polymer membranes such as stimuli-responsive [54] or molecularly imprinted polymer (MIP) membranes [55] are examples of the development of another dimension in that field. On that basis, it is expected that polymeric membranes will play a major role in process intensification in many different fields. 

1 Baker, R.W. (2004) Membrane Technology and Applications, 2nd edn, John Wiley Sons, Ltd, Chichester, Chapters 2, 3, 5, 

2 Mulder, M. (1996) Basic Principle of Membrane Technology, 2nd edn, Kluwer Academic Publishers, Dordrecht, Chapters 2, 3 5. 

4 Hsieh, P. (1996) Inorganic Membranes for Separation and Reaction, Elsevier, Amsterdam. 

5 Marcano, J.G.S. and Tsotsis, T.T. (2002) Catalytic Membranes and Membrane Reactors, Wiley-VCH, Weinheim. 

In the last decade, NHC-Ni complexes have become ubiquitous reagents in catalysis. As shown in this Chapter, sterically hindered NHC ligands have led to improved reactivity and selectivity compared to classical Ni-phosphine reagents. The activation of C-F bond is probably the best example of such improvements. Even if (S)IPr and (S)IMes appear to be the most commonly used NHCs with Ni, the design of new bi- or tridentate ligands as well as asymmetric units appears as a promising area of research. The future of NHC-Ni complexes will probably be sunny. 

A similar fate might be predicted for NHC-Pt analogues even if the reactions explored so far remain limited. Regioselective and/or asymmetric hydrobora-tion as well as hydrosilylation processes are the two most promising transformations catalyzed by NHC-Pt. 

Massicot, R. Schneider, Y. Fort, S. Illy-Cherrey and O. Tillement, Tetrahedron, 2000, 56, 4765-4768. (b) X. Jurvilliers, R. Schneider, Y. Fort and J. Ghanbaja, Appl. Organomet. Chem., 2001, 15, 744-748. 

Acosta-Ramirez, D. Morales-Morales, J. M. Serrano-Becerra, A. Arevalo, W. D. Jones and J. J. Garcia, J. Mol. Catal. A Chim., 2008,288, 14-18. 

in N-Heterocyclic Carbenes in Synthesis, ed. S. P. Nolan, Wiley-VCH, Weinheim, 2006, pp. 163-182. 

The procedures described in the last paragraphs of this Chapter allow the generation of several plausible crystal structures for any given molecule, and one can only hope that the observed structure(s) will be among them. Progress can be expected in the development of simple but more accurate potential functions, due to the availability of a larger database of crystal structures and sublimation enthalpies, along the lines proposed in Section 12.4. 

AV° — —160 + 12 cm mol is considered to be a consequence of the two contributions (1) the difference in the intrinsic molar volume of three tetramers and two hexamers and (2) the difference in the solvation contribution of these complexes. Since the calculations derived by Connolly s method revealed the possibility of either sign for the solvation effect, it could not be decided conclusively at that point which of the two contributions dominates in producing the remarkably large reaction volume observed. 

Wurche is thanked for his skilled assistance with the editing of this chapter. 

is grateful to the Deutsche Forschungsgemeinschaft (Sonderforschungs-bereich SFB 425) and the Fonds der Chemischen Industrie for financial support. 

Supramolecular Chemistry, Concepts and Perspectives, VCH Weinheim, 1995. 

Herimans, in Chemistry under Extreme and Non-Classical Conditions, R. VAN Eldik, C. D. Hubbard, (Eds), Wiley-Spectrum, New York, Heidelberg, 1997, Chapter 12, 515-545. 

The existing rules are useful, not only to categorize existing examples, but also to predict new structures. However, they quite frequently are contradictory and break down, especially when explored systematically. Computational investigations reveal unexpected problems, as two related illustrations from our current research [114] show. 

The full understanding of the nature of main-group element clusters will be very difficult to achieve. 

1 Stock, A., Hydrides of Boron and Silicon, Cornell University Press, Ithaca, NY, 1933. 

10 Muetteeties, E. L., Knoth, W. H., Polyhedral Boranes, Marcel Dekker, New York, 1968. 

27 Gutman, I., Cyvin, S. J., Introduction to the Theory of Benzenoid Hydrocarbons, Springer, Berlin, 1989. 

The authors would like to thank Professor Satoshi Sugita Sueyoshi, Department of Chemistry, Universidad de Guanajuato, for continuing professional development and collaboration and providing valuable comments on agave hydrogel research. 

(2004). Pyrolisis of biomass to produce fuels and chemical feedstock. Energy Convers Manag, 45,651-671. 

Chavez-Guerrero, L., Hinojosa, M. (2010). Bagasse from the mescal industry. Fuel, 89,4049-4052. 

Goldemberg, J. (2007]. Ethanol for sustainable energy future. Science, 315,808-810. 

Jorapur, R., Rajvanshi, A. K. (1997). Sugarcane leaf-bagasse gasifiers for industrial heating applications. Biomass Bioenergy, 13(3], 141-146. 

As illustrated by the schemes above, metathesis reactions in domino processes have swiftly become an established tool in modern organic synthesis. Especially, RRM and domino dienyne metathesis have found extensive uses and will surely continue to catch the attention of synthetic chemists as elegant and atom-economic transformations that allow a quick enhancement of molecular complexity. Next to combinations of metathesis events only, the incorporation of non-metathesis steps into true domino processes has advanced to a remarkable level and will certainly provide even more opportunities in the years to come. 

Financial support of our own work in this area by the Deutsche Forschungs-gemeinschaft, the Ponds der Chemischen Industrie, and the Alexander von Humboldt-Stiftung is gratefully acknowledged. 

(2006) Tetrahedron Lett., 47, 6587-6589 (c) Clavier, H., Correa, A., Escudero-Adan, E.C., Benet-Buchholz, 

We thank the Max Planck Society for generous financial support. M.H. thanks the Max Planck Society for a Minerva postdoctoral fellowship. We thank Dr. C. L. Pereira and Dr. D. Kennedy for the help in editing this chapter. 

For the last 25 years, various groups have been investigating the use of asymmetric catalysis for the synthesis of hexoses. When beginning with achiral starting materials and when asymmetric catalysis is used for the installation of asymmetry, these syntheses are called de novo asymmetric or de novo for short While these de novo approaches have been quite impressive in terms of the scope of products 

Lithium alloy anodes have far higher advantages in capacity compared with current graphite-base anode. Strong points of alloy electrodes are also their superior rapid-charging and low-temperature characteristics, and therefore, they are expected to spread not only over small mobile applications but also out to HEV use. Although there are still issues that have to be overcome for commercializing the lithium alloy system, they can be solved with new attempt and invention. 

This work was done as the CTO project in Mitsui Mining Smelting Co. Ltd., Japan. I would like to thank my colleagues who worked with me on SILX technology, especially Y. Sakaguchi for his earlier work and H. Ide and Y. Todorof for the valuable discussions and comments and preparation of the materials. 

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In recent years devices based on liquid crystal displays have become an inseparable part of our daily life. Flat panel LCD-TV, PC monitors, notebook computers, cellular phones, and PDA would not exist without fluorine-containing liquid crystals. The use of fluorinated substructures, supported by computational methods and the development of novel preparative methods, enables targeted design and synthesis of new materials vith a broad range of custom-tailored properties. 

Several different AM-LCD technologies currently compete on the market. This race will probably be decided economically by the cost of mass production and technically by the ability to achieve the very fast switching time required for LCD-TV, the major economic driving force coming to the LCD market. Use of the unique properties of fluoroorganic materials will most probably play a decisive role in this development. 

Nematic materials are only one member of a large family of a variety of structurally different compounds forming liquid crystalline mesophases. Although only nematics have yet found really widespread use, mostly for display applications, some structurally highly diverse smectic phases also have unique electrooptical characteristics, for example ferroelectricity or antiferroelectricity, which can be modulated by selective fluorination [5, 51]. For 20 years intensive effort has been devoted to making practical use of these phenomena. 

It is impossible to predict which type of mesogen will win the race to become ultimate LCD technology. But it is a safe bet to assume that fluorinated substructures will play a predominant role. 

Lehmann, Fliissige Kristalle, sowie Plastizitat von KristaUen im AUgemeinen, molekulare Urn-lagerungen und Aj egatzustandsanderungen, Engelmann, Leipzig, 1904. 

Enzymatic synthesis of macromolecules has generated tremendous research interest during the past couple of decades due to many inherent advantages over conventional methods, which often utilize acid- and/or metal-based catalysts at high temperatures. However, the use of enzymes for synthesis of functional siHcones and silicone copolymers has been reported only recently. Given the wide range of applications of silicones and their copolymers, in particular for biomedical and personal care use, it is envisioned that the number of enzymatically synthesized novel functional silicone-based materials and products will only increase in the coming years. 

The author is thankful to Professor Stephen J. Clarson, University of Cincinnati, for the motivation and helpful discussions. The author also would like to thank Professor Arthur J. Epstein, Ohio State University, for the encouragement and kind support. 

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The two examples, deliberately chosen for their simplicity, show that computational fluid dynamics facilitate a more in-depth examination of the local flow behavior of twin screw extruders. Local peaks in the mechanical and thermal stresses can be easily identified. By changing the geometry, stresses can be reduced and the quality of the polymer can thereby be optimized. Another application focus is the rapid determination of the dimensionless axis intercepts for the pressure build-up A, and A2 and for the power requirement B, and B2. The significance of these parameters has already been discussed in detail in the two previous chapters. 

The screw zone comprises a conveying element-spacer disc-mixing element-spacer disc and kneading element at a pressure difference of 100 bar and melt flow of -0.01 kg/s. The top figure shows the pressure on the screw surface, while the bottom figure shows the axial velocity in the melt channel at half the channel height 

Nano is a word that is no longer reserved for science but has entered the public consciousness. The field of nanoscience with its promise of amazing nanotechnologies is one of today s most challenging, exciting, multidisciplinary and competitive 

RMs for defining the 5-scale are an essential transitional solution on the way to IRMs with certified isotope amount fractions. These I RMs certified for isotope amount fractions are essential for IDMS, for interference corrections, and for the correction for mass discrimination. Whenever possible, RMs defining the 5-scale should be additionally certified for their isotope amount fractions, even if the resulting uncertainties for the isotope amount fractions are too high for current research on isotopic variations. The aim is to obtain one 5-RM for every stable element, provided as a solution, fixing the origin of the 5-scale of the specific element and preferably certified for its isotope amount fractions, and a second 5-RM with a well-defined offset on the 5-scale. Research should continue to improve the capabilities for the determination of isotope amount fractions. 

For the coming years, around 27 elements have been selected by user communities as of interest in this context [35]. These elements are of interest to geo-and cosmochemists, and also to scientists working in the fields of human nutrition, human medicine, veterinary medicine, and food traceability. For 18 

At BAM, IRMs and 5-RMs will be produced according to the requirements mentioned above. NIST has also started a program to produce new RMs for 5-values [90]. As discussed at the latest meeting of the lUPAC Commission on Isotopic Abundances and Atomic Weights (CIAAW) in July 2009 in Vienna, these activities will be supported by lUPAC. 

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In the future we will witness a drive towards more complexity. In this review, we have discussed a number of preliminary experiments pointing in this direction. In polymer blends, the question of dynamic mixing on a local scale was addressed and the Rouse dynamics in miscible polymer blends was studied. How the tube confinement evolves in blends where the two components have different tube diameters is a completely open question. Also, the question of how 

Going to more complex systems such as aggregates, micelles, polymer brushes or polymers with architectures hke stars, dendrimers, combs, etc. or gels, the scientific arena is wide open for new investigations reveahng new phenomena and new insights. This is even more true for the dynamics of proteins and biomaterials in general, where at present basically only diffusion processes or very local dynamics have been addressed. 

Acknowledgements We are indebted to our collaborators in Jiilich and San Sebastian, who helped to shape many of the experiments as they are presented in this review. In particular we would like to thank Ms. Saida Oubenkhir for the technical support and patience in preparing this manuscript. 

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Investigation of these properties should be one of the significant directions of future development of these compounds, especially worthwhile are the exploration of the possibility of removing the templates from the channels of the hon-eycomb-like material [Tl5(Ti2Cl9)][(Nb6Cli204)3(Ti3CL. )2] and the studies of this and other oxychloride materials as hosts in redox intercalation processes. 

A broader and more important implication of the oxychlorides is the potential of expanding the ligand combination to other transition-metal cluster systems. The advances in soft-chemistry techniques open up new possibilities for the sta- 

Long et al. reported the synthesis of tungsten oxychloride clusters via a soft-chemistry route [60], which confirms the potential for wide applications of the ligand combination strategy in cluster chemistry. 

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Furthermore, the clarity/transparency of PET/clay nanocomposites is also one of the most important issues for some applications, such as packaging, beverage bottles, etc. It is noted that the transparency can be maintained at a clay content of less than 2 wt% (see Table 5.2). At the mean time, reasonable barrier properties (CO2 and UV) are achieved. This demonstrates that a balance could be achieved between clarity and good barrier properties for these nanocomposites. 

The potential of clay/PET composites lies in their industrial application such as barrier materials for barrage bottles, films, fibers, etc. More work is needed to further improve their properties to replace their potential competitor in the market. Moreover, simpler methods are needed to produce these materials at lower cost 

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There are some other very interesting unsolved problems. Notice that we only derived the modified Cassie equation for chemically patterned surfaces. We expect that there is a similar relation for chemically homogeneous rough surfaces. Rigorous verification of the modified Cassie equation is also important. One needs to consider the convergence of local minimizers, which is a difficult mathematical problem and requires further study. 

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It was shown that the incorporation of monooxygenases into cascade networks allows the efficient interconversion of diverse functional groups. DiHerent approaches have proved to be suitable for multistep bio transformations, ranging from fusion enzyme strategies for facile cofactor recycHng to artificial metal-loenzymes. However, monooxygenases seem to perform preferably well within a 

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The kinetically controlled stereoselection depends on very small increments of free activation enthalpy. It is therefore an excellent sensitive probe for dendrimer effects. As monodispersed macromolecules, chiral dendrimer catalysts provide ideal model systems for less regularly structured but commercially more viable supports such as hyperbranched polymers. However, the results obtained by a considerable number of research groups in the field have also established that the structural characteristics of the established dendrimer systems, such as the absence of a well-defined secondary structure, have limited the development of efficient abiotic enzyme mimics based on dendrimers. To achieve this ambitious goal, more effort in dendrimer synthesis will be necessary. The use of dendritic 

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From the historical background of macrocyclic compounds, the factors that make macrocyclic compounds widely usable in a wide variety of applications are as follows  

FeaturesX Pillar[n]arene Crown Ether Cyclodextrin Calix[n]arene Cucurbit[n]urll 

Shape Pillar Crown Bucket Calix Pumpkin 

Original Property Planar Chirality Symmetric Flexible Biocompatible Chirality Nonsvmmetirc Nonsymmetlrc Rigid Structure Symmetric 

It has been pointed out with the aid of an example how the factors that influence chromatographic separation can be systematically examined. The inclusion of the stationary phase as a factor offers an insight into the complexity of the interaction offactors in chromatography. With HEUREKA, a tool has been created with which method development in HPLC can be accomplished multifactorially. 

The global optimum for a separation problem can be better found and wdth fewer manual tasks than previously. Method development should less frequently end in an inextricable cul-de-sac. With HEUREKA, the earlier ideas of automating method development in reversed-phase HPLC have been consistently developed further and put into practice [5]. 

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(a) The Nobel Prize in Chemistry 2010, Heck, R. F, Negishi, E., Suzuki, A. For palladium-catalyzed cross couplings in organic synthesis.(b) The Nobel Prize in Chemistry 2005, Chauvin, Y., Grubbs R. H., Schrock, R. R. For the development of the metathesis 

(2009). Protecting-group-free synthesis as an opportunity for invention. Nature Chemistry, 1, 193-205. 

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(a) Corey, E. J., Russey, W. E., Ortiz de Montellano, P. R. (1966). 2,3-Oxidosqualene, an intermediate in the biological synthesis of sterols from squalene. Journal of the American Chemical Society, 88, 4750-475l.(b) Abe, I., Rohmer, M., Prestwich, G. D. (1993). Enzymatic cyclization of squalene and oxidosqualene to sterols and triterpenes. Chemical Reviews, 93, 2189-2206. 

(a) Strecker, A. (1850). Ueber die kiinstliche BUdung der MUchsaure und einen neuen, dem Glycocoll homologen Korper. Justus Liebigs Annalen der Chemie, 1, 27-45.(h) Eor a review on asymmetric Strecker reaction, see Wang, J., Liu, X., Peng, X. (2011). Asymmetric Strecker Reactions. Chemical Reviews, 111, 6947-6983. 

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V. CONCLUSIONS AND OUTLOOK OF SOME DIRECTIONS FOR FURTHER STUDIES... 

Ring-Substituted PTV Derivatives 27 Vinylene-Substituted PTV Derivatives — Tuning the Gap 30 Conclusions and Outlook 31 Acknowledgements 32 References 32... 

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