Concluding Remarks and Outlook

Aresta, A. Dibenedetto, and E Dumeignil, Biorefinery From Biomass to Chemicals and Fuels, Walter de Gruyter, 2012. 

E Cherubini, The biorefinery concept Using biomass instead of oil for producing energy and chemicals, Energy Comers. Manag, 51 (7), 1412-1421, 2010. 

Petersen, A. Aden, J. Bozell, J. Holladay, J. White, A. Manheim, D. Eliot, L. Lasure, and S. Jones, Top Value Added Chemicals Erom Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas, Aug. 2004. 

Biofibers from agricultural byproducts for industrial applications. Trends BiotechnoL, 23 (1), 22-27,2005. 

Very recently, Fedin, Kim and colleagues synthesized a homochiral metalorganic polymeric material, [Zn2(bdc)(L-lac)(dmf)] (DMF) (36), by using a one-pot solvothermal reaction of Zn(NO3)2, L-lactic acid (L-H2lac) and 1,4-benzenedicarbox-ylic acid (H2bdc) in DMF [53]. This 3-D homochiral microporous framework exhibited permanent porosity and enantioselective host-guest sorption properties towards several substituted thioether oxides. Although 36 could catalyze the oxidation of thioethers to sulfoxides with size and chemoselectivity, no asymmetric induction was observed. 

Although the amorphous nature of MOCPs does not preclude their intereshng catalyhc properhes, the development of shucturally well-defined systems is highly desirable for mechanishc and shucture-activity-selectivity studies. The development of new analyhcal tools that can be apphed to the characterizahon of not only the microstruchire of an MOCP (e.g. to ascertain how many repeat units are actually incorporated into a polymer framework) but also the precatalyst or catalyst in its reshng state, remains a formidable and important challenge. 

The difficulties somehmes encountered in the synthesis of polytopic hgands might be overcome by the development of efficient synthehc protocols (such as click chemistry) or the use of noncovalent bonding interactions (H bond or coordinahon). tn addihon, the development of conhnuous-flow reachon systems might prove advantageous for the practical apphcations of MOCP catalysts. 

1 (a) Noyori, R. (1994) Asymmetric Catalysis in Organic Synthesis, Wiley-lnterscience, New York. 

3 (a) de Vos, D.E., Vankelecom, l.F. and Jacobs, P.A. (eds) (2000) Chiral Catalyst Immohilization and Recycling, Wiley-VCH Verlag GmbH. Weinheim. 

In general, the capillary forces between two vertical walls and between two vertical cylinders are attractive when they have similar wettability (hydrophilic-hydrophilic or hydrophobic-hydrophobic) and are repulsive when they have opposite wettability (hydrophilic-hydrophobic). However, this statement is not applicable for the latter two configurations (i.e., between two floating spheres and between a spherical particle and a vertical wall). Additional parameters (for example, the size and the density of floating objects) are crucially important to determine the lateral component of the capillary force. The effect of the floating object density was particularly discussed for the latter two configurations. 

In order to control the Cheerios effect, we implemented electrowetting-on-dielectric (EWOD) on the vertical plate. By simply turning on/off the EWOD electrode on the plate, we were able to change the contact angle on the plate and reverse the capillary force between the plate and the floating object. This results in reversing of attraction and repulsion behaviors 

The spot for phospho-HSP 25 was identified by mass spectrometry and is indicated by an arrow. 

In summary, modern proteomics approaches offer unprecedented opportunities to identify novel phosphorylated proteins for diagnosis and therapy of major illnesses. The development of new clinical proteomic tools away from labeling 

Parts of the authors work were funded by the German Ministry of Education and Research (BMBF). 

Langridge, J. I., Miliar, A., Vissers, J. P. (2002). A novel precursor ion discovery method on a hybrid quadrupole orthogonal acceleration time-of-flight (Q-TOF) mass spectrometer for studying protein phosphorylation. 

Martin,]. F. (1997). Megakaryocytopoi-esis the megakaryocyte/platelet haemi-static axis. In von Bruchhausen, F., Walter, U. (Eds.), Platelets and their Factors. Springer-Verlag, Berlin, pp. 3-19. 

Molecular Interaction Fields, in 3D QSAR in Drug Design. Theory, Methods and Applications, H. Kubrnyi (ed.) ESCOM, Leiden, 1993, pp. 486-505. 

Goodford, A computational procedure for determining energetically favorable binding sites on biologically important macromolecules./. Med. Chem. 1985, 28, 849-857. 

Robertson, C. L. Brooks, Detailed analysis of grid-based molecular docking A case study of CDOCKER-A CHARMm-based MD docking algorithm, J. Comput. Chem. 2003, 24, 1549-1562. 

Morris, D. S. Goodsell, R. Huey, A. J. Olsen, Distributed automated docking of flexible ligands to proteins parallel applications of AutoDock 2.4. 

Carosati, S. Sciabola, G. Cruciani, Hydrogen Bonding Interactions of Covalently Bonded Fluorine Atoms From Crystallographic Data to a New Angular Function in the GRID Force Field, J. Med. Chem. 2004, 47, 5114-5125. 

We want to thank Professor Vasile Parvulescu from the University of Bucharest (Romania) for motivating and inspiring us in the preparation of this chapter. We would also like to thank the Institute of Physical Chemistry of PAS for its support 

1 Teng, F Han, W Liang, S., Gaugeu, B., Zong, R and Zhu, Y. (2007) Catalytic behavior of hydrothermally synthesized Lao sSro sMnOa single-crystal cubes in the oxidation of CO and CH4. /, CataL, 250, 1-11. 

G Chen, L and Wang, X. (2008) Properties and catalytic performance for methane combustion of LaMnOa perovskite prepared in oil-water two-phase system. Catal, Lett, 126, 96-99. 

3 Kappe, C.O. (2008) Microwave dielectric heating in synthetic organic chemistry. Chent. Soc. Rev., 37, 1127-1139. 

4 Bang, J.H. and Suslick, K.S. (2010) Applications of ultrasound to the synthesis of nanostructured materials. Adv, Mater., 22, 1039-1059. 

The -values of dodeca-6,8-diyne have been doubled, those of 2(5) h ave been increased by 300, those of 2(4) by 550 and that of 2(3) by 650. 

Chart 7.6. Hitherto unsynthesized binary carbon—chalcogen compounds 117 and 118. 

In comparison with classical processes involving thermal separation, biphasic techniques offer simplified process schemes and no thermal stress for the organometal-lic catalyst. The concept requires that the catalyst and the product phases separate rapidly, to achieve a practical approach to the recovery and recycling of the catalyst. Thanks to their tunable solubility characteristics, ionic liquids have proven to be good candidates for multiphasic techniques. They extend the applications of aqueous biphasic systems to a broader range of organic hydrophobic substrates and water-sensitive catalysts [48-50]. 

To be applied industrially, performances must be superior to those of existing catalytic systems (activity, regioselectivity, and recyclability). The use of ionic liquid biphasic technology for nickel-catalyzed olefin dimerization proved to be successful. 

As far as industrial applications are concerned, the easy scale-up of two-phase catalysis can be illustrated by the first oxo aqeous biphasic commercial unit with an initial annual capacity of 100,000 tons extrapolated by a factor of 1 24,000 (batch-wise laboratory development production reactor) after a development period of 2 years [4]. 

Comils, W. A. Herrmann in Applied Homogeneous Catalysis with Organometallic Compounds (B. Cornils, 

Dehmlow in Aqueous-Phase Organometallic Catalysis Concept and Applications (B. Cornils, A. W. Herrmann eds.), Wiley-VCH, Weinheim 1998, p. 207. 

The hydrolysis of the unmodified PBT samples results in significant decreases in molecular weights. After 5 weeks in water at 90 °C, the Mn and M decreased about 40%. 

The hydrolysis of the modified PBT samples results in a much less pronounced decrease in molecular weights. The decrease in M and Mw is only around 16% for modified PBT samples. Clearly, the modification results in a hydrolytically more stable polymer. 

As we come to the end of this chapter, we will attempt to put the results in perspective. We have explored the scope and limitations of modifying a variety of polymers in supercritical and subcritical fluids, while trying to provide a better understanding of the process. It is obvious that the use of supercritical fluids in polymerization and polymer modification has several advantages over more conventional techniques such as melt and solution modification. 

In this chapter it has been shown that CO2 can be used as the reaction medium for polymer modification. Depending on a variety of factors, such as the chemistry of the modification, the polarity of the polymer, and the temperature and pressure, which are needed for sufficient modification of the polymer, one can decide which supercritical fluid is most suitable. 

Goodner, G.W. Roberts, D.J. Kiserow, J.M. DeSimone, Book of Abstracts, 218th ACS National Meeting, New Orleans, Aug. 1999, 22. 

Not very long ago, ionic liquids (ILs) were just considered as potential alternative solvents for multiphasic reactions and were mentioned in the outlook chapter of books dealing with this area, whereas water was already industrialized in key transition metal catalyzed processes [2]. ILs have now attracted more interest It is possible to buy them, which probably promotes their use, and there are more and more physical data available on these solvents. The range of reactions that have been described in these media is probably wider than in SCCO2 or fluorous solvents. But it would not be reahstic to assume that all catalyzed reactions can be transferred to ILs with benefits. The advantages of using ILs have been well described for some reactions which have been reported in this book, and just a few of them have been run on micro-pilot or pilot scale. 

Copyright 2005 Wiley-VCH Verlag GmbH Co. KGaA, Weinheim ISBN 3-527-30721-4 

In some cases, ILs act as both solvents and catalysts, which may simplify processes. Examples are given for reactions catalyzed by Lewis or Bronsted acids (see Section 

They also open the way for association of different processes such as electrochemistry and catalysis, sonochemistry or microwaves and catalysis. 

Examples of industrial development of ILs for catalysis are still scarce. Using IL for industrial reactions raises a series of specific questions (see Section 5.1). The scaling-up of IL synthesis procedures has been considered and is probably not the main difficulty. However, the commercialization and/or transport of these I Ls raise the question of their registration (EINECS for Europe or equivalent). Disposal and eventual recycle of ILs are important concerns and should probably be considered case by case. 

Airbase Sciences Branch, Air Force Research Laboratory, Tyndall Air Force Base, FL, USA 

Department of Chemical and Nuclear Engineering and Center for Emerging Energy Technologies, University of New Mexico, Albuquerque, NM, USA 

Enzymatic Fuel Cells From Fundamentals to Applications, First Edition. Edited by Heather R. Luckarift, Plamen Atanassov, and Glenn R. Johnson. 

FIGURE 20.1 Trend in bioelectrochemistry publications. Cumulative research articles including terms fuel cell and enzyme . The search did not include patent literature or citations within document bibliographies. Search completed May 2013 using Google Scholar. 

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