Perspective and conclusion

4 Mayr, H. and Patz, M. (1994) Angew. Chem., 106, 990-1010 Angew. Chem., 

6 Mayr, H. (2001) Reactivity scales posters. Available at bttp //www.cup.lmu.de/oc/ mayr/C DmayrPoster.btml. 

48 Guiteras Capdevila, M., Enter, E., Gualandi, A., Petruzziello, D., Grilli, S., 

61 For other organocatalytic atropoisomeric reactions, see Cozzi, P.G., Emer, E., and Gualandi, A. (2011) Angew. Chem., 123, 3831-3933 Angew. Chem., Int. Ed., 50, 3847-3849. 

Berkessel, A. and Crdger, H. (eds)(2004) Asymmetric Organocatalysis, Wiley-VCH Verlag CmbH, Weinheim. 

6 (a) Reetz, M.T., Zonta, A., Schimossek, K, Liebeton, K. and Jaeger, K.-E. (1997) Angewandte Chemie, 109, 2961—2963. (1997) Angewandte Chemie International Edition in En ish, 36, 2830—2832. (b) Reetz M.T., Zonta A., Schimossek K., Liebeton K and Jaeger K.-E. (1997) patent application DE-A 19731990.4 (A Process for ihe Preparation and Identification of Novel Hydrolases Having Improved Properties). 

Dijkstra, B.W., Jaeger, K.-E. and Eggert T. (2003) Biocatcdysis and Biotransformation, 21, 67-73.(b) Krumm, H. (2004) Dissertation, Ruhr-Universitat Bochum, Germany. 

21 (a) Miyazaki, K. and Arnold, F.H. (1999) Journal of Molecular Evolution, 49, 716—720. (b) Sneeden, J.L. and Loeh, L.A. (2003) Directed Evolution Library Creation Methods and Protocols (eds F.H. Arnold and G. Georgiou), Humana Press, Totowa, Vol. 231 pp. 65. literature cited therein  

23 Reetz, M.T. and Wang, L.-W. (2006) Bocola in part M. Angewandte Chemie, 118, 1258-1263. Erratum, 2556 (2006) Angewandte Chemie International Edition, 45, 1236-1241. Erratum, 2494. 

We thank CAPES, CNPq, and Humboldt Foundation for partial financial support to CSC and JD. 

1 Chauvin, Y., Gilbert, B. and Guibard, I. (1990) Journal of the Chemical Society, Chemical Communications, 1715—1716. 

4 Colbnan,J.P.,Brauman,J.I.,Tustin,G.and Wann, G.S. (1983) Journal of the American Chemical Society, 105, 3913-3922. 

9 Chauvin, Y., Mussmann, L. and Olivier, H. (1996) Angewandte Chemie-Intemational Edition in En ish, 34, 2698—2700. 

10 Rangits, G., Petocz, G., Berente, Z. and Kollar, L (2003) Inorganica Chimica Acta, 353, 301-305. 

Kinoshita, S., Udaka, S., and Shimono, M. (1957) Studies on the amino acid fermentation. Part 1. Production of L-giutamic acid by various microorganisms. J. Gen. Appl. Microbiol, 3 (3), 193-205. 

(2005) Corynebacterium taxonomy in Handbook of Corynebacterium glutamicum (eds L. Eggeling and M. Bott), CRC Press, Boca Raton, PL, pp. 9-34. 

Takayama, K., and Kinoshita, S. (1967) Taxonomical studies on glutamic acid-producing bacteria. J. Gen. Appl Microbiol, 13 (3), 279-301. 

(1965) Comparative studies on the mechanism of microbial glutamate formation. I. Pathway of glutamate formation from glucose in Brevibacterium flavum and in Micrococcus glutami-cus. J. Gen. Appl. Microbiol, 11 (4), 285-294. 

Otsuka, S., and Tsunoda, T. (1959) Glutamic add formation from glucose by bacteria. II. Glutamic acid and a-ketoglutaric add formation by Brevibacterium flavum No. 2247. /. Biochem., 46 (12), 1597-1605. 

Concepcion, P., Corma, A., and Garcia, H. (2005) Angew. Chem. 

Tsunoyama, H., Sakurai, H., and Tsukuda, T. (2006) Chem. Phys. Lett., 429, 528. 

Rodriguez-Vazquez, M.J., Blanco, M.C., Lourido, R., Vazquez-Vazquez, C., Pastor, E., Planes, G.A., Rivas, J., and Lopez-Quintela, M.A. (2008) Langmuir, 24, 12690. 

Poncelet, P.A. Jacobs, P. Grange, and B. Delmon), Elsevier, Amsterdam, p. 

Oliver-Meseguer, )., Cabrero-Antonino, J.R., Dominguez, I., Leyva-Perez, A., and Corma, A. (2012) Science, 338, 1452. 

Within the framework of genomics and the rational development of new therapeutic strategies, a general question one might ask is What is the role of quantum chemistry in medicinal chemistry in the world of macromolecular systems and in the era of exponentially increasing data on these systems Looking at the examples illustrated above we can postulate that details at the electronic level will definitely play a role in the development 

2 Leach, A. R. in Molecular modelling. Principles and applications, Addison Wesley, 1996. 

9 Koch, W. Holthausen, M. C. A Chemists Guide to Density Functional Theory, Wiley-VCH, Weinheim, Germany, 2001. 

in Theoretical Biochemistry -Processes and Properties of Biological Systems, Elsevier, 2001. 

22 Verzeletti, S. Bonini, C. Marktel, S. Nobili, N. Ci-ceri, F. Traversari, C. Bordignon, C. Hum. Gene Ther. 

1 Yermakov, Y.I., Kuznetsov, B.N. and Zakharov, V.A. (1981) Catalysis by Supported Metal Complexes, Vol. 8, Elsevier, Amsterdam. 

2 Coperet, C., Chabanas, M., PetrofF Saint-Arroman, R. and Basset, J.-M. (2003) Angew. Chem. Int. Ed., 42,156. 

11 Scott, S.L., Crudden, C.M. and Jones, C.W. (eds) (2003) Nanostructured Catalysts, Kluwer Academic/Plenum Publishers, New York. 

13 (a) For oxidic supports other than silica and alumina, see Andres, R., Galakhov, M., Martin, A., Mena, M. and Santamaria, C. (1995) J. Chem. 

24 Vansant, E.F., Van Der Voort, P. and Vrancken, K.G. (eds) (1995) Characterization and Chemical Modification of the Silica Surface, Studies in Surface Science and Gatalysis, Vol. 

The tremendous multiplicity of length- and timescales in polymeric systems clearly calls for systematic, multiscale modeling approaches in which a higher resolution 

Eniture efforts will address other systems such as entangled (linear and branched) polymers where, inspired by the corresponding GENERIC formalism, one should resort to a description in terms of the orientational distribution function of an entanglement segment along the primitive path of the chain. 

and Larson, R.G. (2006) Structure and Rheology of Molten Polymers, Hanser Publications. 

Ciutiss, C.F., Armstrong, R.C., and Hassager, O. (1987) Dynamics (f Polymeric Liquids, 2nd edn, John Wiley Sons, Inc., New York. 

and Phillips, T.N. (2002) Computational Rheology, World Scientific. Keunings, R. (2001) Advances in the computer modeling of the flow of 

Owing to the broken symmetry normal to the surface and the reduced coordination, it is fair to assume that the physical properties at the surfaces are different from those in the bulk of a solid. By now, much is known about these peculiarities of clean surfaces. In many cases, we know where the atoms are, where the electrons are, and how stable both the atoms and electrons are at their chosen locations. We have seen how at some surfaces the atoms rearrange to form complex structures not known 

Let us now recapitulate some of the key points made in this chapter and which will be treated in great detail in the remainder of this volume. Further, we oudine a few challenges and issues that remain to be addressed in future work. 

In most cases, the results of DFT calculations, even with exchange orrection functionals as simple as the LDA or GGA, and LEED analyses agree on the structural details of a particular relaxation or reconstruction, further, DFT can generally provide an adequate a posteriori explanation for why a relaxation or reconstruction takes place, such as for the hex phase of the late 5d fee transition metals. However, there are several surfaces where discrepancies persist, and further attention from experiment and theory alike is needed. 

Demonstrably, rehable and quantitatively correct experimental surface energies are, however, generally lacking. The recent STM-based experiments for Pb are a welcome development. There is a pressing need for more measurements of this kind. 

s work is supported by the European Research Council, the EURYI scheme (see www.erforg/euryi), and the EPSRC. We are grateful to Bo Li and Ding Pan for helping to prepare some of the figures and to Jiri Khmes for help in updating parts 

Twomey, K., Ogurtsov, V.I. et al. (2011) Fabrication and electrochemical characterization of micro- and nanoelectrode arrays for sensor applications. J. Phys. Conf. Sen, 307,012052. 

Oldham, K.B. and Zoski, C.G. (1989) Steady-state voltammetry. Ami. 

(1971) Specifity of responses of cells in the visual cortex. J. Psychiatr. Res.,%,ZQ.  

Henstridge, M.C. and Compton, R.G. (2012) Mass transport to micro- and nanoelectrodes and their arrays a review. Chem. Rec., 12, 63. 

O Mahony, AM. and Compton, R.G. (2009) Microelectrode arrays for electrochemistry approaches to fabrication. Small, 5, 776. 

Several exciting new material based on co-crystalline and nanoporous crystalline phases of syndiotactic polystyrene have been achieved. In particular, several kinds of polymer co-crystalline phases have been prepared, belonging to three different classes 8- and e-clathrates and intercalates. Polymer cocrystals with active guest molecules show unusual physical properties, hence are promising for several kinds of advanced materials. Moreover, the unprecedented achievement of polymeric nanoporous crystalline phases (8 and e) has given very interesting results in the fields of molecular separations, water/ air purification and sensorics. 

As for perspectives of applications of SPS-based co-crystaUine phases, studies will be mainly devoted to films, also trying to exploit the unique availability of three different kinds of uniplanar orientations, which allow macroscopic control of the guest orientation. Particular attention will be devoted to possible applications of the recently discovered e clathrates, mainly due the possibility of controlling the orientation of very long guest molecules, which could give relevant nonlinear optical properties. 

In recent years, advanced materials with special optical properties were mainly developed while for the future, by using co-crystaUine phases with highly polar or paramagnetic guest molecules, the achievement of relevant materials with special electric and magnetic properties are expected. 

Relevant new materials could also be obtained by chemical reactions (e.g., polymerization) between guest molecules, for polymer co-crystals exhibiting guest-guest proximity (e clathrates and intercalates). 

As for possible perspectives of the nanoporous crystalline phases, applications are expected in the field of controlled release of drugs and pesticides. 

Two vibrational progressions with similar energies (1300 and 360 cm ) were identified in simulating cluster silanone (0SiH3)2Si=0 defect [114]. We note that although some reports argue that this silanone defect is not stable under ambient air conditions [114], a stable silanone at room temperature has recently been reported [115]. 

Nowadays, approximately 20% of energy consumption worldwide is used for lighting. In the last two decades, the semiconducting light sources have played a key role in emerging SSL technologies, demonstrating an exponential improvement in the luminous efficacy. In feet, the record values of the luminous efficacy 

The field is, however, in its infancy, and much remains to be investigated before prototypes with competitive efficiencies become a commercial reality. The best reported luminous efficacy values ( 24 Im W ) although larger than those of incandescent light bulbs are much smaller than the state-of-the-art 

Lights Labour s Lost Policies for Energy-Efficient Lighting. International Energy Agency, Paris. 

7 The Climate Group (2012) Lighting the Clean Revolution. The Climate Group, London. 

Naturally, a major task appears to be cellular detoxification under normal and adverse growth conditions. For example, Pdrl 2 functions in the disposal of toxic weak acid catabolites that accumulate when cells are approaching the stationary growth phase [52, 55]. Pdrl2 contributes to the export of catabolic products such as phenylacetate or other carboxylic acids derived from amino acid catabolism. In this context, Pdrl 2 may be considered as an integral part of the so-called Ehrlich pathway, in which carboxylic acids are decarboxylated to the corresponding aldehyde [55,201]. 

Pdrl 2 is highly induced in response to weak organic acids such as sorbic, benzoic, and propionic acids. 

Several yeast and mammalian [202] ABC transporters do have hydrophobic and lipophilic substrates. For instance, Ausl and Pdrll may function in sterol uptake. Translocation of membrane phospholipids was also demonstrated for Pdr5 and Yorl, the C. albicans drug transporters Cdrl-3, as well as several mammalian ABC transporters [202, 203]. Mutant strains expressing alleles PDRl-11 and PDR3-11 display altered phospholipid accumulation and membrane asymmetry [49, 204]. 

1 Anaissie, E. (1992) Opportunistic mycoses in the immunocompromised host experience at a cancer center and review. Clinical Infectious Diseases, 14 (Suppl 1), S43-S53. 

2 Ponton, J., Ruchel, R., Clemons, K.V., Coleman, D.C.. Grillot, R., Guarro, J., Aldebert, D.. Ambroise-Thomas, P., Cano, J.. Carrillo-Munoz, A.J., Gene, J., Pinel, C.. Stevens, D.A., and Sullivan, D.J. (2000) Emerging pathogens. Medical Mycology. 38 (Suppl 1), 225-236. 

TTie Cambridge Structural Database A Quarter of a Million Crystal Structures and Rising, Cambridge Crystallographic Data Centre, version 5.28, November 2006, Cambridge, UK F.H. Allen, Acta Cryst., B58, 380 (2002). 

For an assembly with a mixed bridge see P. Jaumier, B. Jousseaume, E.R.T. Tiekink, M. Biesemans, and R. Willem, Organometallics, 16, 5124 (1997). 

This work was supported from startup funds from University of Nebraska Medical Center and National Institute of Health (giant number 1R15 AR063901-01). 

Aurora, A.J., lannotti, J.R, Derwin, K., 2007. Commercially available extracellular matrix materials for rotator cuff repairs state of the art and future trends. Journal of Shoulder and Elbow Surgery 16, S171-S178. http //dx.doi.Org/10.1016/j.jse.2007.03.008. 

Sugimoto, M.J., Koh, J.L., Ameer, G.A., 2014. A biodegradable tri-component graft for anterior cruciate ligament reconstruction. Journal of Tissue Engineering and Regenerative Medicine, http //dx.doi.org/10.1002/term.1966. 

Vaquette, C., Zhang, Q., Reis, R.L., Ivanovski, S., Hutmacher, D.W., 2014. Advanced tissue engineering scaffold design for regeneration of the complex hierarchical periodontal structure. Journal of Clinical Periodontology 41, 283-294. http //dx.doi.org/10.llll/ jcpe.12214. 

Cummins, C.A., Murrell, G.A.C., 2003. Model of failure for rotator cuff repair with suture anchors identified at revision surgery. Journal of Shoulder and Elbow Surgery 12, 128-133. http //dx.doi.Org/10.1067/mse.2003.21. 

In this chapter, we have reviewed the two-dimensional self-assembly of oligothiophenes and polythiophenes on different surfaces and experimental conditions, as observed by high-resolution STM. This technique allows one to identify the bonding arrangements of molecules at surfaces, with molecular 

Ostoja, S. Guerri, S. Rossini, M. Servidori, C. Taliani, R. Zamboni, Synthetic Metals, 54, 447 (1993). 

Schunack, Y. Naitoh, P. Jiang, A. Gourdon, E. Laegsgaard, I. Stensgaard, C. Joachim, F. Besenbacher, Progress in Surface Science, 71, 95 (2003). 

Besenbacher, Annual Review of Physical Chemistry, 57, 497 (2006). 

De Feyter, F. C. De Schryver, Two-dimensional Dye assemblies on Surfaces studied by STM Top Curr Chem, 258, 205-255 (2005) Springer-Verlag Berlin Heidelberg 2005 Editor Frank WUrthner. 

After this general presentation of the state of the art, the chapter is focused on recent and novel research developments in the domain of low cost and environmentally friendly AC/AC capacitors using neutral salt electrolytes, for example, essentially alkali electrolytes. Besides fundamental investigations to understand the operating principles and properties of these new systems, attention has been paid to use a common technique from industry to evaluate their life cycle, for example, so-called floating. 

Conway, B.E. (1999) Electrochemical Supercapacitors Scientific Fundamentals and Technological Applications, Kluwer Academic and Plenum Publishers, New York. 

Beguin, F. and Frackowiak, E. (eds) (2010) Carbons for Electrochemical Energy Storage and Conversion Systems, CRC Press and Taylor Francis Group, Boca Raton, EL. 

Balakrishnan, A. and Subramanian, K.R.V. (2014) Nanostructured Ceramic Oxides for Supercapacitor Applications, CRC Press. 

Laheaar, A, Delpeux-Ouldriane, S., Lust, E., and Beguin, F. (2014) / Electrochem. Soc., 161, A568-A575. 

Capillary electrochromatography has experienced rapid progress during the last decade, expanding from 17 publications in 1994 to 191 in 2007. This has also led to several books and reviews [93-104] and analytical instrumentation is readily commercially available [105]. The developments in CEC include research on optimum stationary phases (polymer or silica based, adsorbed or imprinted, etc.), mobile phases (aqueous electrolytes with/without admixture of organic solvents or pseudophases) and apparatus design (open-tubular, packed or monolithic capillaries) up to lab-on-a-chip devices for pTAS [107]. 

Pretorius, B. Hopkins, J. D. Schieke, Electroosmosis. New concept for hi speed liquid chromatography, J. Chromatogr., 1974, 99, 23—30. 

Terabe, K. Otsuka, K. Ichikawa, A. Tsuchiya, T. Anolo, Electrokinetic separations with micellar solutions and 

Betthold, M. De Carvalho, Oil in water microemulsions as mobile phases in liquid chromatography, Arud. Chem., 1992, 64, 2267-2272. 

Altria, A review of the background operating parameters and applications of microemulsion liquid 

Future investigations on small animals will depend on further development of calorimeters and of combinations with indirect methods. Until now, no calorimetric experiments were performed with specimens under higher pressure. But some data on metabolic research and pressure are found in the literature [193-195]. In the opinion of the authors, an experimentally difficult, but fascinating field opens here. Invertebrates (like gammarides, worms or snails) from deep freshwater (e.g. 

You can find out all about a man in two days, about an animal in four. 

Lavoiser and P S. de LaPlace, Memoire sur la Chaleur, Memoires de la Academic Royale, 1780. 

Crawford, Experiments and Observations on Animal Heat and the Inflammation of Combustible Bodies being an Attempt to Resolve these Phenomena into a General Law of Nature, Edinburgh, 1778. 

Atwater and E.B. Rosa, Description of new respiration calorimeter and experiments on the conservation of energy in the human body, U.S. Dept. Agr. Off. Exp. Sta. Bull., 63 (1899). 

Polymer characterization usually requires a combination of several analytical tools such as NMR and GPC. Today, a number of analytical techniques exist that can provide molecular mass, structure, and composition information, and MALDI-MS is now emerging as a powerful method for polymer characterization. Some demonstrated advantages of the technique include the ability to determine average molecular mass and distributions without the need of polymer standards and with high speed, precision, and accuracy, to analyze polymer mixtures with minimiun sample work-up, and to provide structural and compositional information via 

Because of the diversity associated with polymer chemistry, there is no universal approach in MALDI-MS for the analysis of polymers. The major challenge in applying MALDI-MS to characterize a particular polymeric system lies in developing a suitable sample preparation protocol tailored to this polymer. This usually involves screening and selecting a suitable matrix from a list of known matrices used for the analysis of similar polymers, and in some cases this requires new matrices to be identified. Once an appropriate matrix is found, however, attention must still be paid to many details in the MALDI analysis procedure to ensure that the final results reflect the true chemical nature of the polymeric system. 

The current MALDI techniques used for polymer analysis have several limitations. For example, they are unable to analyze some narrow-polydispersity polymers, while there is a need to develop sample-preparation protocols for the analysis of important polymers such as polyethylene, perfluoropolymer, and polycationic materials. Although the analysis of polystyrenes with molecular masses of up to 1.5 million using a conventional MALDI-TOF instrument has been demonstrated, it remains to be seen how the technique can be appUed to other high-mass polymers ( 500000 Da). 

In summary, MALDI-MS is an important tool for polymer characterization, with many attributes that complement those of other analytical techniques. Future advances in analytical method development, as well as of our understanding of 

1 Braudy, R.F., Jr. (ed.) (2003) Comprehensive Desk Reference of Polymer Characterization and Analysis, Oxford University Press, New York. 

To establish cost-effective fermentation of biomass, the integration of enzyme production, saccharihcation, and fermentation processes is a desirable strategy. 

Edward, A. R. (2005) The Sustainability Revolution Portrait of a Paradigm Shift, New Society Publishers, Gabriola Island, British Columbia, Cauda. 

Tietze, L. F., Brasche, G., and Gericke, K. M. (2006) Domino Reactions in Organic Synthesis, Wiley-VCH, Weinheim, Germany. 

Benaglia, M. (2009) Recoverable and Recyclable Catalysts, Wiley, Chichester, UK. 

Aldolases are an important class of biocatalyst for carbon-carbon bond formabon, useful in the synthesis of naturally occurring compounds and analogs and with the xmique characteristic that they are capable of building up new polyfxmctional molecular frameworks through consecutive or cascade reactions. 

The discovery of the precise mechanism of the enzymatic aldol addition process in combination with the elucidation of enzyme structure is also of paramount importance. In this way, it becomes more practicable to elucidate the precise transition state(s) involved in the catalytic process, and this is of utmost significance in modifying rationally existing enzymes or de novo design new activities. 

The exploitation of FSA-like aldolases represents a qualitative progress in aldolase-catalyzed synthesis as these enzymes accept diverse donors with the hitherto unique requirement of the hydroxymethylcarbonyl moiety. A systematic study of potential donor substrates with iimovative functionalities and structures is still necessary to assess the potential of these catalysts. Additionally, further mutagenic works on the active site may provide FSA-like aldolases with broader structural tolerance for both donor and acceptor substrates, which would be of paramount utility in organic synthesis. A significant limitation of the FSA-like aldolases is the lack of a set of stereocomplementary enzymes, which has not been found in nature yet. 

10 RECENT ADVANCES IN ENZYME-CATALYZED ALDOL ADDITION REACTIONS 

One hopeful perspective in this field should be a new SIMS technique whereby the best characteristics of ToF-SIMS (the molecular information) and of NanoSIMS (the nanometer-scale resolution) are merged. Clearly, this combination technique should provide spatially resolved molecular information at the nanometer scale. 

6 Briggs, D. (1998) Surface Analysis by XPS and Static SIMS, Cambridge University Press, Cambridge, UK 

26 Prosycevas, L, Tamulevidus, S., and Guobiene, A. (2004) Thin Solid Films, 453, 304. 

27 Dekeyser, C.M., Biltresse, S., Marchand-Brynaert, J., Rouxhet, P.G., and Dupont-Gillain, C.C. (2004) 

37 Robenson, L.M. (2007) Polymer Blends A Comprehensive Review, Carl Hanser Verlag, Munich, pp. 27-28. 

Self-assembly processes have been demonstrated to be an excellent means of building up sophisticated oligo(BINOL) structures [M2102]2+, [M2103]4+, and [Mll2]+. These provide an array of functional groups that could be used for the recognition 

Much work still needs to be done to develop artificial receptors that combine sufficient orientation through an array of hydrogen bond contacts with favorable hydrophobic effects to provide sufficient binding energy to reach the ultimate goal - effective and biomimetic recognition of carbohydrates in water. 

2 In fact, boronic acids have been extensively used in carbohydrate chemistry, for example in chromatographic separations since the early 1970s. However, WulfF and coworkers were the first to employ boronic esters in imprinted polymer carbohydrate receptors (a) G. Wulff, Pure Appl. Chem. 1982, 54, 2093-2102  

Kijima, M. Takeuchi, S. Shinkai, Chem. Lett. 1998, 781-782 (n) M. Takeuchi, T. Imada, S. Shinkai, 

In order to optimize the utilization of polymeric nanoparticles for pharmaceutical applications, it is extremely important to recognize all the relevant phenomena involved and to understand the mechanisms of formations in particular it would be extremely useful to be able to predict the final particles characteristics as a consequence of the operating conditions adopted. 

In this chapter the flash nanoprecipitation, that is the process of solvent displacement, has been investigated in detail, together with the use of intensive mixers, as it allows continuous production and is easily transferable to industrial manufacturing. 

Bottom graph Comparison of PSD of nanoparticles before lyophilization (solid line) and after freezedrying (sucrose 5% w/w (dash-dotted line), sucrose 2.5% w/w + Cremophor EL 2.5% w/w (dotted line)). TBA, = 5 mg/mL, y. = 1.7 m/s, W/S= 1, quench volumetric ratio = 0.33, = 5 Pa, -20°C. 

In the previous sections it has been shown that the particles size, which for parenteral applications must be confined in a relatively narrow range, is strongly influenced by mixing conditions (that depend on mixer type and flow rates), polymer and solvent type, polymer concentration, and loading. 

It has been shown that a power law type can be effective in relating the particle size to the main operating variables, both for solid nanospheres and nanocapsule either with a liquid or fatty core. 

As stated in Section 5.2.2.5.1, biocatalysis is stiU a very small niche area within the field of industrial organic synthesis in general. Even though the combination of ILs and biocatalysts may offer several exciting opportunities, we do not believe that this will change the overall position of biocatalysis significantly. Rather, the combination of ILs and biocatalysis will only become yet another niche area within the field of biocatalysis. 

Eckstein, N. Kaetzik, Curr. Opin. Bidechnd. 2002, 13, 565. 

MacFarlane, J. Golding, S. Forsyth, M. Forsyth, G. B. Deacon, Chem. Commun. 

Schofer, N. Kaetzik, P. Wasserscheid, U. Kragl, Chem. Commun. 2001, 425. 

Eckstein, M. Sesing, U. Kragl, P. Adlercreutz, Biotechnd. Lett. 2002, 24, 867. 

Last but not least, mention should be made of the use of redox active organometallic clusters for the formation of CT complex. An early example was reported by Eisenberg, Miller and co-workers who exploited the trinuclear niobium cluster [Nb3(/i-Cl)6( 7 -C6Me6)3] and prepared the [TCNQ] salt, upon oxidation to the dicationic form. This material was found to be paramagnetic and to display a relatively modest conductivity (urt = 0.001 Scm , semiconductor) [75]. Finally, the pentanuclear trigonal bipyramidal vanadium cluster [(MeCp)5V5(/r -S)6] was shown to undergo CT complex formation with TCNQ affording [(MeCp)5V5(/i -S)6] [(TCNQ)2] [76]. This material, which was structurally characterized, is an n-type semiconductor with a band gap of 0.25 eV. 

Ferrocene and some of its derivatives are well suited for the formation of CT complexes and offer an entry into solid state organometallic chemistry. Because such CT complexes contain radical species, the consideration of their physical properties is of fundamental importance and now constitutes an interdisciplinary research field. The systematic study of the magnetic properties of CT complexes of, notably, decamethylferrocene, by the Miller Epstein group has led to the discovery of bulk ferromagnetic molecular materials and to new insights into the mechanisms of magnetic coupling. Such results have shown that ID materials, as most CT complexes are, can display 3D properties if the molecular components are matched 

Pfeiffer, Thin Solid Films 1989, 179, 233-238 (b) E. Gunther, S. Hiinig, J.-U. von Schiitz, U. Langohr, H. Rieder, S. Soderholm, H.-P. Werner, K. Peters, H. G. von Schnering, H. J. Lindner, Chem. Ber. 1992, 125, 1919—1926, and references cited therein. 

Since the description of liquid crystallinity for cholesteryl benzoate and cholesteryl acetate at the end of the 19th century by Reinitzer [1], an intense activity has been devoted to thermotropic liquid crystals, especially since the early 1970s, owing to the fabrication and application of liquid crystal displays in electronic technology. 

Metal-containing liquid crystals opened the way to new geometries and new topologies, in comparison with wholly organic materials, and allowed further investigation of the relationship between structure and mesomorphic properties. Mononuclear (Ni, Cu, Rh, Pd, Pt, V, Ag, Au, Zn, rare earths) and dinuclear (Rh, Mo, Ru, Ni, Cu and Pd) coordination complexes containing liquid crystals were prepared and studied during the last decade [5]. 

Pfeiffer, Thin Solid Films 1989, 179, 233-238 (b) E. Gunther, 

von Schiitz, U. Langohr, H. Rieder, S. Soderholm, H.-P. Werner, K. Peters, 

Papavassiliou), NATO ASI Series, Series B Physics, Vol. 248, Plenum, New York, 1991, pp.91-95. 

The preceding review of various aspects of adsorptive reactors has hopefully provided some insights as to why this apparently so promising technology has yet to fulfil its potential. The often conflicting (and sometimes incompatible) demands placed on catalyst and adsorbent, the enhancement of unwanted side reactions or catalyst deactivation, and the difficulties of an expedient adsorbent regeneration with realistic overall cycle times can quickly disillusion those trying to harness this particular type of multifunctional reactor. 

It is instructive to compare the example of the seemingly more feasible Claus process with the less tractable direct HCN synthesis. The major difference lies in the much poorer selectivity of both catalyst and adsorbents at the higher temperatures (400 °C rather than 250 °C) in the latter case, which would seem to indicate that adsorptive reactors function better at lower temperatures. The ability to use a process gas stream for elutive regeneration and to overcome problems due to distortive reactant adsorbent on the catalyst using the partial de-integration described in Section 7.5.1 are further points favoring the use of adsorptive reactors in the first instance. 

It should also always be borne in mind, that process integration inherently entails a loss of degrees of freedom (Fig. 7.20), and the designer of a multifunctional reactor must always seek additional design variables, which might enable them to better harmonize the demands of the two underlying operations. The multiscalar architecture of the process and the structured distribution of the functionalities within it must be analyzed in the context of the process synthesis if this objective is to be realized [61], 

Some generalized qualitative guidance which can be derived from the work presented is as follows  

Some of these criteria help to explain the greater success of chromatographic reactors over adsorptive reactors for the gas phase reactions described here. They also point to a niche (if somewhat trivial) application of adsorptive reactors in end-of-pipe environmental processes, in which low concentrations of a gas-borne pollutant are adsorbed from waste gas over a long period before being destroyed by catalytic oxidation in a high-temperature regeneration step utilizing the heat liberated by combustion by means of a gas recycle. 

Polymer-layered silicate nanocomposites are prepared at very low filler content ( 5 wt%), which results in far lighter products in comparison to conventional composites. Besides, the ease of preparation through simple processing such as melt extrusion and injection molding with low production 

Bhattacharya S, Gupta R, Kamal M. Polymeric n/mocomposites theory and practice. Hanser Gardner Publications 2007. 

Pavlidou S, Papaspyrides CD. A review on polymer-layered silicate nanocomposites. Prog Polym Sci 2008 33 1119-1198. 

Ray SS, Okamoto M. Polymer/layered silicate nanocomposites a review from preparation to processing. Prog Polym Sci 2003 28 1539-1641. 

Hussain F, Hojjati M, Okamoto M, Gorga RE. Review article Polymer-matrix nanocomposites, processing, manufacturing, and application An overview. J Compos Mater 2006 40 1511-1575. 

Encapsulation of the chelates into nanopartieles often results in further improvements of their photophysical properties [219,220]. We have also seen above that relatively modest quantum yields can be compensated by introducing several emitting ions in one probe. This is achieved in luminescent metal-organic frameworks [221] or dendrimeric complexes [214] which then present attractive properties, including multifunctionality and nanoscale processability, for chemical sensors and bioprobes. 

The author s research was funded by the Swiss National Science Foundation (grant 20020 119866) and the Swiss Office for Science and Education (grant C07.0116) within the frame of the European Union Cost Action D38. The author thanks the World Class University Program from the Ministry of Education, Science and Technology of the Repubhc of Korea (grant R31-2012-000-10035-0) and Dr Svetiana V. Eliseeva for careful reading of the manuscript. 

APTES 3-aminopropyl(triethoxy)silane (also referred to as APS, APT or APTS) APTMS (3-aminopropyl)trimethoxysilane 

BPPCT 4,4 -bis(4,4,5,5,5-pentafluoro-l,3-pentanedionate-l-yl)-[l,l 2, l -terphenyl]-4 -sulfonyl chloride BSA bovine serum albumin 

EMCCD electron-multiplying charge-coupled device 

In spite of the considerable number of thermoplastic PCNs synthesized by in-situ polymerization in the last 10 years, the area of rubber nanocomposites is not exhausted by far. To date, only a few number of reports have been published on the synthesis of 1,3-butadiene-based PNs. Specifically, as we have pointed out in this chapter, most of the work on the in-situ polymerization concerned with the anionic polymerization or copolymerization of 1,3-dienes by using the n-BuLi initiator. According to this technique, the monomer is intercalated in between the clay galleries and converts into polymer by in-situ addition of the anionic initiator. 

The heat released during the growing of the polymer chains allows to weaken the interaction between the inorganic layers (Coulomb force) increasing the basal spacing until to reach the exfoliation of the filler platelets. 

On the other hand, the development of polybutadiene/day nanocomposites prepared by in-situ metal-catalyzed polymerization is still in its embryonic stage. 

At least in principle it might assist in the design of PB-based PNs in a nanocon-trolled fashion over their structural features and polymer architecture, such as composition and molecular weight. However, as we have briefly showed herein, the nature of the organo-modification of the day, and therefore their surface character, is the key point to tune the physical allocation of the polymerization active centers and to synthesize PB nanocomposites with improved filler dispersion. 

In conclusion, from our point of view, the growing interest in the synthesis of novel metal transition or lanthanide based catalyst systems could offer novel opportunities for further improvements in the nanocompounding process by in-situ polymerization via Ziegler-Natta coordination catalysis. 

PyBOP 1H -benzotriazol-1 -yloxytris (pyrrolidino)phosphonium hexafluorophosphate 

REDOR rotational echo double resonance (NMR spectroscopy) 

CP-MAS cross-polarization magic-angle spinning (NMR spectroscopy) 

1 Tirrell, D. (1994) Hierarchical Structures in Biology as a Guide for New Materials Technology, Tech Report, Washington. 

(2003) Journal of Polymer Science. Part A Polymer Chemistry, 41, 1737. 

Mononuclear blood cells bioavailability of HIV protease inhibitors 

CH is supported by the Swiss National Science Foundation Professorship PP00A-110746 and the University Research Priority Program Integrative Human Physiology of the University of Zurich. 

1 Remmer, H. (1958) Die Beschleunigung des Abbaues als Ursache der Gewohnung an Barbiturate. Naturwissenschaften, 46, 580-581. 

2 Waxman, D.J. and AzarofF, L. (1992) Phenobarbital induction of cytochrome P-450 gene expression. The Biochemical Journal, 281, 577-592. 

Zetterstrom, R.H., Perlmann, T. and Lehmann, J.M. (1998) An orphan nuclear receptor activated by pregnanes defines a novel steroid signaling pathway. Cell, 92, 73-82. 

5 Transgenics Made for Altered Levels of Cell Detoxification Proteins 

Conventional breeding programs for raising abiotic stress-tolerant genotypes 

In the future, we will be able to produce even high-value traits - for example, biopharmaceuticals - in areas of the world which, today, are not farmable at all. Moreover, as recommended by Knablein, this is what we should focus on because then, at the dawn of this new millennium, we would for the first time be capable of producing sufficient amounts of biopharmaceuticals to treat everybody on our planet [137]. 

Blumwald, G.S. Aharon, M.P. Apse, Bio-chim. Biophys. Acta 2000, 1465, 140-151. 

Sentenac, N. Bonneaud, M. Minet, F. La-croute, J. M. Salmon, F. Gaymard, 

Ed ted by P. Braurstein, L. A. Oro P. R. Raithby Copyright WILEY-VCH Verlag GmbH, D-69469 Woinheim (Federal Republic of Germany), 1999 

4 On the Possibility of Single Electronics Based on Ligand-Stabilized Metal Clusters 

Thus cluster chemistry enables the control of a specific size-property relationship for many solid-state nanomaterials and helps overcome the size limitations of lithography, because it enables the tailoring of building units for nanoscale devices. 

It will be shown in the following discussion that ligand-stabilized metal clusters are promising building blocks for a new nanoscaled architecture which can be used to construct microelectronic devices. It will be pointed out that use of the principles 

Physically the transfer of single electrons can be achieved by means of sequential quantum tunneling. Here the probability of a tunneling event is determined by an external voltage or current source applied to the circuit and by the distribution of excess electrons over the constituent sites. Therefore a microelectronic circuit could consist of a certain number of reservoirs of free electrons. These reservoirs should 

Although NHC (N-heterocyclic carbene) catalysis is still underdeveloped compared to other areas of organocatalysis, the number of enantioselective methodologies regardingthe direct C—H bond functionalization of aldehydes 

Enders, K. Breuer, J. Runsink and J. H. Teles, Helv. Chim. Acta, 1996, 79,1899. 

Ishida, K. Kawatsu, Y. Matsuoka, K. Yamada, R. Ikariya, J. Sawayama, S. Hirao, N. Nishiwaki and K. Saigo, Asian J. Org. Chem., 2013,2,140. 

The sequence of shadowgrams is taken every 12 min. Initial length of the cone is 30 mm. Diameters large base (top) 

An introduction to Nonlinear Chemical Dynamics, Oxford University Press. 

Horkay, F. and Me Kenna, G.B. (2009) in Physical Properties of Polymers Handbook (ed. J.E. Mark), Chapter 29, Springer, New York. 

Gerlach, G. and Arndt, K.-F. (2009) Hydrogel Sensors and Actuators, Springer Series on Chemical Sensors and Biosensors, vol. 6. Springer, New York. 

Yoshida, R. (2009) in Chemomechanical Instabilities in Responsive Materials, Springer NATO series A (eds P. Borckmans, P. De.Kepper, A. Khokhlov, and S. Metens), p. 39. 

Meanwhile, also methods have been developed using syngas surrogates such as formaldehyde, paraformaldehyde, or CO2 (see Chapter 3) [209]. Generally, these methods are easier to operate on a small scale, since the special safety measures that are necessary for working with toxic CO can be avoided. Moreover, alternative metals have been suggested that may also be useful for the production of fragrances [210]. 

Another crucial problem is the achievement of high enantioselectivity in asymmetric transformations. 

Since the business of fragrances and odors is always a subject of rapid changes and fashion trends [211], the hydroformylation methodology could be advantageously used to get immediately adapted and to respond to new tendencies in this segment of the society. Especially, the ultimate search for a personahzed perfume, which correlates to the individual person s genotype [212], may contribute to a greater consideration of the potential of the hydroformylation method in the future. 

This is an updated version published as Gusevskaya, E.V., Jimenez-Pinto, J., and Borner, A. (2014) ChemCatChem, 6, 382-411. 

Probably receptors do not respond to the shape of the molecules but to their vibrations, which could be proven by IR spectroscopy Turin, L. (1996) Chem. Senses, 21, 773-791. 

While most of the reported studies deal with a ranking of materials for target applications, systematic studies on the effect of the membrane microstructure on 

Last but not least, the fundamental understanding of the permeation mechanisms within perovsldte and more extensively MIEC membranes is still in its infancy. The most extended models are based on the Nernst-Planck equations (e.g., the Wagner equation) providing a macroscopic view of the permeation process itself. These models usually cannot afford the description of heterogeneous materials including impurities and occluded bubbles, as is the case for most real perovskite layers. To this aim, the development of meso- or microscale models with a proper description of diffusion effects and vacancy generation would be desirable. 

X Molar fraction in the feed/retentate side of the membrane (—) 

Carbon tetrachloride Trichloro acetonitrile Cerium(III) chloride Dichloromethane (DCM) 

2-Iodylbenzoic acid (or) 2-iodoxybenzoic acid Lithium aluminum hydride (LiAlH4) 

Nordlund, DA. (1981) in Semiochemi-cals Their Role in Pest Control (eds D.A. Nordlund, R.L (ones, and W.J. Lewis), John Wiley Sons, Inc., New York, pp. 13-28 and references cited therein. Mori, K. (1992) in The Total Synthesis of Natural Products, Vol. 9 (ed. ). ApSimon), Wiley-Interscience, New York, pp. 1-534. 

Bedorf, N., Gerth, K., and Reichenbach, H. (1993) German Patent (GBF) DE-B 4138042 Chem. Abstr., 

Based on the systematic overview of the research results in the field of LDH-based catalysts, research guide lines to the development of new catalysts using the excessive potential of LDHs material family could be considered, especially concerning  

Comprehensive research data map on structural and textural properties of LDHs as a tool for correlating of catalytic properties with the genesis of active structure depending on mutually interconnected phenomena in synthesis procedure, thermal activation and reaction environment  

Reitzmann, J. Ranogajec, R. Marinkovic-Neducin, Journal of Thermal Analysis and Calorimetry, Vol. 110, p. 227,2012. 

Reitzmann, K. Lazar, Chemical Engineering Journal, Vols. 207-208, p. 913, 2012. 

Hadnadjev-Kostic, T. Vulic, R. Marinkovic-Neducin, Advanced Powder Technology, Vol. 25, p. 1624, 2014. 

Messori, F. Abbate, G. Marcon, P. Orioli, M. Fontani, E. Mini, 

Marcos, S. Diaz-Moreno, V. A. Sole and A. Munoz-Paez, /. Phys. Chem. B, 2001, 105, 7588. 

Guo and P. J. Sadler, in Cisplatin Chemistry and Biochemistry of A Leading Anticancer Drug, ed. B. Lippert, Wiley-VCH, Zurich, 1999, p. 293. 

Berners-Price, L. Ronconi and P. J. Sadler, Prog. Nucl. Magn. Reson. Spectrosc., 2006, 49, 65. 

Arriola, L. Longoria, A. Quintero and D. Guzman, Biol. Trace Elem. Res., 1999, 71-72, 563. 

Ca-CPh2H bond, while the second electron of that bond is used to form a new C-C bond. 

The entire process of the benzylic C-H functionalization by the considered donor/donor-carbene, that is, the reaction 4 + N2CPh2 8 D/D + MeCH2Ph + N2 + THF 5 + MeCH(CHPh2)Ph + N2 + THF is exergonic (-31.8 kcal moH) and is kinetically controlled by the hydrogen abstraction transition state (which requires an energy barrier of about 22.4kcal mol ). Thus, this reaction should be a facile process. 

In this chpter, we analyzed electronic factors affecting the mechanism of transition-metal-catalyzed C-H bond alkylation by diazocarbene precursors. We demonstrated that efficient transition-metal-catalyzed alkylation of C-H, C=C, and C=C bonds by diazocarbenes requires a fine balance  

1) of the triplet and singlet electronic states ofcarbenes availability of singlet and triplet states is crucial for the electrophilic and nucleophilic character of car-bene fragment of metallocarbenes and 

2) in the metal - carbene bond strength a strong metal- carbene bond is required for facile diazocarbene decomposition, while weak metal—carbene interaction is beneficiary for the metallo-carbene reaction with various substrates. 

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VI. Conclusions and Perspective 1. The Bind and Jump Model for Lectin-Mucin Interactions... 

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