Discovering the Future of Molecular Sciences E-Book

• Herausgeber: Wiley-VCH
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 784

Veröffentlichungsjahr: 2014

Beschreibung

The European Young Chemist Award has now been awarded four times (2006, 2008, 2010 and 2012). The authors of the previous books based on the competition have become some of the leading scientists in Europe. These books truly provide a glimpse into the future research landscape of European chemistry.

Fifteen top contributions have been selected for this single volume covering areas of chemistry and materials science. The broad range of themes is presented in an approachable and readable manner equally appropriate for non-specialists on the topic. The overview of intriguing topics includes chemical synthesis and advanced methodologies as well as materials, nanoscience and nanotechnologies.

Leseprobe

Table of Contents

Cover

Related Titles

Title Page

Copyright

Preface

List of Contributors

Part I: Advanced Methodologies

Chapter 1: Supramolecular Receptors for the Recognition of Bioanalytes

1.1 Introduction

1.2 Bioanalytes

1.3 Metal Complexes as Receptors for Biological Phosphates

1.4 Functionalized Vesicles for the Recognition of Bioanalytes

1.5 Boronic Acid Receptors for Diol-Containing Bioanalytes

1.6 Conclusion and Outlook

Acknowledgment

References

Chapter 2: Methods of DNA Recognition

2.1 Introduction

2.2 Historical Outline: The Central Dogma

2.3 Intermolecular Interaction between the Transcription Factors and the DNA

2.4 Miniature Versions of Transcription Factors

2.5 Intermolecular Interaction Between Small Molecules and the DNA

2.6 Outlook

Acknowledgments

References

Chapter 3: Structural Analysis of Complex Molecular Systems by High-Resolution and Tandem Mass Spectrometry

3.1 Dissecting Molecular Complexity with Mass Spectrometry

3.2 Advances in Fourier Transform Mass Spectrometry

3.3 Advances in Mass Analyzers for FT-ICR MS

3.4 Advances in Mass Analyzers for Orbitrap FTMS

3.5 Applications of High-Resolution Mass Spectrometry

3.6 Advances in Tandem Mass Spectrometry

3.7 Outlook:

Quo vadis

FTMS?

3.8 Summary and Future Issues

Acknowledgments

References

Chapter 4: Coherent Electronic Energy Transfer in Biological and Artificial Multichromophoric Systems

4.1 Introduction to Electronic Energy Transfer in Complex Systems

4.2 The Meaning of Electronic Coherence in Energy Transfer

4.3 Energy Migration in Terms of Occupation Probability: a Unified Approach

4.4 Experimental Detection of Quantum Coherence

4.5 Electronic Coherence Measured by Two-Dimensional Photon Echo

4.6 Future Perspectives and Conclusive Remarks

Acknowledgments

References

Chapter 5: Ultrafast Studies of Carrier Dynamics in Quantum Dots for Next Generation Photovoltaics

5.1 Introduction

5.2 Theoretical Limits

5.3 Bulk Semiconductors

5.4 Semiconductor Quantum Dots

5.5 Carrier Dynamics

5.6 Ultrafast Techniques

5.7 Quantum Efficiency

5.8 Ligand Exchange and Film Studies

5.9 Conclusions

Acknowledgments

References

Chapter 6: Micro Flow Chemistry: New Possibilities for Synthetic Chemists

6.1 Introduction

6.2 Characteristics of Micro Flow – Basic Engineering Principles

6.3 Unusual Reaction Conditions Enabled by Microreactor Technology

6.4 The Use of Immobilized Reagents, Scavengers, and Catalysts

6.5 Multistep Synthesis in Flow

6.6 Avoiding Microreactor Clogging

6.7 Reaction Screening and Optimization Protocols in Microreactors

6.8 Scale-Up Issues – from Laboratory Scale to Production Scale

6.9 Outlook

References

Chapter 7: Understanding Trends in Reaction Barriers

7.1 Introduction

7.2 Activation Strain Model and Energy Decomposition Analysis

7.3 Pericyclic Reactions

7.4 Nucleophilic Substitutions and Additions

7.5 Unimolecular Processes

7.6 Concluding Remarks

Acknowledgments

References

Part II: Materials, Nanoscience, and Nanotechnologies

Chapter 8: Molecular Metal Oxides: Toward a Directed and Functional Future

8.1 Introduction

8.2 New Technologies and Analytical Techniques

8.3 New Synthetic Approaches

8.4 Continuous Flow Systems and Networked Reactions

8.5 3D Printing Technology

8.6 Emergent Properties and Novel Phenomena

8.7 Conclusions and Perspectives

References

Chapter 9: Molecular Metal Oxides for Energy Conversion and Energy Storage

9.1 Introduction to Molecular Metal Oxide Chemistry

9.2 POM Photocatalysis

9.3 Energy Conversion

9.4 Promising Developments for POMs in Energy Conversion and Storage

9.5 Summary

References

Chapter 10: The Next Generation of Silylene Ligands for Better Catalysts

10.1 General Introduction

10.2 Synthesis and Catalytic Applications of Silylene Transition Metal Complexes

10.3 Conclusion and Outlook

References

Chapter 11: Halide Exchange Reactions Mediated by Transition Metals

11.1 Introduction

11.2 Nickel-Based Methodologies for Halide Exchanges

11.3 Recent Advances in Palladium-Catalyzed Aryl Halide Exchange Reactions

11.4 The Versatility of Copper-Catalyzed Aryl Halide Exchange Reactions

11.5 Conclusions and Perspectives

References

Chapter 12: Nanoparticle Assemblies from Molecular Mediator

12.1 Introduction

12.2 Assembly or Self-assembly

12.3 Nanoparticles and Their Protection against Aggregation or Agglomeration

12.4 Nanoparticle Assemblies Synthesis Methods

12.5 Applications of Nanoparticle Assemblies

12.6 Conclusion

References

Chapter 13: Porous Molecular Solids

13.1 Introduction

13.2 Porous Organic Molecular Crystals

13.3 Porous Amorphous Molecular Materials

13.4 Summary

References

Chapter 14: Electrochemical Motors

14.1 Inspiration from Biomotors

14.2 Chemical Motors

14.3 Externally Powered Motion

14.4 Asymmetry for a Controlled Motion

14.5 Bipolar Electrochemistry

14.6 Asymmetric Motors Synthetized by Bipolar Electrochemistry

14.7 Direct Use of Bipolar Electrochemistry for Motion Generation

14.8 Conclusion and Perspectives

References

Chapter 15: Azobenzene in Molecular and Supramolecular Devices and Machines

15.1 Introduction

15.2 Dendrimers

15.3 Molecular Devices and Machines

15.4 Conclusion

References

Index

End User License Agreement

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Guide

Cover

Table of Contents

Preface

Part I: Advanced Methodologies

Chapter 1: Supramolecular Receptors for the Recognition of Bioanalytes

List of Illustrations

Figure 1.1

Figure 1.2

Figure 1.3

Figure 1.4

Figure 1.5

Figure 1.6

Figure 1.7

Figure 1.8

Figure 1.9

Scheme 1.1

Figure 1.10

Figure 1.11

Figure 1.12

Figure 1.13

Figure 1.14

Figure 1.15

Figure 1.16

Figure 1.17

Figure 1.18

Figure 2.1

Figure 2.2

Figure 2.3

Figure 2.4

Figure 2.5

Figure 2.6

Figure 2.7

Figure 2.8

Figure 2.9

Figure 2.10

Figure 2.11

Figure 2.12

Figure 2.13

Figure 2.14

Figure 2.15

Figure 2.16

Figure 2.17

Figure 2.18

Figure 2.19

Figure 2.20

Figure 3.1

Figure 3.2

Figure 3.3

Figure 3.4

Figure 3.5

Figure 3.6

Figure 3.7

Figure 3.8

Figure 3.9

Figure 3.10

Figure 3.11

Figure 3.12

Figure 3.13

Figure 3.14

Figure 3.15

Figure 3.16

Figure 3.17

Figure 3.18

Figure 3.19

Figure 4.1

Figure 4.2

Figure 4.3

Figure 4.4

Figure 4.5

Figure 4.6

Figure 4.7

Figure 4.8

Figure 4.9

Figure 5.1

Figure 5.2

Figure 5.3

Figure 5.4

Figure 5.5

Figure 5.6

Figure 5.7

Figure 5.8

Figure 5.9

Figure 5.10

Figure 5.11

Figure 5.12

Figure 6.1

Scheme 6.1

Scheme 6.2

Figure 6.2

Figure 6.3

Figure 6.4

Scheme 6.3

Figure 6.5

Figure 6.6

Figure 6.7

Scheme 6.4

Scheme 6.5

Figure 6.8

Figure 6.9

Figure 6.10

Scheme 6.6

Scheme 6.7

Scheme 6.8

Figure 6.11

Figure 6.12

Figure 6.13

Scheme 6.9

Figure 6.14

Figure 6.15

Figure 7.1

Figure 7.2

Figure 7.3

Figure 7.4

Scheme 7.1

Scheme 7.2

Scheme 7.3

Figure 7.5

Figure 7.6

Scheme 7.4

Scheme 7.5

Scheme 7.6

Scheme 7.7

Figure 7.7

Figure 7.8

Figure 8.1

Figure 8.2

Figure 8.3

Figure 8.4

Figure 8.5

Figure 8.6

Figure 8.7

Figure 8.8

Figure 8.9

Figure 8.10

Figure 8.11

Figure 8.12

Figure 8.13

Figure 8.14

Figure 9.1

Figure 9.2

Figure 9.3

Figure 9.4

Figure 9.5

Figure 9.6

Figure 9.7

Figure 9.8

Figure 9.9

Figure 9.10

Scheme 10.1

Scheme 10.2

Scheme 10.3

Scheme 10.4

Scheme 10.5

Scheme 10.6

Figure 10.1

Scheme 10.7

Scheme 10.8

Figure 10.2

Scheme 10.9

Scheme 10.10

Scheme 10.11

Scheme 10.12

Figure 10.3

Scheme 10.13

Scheme 10.14

Figure 10.4

Scheme 10.15

Scheme 10.16

Scheme 10.17

Figure 10.5

Scheme 10.18

Scheme 10.19

Scheme 10.20

Scheme 10.21

Scheme 11.1

Scheme 11.2

Scheme 11.3

Scheme 11.4

Scheme 11.5

Scheme 11.6

Scheme 11.7

Scheme 11.8

Scheme 11.9

Scheme 11.10

Scheme 11.11

Scheme 11.12

Scheme 11.13

Scheme 11.14

Scheme 11.15

Scheme 11.16

Scheme 11.17

Figure 12.1

Figure 12.2

Figure 12.3

Figure 12.4

Figure 12.5

Figure 12.6

Figure 12.7

Figure 12.8

Figure 12.9

Figure 12.10

Figure 12.11

Figure 12.12

Figure 12.13

Figure 12.14

Figure 12.15

Figure 12.16

Figure 12.17

Figure 13.1

Figure 13.2

Figure 13.3

Figure 13.4

Figure 13.5

Figure 13.6

Figure 14.1

Figure 14.2

Figure 14.3

Figure 14.4

Figure 14.5

Figure 14.6

Figure 14.7

Figure 14.8

Figure 14.9

Figure 14.10

Figure 14.11

Figure 14.12

Figure 14.13

Figure 14.14

Figure 14.15

Figure 14.16

Figure 14.17

Scheme 15.1

Figure 15.1

Figure 15.2

Scheme 15.2

Figure 15.3

Scheme 15.3

Figure 15.4

Figure 15.5

Scheme 15.4

Figure 15.6

Figure 15.7

Figure 15.8

List of Tables

Table 9.1

Table 10.1

Table 10.2

Table 10.3

Related Titles

Pignataro, B. (ed.)

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Pignataro, B. (ed.)

Ideas in Chemistry and Molecular Sciences

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Ideas in Chemistry and Molecular Sciences

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Pignataro, B. (ed.)

Tomorrow's Chemistry Today

Concepts in Nanoscience, Organic Materials and Environmental Chemistry Second edition

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ISBN: 978-3-527-32623-5

Discovering the Future of Molecular Sciences

Edited by

Bruno Pignataro

The Editor

Prof. Bruno Pignataro

Università di Palermo

Dipartimento di Fisica e Chimica

Viale delle Scienze ed. 17

90128 Palermo

Italy

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

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© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

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Preface

This book is the last of the series based on The European Young Chemist Award (EYCA) competition and it reports on some of the latest hits of chemistry by young excellence.

The EYCA is indeed aimed to showcase and recognize the excellent research being carried out by young scientists (less than 35 years old) working in the chemical sciences. In particular, it is intended to honour and encourage younger chemists whose current research displays a high level of excellence and distinction. It seeks to recognize and reward younger chemists of exceptional ability who show promise for substantial future achievements in chemistry-related research fields.

The inaugural award was bestowed during the first European Chemistry Congress, which took place at the ELTE Convention Centre in Budapest in 2006, while the second and the third were in 2008 and 2010 during the same conferences in Torino (Italy) and Nürnberg (Germany), respectively.

The quality of the young chemists competitors was so high that I decided in all these cases to edit books collecting their contributions. Thus always with Wiley-VCH as Publisher and under the patronage of the major European Chemical Societies and the European Association for Chemical and Molecular Sciences (EuCheMS) and of the Italian Chemical Society (SCI) as sponsors I edited the following books: Tomorrow's Chemistry Today-Concepts in Nanoscience, Organic Materials and Environmental Chemistry (2nd Ed. 2009); Ideas in Chemistry and Molecular Sciences-Advances in Synthetic Chemistry (2010); Ideas in Chemistry and Molecular Sciences-Where Chemistry Meets Life (2010); Ideas in Chemistry and Molecular Sciences-Advances in Nanotechnology, Materials and Devices (2010); Molecules at Work-Self-assembly, Nanomaterials and Molecular Machinery (2012); New Strategies for Chemical Synthesis and Catalysis (2012).

The fourth European Young Chemist Award was presented in Prague (Czech Republic) during the fourth EuCheMS Chemistry Congress (2012).

As it occurred for all the previous awards, the scientific quality of the young chemists competitors was again outstanding.

Just to give an idea of their scientific level and therefore of the expected quality of the chapters in the book, I am delighted and proud to report some very short statements extracted from the supporting letters of some of the competitors of the awards invited by me to contribute to this book.

“In my experience, it will be very difficult to find a scientist of this age with better personality and higher capacities than him”; “He has done stellar work”; “She is a superb scientist with the skills to perform incredibly difficult experiments and to model results based on theory. She has shown the ability to imagine innovative ideas for new research directions”; “I consider him among the most brilliant European chemists of his generation”; “The best way to define to him is as truly exceptional”; “I believe he is one of the leaders of the actual generation of European Chemists”; “I can qualify him without hesitation as the best PhD student I had so far in my career”; “He is a rising star in the field of chemistry”; “He is rapidly being recognized worldwide as one of the leading young European chemists”. “He has pioneered a number of new research strands. I consider the candidate to be one of the top, if not the top, person I have mentored”.

Two among the authors of the chapters have got the ERC starting grant and some of them got different awards. Much of the scientific production of all the authors is in high-quality Journals with some of the competitors having papers in Nature, Science, Chem. Rev., Angew. Chem., JACS and other important Journals.

After the brief genesis of the book and the above points on the scientific quality of the authors, let me spend some words about its content.

The book is divided into two parts: “Advanced methodologies” and “Materials, Nanoscience and Nanotechnologies”.

In the first part there are various collected contributions ranging from analytical methodologies involving recognition issues or mass spectrometry to the area of studies involving electronic energy transfer and pump and probe methodologies as well as micro flow chemistry or advanced calculation methodologies.

The first chapter, entitled “Supramolecular receptors for the recognition of bioanalytes” by Amilan Jose Devadoss (in collaboration with Prof Alexander Schiller and Dr Amrita Ghosh), reports on fluorogenic and chromogenic supramolecular sensors for the recognition of important bioanalytes and their applications in various biological studies. Studies conducted by the author and examples from other researchers are considered. Thus, promising examples for the recognition of bioanalytes like pyrophosphate, nucleoside triphosphates, carbohydrates, lipopolysaccharides and nucleic acids are described. Metal complexes with chromogenic or luminescent motif (mainly of the Zn(II) type), new color- and fluorescence-based polydiacetylene vesicle systems and boronic acids have been the considered receptors. Potential application in biological cell staining, drug delivery, and molecular logic functions has also been summarized. In agreement with the authors I believe that this chapter will inspire new advancement in the research area of bioanalytes recognition and in the discovery of molecular sciences in the future.

To the same broad area of research than that by Devadoss et al. belongs the next contribution by Olalla Vázquez. The title is “Methods for DNA recognition”. Owing to the paramount importance of DNA for life, the focus is however here on the molecular bases of double stranded DNA (dsDNA) recognition. Special emphasis is placed on recognizing the most relevant conformation under physiological conditions: the so- called B-form of dsDNA. The interaction of natural transcription factors (TFs) with the DNA, gene expression, and the current developments in the design and preparation of synthetic dsDNA binders are considered. As to this last items, within the discussion on the Metallo-DNA and Polypyrroles and bis(benzamidine) binders, I like to mention that a schematic representation of the cytotoxic pathway of the famous cisplatin and the simple explanation of the cell death is reported. In conclusion, I feel that the chapter, in some aspect, tries to provide a contribution to yet incompletely answered important questions in the field, like those pushed by the author: “How do the large and diverse number of DA-binding proteins recognize their specific binding sites? Which are the rules that govern how proteins bind to DNA sequences?”

The next chapter by Yury Tsybin is dedicated to the astonishing advances in high resolution and tandem MS applied to structure analysis of complex molecular systems. In this chapter, following the presentation of the basic principles in mass spectrometry (MS), the Fourier Transform Mass Spectrometer that gives superior resolving power and mass accuracy among all types of mass spectrometers is introduced. Then the configuration and working principles of some modern MS variants, namely, Orbitrap Fourier Transform MS (Orbitrap FTMS), Ion Cyclotron Resonance FTMS (ICR FTMS) and Time of Flight FTMS (TOF FTMS) are described with particular emphasis on the first two because of their wider spread and commercial availability compared to TOF FTMS. This part of the chapter is followed by two sections with a discussion on the applications of high resolution MS and tandem mass spectrometry (MS/MS) in the analysis of complex mixtures or biological samples. The study of peptides and proteins with the emerging field of native mass spectrometry (which aims at preserving the solution phase protein–ligand interactions) and petroleomics (comprehensive molecular structure analysis of crude oils and complex petroleum fractions by high-resolution FTMS ) are, for example, research areas that should benefit greatly from these methodologies. Great effort is made by the author to give suggestions on how to improve the actual performance of the available instrumentation in order to cope with the always increasing demand for analytical chemistry.

The next contribution by Elisabetta Collini is entitled “Coherent electronic energy transfer in biological and artificial multichromophoric systems” and deals with electronic energy transfer (EET), a phenomenon that is important for efficient light-harvesting in photosynthesis, the development of fluorescence-based sensor technologies, and improvements in solar cell design. In particular the chapter, well balanced between introductory theorethical problems and experimental studies, focuses on the involvement of quantum-coherence in this type of phenomenon and provides some basis to allow to answer the two following fundamental questions outlined by the author: “To what extent such coherences are really relevant for the efficiency and the mechanism of biological and artificial EET processes? Would it be possible to implement quantum interference effects to control and optimize energy transfer pathways?” After an introductory part in which the author briefly talks of the EET phenomenon, the meaning of electronic coherence in energy transfer, the theorethical interpretation of the energy migration, what mentioned above is done by first presenting the developments of new ultrafast spectroscopy experiments and then describing and discussing some experimental studies on coherent electronic energy transfer in two multichromophoric systems: a light-harvesting antenna isolated from a marine cryptophyte alga and the conjugated polymer MEH-PPV (poly[2-methoxy,5-(2′-ethyl-hexoxy)-1,4-phenylenevinylene.

The next chapter is provided by Danielle Buckley and is entitled “Ultrafast Studies of Carrier Dynamics in Quantum Dots for Next Generation Photovoltaics”. It is pointed out here that first generation devices suffer from losses in efficiency because of different causes, while second generation devices make them more appealing because of the lower material and manufacturing costs. Third generation photovoltaics (PVs), also referred to as next generation PVs, aims to correct one or more efficiency losses found in first and second generation devices as well as to lower the costs. Next generation approaches to achieve these improvements include utilizing multi-junction cells, intermediate band cells, hot-carriers, multiple exciton generation (MEG), and spectrum conversion. After some introductory sections talking of concepts that are needed to understand carrier dynamics in quantum dots, this chapter focuses on ultrafast studies of quantum dots that have the potential to contribute to the development of hot carrier and MEG cells. These include transient absorption (TA), time-resolved terahertz spectroscopy (TRTS), and time-resolved photoluminescence (TRPL). In each case ultrafast pulses are used to excite or ‘pump’ a sample with energy at or above the band gap and the subsequent probe or resulting emission provides information about carrier dynamics. Some issues on the chemistry of the quantum dots used in the third generation PVs are also reported. The overall situation described in the chapter suggests a rapid advancement of quantum dot PV devices.

In the next chapter by Timothy Noël entitled “Micro Flow Chemistry: New Possibilities For Synthetic Chemists” the new possibility for synthetic chemists offered by micro flow chemistry are presented. Starting from a introduction of the basic engineering principles of micro flow, this chapter gives an overview of the most important advantages of micro flow chemistry for the organic synthetic chemist with respect to traditional batch techniques. Thus it is stressed that unusual reaction conditions far from the common laboratory practices such as high temperatures and high pressures or the use of hazardous intermediates, are enabled by microreactor technology. Also, scale-up problems that have to be considered to go from laboratory scale to production scale and the reaction screening and the optimization protocols in microreactors are issues considered in this contribution. The chapter ends with a section where the author says how he sees the field evolving in the near future.

On the basis of recent contributions from the author's laboratories and selected highlights from the Houk and Bickelhaupt research groups, the next chapter by Israel Fernández López is entitled “Understanding trends in reactions barriers” and contributes to an old challenge for chemists: the need to control the reactivity of molecules.

In the chapter, the author demonstrates the good performance of the combined activation strain (ASM) model/ energy decomposition analysis (EDA) method to explore and understand trends in reactivity in various fundamental types of reactions in organic chemistry such as Pericyclic Reactions (Double Group Transfer Reactions, Alder-ene Reactions, 1,3-Dipolar Cycloaddition Reactions, Diels-Alder Reactions) Nucleophilic Substitutions and Additions, SN2 Reactions, Nucleophilic Additions to Arynes, as well as Unimolecular Processes.

The second Part of the book provides contributions on a series of materials going from polyoxometalates (POMs) to other metal complexes. Nanoparticle assemblies and porous molecular solids are two other considered themes. The two last chapters deal with molecular machines and motors. Nanoscience and nanotechnology issues are often reported in most of these chapters.

The first chapter in this Part is provided by Haralampos N. Miras and is dedicated to the science of molecular metal oxides or POMs. These molecular systems have attracted the attention of research groups over the years, because of their plethora of unique archetypes with applications ranging from catalysis and medicine to molecular electronics, magnetism, energy, and so on. The chapter shows that after a period in which the discovery of new architectures was connected to serendipity it is now possible to design and control to an important extent both the structure as well as the function of the systems. This is achieved essentially by combining the use of new techniques like ESI/MS and the new synthetic approaches discussed in the chapter. The new discoveries and developments in the area has led to a variety of unprecedented architectures and the emergence of intriguing properties and new phenomena, paving the route for the engineering of materials with innovative functionalities. On the other hand, the capability of a real control over the self-assembly processes of these complex chemical systems opens the door for further discoveries towards a well-established and directed functional future as it is written in the title of this contribution.

Again, the second chapter in this Part, by Andrey Seliverstov, Johannes Forster, Johannes Tucher, Katharina Kastner and Carsten Streb, deals with POMs. Let me start the comments on this contribution stressing that, as outlined by the authors, the POMs possess, among others, a great capacity to incorporate a wide range of heterometals into the cluster shell, thus giving access to a large number of cluster derivatives with tunable physicochemical properties.

In this chapter the focus is on the immense potential of these systems for the development of new energy conversion and storage systems. The authors outline first the electrochemical and photochemical activity of POMs and then the applications are considered. Thus treated themes are: the POM photocatalysis and the conversion of light into chemical reactivity; the energy conversion and the splitting of water into oxygen and hydrogen; the oxidation of water to molecular oxygen and protons by using POMs; the photoreductive H2-generation or the photoreductive CO2-activation always exploiting POMs. In the second part of the chapter the authors describe the important role of POM ionic liquids (POM-ILs) in the area and after that they report a section on POM-based photovoltaics where the discussion is centered on the fact that POM anions have been employed as redox active components for the assembly of photoelectrical cells for sunlight to electricity conversion. A final section is dedicated to POM-based molecular cluster batteries.

The next chapter is provided by Shigeyosh Inoue and is entitled “The next generation of silylene ligands for better catalysts”.

In this chapter after a brief general introduction on silylene (that can be considered as the heavier analog of carbene), bis(silylene), and silylene transition metal complexes, the author reports on the synthesis and catalytic applications of silylene transition metal complexes. Ti, Ni, Pd, Ir, Rh as well as Fe containing complexes have been considered in these respects. The key of the game is that the ligand is always used to modulate the electronic properties of the transition metal. Also, steric effect may be obviously operative when bulky ligands are considered. In agreement with the author I believe that “although a broad range of fascinating achievements have been recently disclosed, this research area is still unexplored, and more fascinating advances will be made in the near future”.

The next chapter is provided by Alicia Casitas and is entitled “Halide Exchange Reactions Mediated by Transition Metals”. Here the author, after having outlined the practical importance of the halide exchange reactions in various fields, gives an overview of the history and developments of these types of reactions with particular emphasis to the nickel-, palladium-, and copper-mediated reactions. The need to improve the actual situation in order to have milder and more environmentally benign type of reactions and the need to have more efficient and practical synthetic methods are underlined.

The next chapter by Marie-Alexandra Neouze Gauthey is entitled “Nanoparticle assemblies from molecular mediator” and is dedicated to the synthesis and applications of nanoparticle assembly. As to the synthesis, the following methods are reviewed: (i) inter-ligand bonding, where a molecule is introduced between the nanoparticles and will remain in the final material; (ii) template-assisted method, where the template molecules will force the organization of the nanoparticles; (iii) deposition of 2D assemblies, where the interaction with a surface helps to organize the nanoparticle assembly; and (iv) pressure driven assemblies. Then the chapter deals with some applications of such materials. For this reason, plasmonic nanostructures for sensing, communication or signal enhancement, magnetic nanostructures, metamaterials, as well as catalysis are considered.

The next chapter is provided by Shan Jiang in collaboration with Andy Cooper and Abbie Trewin and is entitled “Porous molecular solids”. This contribution deals with microporous materials that have pore sizes smaller than 2 nm and are of strong interest as they have potential applications in separations, gas storage, catalysis, sensors, and drug delivery. Porous organic molecular crystals and Porous amorphous molecular materials are both considered. For the first type of systems, porous organic molecules like the well-known calixarenes or other chemical systems are first reviewed. Then an overview is done on the porous organic cage molecules developed by the Cooper's research group and prepared by cycloimination condensation reactions. The work done in other groups is also reported. This is followed by a section dedicated to simulation issues in order to show how useful molecular modeling and simulation tools to design and rationalize the properties of these systems are. A further section deals with applications. As to the amorphous systems, the problems of synthesis and simulation are again taken into account underlining the fact that obviously here they are more challenging with respect to the crystalline systems. In all cases, the structure activity connections and the success since now obtained on the synthetic control of the structures of these systems are highlighted and discussed.

The next contribution is provided by Gabriel Loget and Alexander Kuhn and is entitled “Electrochemical Motors.” Here, some examples of moving objects are first presented. Thus, examples of biomotors, chemical motors such as self-electrophoretic swimmers and bubble-propelled swimmers or externally powered motors (which do not need a fuel molecule for the movement like the magnetically-propelled swimmers) are briefly discussed. It is then noted that, because of morphological or chemical reasons as well as being introduced by an electric or magnetic field, some form of asymmetry is always present in all the reported cases. Thus the authors state and show that asymmetry is crucial for the generation of controlled motion; the key concept for the propulsion of particles is asymmetry. Because bipolar electrochemistry, a phenomenon known for a long time and originally used in industrial application for electrolysis or batteries, intrinsically provides a break of symmetry, which can be induced on any kind of conducting object, it is an appealing alternative to the existing mechanisms for motion generation. The chapter is then dedicated to show the potentiality of this methodology and describe different strategies that, by using bipolar electrochemistry, can trigger different types of motion.

The last chapter by Massimo Baroncini and Giacomo Bergamini is entitled “Azobenzene in Molecular and Supramolecular Devices and Machines” and gives a contribution to the design of synthetic nanomachines able to carry out movements at the molecular and supramolecular scale triggered by external stimuli. In the reported examples, azobenzene moieties are part of molecular and supra-molecular architectures in which photoisomerization controls molecular movements and nanoscale interactions.

According to the authors the results described show that “molecular and supramolecular systems capable of performing large-amplitude controlled mechanical movements upon light stimulation can be obtained by careful incremental design strategies, the tools of modern synthetic chemistry, and the paradigms of supramolecular chemistry, together with inspiration from natural systems.”

The book is aimed at advanced and specialist researchers. It should be relevant for both readers from academia and industry as it will deal with fundamental contributions as well as possible applications. The contributions come essentially from academia researchers. The audience I feel need this book is Chemists in Advanced Methodologies, Materials, Nanoscience, Nanotechnologies, and Chemical Synthesis areas. The audience with an occasional need for this book should be that of Physicists and Engineers.

I am not aware of books that can compete with the proposed one for the peculiarity of being a book written with the contributions of top-level young chemists. All the chapters are written in a clear and simple way and all try to give perspectives for the future.

Going to the conclusions and in connection with these crucial times I would like to say what one of the fourth EuCheMS Congress attendees told me at the end of the event: Future is done! And one can probably be more optimistic by looking at the creativity shown by this generation of scientists and their ability to develop interdisciplinary and collaborative projects with such a high degree of innovation. Putting everything together I really thing that the book helps in discovering at least a part of the future of the Molecular Science.

I cannot finish this preface without acknowledging the various institutions and people that supported the EYCA rendering possible this new book: the Italian Consiglio Nazionale dei Chimici (CNC) and the Italian Chemical Society (SCI) and their Presidents, Roberto Zingales and Vincenzo Barone, for sponsoring the Award; the Symposia Chairs and Experts involved in the selection of finalists; the Jury for their availability for this hard task; my coworkers for their continuous help; Francesco De Angelis, Sergio Facchetti and Nineta Majcen for the help and encouragement; the local organizers with Pavel Drasar for the support; the EYCN, EuCheMS and the fourth EuCheMS Chemistry Congress for their patronage.

Università di Palermo

Palermo, Italy

Bruno Pignataro