The Nozoe Autograph Books: Why Sign Them? Why Publish Them? Why Read Them? Why Treasure Them? Personal and Professional Reflections

Note from the Editor: The Nozoe Autograph Books project involves the publication of the entire 1179 pages of Tetsuo Nozoe's autograph books in 15 consecutive issues of The Chemical Record. In the design of this project, three of us—Eva Wille, Brian Johnson and I—had a vision of bringing a wide range of experiences to our communities of readers. We also had an eye to the archival future. The final design included, with each of these issues of The Chemical Record, an essay that would provide context, novel content and especially enjoyable reading, to round out the project. In the 10 issues published to date, and in the others that will follow, the essays range from personal stories to perspectives in the areas of chemistry near and dear to the heart of Tetsuo Nozoe. Eva Wille's essay is particularly special. The daughter of a professor of chemistry of Nozoe's generation at the Ludwig‐Maximilians‐Universität München (Franz Wille, 1909—1986), Wille is a Ph.D. chemist herself, and for many years, has been and is a major figure in the world of scientific publishing. Thus, she has a unique perspective to share. Indeed, all of the authors of these essays have shared their very personal and professional perspectives, and we are thankful for all of them—and for Tetsuo Nozoe and the thousands of our friends and colleagues who signed his books. —Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu     

My Father,My Grandfather

Note from the Editor: It is with great pleasure and enthusiasm that I introduce this essay which accompanies the publication of the fourth segment of the Tetsuo Nozoe Autograph Books. In the conceptualization stages of this project—which shall appear in 15 consecutive issues of The Chemical Record as well as have a significant internet presence—I proposed to my colleagues Eva Wille and Brian Johnson that each segment be accompanied with a specially invited essay or perspective. This proposal was immediately and enthusiastically accepted. To both celebrate the life and warmth of Tetsuo Nozoe, I can hardly imagine a more appropriate essay than one written by two of his grandchildren and one of his own children! I thank the Masamune Family for their touching contribution to this project. The Nozoe Autograph Books and all the accompanying essays, including this essay, are open access for at least a three‐year period at: http://www.tcr.wiley‐vch.de/nozoe . Jeffrey I. Seeman Guest Editor, University of Richmond Richmond, Virginia 23173, USA     

Extraordinary Transformations to Achieve the Synthesis of Remarkable Aromatic Compounds

Note from the Editor: When we walk around a sculpture, it can speak to us in many ways, sometimes quite differently from various view points. Central to Tetsuo Nozoe and the Nozoe Autograph Book project are novel aromatic compounds. Just look at nearly any page and such compounds jump out at us. We can categorize them in many ways. Their structures. Their physical properties. Their pharmacological and toxicological properties. Their commercial utilities. Their symmetry. Their size. In this essay, Graham Bodwell brings to us his analysis of the various ways in which some of the most remarkable of these compounds have been ingeniously synthesized. We are privileged to have Bodwell's vision and his sense of organization and beauty. Tetsuo Nozoe would have beamed! —Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu     

Facets of the Tetsuo Nozoe Legacy Immortalized in an Enduring Series of International Symposia on Novel Aromatic Compounds (ISNA)

Note from the Editor: According to Robert K. Merton (1988), “Invisible college” is a term used “to designate the informal collectives of scientists interacting in their research on similar problems, these groups being generally limited to a size ‘that can be handled by interpersonal relationships.’ ” Invisible colleges can be highly competitive, even ugly in their priority races, or they can be congenial, even enthusiastically supportive to its members. In the community of organic chemists who studied novel aromatic chemistry in the 1950s–1990s, one man—Tetsuo Nozoe—is largely responsible for bringing together researchers from across the world and setting the tone of brotherhood. Larry Scott, today a senior scholar of that invisible college, warmly shares the spirit of Tetsuo Nozoe with each of us in the following essay. Jeffrey I. Seeman Guest Editor University of Richmond Richmond, Virginia 23173, USA E‐mail: jseeman@richmond.edu     

Tetsuo Nozoe's “Autograph Books by Chemists 1953–1994”: An Essay

Note from the Editor: It is with special pleasure and a warm feeling of gratitude that I introduce Koji Nakanishi's essay which accompanies the publication of the fifth segment of the Tetsuo Nozoe Autograph Books. This project, “Bonding beyond Borders,” is a symbol of the ever‐increasing connectivity among the many members of the chemistry community. Both Nakanishi and Nozoe wrote autobiographies in the Profiles, Pathways and Dreams series that I edited from 1985 to 1997. I learned from their books how close they were as friends and as colleagues. My interest in publishing the Nozoe Autograph Books goes back many years but was stymied by the difficulty of finding a publisher. This interest was rekindled when, in 2006, Nakanishi told me about – and eventually lent me – a one volume specially printed commemorative collection of the Nozoe Autograph Books. At an ACS National meeting, I rushed to show this book to Eva Wille who could not put it down. This was the entry, the personal connection, that led to the publication of the Nozoe Autograph Books by Wiley‐VCH in The Chemical Record. This is another example of bonding, of enthusiasm and commitment, within our community. Jeffrey I. Seeman Guest Editor, University of Richmond Richmond, Virginia 23173, USA     

“Agricultural Chymistry is at present in it's infancy”: The Board of Agriculture,The Royal Institution and Humphry Davy

In this paper I sketch the institutional interactions between the Board of Agriculture and the Royal Institution in the late eighteenth and early nineteenth centuries. This includes analysing the composition of memberships and committees of both bodies in which, inter alia, I challenge Morris Berman's account of their institutional relations. A key figure was Humphry Davy who, because of his career ambitions, occupied a slightly uncomfortable position as Professor of Chemistry to both organisations. Davy's lecture notebooks and his subsequent publication Elements of Agricultural Chemistry reveal that he drew almost all his direct knowledge of the subject from Britain and Ireland. Yet, despite such parochial shortcomings that might be expected of an infant science at time of war, the popularity of his book, particularly in North America, provided continuity between the end of the Board of Agriculture in 1822 and the start of the impact of Justus Liebig's work in the 1840s.     

Rolf Huisgen: A Gentleman Scholar with Energy and Passion

A brief personal tribute to Professor and Mrs. Rolf Huisgen is presented. The essay describes Rolf Huisgen's energy and passion for science and art. Quotations from Huisgen's autobiography ‘The Adventure Playground of Mechanisms and Novel Reactions’ as well as many quotes from his correspondence with the author are presented. The essence and personality of this gentleman scholar are further highlighted by a number of photographs of him and of Trudl and other friends and colleagues.     

Reaction Dynamics in Extreme Environments and Astrochemistry

Ralf I. Kaiser is Professor of Physical Chemistry at the Department of Chemistry and Director of the W.M. Keck Laboratory in Astrochemistry, Department of Chemistry, University of Hawaii at Manoa (USA). He is a current member of the ChemPhysChem Editorial Board.     

Systematic Enumeration and Symmetries of Cubane Derivatives

The feasibilities of Fujita's unit‐subduced‐cycle‐index (USCI) approach, Fujita's proligand method, and Fujita's stereoisogram approach have been demonstrated by applying them to cubane derivatives as probes. They provide us with a new set of theoretical foundations for comprehensive investigation of geometric and stereoisomeric features of stereochemistry. The new set of theoretical foundations is based on mathematical formulations so as to explore mathematical stereochemistry as a new interdisciplinary field of stereochemistry.

     

Rocco Ungaro, 40 years of Calixarene chemistry

Abstract

During the Calix2015 conference that took place in Giardini Naxos in July of this year, the first C. David Gutsche Award for Calixarene Chemistry was awarded to one of the founders of the field, Professor Rocco Ungaro of the University of Parma. In this paper, Rocco Ungaro’s seminal contributions to the field are described. His collaborations with many other groups, his role in the European supramolecular chemistry community and his most important scientific results are briefly summarised.     

Ion Transport in Glyme- and Sulfolane-Based Highly Concentrated Electrolytes

Highly concentrated electrolytes (HCEs) have a similarity to ionic liquids (ILs) in high ionic nature, and indeed some of HECs are found to behave like an IL. HCEs have attracted considerable attention as prospective candidates for electrolyte materials in future lithium secondary batteries owing to their favorable properties both in the bulk and at the electrochemical interface. In this study, we highlight the effects of the solvent, counter anion, and diluent of HCEs on the Li⁺ ion coordination structure and transport properties (e. g., ionic conductivity and apparent Li⁺ ion transference number measured under anion-blocking conditions, ). Our studies on dynamic ion correlations unveiled the difference in the ion conduction mechanisms in HCEs and their intimate relevance to values. Our systematic analysis of the transport properties of HCEs also suggests the need for a compromise to simultaneously achieve high ionic conductivity and high values.     

On the connections between the quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT): a letter from Richard F. W. Bader to Lou Massa

A 31-year-old letter from Professor Richard F. W. Bader to Professor Lou Massa outlining the connections between the quantum theory of atoms in molecules (QTAIM) and density functional theory (DFT) especially with regard to the first Hohenberg-Kohn theorem is brought to light. This connection has not often been the topic of such a focused review by Bader and is presented here for the first time. The scientific importance of this letter is, in the opinion of the presenter, as timely today as it was back then in 1986. In Bader’s own opening words: “... that if I sent you a summary of what I think are the important connections between our work and density functional theory, ...”. He then takes us in a grand tour of the foundations of QTAIM culminating into the antecedents of a paper he later published with Professor Pierre Becker, whereby the Hohenberg-Kohn theorem is shown to operate at the level of an atom-in-a-molecule. Bader closes his letter by suggesting to Massa: “Study these two charge distributions – they are proof of the theorem of Hohenberg and Kohn”. By that Bader meant that when the charge distributions of two atoms or groups are identical within a given precision, then the kinetic and total energy contributions of these atoms to the corresponding molecular quantities are also identical. It is revealing to follow the intellectual threads weaved by Bader which provides us with a glimpse of his thought processes and intuition that guided him to some of his key discoveries. The lucidity, rigor, and clarity characteristic of Bader and the informality of style of a letter makes it of pedagogic and historic interest.

     

The Relationship of William Henry Perkin,Jr. and Sir Robert Robinson: Teacher and Student,then Student and Teacher

William Henry Perkin, Jr. FRS, the son of the inventor of mauve and other commercial dyes and credited for initiating the industrialization of chemistry, was himself a notable chemist. He was the Professor of Organic Chemistry at Manchester from 1892–1912 and then was the Waynflete Professor of Chemistry at Oxford and the first Head of the Dyson Perrins Laboratory from 1912–1929. One of Perkin's graduate students and research assistants at Manchester was Robert Robinson, subsequently Sir Robert Robinson, FRS and recipient of the 1947 Nobel Prize in Chemistry. Perkin and Robinson had perhaps the most productive and broad collaboration between a professor and one's student. Together, during and after Robinson's student days, they had 71 joint publications, 25 of which involved just the two of them, 17 of which involved the structure determination of strychnine, and eight of which were published after Perkin's death in 1929. Upon Perkin's early death, Robinson succeeded him as the fourth Waynflete Professor of Chemistry at the Dyson Perrins Laboratory, Oxford University. This Essay will examine the professional relationship of Perkin, Jr. and Robinson as revealed in their joint publications on the structure of strychnine.     

Our Odyssey with Functionalized Chiral Phosphines: From Optical Resolution to Asymmetric Synthesis to Catalysis

Our journey in organophosphorus research over the past 26 years is compiled in this Personal Account. Advances in palladacycle design have engendered a shift in our focus from template‐mediated transformations to catalysis for the direct preparation of chiral phosphines containing a wide variety of functional groups. Novel approaches to access previously inaccessible phosphines and their applications in cancer research are summarized herein.

     

Francis Bacon and the Art–Nature Distinction

Abstract

Commentators generally expound Bacon's position on the art–nature relationship in terms of how much it retained or departed from traditional conceptions. This paper argues that an appreciation of the Baconian meaning of the terms "art" and "nature" requires a close examination of his wider cosmogonical speculations. Bacon's cosmogonical account moves from a state of unbridled chaos to the relatively stable system for which the term "nature" is normally used. The fundamental principle lying at the heart of Baconian cosmogony is an enriched and appetitive matter: eternal, unchanging, and the plenipotentiary source of all things. Successive limitations of matter's absolute power produced a lazy and habitual nature, which Bacon labelled "nature free." To shift nature from this otiose condition, the Baconian operator recapitulates the original binding of matter. Bacon designated the systematic procedures of binding nature the science of magic. Magic is Bacon's human counterpart to the original cosmogonical process that gave rise to the current system of nature. In Bacon's cosmogony, all possible worlds unfold out of matter: the function of art is to shake out nature's hidden folds. Hence, the distinction between naturalia and artificialia maps on to the distinction between actual and potential. Nature free is without purpose, but art — nature bound — knowingly brings into being an alternative nature designed for human utility.     

Development of C3‐Symmetric Tris‐Urea Low‐Molecular‐Weight Gelators

This article describes recent developments in C₃‐symmetric tris‐urea low‐molecular‐weight gelators and their applications. The C₃‐symmetric tris‐ureas are excellent frameworks to form supramolecular polymers through noncovalent interactions. In organic solvents, hydrophobic tris‐ureas form supramolecular gels. Amphiphilic tris‐ureas form supramolecular gels in aqueous media. Functional supramolecular gels were prepared by introducing appropriate functional groups into the outer sphere of tris‐ureas. Supramolecular hydrogels obtained from amphiphilic tris‐ureas were used in the electrophoresis of proteins. These electrophoreses results showed several unique characteristics compared to typical electrophoreses results obtained using polyacrylamide matrices.

     

Recent Advances in Layered Metal Chalcogenides as Superconductors and Thermoelectric Materials: Fe‐Based and Bi‐Based Chalcogenides

Recent advances in layered (Fe‐based and Bi‐based) chalcogenides as superconductors or functional materials are reviewed. The Fe–chalcogenide (FeCh) family are the simplest Fe‐based high‐T_c superconductors. The superconductivity in the FeCh family is sensitive to external or chemical pressure, and high T_c is attained when the local structure (anion height) is optimized. The Bi–chalcogenide (BiCh₂) family are a new group of layered superconductors with a wide variety of stacking structures. Their physical properties are also sensitive to external or chemical pressure. Recently, we revealed that the emergence of superconductivity and the T_c in this family correlate with the in‐plane chemical pressure. Since the flexibility of crystal structure and electronic states are an advantage of the BiCh₂ family for designing functionalities, I briefly review recent developments in this family as not only superconductors but also other functional materials.

     

Richard Kirwan's Phlogiston Theory: Its Success and Fate

Abstract

First proposed in the early 1780s, Richard Kirwan's phlogiston theory was the most successful enunciation of the English pneumatic approach to phlogiston. Phlogiston was identified with a material substance, inflammable air. In this paper, I explore the nature of Kirwan's theory, its success in the mid-1780s, the unprecedented collective attack on Kirwan's Essay on Phlogiston by Lavoisier and his colleagues, and Kinvan's ultimate abandonment of phlogistic explanation.