Gray, George William

George Gray was born on September 4, 1926 with John and Jesse Gray in Denny, Scotland. The family also had a daughter, Catherine, six years older than him.

Childhood

In childhood, his main interests were ship modeling, reading, growing plants and gardening. George's mother was more attached to his sister than to the boy, considering him too lively and mischievous, but his father was a friend to him. He was a pharmacist in Denny, educated by a chemist and botanist, to whom George owed his early interest in science. George's father himself managed his business, and thanks to the fact that George showed a special interest in chemistry, he was allowed to help in weighing materials and making tablets, powders and solutions. Father took George for walks on Sundays and discussed with him the plants, their components and the chemistry of living processes. Therefore, by the time he was 10 years old, George was familiar with atoms and molecules, and he never wanted to become anyone other than a chemist. His father greatly influenced him as George developed his interests in science. He had a collection of books on the history of science, from which George learned about the achievements of scientists such as Faraday, Black, Priestley, Gay-Lussac and Lavoisier.

Education

He enrolled at the University of Glasgow and studied with leading research chemists such as J. W. Cook, an outstanding chemist working in the study of steroids, and J. Montef Robertson, the youngest professor at the University of Great Britain and a renowned specialist in X-ray crystallography. . In addition to studying chemistry during the war years, George also studied additional disciplines in mathematics and physics, graduating from university in 1946.

Then his father’s illness and the subsequent job offer from Montef Robertson forced George to move to Kingston upon Hull. There he took the position of laboratory assistant at London University College (in Halle). At the same time, George was also offered to work in an Anglo-Iranian company in Persia, but he refused this opportunity to continue working at the chemistry department in Halle, where he remained for the next 40 years. In the first year of work, he was appointed assistant lecturer. After that, he continued his studies, studying liquid crystals. Subsequently, he presented his dissertation in 1953, entitled "The Study of the Synthesis and Mesomorphism of Certain Aromatic Carboxylic Acids," for a Ph.D. at the Department of Natural Sciences, University of London.

After several years of studying liquid crystals and cell membranes, as well as teaching organic chemistry, he was appointed senior lecturer in 1960. His success and growing authority led to the fact that in 1964 he received a doctorate in chemistry, and in 1978, at the age of 52, a professor of chemistry. Reflecting on his time in Hull, Gray said ^[2] :

It was an action-provoking environment in which one could work, perhaps better than in more affluent institutions - everyone sought to succeed, helped each other and recovered from the lost years of the war. Indeed, I am very indebted to Hull University, which provided me with freedom to research, develop my own ideas, assisted and allowed me to work in a constantly improving environment, with the support of many wonderful colleagues. Because of this, I stayed in Hull for more than 40 years before leaving in 1990, after becoming the head of the chemical faculty and senior professor.

Hall University, 1946-1970

Gray's systematic research on the synthesis and description of mesomorphic materials began in 1946. Gray's early work included the synthesis and determination of the mesomorphic properties of alkoxybenzoic and alkoxynaphthalenic acids. In his studies, Gray determined the transition temperatures, melting points, and transparency of homologous series of substituted acids depending on the length of the terminal alkoxyl chain and in some cases determined the presence of smectic (lamellar) phases ^[3] .

Around 1952-53 Gray's research in liquid crystals has expanded by examining the effects of aliphatic chain length and lateral substitution on the mesomorphic properties of materials. In addition, he switched his work to the study of the construction and structure of the central aromatic ring and the linking groups, usually Schiff bases, which were attached to it. Further studies of 4-p-n-alkoxybenzylidenamino-3′-, 2′-, 2- and 3-chlorobiphenyls were also carried out ^[4] . He found that the nematic thermal stability of the 2'-chloro and 2-chloro-isomers is much lower than that of the 3'- and 3-isomers. This was explained by inter-ring twisting of biphenyl rings due to the coplanarity of chlorine atoms in the ortho positions. It was found that isomeric mono-anils containing bromide and methyl substituted substituents give similar results. Comparing the mesomorphic properties of mono-anils with various substituents in the 2nd position, he came to the conclusion that the nematic thermal stability decreased with an increase in the size of the substituent, i.e. with an increase in the inter-ring angle, and therefore free rotation could not occur about 1: 1 'bond in a nematic state. The result was that for biphenyl it was assumed that the inter-ring angle is certainly much smaller than 45 ° in the solution, and can be as low as 0 °, i.e. the angle of biphenyl in the crystalline state. Although these conclusions were speculative and were not confirmed by later studies of neutron scattering on the molecular dynamics in liquid crystals, it is clear that Gray began to build property-structure correlation for the formation and stability of the mesophase. His cumulative studies formed the basis of his book “Molecular Structure and Properties of Liquid Crystals” (1962) ^[5] . At that time, it was the most important work in chemistry ever published on liquid crystals, and it gave Gray international recognition. However, he also believed that writing a book was especially important because he saw a possible end to his research on liquid crystals, as funding became increasingly scarce.

In his research, which was published as a 13-band series of articles on mesomorphism and chemical structure in the Journal of the Chemical Society, Gray developed the following structure-property correlations for the molecular design of liquid crystals:

• a constant change in the temperature of the liquid crystal transition in homologous series;
• the dependence of nematic thermal stability on the size of the molecule and the transverse substituent;
• the strong influence of steric twisting by the side group in the depressing heat resistance of the mesophase;
• the role of the size and type of aromatic cores in phase type and phase stability;
• effects of screening the nucleus while reducing the inhibitory effects of the side groups;
• an important order of effectiveness of the nematic terminal group;
• a more subtle dependence of smectic thermal stability on the combination of the size of the side group and the dipole moment.

Funding Reduction

In 1960, they could not even imagine the existence of flat displays, and therefore funding for liquid crystal research became increasingly scarce, especially for universities such as Hull, and therefore Gray turned to industry and, in particular, to Reckitt & Sons Ltd for help. Over the next decade, the company funded research on the bacterial and bactericidal action against various organisms, as well as research on the structures and properties of their lipopolysaccharides. As a result of these studies, seven candidate dissertations were defended.

Flat Panel Display Program, 1970-1972

During the 1960s, it became clear that funding for liquid crystal research would not resume. Gray turned to the Council of Scientific Research for support, but he was repeatedly refused. Therefore, it seemed to him that in the foreseeable future he was destined to work with biological membranes. Then, in the late 1960s, the American Radio Company (ARC) began to show interest in displays, alternative to a cathode ray tube and, in particular, displays based on liquid crystals. The Royal Radar Institution (KRU) became aware of this and aroused great interest. The switchgear, at the suggestion of George MacFarlane, also decided to take up these studies. A working group was assembled, which included J. Gray.

The first meeting on this issue took place on October 1, 1968. At it, Gray outlined the principles of creating liquid crystals, which aroused genuine interest in the leadership.

In October 1969, a year after the meeting, the first draft report of the Working Group appeared, which proposed working on eight topics, excluding liquid crystals. The final version was released in December, and it differed from the original one in that liquid crystals were included in a number of promising areas. As a result, in April 1970, Gray was offered a two-year contract for the study of “substances exhibiting a liquid crystalline state at room temperature” at a maximum cost of 2177 pounds per year ^[6] .

Scientific Revolution

First Steps

Work on materials began in Halle in October 1970 with two researchers: doctoral student John Nash and Ken Harrison. However, the devices of that time used the dynamic scattering mode, in which materials with negative dielectric anisotropy were required, and therefore low-melting materials with rod-like structures and side dipoles with respect to molecular long axes were studied. But problems were soon discovered for many families of materials; they often showed electrolytic instability, ease of oxidation or decomposition when exposed to ultraviolet radiation. Thus, the Hull group studied substances with various Schiff bases, azobenzenes, stilbenes, carbonates, carbonate esters and Schiff ultrapure bases, but all this was ineffective.

New Approach

In 1970, the discoveries of Frank Leslie and J.F. Dreyer, presented at the third International Liquid Crystal Conference in Berlin, led to the invention of the twisted nematic liquid crystal display. This device required materials with positive dielectric anisotropy and nematic phases at room temperature ^[7] . Thus, the search was carried out for stable, with positive dielectric anisotropy, low-melting nematogens that could operate in wide temperature ranges.

Problem

In the search for suitable materials, Gray realized that a terminal nitrile moiety must be introduced into the liquid crystal bases and Schiff esters, excluding the inclusion of a central linking group to increase stability. These transformations led to the synthesis of currently known cyanobiphenyls ^[8] . The most important of these was 4-n-pentyl-4'-cyanobiphenyl (known worldwide under the abbreviation 5CB), which was first synthesized by Ken Harrison in 1972. This was the first example of a colorless, photochemically, oxidatively and electrolytically stable nematogen with a melting point near room temperature and physical properties suitable for use in flat panel displays.

Obviously, one substance was not enough, Harrison and Nash synthesized a series of homologs of 4-n-alkyl-4'-cyanobiphenyl (K3n series) and 4-n-alkoxy-4'-cyanobiphenyl (M3n series). From his early research, Gray knew that the homologous series would exhibit an oddly uniform effect on the temperature of the transition from the nematic phase to the isotropic liquid, and that members with an odd number of carbon atoms in the alkyl chain would have higher rates than even homologues for K3n series. Thus, 3CB, 5CB, and 7CB were the obvious choice. The length of five carbon atoms, that is, for K15 and M15, was essentially sufficient to create a nanosegregation system between the non-polar aliphatic chain and the aromatic biphenyl moiety. As the alkyl chain increased in both series, smectic phases were found, which indicates that the aliphatic parts of the materials began to dominate in intermolecular interactions. Also, from a practical point of view, it was necessary to increase the temperature of the transitions from the nematic phase to the liquid in mixtures ^[9] . This was achieved by increasing the number of aromatic rings in the K series by one phenyl ring to give terphenyl analogues. Thus, a way was found to create practical materials.

A patent for these substances was filed on November 9, 1972. After that, two consortia were created, devices and materials, for the use of new technologies in flat panel displays. A consortium of materials included KRU, Hall University and BDH Chemicals. After discussions with Dr. Ben Sturgeon, Research Director, BDH is contracting by the end of December 1972 and providing 5CB samples in less than three months. Thus, when developing the process at BDH Chemicals, high-purity cyanobiphenyl and terphenyl liquid crystals were used in many different mixtures, thereby becoming one of the main substances for the development of materials for flat panel displays. Already in 1974, a material was synthesized that fully met all the requirements of manufacturers of watch displays.

Search New

Since the mid-1970s, when George's research focused on the application of his work in display materials, he began to look for new ones that could take the place of cyanobiphenyls. His subsequent work formed the basis of many fundamental studies of materials in the rapidly growing topic of liquid crystals, thereby becoming an excellent example of the multidisciplinary nanoengineering of new states of matter. However, not everything was smooth. As Gray noted ^[10] :

These results are often called my application for fame, but there are those (mostly not involved in this area) who like to emphasize the negative aspect that not a single European production of displays used the materials we received. Perhaps this should have upset me, because the British really love to succeed and be successful. Honestly, I was very little interested in the fact that UK Ltd did not bring benefits from the work and that this area was completely studied in Japan and the Far East. I was glad to see that society, in its broadest international significance, uses my science, and was not too worried that the treasury of Electronic Companies did not receive profit. However, I liked the fact that the UK chemical industry has benefited financially from my work - a conveniently forgotten fact. In addition, I would like to emphasize some other much more extensive and equally important advantages and consequences for me that arise from our simple discovery of cyanobiphenyls.

After cyanobiphenyls, 1974-1990

Soon after the cyanobiphenyls achieved commercial success, Nash and Harrison left Hull and were replaced by other students and doctoral students. Subsequent studies were aimed not only at finding materials for image devices, but also for expanding the fundamental scientific base.

Subsequently, as part of a joint grant, Gray began to work with Leadbetter. Their joint work lasted 15 years and gave rise to their long-standing friendship. Thanks to various forms of funding for joint work, they deeply studied the structure and molecular dynamics in nematic and smectic liquid crystals. Although the development of biphenyls and their mixtures continued, the increase in funding made it possible to conduct a study conducted by the Hull group in a broader aspect, which led to the following fundamental successes emphasized by Gray:

• A more complete understanding of smectics and their polymorphism associated with the synthesis and study of new materials demonstrating the SmB, SmF, and SmI phases with Goodby in collaboration with Leadbetter ^{[11] [12] [13]} ;

• The rationalization of the smectic nomenclature, which was achieved at a meeting in Halle with the participation of Goodby, Sackmann and Demus, a solution to the serious problem of the same phases to which various researchers attributed different groups ^[14] ;

• Development of new alicyclic mesogens (bicyclooctanes and cubans), discovered together with Toyne, in collaboration with Kelly ^{[15] [16]} ;

• A study of molecular factors determining the formation of SmC, with Goodby ^{[17] [18]} ;

• Development of phase identification using optical microscopy with Goodby ^[19] ;

• Synthesis of deuteromesogens for neutron research involving Mosley in collaboration with Leadbetter ^{[20] [21]} ;

• Development of new chiral mesogens; work with McDonnell, in which it is shown that the position of the chiral center of a given optical configuration in a chiral alkyl group determines the alternation of the spiral coil in an alternating manner depending on parity (Gray-McDonnell rules) ^{[22] [23]} ;

• High quality dye parameters, with Coates and McDonnell ^{[24] [25]} ;

• Discovery of the “blue phases” of chiral nematic liquid crystals using Coates ^[26]

By 1980, the members of the Hull research team had basically diverged. In Halle Gray, who was a member of the University Grants Committee, he implemented a strategy to expand stronger research teams by attracting other research staff from weaker teams, thereby reducing the amount of research conducted in the department. Thus, the University continued research on liquid crystals and their properties, some of which prompted the Hull Liquid Crystal Group to return to the forefront of new display materials.

Finding a Successor and Resignation

During the 1990s, Gray's resignation was near. He found a successor in the person of John Goodby, with whom he had previously worked. Upon his retirement, Gray became the research coordinator at Merck in Poole, as well as the organizer of the highly successful Merck CASE student conferences, which are held today. A couple of years later, Gray became a home-based consultant in Wimborne, Dorset.

Although liquid crystals were a priority in George Gray's research, he also loved chemistry in general. Therefore, he was sad to see that the subject was attacked by the media in the early 1990s. Gray was obviously offended by this because he had slides from the cover of Chemistry in the UK magazine, where he emphasized those parts of the text regarding the carcinogenic nature of man-made materials. Gray believed that chemistry gave so much to society, from medical care to advanced materials, and the media that published articles on the subject were inaccurate and ignorant. In this regard, he summed up his feelings with the following words taken from his presentation of the prize in Kyoto ^[27] :

Is there any promise in all of this for young people who want to achieve these kinds of things? Obviously, training and education are very important issues, and hard work and determination are prerequisites. Luck and coincidence may be unpredictable elements in life, but at least their likely impact can be optimized by taking every opportunity to advance your goals and ambitions. In other words, never back down from opportunities. Mistakes are inevitable in any career, but if you have a sense of humor, then you can laugh at them, but firmly deciding that the same mistake will not be repeated. The most important thing is to be 100% competent in everything you do, paying close attention to detail and accuracy, and, if you can, aiming at bringing the greatest benefit to humanity.

Gray's contribution to liquid crystals over 40 years of research has been recognized at several awards:

1980 - Prize for Optoelectronics

1983 - Elected Member of the Royal Society

1985 - Clifford Patterson Lecturer Royal Society

1987 - Royal Medal of the Leverhulm Royal Society

1989 - Elected Member of the Royal Society of Edinburgh

1991 - Award in the field of fine chemistry and medicinal groups of the Royal Chemical Society;

Honorary Doctor of Science, University of Hull;

Commander of the Superior Order of the British Empire

1993/94 - Gold Medalist and Lecturer at the Chemical Industry Society

1994 - Doctor of Science, University of Trent, Nottingham,

1995 - Kyoto Prize Laureate

1996 - Foreign member of the Japanese Academy of Sciences;

Honorary Doctor of Science, University of Southampton;

Carl Ferdinand Brown Gold Medal from the Society for Information Displays (SID)

1997 - Fredericks Medal of the Russian LCD Society;

Honorary Doctor of Science, University of East Anglia

1998 - Honorary Member of the International LCD Society

1999 - Incoming member of the Defense Assessment and Research Agency

2001 - Honorary Doctor of Science, University of Aberdeen;

Elected Honorary Member of the Royal Irish Academy

2002 - Honorary Doctor of Science, University of Exeter

Gray has published over 250 scientific papers and 100 patents, and has also written several textbooks. His first book on liquid crystals probably remained his favorite. However, he was very pleased to be the senior editor of the four-volume Handbook of Liquid Crystals, which was published by VCH in 1998, and editing a series of textbooks on liquid crystals by Taylor and Francis, being the editor of the Journal and Liquid Crystals published by Taylor and Francis. His studies at Hull earned recognition for the University as Queen of Technology Achievement Prize in 1979, the first such award to a university in the UK. And in November 2005, the Historic Chemical Sign was awarded to Hull University by the Royal Society of Chemistry. Of these, one of the most important is the Kyoto Prize.

When George moved to Hull, he also met Marjorie Kanawan, who worked in a pharmacy and was also a nurse. They married in 1953 and subsequently they had three daughters. The eldest, Veronica, has three children; Elizabeth was their second daughter, who passed away several years before the death of George and Marjorie; and the youngest, Caroline, has a son. Caroline became a research chemist at SmithKline Beecham pharmaceutical company, working on the synthesis of new pharmaceutical products. Marjorie and George were a loving and charming couple, and around them it was always warm and cozy. Speaking about Marjorie, George said: “A scientist (like me), who gives a lot to science, sacrifices for many years, needs to have a very good woman with him. I was lucky to find all this with my wife” ^[28] . Therefore, it was very touching that they both passed away with a difference of less than two weeks.

Bruce, DW, Coles, HJ, Goodby, JW & Sambles, JR 2006 Discussion Meeting on new directions in liquid crystals. Phil. Trans. R. Soc. A 364, 2565-2843.

Collings, PJ 1990 Liquid crystals, nature's delicate phase of matter. Princeton University Press.

Collings, PJ & Hird, M. 1997 Introduction to liquid crystals: chemistry and physics. London: Taylor & Francis.

Dreyer, JF 1970 A liquid crystal device for rotating the plane of polarized light. (Abstract.) In Proceedings of the 3rd International Liquid Crystal Conference, Berlin, 24-28 August, p. 25.

Heilmeier, GH, Zanoni, LH & Barton, LH 1968a Dynamic scattering: a new electrooptic effect in certain classes of nematic liquid crystals. Proc IEEE 56, 1162-1171. ( http://dx.doi.org/10.1109/PROC.1968.6513 )

Heilmeier, GH, Zanoni, LH & Barton, LH 1968b Dynamic scattering in nematic liquid crystals. Appl. Phys. Lett. 13, 46. ( http://dx.doi.org/10.1063/1.95846 )

Hilsum, C. 1984 The anatomy of a discovery. In Technology of chemicals and materials for technology (ed. ER Howells), pp. 43-109. Chichester: Ellis Horwood. Hird, M., Goodby, JW, Lewis, RA & Toyne, KJ 2003 The fascinating influence of fluoro substituents on the synthesis and properties of liquid crystals. Mol. Cryst. Liq. Cryst. 401, 1-18. ( http: //dx.doi (inaccessible link) . org / 10.1080 / 744814910)

Hulme, DS, Raynes, EP & Harrison, KJ 1974 Eutectic mixtures of nematic 4′-substituted 4-cyanobiphenyls. Chem. Commun., 98-99. ( http://dx.doi.org/10.1039/C39740000098 )

Jones, B. 1935 Apparent cases of liquid-crystal formation in p-alkoxybenzoic acids. J. Chem. Soc., 1874. (http: // dx.doi.org/10.1039/JR9350001873)

Kauffman, GB 1991 Chemophobia. Chemy Br. 27, 512-516.

Leslie, FM 1970 Distortion of twisted orientation patterns in liquid crystals by magnetic fields. Mol. Cryst. Liq. Cryst. 12, 57-72. ( http://dx.doi.org/10.1080/15421407008082760 )

Lydon, JE 1984 Smectic liquid crystals — textures and structures. Glasgow: Leonard Hill.

Parkinson, DH 1967 First Report of RRE Working Party on Solid State Displays and Lamps. Raynes, EP 1980 RSRE Memo, 3266; see also P. Raynes, in Handbook of liquid crystals, vol. 1 (Fundamentals of liquid crystals) (ed. JW Goodby, PJ Collings, T. Kato, C. Tschierske, HF Gleeson & P. ​​Raynes), pp. 351-363 (Wiley-VCH, Weinheim, 2014).

Schiekel, MF & Fahrenschon, K. 1971 Deformation of nematic liquid crystals with vertical orientation in electric fields. Appl. Phys. Lett. 19, 391-393. ( http://dx.doi.org/10.1063/1.1653743 )