Dimensionality of Chemistry - A 21st Century Science for Global Sustainability

Goverdhan Mehta School of Chemistry University of Hyderabad

A ‘selfie’ with the chemistry world……

Advances in Chemical Research (ACR2021), Gitam University, April 19, 2021 Contours of presentation

• Serenading chemistry - An omnipresent science • The past as present and future – Refreshing chemistry • Glimpsing the horizon – Chemistry as sustainability science • Road ahead – Some key messages

A bouquet of chemistry ‘matters’ that matter “Chemistry ought not to be for chemists alone” - Miguel de Unamuno

‘…Life, Universe and Everything’ Chemistry – a source of happiness….

‘...I feel sorry for people who don’t know anything about chemistry. Chem -Connectome They are missing an important source of happiness....’ - Linus Pauling

1901-1994

S.A. Matlin, G. Mehta, H. Hopf, Chemistry Embraced by All. Science, 2015, 347, 1179 Chemistry is in everything. and everything is in it, it is the basis of life, without it we wouldn't exist.

Green tea has ~ 200 chemicals

Coffee has ~ 1000 chemicals

Wine has >1000 chemicals

Light cigarette ~ 4000 chemicals

An amazing science of familiar things Tears at breakfast! Chemistry of

Allilinase

H2O flavor Allilin Sulfenic acid

LFS Inhibit the enzyme

gas Onion uttapam

syn-Propanethial-S-oxide

Water soluble Biosci. Biotech. Biochem. 2012, 76, 447.

An amazing science of familiar things Tears at breakfast! Chemistry of onion

Allilinase

H2O flavor Allilin Sulfenic acid

LFS Inhibit the enzyme

gas

syn-Propanethial-S-oxide

Water soluble Biosci. Biotech. Biochem. 2012, 76, 447.

An amazing science of familiar things Chemistry and music

Durability and the quality of sound of musical instruments depend heavily on the chemical treatment of the wood and on the varnish blend used in the finishing.

Nitrocellulose lets the wood "breathe“ preserves its natural tones.

Serotonin and happiness Serotonin

To enjoy, get chemistry right! Release happy molecule: modulates mood, cognition, reward, ..etc Chemistry within us ……Awesome molecular machine! 1,00,000 +proteins and ~ 47,000 enzymes…. (working 24X7)

Chemical composition of the human body

Ca 1.5% N P Hydrogen 3%1.2% 10% Oxygen 65%

Carbon 60 elements 18% Be 0.000000005% Boron : 0.000069% Prevents bone breakdown ; maintains mental alertness

Bromine added as essential 28th element , May 2014 Chemistry – Tracing the roots and to the present BCE

Art & craft of mixing substances Millennia A giant knowledge leap

Alchemy to modern science 16th Century Evidence based Science

1869 Discipline in a Table - systematization

Mendeleev’s periodic law

20th Century ‘Molecularization’ of chemical matter

20th Century A century of evolutionary march of chemistry

20h Century Value added products from almost anything “Utility science” and everything

Molecular understanding of life processes and “Core Science” chemical matter

Interdisciplinarity in forefront “Integrative Science”

Resource stressed planet “Sustainability Science”

21st Century S. A. Matlin, G. Mehta, H. Hopf, A. Krief. Nature Chemistry 2015, 7(12), 941 21st Century realities – A pivotal role for chemistry

20h Century

Most material used on the planet is chemically processed; Anthropogenic mass produced pp per week is 6X the pWt; ~ 1.1 teratonnes … THIS IS UNSUSTAINABLE????

‘Global human-made mass exceeds all living biomass’ - . E. Elhacham et al. Nature, 588, 2020 , 442

Rapid depletion of CO lithium (White Gold) and 2 rare earths <415 ppm

Resource stressed planet “Sustainability Science”

21st Century

S. A. Matlin, G. Mehta, H. Hopf, A. Krief. Nature Chemistry 2015, 7(12), 941-943 Sustainability: Living prophecies Antoine Lavoisier Augustus Kekule 1743-1794 1829-1886

‘die chemie ist also die Humphry Davy ‘Nothing is lost, nothing is created, Dmitri Mendeleev 1778-1829 Lehre von den stofflichen 1834-1907 everything is transformed’ metamorhosen der materie’ - Antoine Lavoisier - Kekulé

Jacob Berzelius 1779-1848 Alfred Werner 1866-1919

Wohler 1827 Michael Faraday 1791-1867 Adolf von Baeyer 1835-1917 ‘Green’ is in the DNA of Chemistry ‘Ammonium cyanate is urea’ 100% atom economy; Friedrich Wohler No reagent, no solvent 1800-1882 Wllhelm Oswald 1853-1932 The idea of sustainability is embedded in chemistry but

Justus von Liebig there have been some worrisome mutations ? 1803-1873 Victor Grignard 1871-1935

Marcellin Berthelot ‘Study the past, if you would define the future’ - Confucius G. N. Lewis 1827-1907 1875-1946 A transformative perception of chemistry

More from less Resource prudence

Liebigs Law ‘..Growth is controlled not by the total amount of Limit resources available, but by the scarcest resource..’ Justus von Liebig (1803-1873) Liebig's barrel A world of ‘abundant resources’ familiar to chemists in now passé Way forward - Turning by-products from one process into raw materials for another - Recognize…. Waste does not exist – Only material changes form.

Circular Chemistry

S. A. Matlin, G. Mehta, H. Hopf, A. Krief. Nature Chemistry 2015, 7(12), 941-943 Sustainability -‘Circular Economy’ to ‘Circular Chemistry’

Resources

Waste

Geng, Sarkis, Bleischwitz, Nature, 2019, 565, 153- 55 Keize, Bakker, Slootweg, Nature Chemistry, 2019, 11, 190 Sustainability -‘Circular Economy’ to ‘Circular Chemistry’

C H R3 E M Reduce I Reuse S Recycle T R….R10 R Y

…not merely Green Chemistry 2.0

Geng, Sarkis, Bleischwitz, Nature, 2019, 565, 153- 55 Keize, Bakker, Slootweg, Nature Chemistry, 2019, 11, 190 Chemistry: Securing a Sustainable Future

Recognise the end of - Make, use, dispose era; Onset of - Reuse, refurbish, re- and upcycle era

Cradle to Cradle ‘C2C’ Chemical Design’

… design concepts where…products are created according to the principles of an ideal circular economy, beyond the conventional recycling, inspired by eco-efficiency and sustainability .

“There is no such thing as ‘away’. When we throw anything away it must go somewhere.” Break for reflection

…Chemistry is empowering

• Enabler of silo-free thinking; • Source of “liquid knowledge” • Soft challenge to challenge flow. Molecular level view of everything and molecular creation is central to chemistry

Molecular machines ……molecular gastronomy….molecular condoms*! *PNAS, May 2017

Chemists create their own molecular cosmos

“Chemistry has become today the science of bodies that do not exist” - Auguste Laurent - 1854 N L chemistry 2016

..Chemistry creates its subject. This creative ability, similar to that of arts, essentially distinguishes chemistry among the natural and historical sciences. - M. Berthelot - 19th century Sizing the molecular cosmos

1080 to 10200 unique chemical structures possible

That is not far from infinity; impractical? …and there is not enough mass in the Universe !

A galloping pace.. 170 M in SciFinder Registry 2020;

CAS Registry’s 100 Millionth entry Only a fraction is useful! June 2015

Chemistry is also the science of the possible Just about any chemical can be accessed today but …..should we ? Mantra to remember… Resource only what is needed for human advancement and well-being; in risk free, non-hazardous way with minimal environmental footprint.

Global human-made mass exceeds all living biomass, Nature, Dec, 2020.

Adopt new symbols – Beyond the Periodic Table

Su Id

* S. A. Matlin, G. Mehta, H. Hopf and A. Krief, Nature Chemistry, 2016, 8, 393 Pivotal role……on the path to sustainability

Human health Energy and environment

• Sustainable energy •OverDrug 2,000discovery- 20,000 diseases are known; a Chemistry • CO2 fixation, Climate majority• Wellbeing are incurable!

Advanced materials Sustainable agriculture

• Intelligent & functional • Innovations in crops • Sensing and imaging • Nutritional security • Urbanization challenge • Crop protection New opportunities, challenges and promises to keep; Chemistry can!

Sustainability Science Sustainable Energy and Environment

• Solar - PV, Solar-thermal • CO2 fixation & recycling • Renewable - Biomass • CO2 sequestration • Water Splitting – H2

Powering the planet: Sun pours more energy on to the earth’s surface in an hour than the planet uses in a year!

From Silicon to Organo-electronics to Perovskites to Graphene….~25% eff..

Perovskites Graphene Sustainable Energy and Environment

• Solar – PV, Solar-thermal • CO2 Sequestration • Renewable - Biomass • CO2 Fixation & recycling • Water Splitting – H2

Harness Nature’s photosynthesis machinery

Algae based biofuels C H 2O H Cat. C HO H CH3OH

C H 2O H Glycerol Catalyst Hydrocarbons Valorization Biodiesel Blue green Algae: photosynthetic power cell energy and environment Cellulosic waste to hydrocarbons

Shiramizu & Dean Toste, Angew Chem. 2012, 51, 8012

Platform Chemicals: Catalytic up-gradation of bio-derived feed stocks

while minimizing generation of by-products, particularly CO2.

Hexoses from biomass Platform chemicals Reviews: Dean Toste et al. Chem 2016,1, 32; ChemSusChem 2019, 12, 2835 – 2858 Water as a fuel! Solar electrolysis

Use of Sunlight to split water or artificial photosynthesis is the Holy Grail of renewable energy research

Arrays of microwires coated with catalysts to split water

using sunlight to make H2. Energy and Environment - CO2 Sequestration

CO2 capture: Colossal cages in zeolitic imidazolate (ZIF) frameworks as selective carbon dioxide reservoirs

ZIF’s have complex cages, up to 264 vertices, and as many as 7,524

atoms that can store ~100 times CO2 Yaghi et al. Science, 2015; DOI: 10.1126/science.aac8343 07

CO2 Capture: Polymeric organic frameworks (POF)

Phloroglucinol based; 18% CO2 Porphyrin-quinoline; 1-5 Towards carbon dioxide fixation

H2O, Cat.

H2 CO2 CH3OH Ni5Ga3 F. Studt et al. Nature Chemistry, 2014, doi:10.1038/nchem.1873

CO2 activation via single-electron pathway

Jamison et al. Nature Chemstry, 2017 doi: 10.1038/nchem.2690

Uribe-Romo et al. J. Mater. Chem. A. 2017. doi : 10.1039/c7ta00437k Human health & wellbeing

Drugs for emerging and resistant diseases, modulation of cognitive functions and interpersonal behavior……..

On average antibiotics add 20 years to each person’s life

Fight against tuberculosis Eradicating malaria?

Ethambutol MDR -TB

From Chloroquine to Artemisinin Mortality rate of 1.2 million per year Rifampicin Badaquiline Isoniazid Pyrazinamide Human health & wellbeing

Drugs for emerging and resistant diseases, modulation of cognitive functions and interpersonal behavior……..

India has the highest bacterial disease burden – NDML threat

Anti-AIDS Battling ‘avian flu’

AZT Darunavir

Oseltamivir (Tamiflu) Zamamivir Peramivir

Impressive responses to recent pandemics like Zica and Ebola Towards the conquest of Covid – 19.... March 2020 Onwards

Favipiravir Arbidol Remdesivir Dexamethasone

Focus on ‘repurposing’ - racing against time - shrinking timelines Work in progress...... opportunities

• The NHS estimates that of the Covid-19 patients hospitalised, 45% will need ongoing medical care, 4% will need inpatient rehabilitation.

• Many young and previously healthy people infected with Covid-19 will struggle with recurring pain, fevers, fatigue and gastro-intestinal problems. Chemistry will show the way for sustainable health

Who can make Mona Lisa smile? Chemistry can!

Mood modifier

Depression, mood swings and mental health in post-pendemic world with aging population emerging as a major health issue Emerging materials landscape

"smart" materials that will allow the wings of a craft to change shape for optimal flying conditions.

Polymers with dynamic “shape memory“: On thermal/ electric/ light stimuli shape memory polymers exhibit reversible change from rigid polymer to elastic state.

‘Carbyne’ 40 times harder than diamond

Thinnest nanofiltration Imaging Large-area graphene-oxide membranes membrane Pulmonary angiography Solving world’s drinking water problem?

30 nm thick; rejects molecules >1.7 nm Nat. Commun. doi: 10.1038/ncomms10891 (2016) Contrast agents Sensing wonders at atto- and zeptomolar conc. 0.000000000000000000001 M

New architectures for sensing, imaging, memory storage, optical communications & – CHEMICAL SENSING ZnO ZnO nano-wires 10-50 nm diameter - 20,000 could one-thousandth the fit in the eye of a full-sized needle diameter of a human hair MOF

Artificial Nose – Smell Receptor • To detect diseases like cancer, malaria.. ‘NaNose’ can sniff VOC to detect • To sniff chemicals, poisons, explosives… lung cancer with 90% accuracy • To sequester and separate gases Break for contemplation

• Systems thinking in chemistry • Primacy of practising diversity • Persona and professionalism • Chemistry needs rejuvenation Chemistry teaching-learning in the 21st Century

New pedagogy - Create space for….

• Systems thinking at the core ‘One World Chemistry’ • Enhanced contextualization Chemistry ingenuity must factor the intrinsic interconnections between • Emphasis on connections human, animal, environmental and societal systems. • Adherence to ethical dimension • Inculcate cultural competencies http://www.iocd.org/OWC/intro.shtml

P.G.Mahaffy, A.Krief, H.Hopf, G.Mehta, S.A.Matlin, Nature Reviews Chemistry 2018, 2(4), 0126. Chemistry’s future as an ethical science

• Ethical concerns must encompass responsible practice of chemistry with a strong pitch for environment and sustainability;

• Adherence to method and values of science – embrace scientific temper ;

• Ethical concerns to expand beyond the traditional issues about research practices and transparency; personal conduct & practice of collegiality;

Value diversity*

• Ingrain ethical values as an integral part of chemistry education.

* G. Mehta, V. W.Yam, A.Krief, H.Hopf, S. A. Matlin, Angew. Chem. Int. Ed. 57, 2018, 14690

* https://www.acs.org/content/dam/acsorg/global/international/scifreedom/global-chemists-code-of-ethics.pdf Chemistry - Commitment to Diversity

A holistic view of diversity

Angewandte Chemie, Intl. Ed. 2018, 57(45), 14690. Chemistry - Commitment to Diversity

A holistic view of diversity

Power of Diversity: First mRNA Covid 19 Vaccine Development

Katalin Kariko Ugur Sahin Hungarian Turkish

Ozlem Tureci A.Bouria Turkish Greek Commitment to Diversity: Inculcate cultural competencies

• Diversity and research practices are more about culture than compliance. • Need to be embedded in research culture as part of teaching & training.

Angewandte Chemie, Intl. Ed. 2019, 58(10), 2912. Persona and professionalism – Why and how it matters?

I. Langmuir Langmuir won a Nobel Prize for surface chemistry, 1881-1954 hobnobbed with the likes of Albert Einstein and Niels Bohr. Highly Influential, very interactive and communicative, appeared on the cover of magazines, guided innovations at G.E.

G. N. Lewis Lewis built the UC Berkeley, chemistry into the best 1875-1946 in the world. Brilliant but recluse. Should have got two Nobel prizes but got none. Allegedly committed suicide in his lab in 1946,

Pro-Tips: • Align persona to professional demands; • No room for cognitive dissonance. • Always respect and accommodate the scientific contributions and creativity of peers and competitors

Ref: Cathedrals of Science: The Personalities and Rivalries That Made Modern Chemistry, Patrick Coffey, Oxford University Press, 2008 Persona and professionalism: Humility in Science

A legacy of passion with humility… Albert Einstein is reported to have remarked that Mme.Curie was probably the only person who was not corrupted by the fame that she had won. Marie Sklodowska Curie 1867-1934

Father of chemistry and chemical industry in India

One who could integrate ideas with idealism; A venerable legacy of humility and patriotism Acharya P. C. Ray 1861-1944

" A good scientist is a humble scientist!” - Dan Shechtman , Nobel Leaurate 2011

Daniel Schechtman 1941- Why have I taken you through this unusual journey?

Because, the discipline needs not only smart, creative chemists but also its new champions with redefined values and directions in the 21st century.

Maitlin, Mehta, Hopf and Krief, Chem. Eng. News, perspective article, Feb 2017 Thank you for your kind attention

A big thank you to Eli-Lilly, Jubilant Bhartia Foundation and Dr. Reddy’s Research Laboratory (DRL) for research support.

A crystal of aspirin

Chemistry is stunningly beautiful!