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 onion 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 bar Towards carbon dioxide fixation H2O, Cat. H2 CO2 CH3OH Ni5Ga3