A Dream and Reality to Chemical Science in India- Acharya Prafulla Chandra Rây

 

Gourisankar Roymahapatra,1 Ben Bin Xu,2 Zhanhu Guo2 and Chittaranjan Sinha3,*

 

1 Department of Applied Sciences, Haldia Institute of Technology, Haldia 721657, India

2 Department of Mechanical and Construction Engineering, Faculty of Engineering and Environment, Northumbria University, Newcastle Upon Tyne NE1 8ST, UK.

3 Department of Chemistry, Jadavpur University, Kolkata 700 032, India.

*Email: crsjuchem@gmail.com (C. Sinha)

 

 

Acharya Sir Prafulla Chandra Rậy, a member of Companion of the Indian Empire (CIE, the Most Eminent Order of the Indian Empire founded by Queen Victoria), Founder Fellow of the Indian National Science Academy (FNI, Delhi which is now renamed as FNA), Fellow of the Royal Asiatic Society of Bengal (FRASB, Kolkata), Fellow of the Indian Association for the Cultivation of Science (FIAS, Kolkata), and Fellow of the Chemical Society (FCS, London), is a pathfinder and originator of India's modern chemistry – teaching and research, chemical industry, philanthropist, industrialist and educationist. He was born on August 2, 1861 in the village Raruli, Khulna, (now in Bangladesh). He learned science by attending as an external student, particularly chemistry from Prof. Alexander Peddler, Presidency College (now Presidency University, Kolkata). It was the only college, where science teaching started in pre-independent India. After receiving Gilchrist Scholarship, he joined the Edinburgh University UK in 1882 and received B. Sc. in Chemistry from Prof. Alexander Crum Brown in 1885 and D. Sc. in 1887. His research thesis entitled, "Conjugated Sulphates of the Copper-Magnesium Group: A Study of Isomorphous Mixtures and Molecular Combinations" earned Hope Prize from the University.[1,2] The double sulfates known in his times are a few only like Mohr’s salt (i.e., (NH4)2SO4,FeSO4·6H2O); cyanochroite, K2SO4, CuSO4·6H2O. Prafulla Chandra worked in the laboratory of organic chemist and the global research tempted to physical chemistry at that time. He found out more space in double-double sulphates, like Mm2SO4, MbSO4. 6H2O, Mm2SO4, Mb/SO6H2O (where Mm refers to monovalent; Mb or Mb/ refers to the bivalent metal ion).[3] However, the structure of such salts was known much later, after the discovery of single crystal X-ray diffraction measurements in early 1930’s and the present form only appeared after 1960’s.[4] Rây was elected as Vice-President of the University of Edinburgh Chemical Society in 1888 and the President was Prof. Alexander Crum Brown.

 

¥The portrait is drawn by Mr. Bitihotra Roymahapatra, which is also been used in designing the cover page of this special volume.

 

Chemical Research in India

He returned India in 1888, joined the Presidency College in July 1889, and engaged in teaching and research in Chemistry. His first research publication entitled, “On the Chemical Examination of Certain Indian Food Staffs, Part I, Fats & Oils” was published in 1894 Journal of the Asiatic Society of Bengal.[5] His brilliant discovery appeared in the same journal in 1896 on mercurous nitrite (Hg2(NO2)2), a compound consisting of Hg(I)-Hg(I) bond, the simplest example of two atom metal cluster.[6] It raised huge controversy related to the oxidation state (i.e., Hg(I)) and had been settled by Prof. Animesh Chakravorty by preparing the compound following the same procedure and determining its X-Ray structure.[7] The discovery of mercurous nitrite was reported by Nature magazine immediately after its publication and wrote “The Journal of the Asiatic Society Bengal can scarcely be said to have a place in our chemical libraries; the current number, however, contains a paper by Dr. P. C. Ray, of the Presidency College, Calcutta on Mercurous Nitrite, that is worthy to note------”.[8]

The preparation, stability and vapor density measurement of NH4NO2[9] and its demonstration in Royal Society of Chemistry (RSC), London meeting earned congratulation from the Nobel Laureate, Prof. William Ramsay. Nature magazine published the news “..success in preparing ammonium nitrite in a tangible form, a further accomplishment in determining the vapour density of this very fugitive compound'.[10] During this time, Rây and his group isolated different double nitrites of type 2MNO2· Hg(NO2)2 (two different metals M & Hg, form mixed nitrites); however, the conductance and chemical characteristics of these compounds are believed to be a complex type of M2[Hg(NO2)4].[11] A series of nitrito Hg(II) additive compounds of ethylenediamine (en) was characterized by Rây by measuring the conductance as 1:2 electrolyte, [Hg(en)2](NO2)2.[12] In 1912, his group published sixteen research papers in three different journals of Royal Society of Chemistry. He was rightly named the fame of ‘Master of Nitrites’ by Professor W. E. Armstrong.[13]

Since 1916 onwards, Rây started to work on chemistry of thiols with mercury. He was probably interested to explore Hg-S chemistry from its relevance in Ancient Indian Culture where Makardhwaj (mixture of Hg, Au, Ag, S) was used as medicine for the treatment of many diseases.[14] Aliphatic thiols (RSH) reacted with Na2[Hg(NO2)4] to isolate compounds like Hg(RS)NO2. PCR worked on the reaction of thiourea with Hg(II) salts and thione-thiol tautomerism was recommended. In later period, the structures of the compounds in many cases were proved by X-Ray diffraction measurements. Although the concept and realization of ionic liquids appeared currently, however, Ray noticed this character long back in 1916 when he worked on mercury mercaptide nitrites and alkyl iodide. He proposed composition [R2S·RI·HgI2] and the conductivity measurement confirmed the ionic structure, which has been proven by X-Ray structure as [Me3S][HgI3].[15,16] Ray contributed substantially to the Au(I,III)-S chemistry. Au(III)-R2S chemistry, [AuCl3(R2S)], and its reduced product [AuCl(R2S)] were credited the first time to P. C. Rậy.[17]

In coordination chemistry, he established the complexes of heavier transition series like Hg, Au, Ir, Pt along with the chemistry of many metals, metalloids including alkali and alkaline earth metals, Cu, Ag, Fe, Mn, Zn, Cd, P, As and Sb. His research is collected in a book published in Kolkata.[18] In the early third decades of twentieth century, Rây started to develop platinum group metal chemistry of sulfur compounds. In 1923, with the reaction of Et2S with chloroplatinic acid (H2PtCl6) in ethanol for two or three days, he isolated yellow crystalline complex of composition [PtCl4(Et2S)2] and also [PtCl2(Et2S)2]. He reported the mixed-valent Pt(II,IV) (not trivalent) complex also. Both yellow and white compounds [PtCl2(Et2S)2] were characterized as cis and trans structure, respectively following Werner’s coordination theory. PCR also examined the substitution reaction using bases like NH3, EtNH2, pyridine (py) of [PtCl2(Et2S)2].[19,20]

Towards the end of his research in the University College of Science, University of Calcutta, Rây and his associates started to work on Ir and Rh chemistry of thiolato compounds. They reacted IrIVCl4 with Et2S in hot ethanol and isolated orange-yellow crystals of composition [IrCl3.3Et2S]. The reaction was so specific that could not be arrested by adding a strong oxidizing agent like aqua regia. From different physicochemical measurements and his chemical intuition, he concluded that it is a hexacoordinated compound of type [IrCl3(Et2S)3], which can have two geometrically isomeric forms, i.e., the facial (abbreviated fac; also called cis) and meridional (mer) isomer, which is also called the trans isomer.[21]

 

Fig. 1 Isomeric square planar, [PtCl2(Et2S)2], and octahedral, [IrCl3.3Et2S], complexes.

 

Rây also designed few reagents to carry out organic transformation. The use of acidified H2S as thiolating agent was recommended for the first time to synthesize thioketones and Ray reported in Nature the preparation of thiocamphor.[22] P. C. Rây reported the use of thallium fluoride (TlF) for preparing fluoroorganics and also other fluorinating agents like AgF, ZnF2 for the preparation of fluoroformateesters.[23,24]

His broad areas of scientific research include (i) chemistry of nitrogen oxyacids and their metal derivatives, (ii) organic nitro compounds and nitrates, (iii) organic thio compounds and their metal derivatives, (iv) chemistry of platinum group metals, (v) mercury alkyl/aryl compounds, (vi) fluorination of organic compounds, (vii) isomorphism and chemical homology, and (viii) classical physical chemistry like catalysis, thermal decomposition, measurement vapor densities and ionic conductance. So, Acharya Rậy is all along a chemist, who travelled all unknown paths of organic, inorganic, analytical and pharmaceutical chemistry.

 

Fig. 2 Fluorinating agent, TlF in C-H activation reaction and synthesis of organo-fluoro compounds.

 

Quanta of Research

In India, Acharya P. C. Rây started the first model Research laboratory both in academia (Presidency College & later Science College, Kolkata) and in industry (Bengal Chemical & Pharmaceutical Works Ltd.). Among his more than 150 research publications, 8 publications appear in Nature magazine; and 86 articles appear in the journals of the Royal Society. In the Journal of the Indian Chemical Society (1924-1936), he published 37 research papers (he was the founder and first President of the Indian Chemical Society started in 1924) and in German language, there are 11 publications. Out of 150 publications, there are 71 articles published as a single name (P. C. Rây); two-author articles are 68. One can imagine how much intellectual and physical labor he had invested against many odds to establish an experimental laboratory. Along with purchasing chemicals and glass wares, he had invested his own earnings, no financial support was given by British Raj to a person whose laboratory was the centre of the Swadeshi Movement! His brilliant research in the laboratory and inspiring class demonstration attracted enthusiastic young men to join in the modern chemical research, what he started in India.

In his long and distinguished career as a research worker, he had evoked a true spirit of scientific enquiry among his many disciples, which has resulted in the creation of the flourishing school of chemistry who had shown their ability not only in India but also in other parts of the world. He recognized the first modern Indian research school in chemistry and was regarded as the Father of Chemistry in India. The Indian Chemical Society, a premier Scientific Society and the oldest such society in India, was founded on 9th May 1924, and Acharya Prafulla Chandra Rậy was the First President along with his disciples J. N. Mukherjee, J.C. Ghosh and S.S. Bhatnagar. To begin with, Indian Chemical Society started the publication of The Journal of the Indian Chemical Society.[25]

 

Last Recognition: International Chemical Landmark Plaque

The International Year of Chemistry was celebrated in 2011 by the United Nations. The Royal Society of Chemistry (RSC, UK) used this platform to honor his life and work at his 150th Birth Anniversary by establishing an International Chemical Landmark Plaque in the Presidency College (now Presidency University, Kolkata), the place where the dream of research and teaching in chemistry was blossomed.

 

Fig. 3 Photo Courtesy (own collection of Prof. Chittaranjan Sinha).

This is the first ever landmark plaque, which was placed outside Europe. The name of Acharya Rây was nominated as the first Indian for Fellow of Royal Society on 16th December 1912 by William A. Tilden, Herold Baily Dixon, Henry E. Roscoe, Victor H. Veley, Alexander Crum Brown, Martin O. Forster, James Walker, Arthur W. Crossley, William Henry Perkin, Hugo Müller, Thomas H. Holland, James E. Reynolds, Herbert B. Baker, Percy F. Frankland, Alexander Pedler, William J. Pope and Alexander Scott. However, for some reasons, it was not realised. Everybody believed that an Author of “India: Before and After The Mutiny”, an essay published by Rây in 1885 as a participant in Essay Competition of Edinburgh University where he criticised the British imperialism and a Gandhian, could not be successful.

Acknowledgements

Special thanks to Mr. Bitihotra Roymahapatra, Student of Class X, Vivekananda Mission School, Haldia Township, Haldia 721657, India, for drawing the beautiful portrait of Acharya P. C. Rây, which is also been used in the cover page of this special volume.

 

References

[1] A. Chakravorty, Glimpses of Acharya P. C. Rây’s Work in Chemical Sciences, Indian Chemical Society, Kolkata, 2019

[2] A. Chakravorty, The doctoral research of Acharya Prafulla Chandra Rây, Indian Journal of History of Science, 2015, 50, doi: 10.16943/ijhs/2015/v50i4/48315.

[3] P. C. Rây, 2. on the conjugated sulphates of the copper-magnesium group, Proceedings of the Royal Society of Edinburgh, 1889, 15, 267-283, doi: 10.1017/s0370164600005502.

[4] H. Montgomery, E. C. Lingafelter, The crystal structure of Tutton’s salts. I. Zinc ammonium sulfate hexahydrate, Acta Crystallographica, 1964, 17, 1295-1299, doi: 10.1107/s0365110x64003231.

[5] P. C. Rây, On the chemical examination of certain Indian food stuffs. Part-I, Fatts and Oils, Journal of the Asiatic Society of Bengal, 1894, 1, 59-80.

[6] P. C. Rây, On Mercurous Nitrite, Journal of the Asiatic Society of Bengal, 1896, 65, 1-9.

[7] S. Samanta, S, Goswami and A. Chakravorty, On Mercurous Nitrite and a basic mercurous nitrate derivative, Indian Journal of Chemistry, 2011, 50A, 137 - 140.

[8] Review ‘Notes’, Nature, 1896, 54, 83.

[9] P. C. Rây, S. C. Jânâ, CLXX.—The vapour density of ammonium nitrate, benzoate, and acetate, Journal of the Chemical Society, Transactions, 1913, 103, 1565-1568, doi: 10.1039/ct9130301565.

[10] Review ‘Notes’, Nature, 1912, 89, 15 August.

[11] P. C. Rây, N. Dhar, Equivalent conductivity and ionisation of nitrites, Journal of the Chemical Society, Transactions, 1913, 103, 10-18, doi: 10.1039/ct9130300010.

[12] P. C. Rây, J. N. Rakshit, R. Lal Datta, Nitrites of the mercurialkyl- and mercurialkylaryl-ammonium series, Journal of the Chemical Society, Transactions, 1912, 101, 616-620, doi: 10.1039/ct9120100616.

[13] R. Singh, Master of Nitrites: Acharya Prafulla Chandra Ray, 25 September 2020. Retrieved 8 August 2021.

[14] P. C. Rây, A History of Hindu Chemistry, 1902, Vol 1and 1908, Vol 2; Williams and Norgate, London.

[15] P. C. Rây, N. Adhikary, J. Ind Complexes of Mercuric Iodide with Alkyl Sulphonium Iodides, Journal of Indian Chemical Society, 1930, 7, 297-303.

[16] R. H. Fenn, J. W. H. Oldham, D. C. Phillips, Crystal structure of (CH3)3S.HgI3 and the configuration of the HgI3–ion, Nature, 1963, 198, 381-382, doi: 10.1038/198381a0.

[17] P. C. Rây, Varying valency of Gold with respect to Mercaptanic radicals Part I, Journal of Indian Chemical Society, 1924, 1, 63-73; P. C. Rây, K. C. B. Ray,Complex compound of Gold with Mercaptanic Radicals. Part-II Residual affinity of Chloroauric Acid, 1928, 5, 527-533; P. C. Rây, D. C. Sen, Studies on the Complexes of the Chlorides of Gold with organic Sulphides, 1930, 7, 67-77.

[18] A. Bhattacharya Ed., Research Papers of Acharya Prafulla Chandra Rây, Deep Prakashan, Kolkata, 2006.

[19] P. C. Rây, Varying valency of platinum with respect to mercaptanic radicles, Journal of the Chemical Society, Transactions, 1923, 123, 133-141, doi: 10.1039/ct9232300133.

[20] P. C. Rây, K. C. B. Ray, Varying valency of Platinum with respect to mercaptanic radicals Part-II, Journal of Indian Chemical Society, 1925, 2, 178-190; P. C. Rây, B. C. Guha, K. C. B. Ray, Varying valency of Platinum with respect to mercaptanic radicals Part-III, 1926, 3, 155-160 and P. C. Rây, B. C. Guha, K. C. B. Ray, Varying valency of Platinum with respect to mercaptanic radicals Part-IV. The inadequacy of Werner’s Theory to explain certain anomalous cases, 1926, 3, 358-370; P. C. Rây, P. C. Mukherjee, Actions of Bases on Complex Compounds derived from Organic Thiocompounds and Platinum Chloride, Journal of Indian Chemical Society, 1929, 6, 885-891.

[21] P. C. Rây, N. Adhikary, A. N. Ray, Complexes of Antimony Halides with Sulphonium Halides, Journal of Indian Chemical Society, 1932, 9, 251-255; P. C. Rây, N. B. Adhikary, R. Ghosh, Complex Compounds of Iridium Part II. Compounds of Organic Sulphides and Pyridine, Journal of Indian Chemical Society, 1933, 10, 275-279.

[22] P. C. Rây, Synthesis of thiocamphor and other cyclic thioketones, Nature, 1934, 134, 1010, doi: 10.1038/1341010a0.

[23] P. C. Rây, P. B. Sarkar, A. Rây, Fluorination of organic compounds: monofluoracetone, Nature, 1933, 132, 749-750, doi: 10.1038/132749b0.

[24] P. C. Rây, H. C. Goswami, A. C. Roy, On the Fluorination of Organic Compounds Part I, Journal of Indian Chemical Society, 1935, 12, 93-95; P. C. Rây, A. C. Roy, On the Fluorination of Organic Compounds Part II, Journal of Indian Chemical Society, 1936, 13. 427-428.

[25] http://indianchemicalsociety.com/userpanel/about-us.aspx

 

About the Guest editors:

 

Dr. Chittaranjan Sinha M. Sc., Ph. D., Professor & Former Head, Department of Chemistry, Jadavpur University, Kolkata-700 032, India is working on the design of chemosensors and detection of ions/molecules. Environmentally important ions/molecules like Zn2+, Al3+, Cr3+, Cu2+, Pd2+, Phosphates, F-, CN-, ATP, Cytosine etc. are analyzed at nM concentration by using spectrofluorometric techniques. His research encompasses photochromism, electrochemistry, Coordination Polymers/Metal Organic Frameworks, functionalization and exploration of known antibiotics (sulfonamides) etc. So far, he has published 470+ internationally cited articles with 8250 citations. More than 15 Book Chapters are also published by Prof. Sinha. Dr. Sinha participated more than 150 national and international chemical; science conferences/seminars/workshops. His name is enlisted in top 2% scientists of the world in the list prepared by Stanford University and Elsevier on 2020, 2021, 2022 and 2023.  Dr. Sinha received International Lecturer Award from Padova University, Italy in 2011. He was awarded Best Chemistry Teacher in Post-Graduate level by Tata Chemicals in Association with Association of Chemistry Teachers and Confederation of Indian Industries in 2012. Prof. Sinha was also awarded William Ramsay Distinguished Researcher Award 2022 in Inorganic Chemistry by International Multidisciplinary Research Foundation (IMRF), Institute of Higher Education and Research. He is Elected Fellow of West Bengal Academy of Science & Technology (FAScT) since 2018. He served as Secretary of World Science Congress and arranged Student’s competition and State level and National/International conferences. He is a life-time Fellow of Indian Chemical Society (FICS) and served the society as Hon. Secretary for two terms (2017-19 and 2020-22). Indian Chemical Society is the oldest Chemical Society in India established by Father of Indian Chemistry, Acharya Prafulla Chandra Ray in 1924.  Prof. Sinha has supervised 52 Ph. D. Scholars; more than 70 Master’s Thesis and conducted 21 Govt. Research Projects. He served as Editor (Inorganic Chemistry Section) of the Journal of the Indian Chemical Society published by the Indian Chemical Society; currently Senior Editor of Current Organocatalysis and Current Microwave Chemistry published by Bentham Science Publishers. He is also engaged in the science popularization, support to financially challenging meritorious students for higher studies and has conducted a school (up to VIIIth Standard) blessed by Ramakrishna Mission at his native place. For his outstanding research contribution in the field of Metal Organic Framework (MOF), he has been admitted as a Fellow of The Royal Society of Chemistry (FRSC) in August 2023.

 

Dr. Gourisankar Roymahapatra, currently working as an Associate Professor of Chemistry at the School of Applied Science and Humanities, HIT Haldia, India, is a passionate researcher of chemistry. He completed his Ph.D. from Jadavpur University, Kolkata (2014) with N-Heterocyclic Carbene Chemistry as a major field under the mentoring of Dr. Joydev Dinda of HIT Haldia, and Prof. Ambikesh Mahapatra of Jadavpur University. Dr. Roymahapatra graduated (BSc) from Midnapore College (2000), did MSc in Physical Chemistry (2003), and in Organic Chemistry (2005), from DAV PG College, Kanpur, India. Before joining to academia, he worked at MCC PTA Chem. Corp. Pvt. Ltd India (MCPI), Haldia, (2003 ~ 2011) as a Senior Chemist. He worked at the Global Institute of Science and Technology (GIST Haldia), as a Lecturer in Chemistry in the year 2011 and then he moved to HIT Haldia in 2015 as an Assistant Professor of Chemistry. His area of research interest includes NHC complexes, organometallics, catalysis, antibiotics, anti-carcinogenic, gas adsorption, super alkali, and computational chemistry.  Dr. Roymahaptra received ‘NCQC-2007 Per-Excellent Award’ and ‘CCQC-2010 Gold Award’ for his contribution in Quality Control during his tenure at MCPI Haldia.  For his contribution in research, he got the ‘Distinguished Young Scientist Award in Chemistry -2014’ from the ‘World Science Congress’, India; the prestigious ‘Bharat Gaurabh Award – 2018’ from IISF, India; and the ‘Indian Chemical Society Research Excellent Award 2021’ from the Indian Chemical Society, ‘Best Researcher Award’, from the Research Education Solution, Noida, India. Dr. Roymahapatra is a Life Fellow of the Indian Chemical Society (FICS), and a Life Fellow of the Institutes of Chemistry (India) (FIC), Life Fellow of Renewable Energy Society of India (FRESI) He is the Vice-president of Haldia Vigyan Parishad (HVP) from 2018-2020, and 2021-2023. Dr.Roymahaptra is the editor of ‘Education in Chemical Science and Technology, and ‘Chemical Warta’ published by the Indian Chemical Society, ES Energy and Environment published by ES Publisher, USA. Dr. Roymahapatra is the editorial board member and reviewer of several national and international journals. He was the Guest Editor of “Prof. D. C. Mukherjee Special Issue”, J. Indian Chem. Soc. Vol 98, Issue 5, 2021; and also the Guest Editor of “Padma Shri Prof. G. D. Yadav 70th Birthday Special Issue”, J. Indian Chem. Soc. (in press). 

 

Dr. Zhanhu Guo earned his Ph.D. degree in chemical engineering from Louisiana State University (LSU) in 2005. He received three-year postdoctoral training in Mechanical and Aerospace Engineering at the University of California Los Angeles (UCLA). He is a Professor of Mechanical & Construction Engineering at Northumbria University Newcastle, UK. Professor Guo is a life-time Fellow of Indian Chemical Society (FICS, India), a Fellow of the Royal Society of Chemistry (FRSC, UK), a Fellow of Engineered Science Society (FESS, USA), and a Fellow of Institute of Materials, Minerals & Mining (FIMMM). His current research interests are in the areas of multifunctional nanocomposites research and education.

 

Dr. Ben B Xu is a full professor in materials and mechanics with a multi-disciplinary research interest covering soft matter, smart surface, functional materials, energy materials, applied mechanics, micro-engineering, flexible/wearable electronics, sustainable engineering and technologies. Ben obtained his PhD in Mechanical Engineering at Heriot-watt University (Scotland) in 2011 and subsequently worked as a postdoc researcher at University of Massachusetts Amherst (2011-2013).  Ben is a vice chair for division of 'composites' in AICHE (US) and chairing the Materials Characterisation & Properties Group in the Institute of Materials, Mining and Minerals (IoM3). He has published 7 patents, 9 book (incl. chapters) and over 200 peer-reviewed articles in the leading journals, including Sci. Adv., Nat. Commun., Adv.  Mater., Adv. Energy. Mater., Adv. Fun. Mater., Energy. Environ. Sci., Nano Energy, Small, Phys. Rev. Lett., etc (h-index 41). Ben has been invited to give 100+ invited/plenary talks in international conferences/leading institutions, chaired 30+ international events and reviewed paper publications for 100+ journals, and won multiple awards (2016 Young investigator award from the International Polymer Networks Group, etc.). Ben is also an associate editor for Advanced Composites and Hybrid Materials (SpringerNature), EcoMat (Wiley) and Advanced Devices and Instrument (AAAS).  He is a named expert in COVID-19 action database acknowledged by UK Parliament, with his work of ‘Masks for COVID-19’ archived in the WHO Covid-19 literature database. Ben is an elected Fellow of the Royal Society of Chemistry (FRSC), Fellow of the Indian Chemical Society (FICS), Fellow of the Institute of Materials, Mining and Minerals (FIMMM), Fellow of the Royal Society for the Encouragement of Arts, Manufactures and Commerce (FRSA), a chartered scientist and a chartered engineer.




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