Eco-01/Tma/2012-13 Solved Assignment 512


Sep 8, 2016 - Chrysophyllum cainito (Star apple) leaf extract stabilized colloidal metal nanoparticles and their .... dimensions of Sustainability, involving all company functions from Research and Development to ...... [email protected]icloud.com.

Sustainability through Green Chemistry

4th-8th September 2016 Venezia, Italy Chairman: prof. Pietro Tundo

Registration Exhibition room

Welcoming Reception

14.00

17.30 19.00

Sunday September 04

PL1 - Prof. Isabel Arends Toniolo Theatre

Lunch K1 F. Sevilla

12.00

12.45 14.15

M3 M. Galimberti

M4 H. Arafune

M5 A. Grassi

Coffee Break

15.25

15.45

16.05

16.25

B5 A. Kulazhskaya

B4 K.P. Ho

B3 C.P. Ferraz

B2 B. Ramalingam

B1 S. Vecchiato

Auditorium

* Monday afternoon: open round table:

OP5 B. Abegaz

OP4 Y. Chen

OP3 P. Anastas

OP2 F. Fumian

OP1 A. Hay

Conference room

K3 X. Wu

R5 A. Guida

R4 C. Samorì

R3 F. Trovò

R1 B. De Carvalho Bello R2 L. Scrano

K4 G. Ferrari Small Conference room

Industries Small room Toniolo Theatre

Poster Session Exhibition room

M2 Y. Tsujii

15.05

16.45 17.30

M1 R. Tuba

14.45

Toniolo Theatre

Coffee Break

11.30

K2 A. G. Correa

Opening Ceremony Toniolo Theatre

9.00

Monday* September 05

Coffee Break Poster Session Exhibition room

16.30 16.50 17.30 19.00 22.00

IP9 D. Tschaen

IP8 O. Piccolo

IP7 T. Liu

K11 W. Zhang Conference room

IP5 Y.M.A. Yamada IP6 M. Yadegari

IP4 A. Goswami

IP3 A. Gervasini

IP2 M.J. Muldoon

K7 O. Demchuk Conference room IP1 N. Ishito

Z. Lerman M. De Martino X. Wu C. Brett R. Ballini

Toniolo Theatre

K20 N. Tarasova

P. Tundo B. Abegaz-Molla E. Ravera W.C. Wanyonyi J.C. Rodriguez-Reyes A. Hubina S.R. Wan Alwi N. Moreau N. Orlandi

Toniolo Theatre B. Han A.S. Elsayed Sayed A. Akhmetshina I. Carrera M. Ismail

K8 I. Evstigneeva

Small room Toniolo Theatre

* Tuesday afternoon: open round table – Natural products/plants extractions

Gala dinner

M14 P. Barthelemy

B14 G. Selvaraju

B13 L. Yan 16.10

15.50

15.30

M13 T. Morinaga

Lunch PL3 Prof. Takashi Tatsumi Toniolo Theatre K9 S. K10 D. Bianchi Tantayanon Small Auditorium Conference room M12 B12 T. Sato F.-T. Luo

12.45 14.15 15.00

M11 E. Sabbioni

B11 S. Trita

B10 S.T. Ahmed

B8 O. HaskeCornelius B9 M. Tudorache

B7 W. Oberhauser

12.25

M10 M.E. Çorman

M9 A.K. Rathi

11.45

12.05

M8 D. Suttipat

Coffee Break

10.55 11.25

M7 D. Wibowo

PL2 - Prof. Chao-Jun Li Toniolo Theatre K5 P. Metrangolo K6 L.-N. He Small Conference Auditorium room M6 B6 A. Moores M.A. Jhons

10.35

10.15

9.45

9.00

Tuesday* September 06

SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

CONTENTS

Welcome message from the chair of the conference ................................ 2 Welcome message from the IUPAC president ......................................... 3 Conference committees ............................................................................... 4 Conference Topics ....................................................................................... 6 Transport ..................................................................................................... 7 Conference venues....................................................................................... 8 Centro culturale Candiani map ................................................................. 9 Going to Venezia ....................................................................................... 11 Abstracts Oral Presentations ................................................................... 12 Abstract Poster presentations ................................................................ 165 List of participants .................................................................................. 335

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WELCOME MESSAGE FROM THE CHAIR OF THE CONFERENCE

After Dresden, Moscow, Ottawa, Foz do Iguaçu and Durban, the IUPAC Green Chemistry Conferences will move to Italy...to Venice. We believe that the perception that Society has of the role of chemistry is being elevated by these IUPAC Conferences, and that chemists deserve to be perceived as people who create a dialogue with politicians, economists, entrepreneurs, and opinion formers. Green Chemists map the way to a sustainable future, and foster the development of industrially significant, and economic, breakthrough technologies. It is my pleasure, together with the Organizing Committee, to welcome you to Venezia for the 6th IUPAC Conference on Green Chemistry. This edition will gather more than 350 scientists from more than 70 countries all over the world.

Pietro Tundo Chairman, Organizing committee University of Venice, Ca' Foscari, Italy

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WELCOME MESSAGE FROM THE IUPAC PRESIDENT

On behalf of the International Union of Pure and Applied Chemistry – IUPAC- I sincerely welcome participants and guests of the 6th International IUPAC Conference on Green Chemistry. Five topics to be discussed at the Conference: Green Materials, Green Bioprocesses, Green Energy, Green industrial processes and Molecular innovation, Green Policy, Sustainability and Safety, - cover the areas of great importance, enabling the humanity with the tools to achieve the Sustainable Development Goals. I hope, that the broad exchange of opinion and experience in the fields of elaboration of specific technologies and production structures, which will be performed in the framework of the Conference, will help chemists worldwide to implement principles and approaches of green chemistry into practice. And the beauty of Venice will make the 6th International IUPAC Conference on Green Chemistry unforgettable.

Natalia P. Tarasova IUPAC President Corresponding member of the Russian Academy of Sciences Director of the Institute of Chemistry and Problems of Sustainable Development D.I. Mendeleev University of Chemical Technology of Russia

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CONFERENCE COMMITTEES International Advisory Board

• Paul T. Anastas: Yale University, Center for Green Chemistry & Green Engineering – New Haven, United States • Christopher M. A. Brett: Universidade de Coimbra, Departamento de Química – Coimbra, Portugal • Buxing Han: Chinese Academy of Sciences, Institute of Chemistry – China • Jianguo Hou: University of Sciences & Technology of China, Nat’l. Lab. for the Physical Sciences – Hefei, China • Dieter Lenoir: GSF Research Center, Institute of Ecological Chemistry – Neuherberg, Gemany • Anna S. Makarova: Mendeleyev University of Technology, UNESCO Chair “Green Chemistry for sustainable Development” – Moscow, Russia • Cláudio José de Araujo Mota: Federal University of Rio de Janeiro, Chemistry Institute – Rio de Janeiro, Brasil • Patrick Moyna: Universidad de la República, Facultad de Quimica – Montevideo, Uruguay • Egid B. Mubofu: University of Dar es Salaam, Department of Chemistry – Dar es Salaam, Tanzania • Virinder S. Parmar: University of Delhi, Department of Chemistry – India • Natalia Plechkova: Queen’s University of Belfast, Chemistry and Chemical Engineering – Belfast, United Kingdom • Janet L. Scott: Center for Sustainable Chemical Technologies -University of Bath, Bath, United Kingdom • Kenneth R. Seddon: Queen’s University Belfast, School of Chemistry – Belfast, United Kingdom • Supawan Tantayanon: Chulalongkorn University, Chemistry Department – Bangkok, Thailand • Natalia P. Tarasova: Mendeleyev University of Chemical Technology – Moscow, Russia • Takashi Tatsumi: Tokyo Institute of Technology, Chemical Resources Laboratory – Yokohama, Japan • Takashi Ushikubo: Tokyo University of Science – Tokyo, Japan • Patricia Vázquez: National University of La Plata (UNLP), Department of Chemistry – Buenos Aires, Argentina

Conferences Board

• Wolfgang F. Hoelderich: Department of Chemical Technology and Heterogeneous Catalysis, University of Technology, RWTH Aachen, Germany 1st IUPAC Conference on Green Chemistry – Dresden, Germany • Ekaterina S. Lokteva: Moscow State University, Chemistry Department – Moscow, Russia 4

SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

2nd IUPAC Conference on Green Chemistry – Moscow, Russia • Philip Jessop: Queen’s University, Department of Chemistry – Canada 3rd IUPAC Conference on Green Chemistry – Ottawa, Canada • Vânia G. Zuin: Federal University of São Carlos, Department of Chemistry – São Carlos, Brasil; 4th IUPAC Conference on Green Chemistry – Foz do Iguaçu, Brasil • Liliana Mammino: University of Venda, Department of Chemistry – Thohoyandou, South Africa; 5th IUPAC Conference on Green Chemistry – Durban, South Africa

National Organizing Committee

• Luigi Ambrosio: CNR – Dipartimento di Scienze Chimiche e Tecnologie dei Materiali – Rome, Italy • Antonella Gervasini: Università Statale di Milano – Milano, Italy • Mauro Marchetti: CNR Istituo di Chimica Biomolecolare – Sassari, Italy • Renato Noto: Università di Palermo – Palermo, Italy • Nausicaa Orlandi: President Consiglio Nazionale dei Chimici • Giuseppe Resnati: Politecnico di Milano, Dipartimento – Milano, Italy • Nicola Senesi: Università degli Studi di Bari – Bari, Italy • Armando Zingales: Past President Consiglio Nazionale dei Chimici

Local Organizing Committee

• • • •

Fabio Aricò: Università Ca’ Foscari di Venezia – Venice, Italy Emilia G. Pasta: Università Ca’ Foscari di Venezia – Venice, Italy Lucio Ronchin: Università Ca’ Foscari di Venezia – Venice, Italy Andrea Vavasori: Università Ca’ Foscari di Venezia – Venice, Italy

Web Manager • Roberto Dallocchio: CNR Istituto di Chimica Biomolecolare – Sassari, Italy Conference Staff • • • • • •

Marco Piccini: Università Ca’ Foscari di Venezia – Venice, Italy Mariachiara Spennato: Università Ca’ Foscari di Venezia – Venice, Italy Giulia Carraro: Università Ca’ Foscari di Venezia – Venice, Italy Pier Paolo Guolo: Università Ca’ Foscari di Venezia – Venice, Italy Riccardo Bevilacqua: Università Ca’ Foscari di Venezia – Venice, Italy Loris Calgaro: Università Ca’ Foscari di Venezia – Venice, Italy

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CONFERENCE TOPICS Green Materials Chairs: Attilio Citterio, Elvio Mantovani • Innovative materials for sustainable construction and cultural heritage • Nanomaterials • Polymers and polymer composites Green Bioprocesses Chairs: Mauro Marchetti, Janet Scott • Biocatalysis and biotransformation • Biofuels • Bio-based renewable, chemical feedstocks • Bio-based materials Green Energy Chairs: Buxing Han • Energy storage to facilitate uptake of renewable energy sources • Chemistry for improved energy harvesting • Nuclear power • Pollution Prevention Green industrial processes and Molecular innovation Chairs: Wolfgang Hoelderich, Philip Jessop, Kenneth Seddon • Green catalysis • Green solvents • Pharma • Microwave, ultrasound and flow chemistry technology • Separations and analysis Green Policy, Sustainability and Safety Chairs: Paul Anastas, Liliana Mammino • Green metrics and Greenness evaluation • Green Chemistry Education • How to influence policy to drive acceptance of Greener Technologies? • Climate Change Mitigation

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

TRANSPORT Public Transport Tram, Bus, Water-bus lines allow to travel around Venice, Mestre and the Marco Polo airport very easily. However, please bear in mind that most of Venezia island is not served by taxi or car but only by waterbus and water-taxi (the latest are very expensive). Taxi and car are allowed only as far as Piazzale Roma a specific part of Venezia near the train station. In the rest of the island cars/taxi are not allowed! On the other hand Venezia Mestre is served by taxi, tramway and car can be freely used.

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CONFERENCE VENUES The 6th International IUPAC Conference on Green Chemistry will take place in two venues about 5 minutes walk from each other: 1. Centro Culturale Candiani which is Cultural Centre of the City of Venice. Address: Piazzale Candiani, 7 – 30174 Venezia Mestre 2. Teatro Toniolo, Andress: P.tta Cesare Battisti, 1 - 30172 Mestre-Venezia

North

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

CENTRO CULTURALE CANDIANI MAP

Main entrance Level 0

North

Main entrance Level 0

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

Main entrance Level 0

North

Main entrance Level 0

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

GOING TO VENEZIA Going to Venezia from Centro Culturale Candiani is quite easy. You have to reach Piazzale Cialdini (tram stop Mestre Centro A1 Cialdini) e take tram number 1 direction Venezia). last stop will be Venezia (see tram Map). Departures from Mestre to Venezia every five minutes; From 6:20 am until 0:02 am (Monday to Saturday); Sunday From 6:20 am until 0:32 am. Departures from Venezia to Mestre every five minutes; From 6:48 am until 1:30 am (Monday to Saturday); Sunday From 6:20 am until 0:32 am. You can use also the bus number 4L leaving from Piazzale Cialdini (stop Mestre Centro B1). Departures from Mestre to Venezia every ten minutes; From 6:16 am until 0:20 am (Monday to Sunday). Departures from Venezia to Mestre every ten minutes; From 6:14 am until 11:56 pm (Monday to Sunday).

Map from Centro Culturale to Piazzale Cialdini

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ABSTRACTS ORAL PRESENTATIONS

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PLENARY LECTURES

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PL1 – Monday, the 5th of September Enzymes as Green Catalysts for conversion of Biobased Molecules I.W.C.E. Arends*, C.G. Boeriu, L.G. Otten, F. Hollmann. Department of Biotechnology, Delft University of Technology, The Netherlands, Country *Corresponding author: [email protected]

Keywords: biotransformations, oxidations, reductions, oleic acid.

Abstract Nature uses enzymes to catalyze a wealth of biotransformations. However in practice these transformations are carried out in-vivo under conditions which are far from suitable for large scale production of chemicals. It is our challenge to engineer or design enzymes in such a way that they can be employed in-vitro as catalysts [1]. In the lecture it will be discussed how different classes of enzymes can be employed as highly promising catalysts for a variety of reactions that are pivotal for the conversion of biobased molecules. Some notable examples from our lab which will be presented are the reduction of volatile fatty acids using Pyrococcus furiosus strains [2], the oxidation of alcohols using a variety of enzymes and cofactor regeneration methods [3], enzymatic reductions using water as electron donor [4], the hydration of oleic acid leading to i.e. polymeric building blocks [5, 6]. Also the need for integrated processes with upstream treatment of biomass will be highlighted. References [1] F. Hollmann, I.W.C.E. Arends, K. Buehler, A. Schallmey and B. Bühler, Green Chem. 2011, 13, 226265. [2] Y. Ni, P.L. Hagedoorn, J-H. Xu, I.W.C.E. Arends and F. Hollmann, J. Mol. Catal. B: Enzymatic2014, 103, 52-55 [3] D. Holtmann, M.W. Fraaije, I.W.C.E. Arends, D.J. Opperman and F. Hollmann, Chem. Commun. 2014, 50, 13180-13200. [4] M. Mifsud, S. Gargiulo, S. Iborra, I.W.C.E. Arends, F. Hollmann and A. Corma, Nat. Commun. 2014, 5:3145, 1-6. [5] A. Hiseni, L.G. Otten and I.W.C.E. Arends, Appl. Microbiol. and Biotechn. 2016, 100, 1275-1284. [6] A. Todea, A. Hiseni, L.G. Otten, I.W.C.E. Arends, F. Peter and C.G. Boeriu, J. Mol. Catal. B: Enzymatic2015, 119, 40-47.

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PL2 – Tuesday, the 6th of September Exploration of New Chemical Reactivities for Synthetic Efficiency Chao-Jun Li* Department of Chemisty and FQRNT Center for Green Chemistry and Catalysis,, McGill University, 801 Sherbrooke Street West, Montreal, QC H3A0B8, Canada *Corresponding author: [email protected]

Keywords: Reactions in water, C-H functionalization, OH-actiavtion

Abstract Rapid and efficient molecular making plays an important role in the development of any new product in the pharmaceutical, fine chemicals, materials, and biotech industries. However, conventional tools for chemical synthesis commonly starts with fossil feedstocks and often requires lengthy routes as well as overall low efficiency in time, manpower, and material utilizations. Thus, exploration of new reactivities towards high efficiency is crucial for future sustainability in chemical syntheses. Toward this long-term objective, we have been exploring various unconventional chemical reactivities that can potentially simplify synthesis, reduce overall waste generation and maximize resource utilization. These include: (1) developing Grignard-type reactions in aqueous media to simplify protection-deprotections; (2) developing nucleophilic addition reactions by using C-H bonds as surrogates for organometallic reagents, to simplify halogenation-dehalogenation and avoid the utilization of a stoichiometric amount of metal for such reactions (possibly in water); (3) developing direct C-H and C-H coupling (Cross-Dehydrogenative-Coupling) to explore the possibility of chemical transformations beyond functionalization and defunctionalization in syntheses; and (4) developing direct transformation biomass alcohols, amino acids, and lignin-based phenols. This talk will present some of the more recent progress on these topics from our laboratory.

References [1] [2] [3] [4] [5] [6]

Li, C.-J. Acc. Chem. Res. 2002, 35, 533. Li, C.-J. Acc. Chem. Res. 2010, 43, 581. Li, C.-J. Acc. Chem. Res. 2009, 42, 335. Li, C.-J.; Trost, B. M. Proc. Natl. Acad. Sci. (USA), 2008, 105, 13197 Dai, X.-J.; Li, C.-J. J. Am. Chem. Soc. 2016, 138, 5433. Chen, Z.; Zeng, H.; Girard S. A.; Wang, F.; Chen, N.; Li, C.-J. Angew. Chem. Int. Ed. 2015, 54, 14487.

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PL3 – Tuesday, the 6th of September Advance Zeolite Catalysts for Sustainable Production of Basic Chemicals Takashi Tatsumi Tokyo Institute of Technology, Japan, [email protected]

Keywords: Zeolite, MTO, Biomass conversion, CO2, Solar H2 Abstract Our comfortable modern life is supported by numerous chemical, in particular petrochemical, products. We need to develop the methods for manufacturing chemical products from more substantial fossil resources and for the long term, preferably from renewable resources. Because of the shale gas revolution, the use of methane as chemical feedstock as well as fuels to the lower olefins. At this time methanol is considered as getting more available chemical feedstock. Methanol to olefins (MTO) reaction is a promising route to the lower olefins. For the MTO reaction, currently, industrial processes use ZSM-5 (MFI) and SAPO-34 (CHA) zeolites. We have found CIT1 (CON) zeolite is promising for selectively converting methanol to propylene and butenes without serious loss of activity. It is to be noted that in China lower olefins started to be produced from coal through coal gasfication followed by the MeOH synthesis and subsequent MTO reaction. While fossil fuels will be the dominant factor in the future energy and chemicals scenario for a couple of decades to come, we need to develop methods of alternative chemicals production. Bioethanol has been widely used as additive and alternative to gasoline. Ethanol can be easily converted to ethene and in Brazil etc. BiproPE and PET30 (30% from biomass and 70% from petroleum) are commercialized. Even PET100 can be manufactured by synthesizing p-xylene via various routes using zeolite catalysts starting from biomass resources. These are called drop-in replacements. Compared to petroleum and natural gas, biomass has low H/C and high O/C ratios and low calorific value. Thus biomass could be useful for the production of chemical products that are not manufactured on a massive scale in the current petrochemical industry instead of drop-in replacements. It has long been recognized that 5-hydroxymethylfurfural (HMF) is a bio-based “platform” material for producing useful chemicals and polymers. Increasing research interest has been paid to the synthesis of HMF from sugars, particularly from glucose. We have found an effective transformation of glucose to HMF over Beta (*BEA) zeolite by finely tuning acid properties. Meanwhile, a great deal of effort has been devoted to the production of sorbitol, as bio-based feedstock, from cellulose. For example, sorbitol can be converted to isosorbide (1,4:3,6dianhydrosorbitol) through double intramolecular dehydration. Isosorbide can be used to produce polymers such as polyester and polycarbonate. We have developed highly active zeolite catalysts for the dehydration of sorbitol to isosorbide in water. For a future sustainable chemicals scenario, it may be desirable to develop efficient methods for utilizing CO2 by using renewable energy, which could be the ultimate goal. Photocatalytic decomposition of water by visible light, which accounts for a great majority of sunlight, is an enormous challenge and it is absolutely necessary to activate the research in this field. In Japan a 10year national project named ARPChem (Artficial Photosynthesis of Chemicals) that targets the recycling CO2 by using solar H2 started in 2012. At this moment this project focuses on the production of light olefins as chemical feedstock. We are developing the process consisting of methanol synthesis from CO2 and H2, followed by the MTO reaction catalyzed by zeolites.

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PL4 – Wednesday, the 7th of September Sustainable Chemistry – Addressing future societal challenges Martin Kayser BASF, Germany [email protected]

Abstract Chemistry is essential in modern life as more than 95% of all manufactured goods are directly touched by chemicals. The global chemical industry has developed countless products improving people’s lives, enabling life-saving medical solutions, cleaner water, a healthy and more abundant food supply, cleaner and more efficient sources of energy and advanced building and construction materials to design the cities of the future. Therefore, chemicals address a variety of today’s societal challenges and contribute to sustainable development. However, some chemicals possess intrinsic hazardous characteristics and hence require applicable management practices to control their risk. Science- and risk-based regulation in combination with voluntary industry initiatives like Responsible Care® and the Global Product Strategy (GPS) are best suited to achieve sound management of chemicals, which forms the prerequisite for Sustainable Chemistry. Sustainable Chemistry is not limited to substitution of hazardous chemicals, but describes a more holistic approach taking the entire product life cycle, recycling aspects and the three sustainability pillars (economy, ecology, society) into consideration.

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PL5 – Thursday, the 8th of September Chemistry in water usingmicelles: Applications in the pharmaceutical industry J. Kaschel1, J. Klee1, T. Lindner1, J. K. Pratt2, A. M. Reingruber (née Linsenmeier)1,3and W. M. Braje1* 1

Neuroscience Discovery Research, AbbVie Deutschland GmbH& Co. KG, Ludwigshafen, Germany 2 Oncology Discovery Research, AbbVie Inc., North Chicago, Illinois, USA 3 now Bayer CropScience AG, Frankfurt, Germany *Corresponding author: [email protected]

Keywords: metal-catalyzed reactions, micelles, water Abstract In a typical chemical reaction in the pharmaceutical industry, solvent use accounts for 60-90% of waste created. [1] Additionally, organic solvents play a dominant role in the overall toxicity profile of most processes and are therefore the chemicals of greatest concern. Strategies to minimize the economic and environmental footprint of organic solvents are of utmost interest. One alternative to organic solvents follows the lead of Nature: water. To circumvent the solubility issues, newly developed surfactants by the group of Prof. Lipshutz offer an opportunity to enable organic reactions to proceed efficiently in water at room temperature. These environmentally benign surfactants spontaneously self-aggregate in water and the resulting micellar arrays serve as nanoreactors.[2] We will disclose applications of micellar catalysis for the most important reaction types performed in the pharmaceutical industry (e.g. transition-metal-catalyzed reactions such as Buchwald-Hartwig aminations, Suzuki and Negishi couplings). Often times such reactions in water display advantages compared to conventional reaction conditions in organic solvents. [3] This green and cost effective methodology enables reactions to be performed under environmentally benign conditions by avoiding hazardous, toxic and expensive organic solvents and shows potential to bridge the different needs of medicinal and process chemistry.

References [1] D. J. C. Constable, C. Jimenez-Gonzalez, R. K. Henderson, Org. ProcessRes. Dev. 2007, 11, 133-137. [2] a) B. H. Lipshutz, S. Ghorai, A. R. Abela, R. Moser, T. Nishikata, C. Duplais, A. Krasovskiy, R. D. Gaston, R. C. Gadwood, J. Org. Chem. 2011, 76, 4379-4391; b) B. H. Lipshutz, P. Klumphu, J. Org. Chem. 2014, 79, 888-900; c) B. H. Lipshutz, S. Ghorai, Green Chem..2014, 16, 3660-3679. [3] a) B. H. Lipshutz, S. Handa, Y. Wang, F. Gallou, Science. 2015, 349, 1087-1091; b) F. Gallou, N. A. Isley, A. Ganic, U. Onken, M. Parmentier, Green Chem. 2016, 18, 14-19; c) W. M. Braje, A. M. Linsenmeier, Tetrahedron2015, 71, 6913-6919.

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PL6 – Thursday, the 8th of September Synergy in Bioenergy, Food and Materials from Biomass F. Galembeck Institute of Chemistry, University of Campinas, Brazil [email protected]

Keywords: Synergy, Biomass, Food, energy and materials, Sustainability Abstract The use of biomass as a source of energy and raw materials shows an overall growing trend with ups and downs related to oil prices that are in turn heavily affected by political and strategic factors. Nevertheless, there are many signs of increasing use of renewable resources but at different rates, depending on the country and world region. A frequent objection to the growing use of biomass as a source of energy and raw materials is that this will compete with food production, contributing to increase food prices and thus decreasing the possibility to have adequate supply for a growing population across the world. The Brazilian experience from the past four decades shows that synergy [1] may be created in the multipurpose use of agricultural land showing how the energy push took place in parallel with a large increase in food supply and a relatively small increase in the used land, thanks to technological inputs in every front: soil conservation and improvement, agricultural practice, logistics and industrial processing. A side product is the large increase in the production of biomass residues that leads to efforts for their utilization, contributing to CO2 sequestration from the atmosphere while increasing fuel and raw materials supplies. Some specific cases will be presented [2], discussing opportunities offered by biomass, together with two special features of materials from biomass that were understood only recently: the "mystery of natural rubber" and the ever surprising richness of the properties of cellulose. The presentation will conclude with the examination of research needs [3] and perspectives for increased food, energy and materials production from biomass, leading to a sustainable global economy.

References [1] F. Galembeck, Energy Environ. Sci.2008, 3, 393-399. [2] F. Galembeck, Y. Csordas, G. Macedo in Materials for a Sustainable Future, (Eds.: T. M. Letcher and J. L. Scott), RSC, London, 2012, pp. 179-197.

[3] F. Galembeck, J. Braz. Chem. Soc.2015, 26, 1743-1744.

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KEYNOTE LECTURES

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K1 – GREEN MATERIALS Green Analytical Chemistry: Chemical Sensors Based on Green-Synthesized Nanostructured Reagents Fortunato Sevilla III Research Center for the Natural and Applied Sciences, University of Santo Tomas, Manila, Philippines *Email: [email protected]

Keywords: Green nalytical chemistry; Chemical sensors; Green synthesized sensing reagents; Nanostructured reagents Abstract Chemical sensors present a green methodology in analytical chemistry. These analytical devices peerform measurements through the transduction of a physicochemical property, such as color and electrical conductivity, of the sensing phase into an electrical signal. The sensing phase consists of a solid-phase or immobilized reagent which interacts with the analyte and consequently exhibits a change in its property. Nanostructured materials, such as gold nanoparticles, carbon nanotubes and graphene, have been employed in the sensing phase, enabling the measurement of low concentrations of analyte. Measurements with chemical sensors are consistent with the paradigm of green chemistry, involving small amounts of samples, minimal or no pretreatment and practically zero reagent consumption. Likewise, green synthesis, particularly of nanomaterials, have been applied in the preparation of the sensing phase of some chemical sensors. Examples of these sensors will be presented.

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K2 – GREEN BIOPROCESSES Organocatalytic Multicomponent Reactions in the Discovery of Enzyme Inhibitors A. M. Deobald, D. A. dos Santos, J. L. Monteiro, D. G. Rivera, M. W. Paixão and A. G. Corrêa* Centre of Excellence for Research in Sustainable Chemistry, Department of Chemistry, Federal University of São Carlos, São Carlos, SP – Brazil *Corresponding author: [email protected]

Keywords: organocatalysis, multicomponent reactions, asymmetric synthesis, microwave Abstract A number of organocatalysts and processes, such as one-pot, tandem, cascade or multicomponent reactions, have been reported. The many advantages of organocatalysis - robust, non-toxic, affordable, inert atmosphere, easy reaction manipulation, etc. - allow the preparation of bioactive compounds using simple and metal-free procedures, thus avoiding false positives in the biological evaluation [1]. In this presentation, we will discuss our latest results on the synthesis of natural-product-like hybrids employing organocatalytic multicomponent reactions, such as Passerini (1) and Ugi (2) [2], and their evaluation as potent inhibitors of cholinesterases and cysteine proteases.

NH

O HN O

O

O

N

O

6 1

6

I

O

O 2

References [1] J. Aleman, S. Cabrera, Chem. Soc. Rev. 2013, 42, 774-793. [2] A. G. Corrêa, M. W. Paixão, A. M. Deobald, D. G. Rivera in Green Syntheses, Vol. 1, Ch. 11 (Eds.: P. Tundo, J. Andraos), CRC Press, London, 2014, pp. 139-148.R. Echemendia, A. F. de La Torre, J. L. Monteiro, M. Pila, A. G. Correa, B. Westermann, D. G. Rivera, M. W. Paixão, Angew. Chem. Int. Ed. 2015, 54, 7621 –7625.

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K3 – OPCW SESSION Promoting peaceful chemistry and ensuring chemical safety, security and sustainability The OPCW’s role and its initiative on Green Chemistry X. Wu OPCW-TS, The Hague – The Netherlands NL Corresponding author: [email protected]

Article XI of the Chemical Weapons Convention (CWC) provides a set of objectives which are designed to foster international cooperation between States Parties for the sustainable economic and technological development in the area of chemistry. The cooperation involves different stakeholders including S&T, National Authorities (NA) and aims at removing burdens related to and hence facilitating the right of States Parties to conduct scientific research, develop, store, produce and transfer chemicals for peaceful purposes. Thus, the Convention offers tangible benefits to the States Parties in addition to the disarmament goals. In the framework of the implementation of article XI the support actions of the OPCW-TS are focusing on the peaceful applications of chemistry. Green chemistry meets the OPCW objective to foster safety and security at chemical plants by providing the alternative to replace potentially hazardous toxic chemicals,. The OPCW initiative on green chemistry is being implemented within the framework of the decision on the “Components of an Agreed Framework for the Full Implementation of Article XI” (C-16/DEC.10, dated 1 December 2011), taken by the Conference of the States Parties at its Sixteenth Session, which calls upon the Secretariat of the OPCW to “cooperate with and advise National Authorities with a view to finding non-toxic chemical substitutes to reduce the risks associated with toxic chemicals as well as to promoting activities from a health, safety, anti-terrorism, and general security point of view”.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K4 – RESTORATION OF CULTURAL HERITAGE New Sustainable Technology to Recover Returned Concrete

1

G. Ferrari1*, A. Collina1 and A. Brocchi1 Research & Development Laboratories, Mapei S.p.A., Italy *Corresponding author: [email protected]

Keywords: Construction, Concrete, Aggregates, Sustainability, Circular economy Abstract Concrete is the second most used material in the world, after water. More than 10,000 million cubic meters are globally produced every year, with the consumption of more than 19,000 million Tonnes of natural aggregates (coarse aggregates and sand). For different reasons, about 200 million cubic meters of concrete (2 per cent of the global production) are not placed at the jobsite and are returned to the ready-mixed production plant where, in most cases, are disposed to landfill as waste material. Recently, a new technology to treat returned concrete has been developed: one cubic meter of returned concrete is treated with non-dangerous additives and transformed, in few minutes, into 2.3 Tonnes of aggregates, without any waste production. The new aggregates can be used to produce new concrete materials, with excellent mechanical performance and environmental compatibility. The new method has many advantages because it allows to save virgin aggregates and to reduce the natural resource depletion. Furthermore, returned concrete is 100% recovered and no waste is produced, completely eliminating landfill disposal. For these reasons, the new technology has a positive effect on the environmental impact of returned concrete, with hundred-fold reductions of the main parameters characterizing the environment footprinting. Furthermore, the new technology allows a reduction of the costs both for waste disposal and for aggregates supplying, representing an excellent example circular economy.

Figure 1. Example of newly formed aggregate from returned concrete

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K5 – GREEN MATERIALS Innovative Solutions for a Greener Fluorine Chemistry F. Baldelli Bombelli1, G. Cavallo1, V. Dichiarante1, R. Milani2, G. Resnati1, G. Terraneo1 and P. Metrangolo1-3* 1 NFMLab, DCMIC “Giulio Natta”, Politecnico di Milano, Milan, Italy 2 HYBER Centre of Excellence, Department of Applied Physics, Aalto University, Finland 3 VTT-Technical Research Centre of Finland, Espoo, Finland *Corresponding author: [email protected]

Keywords: Hydrophobin, Natural Surfactants, Fluorine, Coating, Nanomaterials Abstract Under the major background of current economic shifting, a lot of new applications of fluorine chemical products is springing up and becoming the new growth points of fluorine chemical products. In particular, the new energy, new materials, energy saving and environmental protection, electronic information, high-end medicines, pesticides, textile and other fields are needing more and more fluorine-containing fine chemicals. On the other hand, the use of fluorinated chemicals have raised numerous environmental and health concerns due to, e.g., their persistency in the biosphere. This has prompted many new research directions in the search for more sustainable fluorinated solutions. In this lecture, it will be presented how Hydrophobins, natural biosurfactants containing no fluorine, are very effective surfactants for fluorinated oils [1], polymers [2] (see Figure), and gases [3,4]. Furthermore, new, more sustainable branched fluorinated molecules will be presented as effective 19F MRI contrast agents, as well as ligands for innovative fluorinated nanomedicines.

A protein nanosized primer layer enables the otherwise inefficient binding of a perfluoropolyether onto a polystyrene surface, reducing its oleophilic character.

References [1] R. Milani, E. Monogioudi, M. Baldrighi, G. Cavallo, V. Arima, L. Marra, A. Zizzari, R. Rinaldi, M. Linder, G. Resnati, P. Metrangolo, Soft Matter 2013, 9, 6505–6514. [2] L. Gazzera, C. Corti, L. Pirrie, A. Paananen, A. Monfredini, G. Cavallo, S. Bettini, G. Giancane, L. Valli, M. B. Linder, G. Resnati, R. Milani, P. Metrangolo, Adv. Mater.Interfaces2015, 2, DOI: 10.1002/admi.201500170. [3] L. Gazzera, R. Milani, L. Pirrie, M. Schmutz, C. Blanck, G. Resnati, P. Metrangolo, M. P. Krafft, Angew. Chem. 2016, in press. [4] P. Metrangolo, G. Resnati, R. Milani, M. P. Krafft, US 62/202,346.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K6 – GREEN BIOPROCESSES Carbon Dioxide Chemistry: Carbon Capture and in Situ Conversion Liang-Nian He* State Key Laboratory and Institute of Elemento-Organic Chemistry, Nankai University, P. R. China *Corresponding author: [email protected]

Keywords: Carbon dioxide, Catalysis, Sustainable chemistry, Synthetic methods Abstract As an abundant, nontoxic, non-flammable, easily available, and renewable carbon resource, CO2 is very attractive as an environmentally friendly feedstock for making commodity chemicals, fuels, and materials[1]. Unfortunately, few reactions involving CO2 are thermodynamically feasible originating from low reactivity of CO2. In addition, On the other hand, the reactions involving CO2 are commonly carried out at high pressure, which may not be economically suitable and also pose safety concerns. Therefore, developing efficient catalysis for CO2 conversion especially under mild conditions is extraordinary desirable and remains a great challenge. In 2011, we proposed the “carbon capture and utilization” strategy as an alternative approach to circumvent the energy problem in carbon capture and storage process [2]. The essence of this strategy could be simultaneous activation of CO2 upon its capture and thus in situ catalytic transformation into value-added chemicals and fuel-related under mild reaction conditions, avoiding additional desorption step [3]. Chemicals O

O O Absorbents

CO2

R

-

O

Absorbents

N H

N H

R

O

N R R1 R2

Catalyst

Fuels Car bon Capt ure w ith si mult aneous acti vati on

HCOOH CH3OH Subsequent Cat alyti c Conversi on

As a consequence, we have developed efficient absorbent to reach equimolar absorption. The capture CO2 could simultaneously result in its activation, thus subsequent conversion into chemicals and energy related products more easily rather than going through desorption process. References [1] a) M. Aresta, A. Dibenedetto, A. Angelini. Chem. Rev.2014, 114, 1709; b) B. Yu, L.-N. He. ChemSusChem2015, 8, 52; c) Z. Z. Yang, L. N. He.Energy Environ. Sci.2012, 5, 6602; d) Q. Liu, L. Wu, R. Jackstell, M. Beller. Nat. Commun.2015, 6, 5933. [2] a) Z.-Z. Yang, L.-N. He.RSC Adv.2011, 1, 545; b) Z.-Z. Yang, L.-N. He.Energy Environ. Sci.2011, 4, 3971; c) A.-H. Liu, A. Yu, L.-N. He.Angew. Chem. Int. Ed.2012, 51, 11306; d) J. Kothandaraman, A. Goeppert, M. Czaun, G. A. Olah, G. K. S. Prakash.J. Am. Chem. Soc.2016, 138, 778. [3] a) Y.-N. Li, L.-N. He, Green Chem.2013, 15, 2825; b) L.- N. He, et al in Carbon Dioxide Chemistry, Chinese Science Publisher, Beijing, 2013, pp. 220-337.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K7 – GREEN INDUSTRIAL PROCESSES AND MOLECULAR INNOVATION New Green Catalysts for Cross-coupling Reactions

1

Oleg M. Demchuk Department of Organic Chemistry, Maria Curie-Sklodowska University in Lublin, Poland *Corresponding author: [email protected]

Keywords: Cross-coupling reactions, C,P-ligands, Catalyst design, Water-soluble phosphines, Fluorous-phase-soluble phosphines Abstract. The majority of the catalytic reactions could be considered as “green” or “partially green”, since they always satisfy some principles of Green Chemistry. Nevertheless, especially in the cases of homogeneous transition metal mediated cross-coupling reactions, only rarely all twelve the principles are obeyed. Most cross-coupling reactions are still carried out in organic solvent at relatively high temperature, and they are promoted by significant amount of conventional catalysts, suitable for a single use only [1]. Such traditional approach also complicates a procedure of products isolation, and may force a chromatographic purification step. The multiphase homogeneous catalysis, mediated by highly active, even at low temperature, transition metal complexes of special phosphines [2] (soluble only in one of the phases), could be considered as an alternative to that. Herein we are intended to demonstrate synthesis and application of new highly electron rich, sterically hindered, chelating monophosphine ligands of C,P-type of complexation, designed to be used in difficult cross-coupling reactions under the mild and sustainable conditions. Several ligands, soluble in water or soluble in fluorous solvents, could be obtained in syntheses, based on the common modular synthetic pathway, in high yields. OH

O

O

OR

PCy2 OMe

MeO X

O

OMe

R LG, base ... . R = Me, Sug , PEG LG = I, SO4Me, T...s X = H, CH, MeO

O

MeO X

OR

1) NaI, NaIO4, AcOH 2) Rf I, Cu ... X = H, MeO R = Me

PCy2 OMe

OMe

O PCy2 OMe Rf

MeO X

CO2Cl2, CPME NaBH4, THF

OMe

~ 60% overall OR PCy2 OMe R1 MeO X ... R1 = H, Rf ... . R = Me, Sug , PEG ... X = H, CH, MeO

OMe

Figure1. The synthesis of new ligands.

The results of our studies on catalyst design and synthesis, green catalysis, and finally, on catalyst recovering and reusing, as well as some other issues, will be discussed in details. References [1] A. de Mejiere, S. Bräse, M. Oestreich (eds) Metal Catalyzed Cross-Coupling Reactions and More, Wiley, 2014.

[2] O. M. Demchuk, R. Jasiński, Phosphor. Sulfur Silicon Relat. Elem. 2016, 191, 245-253.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K8 – UNESCO/PHOSAGRO/IUPAC SYMPOSIUM Reducing heavy metals in our food chain with greener mineral fertilizers Irina Evstigneeva1 Director for Corporate Finance and IR at OJSC PhosAgro, Russia *Corresponding author: [email protected],

1

Abstract The danger of heavy metals pollution. Influence of selected heavy metals on humans, animals, plants. Pathways of heavy metals in the food chain of animals and humans. Systematic policies to reduce pollution with heavy metals as a tool to improve the efficiency of land use and the use of groundwater resources. Labelling, regulation of content and other ways of environment protection from the harmful effects introduced into the soil of nutrients.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K9 – GREEN MATERIALS Chrysophyllum cainito (Star apple) leaf extract stabilized colloidal metal nanoparticles and their applications Supawan Tantayanon* and Rakhi Majumdar Department of Chemistry, Chulalongkorn University, Bangkok 10330, Thailand E-mail: [email protected]

Keywords: metal nanoparticles, green synthesis, Chrysophyllum cainito, polyphenols, catalysis.

Abstract: A simple green chemical method for the one step synthesis of metal nanoparticles (MNPs) has been described by reducing the metal salts with the leaf extract of Chrysophyllum cainito in aqueous medium at room temperature. The phytochemicals present in the leaf extract were highly efficient to reduce the metal ions into metal atom (0) and stabilize the as synthesized MNPs without any additional capping agents. The synthesized MNPs are stable at room temperature. The stabilized MNPs have been characterized in detail by spectroscopic, electron microscopic, light scattering and X-ray diffraction measurements. Interestingly, the synthesized MNPs have been shown as efficient catalyst for reduction reactions and C-C coupling reactions. In addition, the MNPs have significant in vitro antibacterial activity against both gram positive and gram negative bacteria. A novel organicinorganic trihybrid material has also been synthesized by in-situ generation of palladium nanoparticles (PdNPs) in a hybrid gel matrix based on renewable chemicals [1]. The xerogel of this trihybrid material has been used as a recyclable heterogeneous catalyst for C-C coupling and reduction reactions in aqueous medium.

References

[1] R. Majumdar, S. Tantayanon, B.G. Bag, Chemistry-An Asian Journal, 2016, DOI: 10.1002/asia.201600773.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K10 – GREEN BIOPROCESSES From biomass to advanced biofuels D. Bianchi* and C. Perego Eni S.p.A. - Renewable Energy and Environmental R&D Center–Istituto eni Donegani; Via G. Fauser 4; 28100 Novara Italy *Corresponding author [email protected]

Keywords: Waste biomass, Biofuels, Biological processes, Thermochemical processes

Abstract Liquid carbon-neutral biofuels are largely considered a possible way to face the new energy needs without dramatically increasing the carbon dioxide concentration in the Earth atmosphere. For European oil companies, diesel fuels are most important since, in Europe, the diesel to gasoline ratio is steadily increasing. Few technologies are currently applied to produce diesel fuels based on renewables, most of them based on first generation feedstock, in competion with the food, feed and land use. This contribution will be focused on the emerging technologies for the production of “advanced” biofuel starting from waste biomass including those under development by eni SpA. Considerable industrial achievements have been recently reported, for instance, in the hydrotreating of vegetable oils and animal fats (HVO). Ecofining HVO technology [1], jointly developed by eni/UOP, has been already applied by eni in the green refinery of Venice (Italy). In order to find alternative feedstocks, there is also significant interest for routes to transform cellulosic sugar (i.e., produced via a proper hydrolysis of lignocellulosic biomass) into microbial lipids [2]. This fermentation would provide a possible way to overcome the productivity limitations of classic oleaginous crops. Even larger oil productivity can be achieved, by cultivation of photo synthetic microalgae, growing on carbon dioxide from industrial activities, power plants and natural gas wells, able to accumulate a significant amount of oils (triglycerides) as energy storage material inside the cell. Alternatively, diesel biofuels can be obtained by thermochemical transformation, such as pyrolysis, gasification and hydrothermal liquefaction of waste biomass followed by the upgrading of the resulting liquid or gaseous intermediates [3]. Eventually, it is most likely that the success of one or the other of these technologies will depend on several factors, including the availability and the quality of the feedstock, the complexity of the process, the integration with the existing refinery processes, and the quality of the final biofuel. References [1] J. Holmgren, C. Gosling, R. Marinangeli, T. Marker, G. Faraci, C. Perego, Hydrocarbon Processes, September 2007, 67-71. [2] S. Galafassi a, D. Cucchetti, F. Pizza, G. Franzosi, D. Bianchi, C. Compagno, Bioresource Technology 2012, 111, 398–403. [3] A. Bosetti, D, Bianchi, D.G. Moscotti, P. Pollesel, US 20140235910 A1, 2014.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K11 – GREEN INDUSTRIAL PROCESSES AND MOLECULAR INNOVATION Pot-Economic Cascade Reactions with Recyclable Organocatalysts Wei Zhang, Ph.D. Professor and Director for Center for Green Chemistry Department of Chemistry, University of Massachusetts Boston [email protected]

Keywords: Organocatalysis, Pot Economy, Asymmetric synthesis, Fluorous, Cascade reaction Abstract Organocatalysis has advantages of toxic heavy metal-free, mild reaction conditions, novel mood of activation, and good structural amenability. However, organocatalysis usually requires high catalyst loading (up to 20 mol%). Fluorous technology provides an efficient way to address the catalyst separation and recovery issue. This presentation highlights our recent effort on the development of recyclable organocatalyst-promoted cascade reactions involving fluorination, Michael addition, Robinson annulation, Mannich reaction, and other transformations for asymmetric synthesis of biologically interested compounds with multiple stereocenters.

OHC

OH HO OMe OHC * * * * ** * * F * * * * Ph Ph 2 R R1 F EtO2C

*

N

O *

R1 F

R2

N

R1

EtO2C

R

*

* *

OR N R1

N

R3 O

R2

O

R2

F R1 R2

NH * * * *

S

*

R3 O

R1

OR R3

CO2R F Ar' O

NH

* *

N R3

*

F R2

Ar

O

*

O * *

R2

R2'

R1 O

N

N H

recycable F-catalyst O

OR

C8F17

NH

O

O

*

O

* * R3

O

Ph

2 N R

O

F

N

S *

O *

Ar

OMe F

NO2

O

EtO2C

O

Et

* *

Ar F

'

Ar CO2R

NO2

Organocatalyst-promoted one-pot asymmetric synthesis

References [1] Zhang, X.; Zhi, S.; Wang, W.; Liu, S.; Jasinski, J. P.; Zhang, W. "A Pot-economy and Diastereoselective Synthesis Involving Catalyst-free Click Reaction for Fused-triazolobenzodiazepines" Green Chem.2016, 18, 2642-2646. [2] Huang, X.; Pham, K.; Yi, W.; Zhang, X.; Clamens C.; Hyatt, J. H.; Jasinsk, J. P.; Tayvah,U.; Zhang, W. “Recyclable Organocatalyst-promoted One-pot Asymmetric Synthesis of Spirooxindoles Bearing Multiple Stereogenic Centers” Adv. Synth. Catal.2015, 357, 3820-3824. [3] Jiang, L.; Yi, W.-B.; Lu, G.; Cai,C.;Zhang, W. “Direct Trifluoromethylthiolation and Perfluoroalkylthiolation of SP2C-H Bondswith NaSO2CF3 or NaSO2Rf” Angew. Chem. Int. Ed. 2015, 54, 14965-14969. [4] Zhang, W. “Green Chemistry Aspects of Fluorous Techniques – Opportunities and Challenges for SmallScale Organic Synthesis” critical review, Green Chem. 2009, 11, 911-920. [5] Zhang, W. “Fluorous Linker-Facilitated Chemical Synthesis” Chem. Rev.2009, 109, 749-795.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K12 – GREEN MATERIALS The Sustainable Development Challenge: Pirelli Tyre's View Luca Giannini1 Pirelli Tyre SpA, Italy *Corresponding author: [email protected] 1

Keywords: Tyres, Rubber, Sustainability, Life Cycle, Open Innovation Abstract Tyres are complex engineered products, integrating hundreds of raw materials and diverse technological inputs. Tyres account for 20-30% of the Carbon Footprint of the EU medium car: a cornerstone of Sustainable Transportation is the development of more and more sustainable tyres, achievable through the integration of electronics and through new design, processes and materials (polymers, nanofillers and chemicals). Pirelli adopts a management approach integrating the Economic, Social and Environmental dimensions of Sustainability, involving all company functions from Research and Development to Purchasing, Human Resources and Finance. Pirelli's sustainability plan [1] integrates and supports the group's industrial plan with a vision to 2020, and was developed in accordance with the “Value Driver” model inspired by the UN PRI (Principles for Responsible Investment) and UN Global Compact to encourage dialogue between investors and firms on sustainability issues (ESG, Environmental, Social, Economics). Pirelli’s Environmental Strategy is based on a Life Cycle approach identifying the impact of each stage in terms of energy and water KPIs and setting Objectives accordingly. Tyre development is driven by vehicles manufacturers, legislation and market forces: Pirelli integrates the former inputs into an Open Innovation Model, involving collaborations with leading OE manufacturers, selected Suppliers and Research Institutes. Environmental Sustainability is a key objective of technical developments, aiming at minimizing tyre Rolling Resistance while keeping the other tyre performances. New Materials are a fundamental part of Pirelli’s Innovation Strategy: Pirelli is developing, through Joint Development Agreements with suppliers, polymers featuring exclusive solutions to resolve trade-offs between Rolling Resistance, Wet and Winter performances, and through University Collaborations new Biofillers and Nanofillers to support lighter structures and further contribute to reduce the environmental impact of tyres minimizing the impact of raw materials (developing renewable materials and low footprint mineralorigin fillers). Pirelli set the target to reduce the RR of its car tyres by 40% in 2020 vs 2009. Green Performance Products, which combine performance and respect for the environment, represented 48% of total Pirelli tyre 2015 turnover. References [1] http://www.pirelli.com/mediaObject/corporate/documents/common/ir-booklet/sustainability16/original/sustainability-16.pdf.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K13 – GREEN POLICY, SUSTAINABILITY AND SAFETY L’Oréal’s Commitment to Green and Sustainable Chemistry Michel PHILIPPE L’Oréal, France [email protected]

The integration of green chemistry principles [1] in the development of any new process or new ingredient is a pivotal element of sustainable development. The objective of this presentation is to provide a rapid description of the commitment of L’Oréal [2], worldwide leader in cosmetic products. Within the scope of its Sharing beauty With All sustainability agenda, L’Oréal will innovate so that by 2020, 100% of its products will have an environmental or a social benefit. The reduction of the environmental footprint of formulae, combined with the increasing use of renewable raw materials that are sustainably sourced or derived from Green Chemistry will be major drivers for reaching this objective. The approach of L’Oreal group [3] in the use of renewable raw materials [4], the development of eco-friendly processes [5] and the development of new ingredients with favorable environmental profile are presented in more details. As an illustration of green process implementation, several examples of development were selected. Among them, C- glycosides of interest in our different applications such as skin care active ingredients [6] will be described. References [1] P. Anastas and J.C.Warner, Green Chemistry, Oxford University Press, New York, 1998, p. 30. [2] www.loreal.com [3] M. Philippe, B. Didillon and L. Gilbert, Green Chem., 2012, 14, 952-956. [4] Q. Zhang, M. Benoit, K. De Oliveira Vigier, J. Barrault, G. Jégou, M. Philippe and F. Jérôme, Green Chem., 2013, 15, 963-969. [5] J. Hitce, M. Crutizat, C. Bourdon, A. Vivès, X. Marat and M. Dalko-Csiba, Green Chem., 2015, 17, 3756 – 3761. [6] M. Philippe, A. Cavezza, P. Pichaud, S. Trouille and M. Dalko-Csiba, Carbohydrate Chem., Chemical and Biological approach, 2014, 40, 1-10.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K14 – GREEN INDUSTRIAL PROCESSES AND MOLECULAR INNOVATION A Green Procedure for Solketal Production from Acetone and Glycerol using CO2 as Switchable Catalyst J A C Nascimento1, B P Pinto2, A L L Fortuna1and C J A Mota1,2* Escola de Química, Universidade Federal do Rio de Janeiro, Brazil 2 Instituto de Química, Universidade Federal do Rio de Janeiro, Brazil *Corresponding author:[email protected] 1

Keywords: Glycerol, Carbon dioxide, Bioaddtives, Design of Experiments Abstract Biodiesel is one of the main biofuels used worldwide. The increase of its use has reduced the price of glycerol, which is produced in approximately 10 wt% as byproduct of biodiesel production [1]. Glycerol is used in a large variety of applications such as personal care products, pharmaceuticals, polymers, food, etc. Nevertheless, these applications cannot drain the large amounts of glycerol being produced. Solketal is produced from the acid-catalyzed reaction of glycerol and acetone [2] and can be used as a renewable fuel additive [3]. We wish to report the production of solketal from the reaction of acetone with glycerol in the presence of CO2, which acts as switchable acid system (Scheme 1).

Scheme1. Reactionofglycerolwithacetoneunder CO2 as acidcatalyst.

In this work, a design of experiments (DoE) was used to study the ketalization of glycerol with acetone using carbon dioxide as switchable homogeneous catalyst. Experimental tests were carried out according to a fractional factorial design, with 2 levels and 4 parameters (24-3). A Parr® reactor of 100 mL volume and mechanical stirring was used to run the reactions. The parameters studied were temperature, initial pressure of CO2, glycerol/acetone molar ratio and reaction time. The results of glycerol conversion were analyzed by GC-MS. In all cases, solketal was the only product observed. The highest conversion observed was 71%, at 110oC, 45Bar, 1:2 molar ratio and 2 h. The procedure is being tested in reactions of crude glycerol of biodiesel production, where the excess of basic catalyst and other salts impairs the use of heterogeneous acid catalyst [4].

References [1] C. J. A. Mota, C. X. A. da Silva, V. L. C. Gonçalves. Quim Nova.2009, 32, 639-648; [2] C. X. A. da Silva, V. L. C. Gonçalves, C. J. A. Mota. Green Chemistry. 2008, 11, 38-41; [3] C. J. A. Mota, C. X. A. da Silva, N. Rosenbach, J. Costa, F. da Silva. Energy Fuels. 2010, 24, 27332736. [4] C. X. A. da Silva, C. J. A. Mota. Biomass & Bioenergy. 2011, 35, 3547-3551.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K15 – GREEN ENERGY Rational Design of Nanostructured Photocatalysts for Efficient Solar Fuels Y. F. Zhao, L. Shang and T. R. Zhang* Key Laboratory of Photochemical Conversion and Optoelectronic Materials/Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, China *Corresponding author: [email protected]

Keywords: Photocatalysis, Water splitting, CO2 photoreduction, Solar fuels, Hydrogen Abstract The efficient conversion of solar energy into fuels through the photocatalytic water splitting into hydrogen and photoreduction of CO2 into high value-added chemicals is very important for the development of a sustainable energy future [1]. To achieve this goal, photocatalysts must be rationally designed and controllably synthesized for improved performances. Nanostructured phtocatalysts have attracted much attention due to their unquie physical and chemical propertires compared with corresponding bulk materials. Recent research progress in my group has been reported on the rational design and controlled synthesis of nanostructured photocatalysts for highly efficient visible lightdriven H2 evolution and photocatalytic conversion of CO2 and CO into fuels by enhancing the light absorbance and separation of electron-hole pairs of photocatalysts. (1) By developing high conductive support for photocatalysts, the quantum efficiency of photocatalytic H2 production achieved 33% at 420 nm; (2) By creating more defects in photocatalysts, the photocatalytic reduction of CO2 with water by ultrathin ZnAl-LDH nanosheets exhibited stable activities of ≈7.6 μmol g-1 h-1; (3) By constructing heterogeneous interface structure, NiO/Ni nanocatalysts exhibited an unexpectedly high selectivity for C2+ hydrocarbons in the CO hydrogenation reaction under visible-light irradiation.

Figure 1. Illustration of NiO/Ni nanocatalysts selectively photocatalized the CO hydrogenation reaction for C2+ hydrocarbons under visible-light irradiation.

References [1] D. B. Ingram, S. Linic, J. Am. Chem. Soc.2011, 133, 5202-5205.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K16 – GREEN ENERGY Design and Synthesis of Organic Dyes and Their Application in New Generation Photovoltaics Gianna Reginato,1*Alessio Dessì,1 Massimo Calamante,1 Alessandro Mordini,1 Lorenzo Zani1 1

CNR-ICCOM-Istituto di Chimica dei Composti Organometallici (ICCOM), Via Madonna del Piano 10, 50019 Sesto Fiorentino (FI), Italy. *Corresponding author: [email protected]

Keywords: Dyes, renewable energy, solar cells. Abstract Dye-Sensitized Solar Cells (DSSC) represent a very promising technology to convert solar energy in electric current, due to their low cost of production and their colorful and decorative features.1 The core component of a DSSC is the sensitizer. In this contest metal-free organic dyes2 have been successfully used, offering the advantages to enhance light harvesting by tuning the absorption over a broad spectral range and pursuing high extinction coefficents. Furthermore, expensive and hazardous metals are avoided. Our interest in the field involved the design, with the aid of DFT computational analysis, and the synthesis of new organic dyes in order to study their structure–property relationships and exploit a possible application in DSSC.3

D

π

A

 D Donor group  π Conjugated spacer

 A Acceptor/ and anchoring group Organic dyes possessing donor and acceptor moieties bridged by a π-conjugated unit (called D-π-A structure) have been mainly investigated. Some of these dyes showed interesting features such as extremely intense light absorption in the visible spectrum, good stability and very good power conversion efficiencies,3c proving to be suitable for application in transparent thin-layer DSSCs. References [1] A. Hagfeldt, G. Boschloo, L. Sun; L. Kloo, H. M. Petterson Chem. Rev. 2010, 110, 6595. [2] C.-P. Lee, R. Y.-Y. Lin, L.-Y. Lin, C.-T. Li, T.-C. Chu, S.-S. Sun, J. T. Lin, K.-C. Ho, RSC Adv. 2015, 5, 23810. [3] a) B. Cecconi, A. Mordini, G. Reginato, L. Zani, M. Taddei, F. Fabrizi de Biani, F. De Angelis, G. Marotta, P. Salvatori, M.Calamante Asian J. Org. Chem. 2014, 140; b) D. Franchi, M. Calamante, G. Reginato, L. Zani, M. Peruzzini, M. Taddei, F. Fabrizi de Biani, R. Basosi, A. Sinicropi, D. Colonna, A. Di Carlo, A. Mordini Tetrahedron 2014, 70, 6285; c) A. Dessi, M. Calamante, A. Mordini, M. Peruzzini, A. Sinicropi, R. Basosi, F. Fabrizi de Biani, M. Taddei, D. Colonna, A. Di Carlo, G. Reginato, L. Zani, Chem Commun. 2014, 13952; d) A. Dessì, M. Calamante, A. Mordini, M. Peruzzini, A. Sinicropi, R. Basosi, F. Fabrizi de Biani, M. Taddei, D. Colonna, A. Di Carlo, G. Reginato, L. Zani, RSC Advances, 2015, 5, 32657.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K17 – GREEN POLICY, SUSTAINABILITY AND SAFETY / EDUCATION Building biorefineries for the bioeconomy: an interdisciplinary postgraduate green chemistry course V. G. Zuin* Department of Chemistry, Federal University of São Carlos, Brazil Green Chemistry Centre of Excellence, University of York *Corresponding author: [email protected]

Keywords: bio refineries, green chemistry in HEI, postgraduate courses.

Abstract Nowadays there is a demand for the introduction of new concepts and practices related to sustainability in RD&I and education in Chemistry, especially in the undergraduate and postgraduate courses, when green chemistry and biorefinery are considered in the context of the bioeconomy. In this work an interdisciplinary short-course at the post-graduate level developed at UFSCar in 2015 titled “Building biorefineries for the bioeconomy” - connecting several areas as chemistry, economy, biology, social sciences, management and law - will be presented [1]. The course involved lectures, interactive exercises and real case studies. Analyzing the availability, composition and production methods of different Brazilian agro-industrial resources and their by-products was vital for exploring their valorization, industrial challenges for their use and associated environment, social and economic impacts. For instance, searching the volumes available of some biomass residues helped identifying whether they can be used for a high-volume low-value application such as solvents or plastics or for a high-value low-volume application such as cosmetics or nutraceuticals. The students´ projects showed their integrated building capacity and knowledge exchange. The proposal contributed to develop a new understanding of the role of chemistry in the context of the bioeconomy, comprehending (and expanding) the original content knowledge presented in the syllabus course. More than this, the socioconstruction of knowledge were understood as constituent elements of science and technology processes radically compromised with critical thinking and actions towards socio-eco-justice and sustainability, especially important in Brazil [2,3]. References [1] V.G. Zuin (submitted). [2] J. Sjostrom, I. Eilks, V.G. Zuin, 2016, Sci. Ed, 25, 321-341. [3] D.P. Zandonai, K.C. Saqueto, A.P. Lopes, V.G. Zuin. In: Science education research and practical work. I.Eilks, S. Markic & B. Ralle (Eds.), Shaker: Aachen, Germany, 2016. Fapesp, Newton Fund and CNPq

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K18 – GREEN INDUSTRIAL PROCESSES AND MOLECULAR INNOVATION Definition of green synthetic tools based on safer, recoverable and biomass derived reaction media Luigi Vaccaro Laboratory of Green Synthetic Organic Chemistry, CEMIN, Università di Perugia, Via Elce di Sotto 8, 06123 Perugia Web: http://www.dcbb.unipg.it/greensoc; E-mail: [email protected]

Keywords: Catalysis, Biobased chemicals, Flow chemistry, Waste minimization Abstract Our research program is mainly committed to the definition of efficient and sustainable synthetic tools by combining the development of several crucial areas of investigation: i) use of safer reaction media (such water, azeotropes or bio-based reaction media) or solvent-free conditions (SolFC), ii) preparation and use of heterogeneous recoverable and reusable catalytic systems based on supports tailor-made for their use in greener reaction media or under SolFC; iii) definition of flow reactors able to allow the recovery of products with minimal waste production [1]. Our efforts have been recently directed towards the development of chemically and environmentallyefficient synthetic protocols for metal-catalyzed transformations for C-C bond formation[2] and some representative examples from our laboratories will be presented in this communication.

References 1. For some recent examples see: L. Vaccaro et al. Org. Lett.2016, 18, 2680–2683; Adv. Synth. Catal.2016, DOI: 10.1002/adsc.201600287; Green Chem.2015, 17, 365-372; Chem. Commun.2015, 51, 15990-15993; Green Chem.2015, 17, 365-372; 2. For some frecent examples see: L. Ackermann, L. Vaccaro et al. Green Chem., 2016, DOI: 10.1039/C6GC00385K; Green Chem., 2016, DOI: 10.1039/C6GC00385K.

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K19 – GREEN INDUSTRIAL PROCESSES AND MOLECULAR INNOVATION Irina Evstigneeva Director for Corporate Finance and IR at OJSC PhosAgro, Russia *Corresponding author: [email protected]

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

K20 – UNESCO/PHOSAGRO/IUPAC SIMPOSYUM N. Tarasova IUPAC President, Russia [email protected]

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SEPTEMBER 4 – 8, 2016 ▪ VENEZIA

WINNER OF THE 2016 IUPAC-CHEMRAWN VII PRIZE FOR GREEN CHEMISTRY Green Reaction Media Protocols: From Solvent-Free to Catalysis State-ofthe-Art A. Maleki* Catalysts and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran. *Corresponding author: [email protected]

Keywords: Nanomaterials, Biopolymer composites, Magnetically recyclable, Heterogeneous nanocatalysts, Multicomponent reactions.

Лишь один неверный шаг слишком уж настойчивой фирмы, и ключ будет опубликован, а в результате пострадают все фирмы программного обеспечения. Нуматака затянулся сигарой «умами» и, выпустив струю дыма, решил подыграть этому любителю шарад. - Итак, вы хотите продать ключ, имеющийся в вашем распоряжении. Интересно.

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