CHEM-E1110 Lignocellulose Chemistry - Introduction Tapani Vuorinen

Contents Chemical structure, physicochemical properties and chemical reactivity of cellulose, hemicelluloses, lignin and extractives Emphasis on reactivity and reaction mechanisms and kinetics Preparative fractionation of lignocellulose to its constituents Extractives, holocellulose, hemicelluloses Chemical characterization of the fractions by spectroscopy and chromatography FTIR and Raman spectroscopy Solid and liquid state NMR spectroscopy Gas chromatography-mass spectroscopy

Learning outcomes Knowledge on characteristic reactions of the polysaccharides and lignin Ability to intercorrelate the components’ chemical structure with their physicochemical properties and chemical reactivity Laboratory skills to Fractionate lignocellulose to its main constituents (extractives, hemicelluloses, cellulose, lignin) Characterize the chemical structure of the constituents by chromatography and spectroscopy

Workload and schedules Lectures, weeks 44-49, L2/PUU1 (Vuorimiehentie 1), lecture notes/learning diary Wednesdays at 13:15-15:00 (weeks 44-48) Thursdays at 12:15-14:00 (weeks 44-49) Tuesday at 10:15-12:00 (week 49) Laboratory works, weeks 44-49, PUU1 teaching laboratory, a single report in the end Fridays at 13:00-17:00 (weeks 44-48) Friday at 11:00-15:00 (week 49) Presentation of lecture notes and end discussion, week 50 Times to be agreed separately by each group

Topics of lectures (changes are possible) Date Time Contents 1/11 13:15-15:00 Introduction, fractionation and analysis of lignocellulose 2/11 12:15-14:00 Basics of carbohydrates – structure, functionality 8/11 Basics of lignin – formation, structure, functionality 9/11 Basics of kinetics, aryl alkyl ether bond cleavage in non-phenolic lignin 15/11 Aryl alkyl ether bond cleavage in phenolic and oxidized lignin 16/11 Radical, electrophilic and nucleophilic oxidation of lignin 22/11 No lecture 23/11 Glycoside and ester hydrolysis 29/11 Endwise degradation of 1,4-linked polysaccharides 30/11 Catalytic and non-catalytic oxidation of polysaccharides 5/12 10:15-12:00 Phenol-aldehyde condensation and lignin-carbohydrate complexes 7/12 Alkylation and esterification of lignocellulose, summary

Supporting reading Papermaking Science and Technology book series at https://ebooks.papereng.fi/ebooks/aalto/ Volume 3: Forest Products Chemistry Volume 20: Biorefining of Forest Resources

Topics of lab works (changes are possible) Date Time Contents 3/11 13:00-17:00 Own sample preparation for fractionation; detection and quantification of carbohydrates and reducing sugars by absorption spectroscopy 10/11 Acetone extraction of own sample; solid and liquid state 13C and 1H NMR spectroscopy of selected (lignocellulose and lignin) samples 17/11 Holocellulose preparation and quantification of dissolved carbohydrates; FTIR spectroscopy and GC-MS (after methanolysis) of acetone extracts 24/11 Isolation of hemicelluloses; FTIR spectroscopy of acetone extracted lignocellulose and holocellulose; UVRR spectroscopy of holocellulose 1/12 Catalytic oxidation of cellulose monitored by iodometric titration, quantification of aldehyde and carboxylate groups by iodometric and coductometric titration, respectively; FTIR spectroscopy of hemicelluloses 8/12 11:00-15:00 Degradation of hemicelluloses in acid and alkali monitored for reducing sugars and total carbohydrates, respectively

Guidelines for laboratory works Passing CHEM’s laboratory safety training is required to work in the laboratory (teacher Kirsi Yliniemi) Study at https://mycourses.aalto.fi/course/view.php?id=15279 Be present in time (PUU1, lobby) Take your own lab coat with you if you have one Works in groups of ca. 3 students Stay always with your own group