Investigation of Encapsulation of Aromatic Polluants by Β-Cyclodextrin in Presence of Linear Aliphatic Alcohols Shivalika Tanwar
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Investigation of encapsulation of Aromatic polluants by β-Cyclodextrin in presence of linear aliphatic alcohols Shivalika Tanwar To cite this version: Shivalika Tanwar. Investigation of encapsulation of Aromatic polluants by β-Cyclodextrin in presence of linear aliphatic alcohols. Organic chemistry. Université Sorbonne Paris Cité, 2018. English. NNT : 2018USPCD076. tel-02613822 HAL Id: tel-02613822 https://tel.archives-ouvertes.fr/tel-02613822 Submitted on 20 May 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Université Paris 13-UFR SMBH THESE Pour Obtenir le grade de DOCTEUR DE L’UNIVERSITE PARIS 13 Discipline : Chimie Ecole doctorale Galilée Présentée et Soutenue publiquement par Shivalika TANWAR Le 26 Novembre 2018 Investigation of encapsulation of Aromatic pollutants by β-Cyclodextrin in presence of linear aliphatic alcohols Directrice de thèse: Prof. Nathalie DUPONT JURY Professeur. D LANDY Rapporteur Professeur. F PILARD Rapporteur Docteur. E GUENIN Examinateur Docteur. F SCHOENSTEIN Examinateur Docteur. S BLANCHARD Examinateur Professeur. N DUPONT Directrice de thèse 1 Acknowledgement I would never have been able to complete my doctoral studies without my continuous faith in God along with the help and support from my family and friends. Thus, I would like to take the opportunity to express my greatest appreciation. First of all, I would like to thank the members of the evaluation committee for their kind agreement to revise this work. Hence I would like to acknowledge Professor D. Landy and Professor F. Pilard for accepting to be referees. Thank you for your time to evaluate my thesis. Equally, I would like to express my gratitude to Doctor Erwann Guenin, Doctor S Blancard and Doctor Frédéric Schoenstein for their acceptance to be examiners. I would like to acknowledge my mentor and advisor, Professor Nathalie DUPONT, for encouraging my growth and competence to become a more self-directed, self- motivated, and highly –independent scientific researcher. Thank you for having time to answer all my questions, for providing endless guidance toward the success and giving me constant motivation. Furthermore, I would like to thank our team members, SBMB for their timely help and advices on all matters. Your support made my three years easier. Also, I would like to acknowledge Institute Galilée (University Paris 13) for funding my thesis. I would like to express my great thanks to IUT, Saint Denis for allowing me to use characterization techniques like Powder XRD and DSC. Many thanks to past and present PhD students and engineers in the CSPBAT laboratory. I want to especially thank to Inga Tijunelyte, Raymond Gilibert, Hanane Moustaoui and Agnés Victorbala for their discussions about science and help during the tough phases. Additional thanks to the master students who were present in our team during my thesis. Last but not the least I thank you all my friends and family for understanding, support and encouragement. Lastly, I thank my husband Varun, for his love and care during these years. Thank you all!! 2 Abbreviations CSD- Cambridge Structural Database αCD - Alpha cyclodextrin βCD- Beta cyclodextrin ϒCD- Gamma cyclodextrin REF- Reference δCD- Delta cyclodextrin MM- Molecular mechanics CD(s)- Cyclodextrin(s) MD- Molecular dynamics BTEX- Benzene, Toluene, Ethylbenzene, QM- Quantum Mechanical Xylenes DNA- Deoxyribonucleic acid PAH(s)- polycyclic aromatic HPLC- High pressure liquid hydrocarbon(s) Chromatography AH(s)- Aromatic hydrocarbon(s) LC- Liquid chromatography NMR- Nuclear magnetic resonance HRGC-MS- High resolution gas PXRD- Powder X-ray Diffraction chromatography-mass spectroscopy DSC- Differential Scanning Colorimetry LC-FD- Liquid chromatography fluorescence detection BEN- Benzene USAEME- Ultrasound-assisted FB- Fluorobenzene emulsification microextraction TOL- Toluene DLLME- Dispersive liquid–liquid TFT- α,α,α trifluorotoluene microextraction PHE- Phenol D2O- Deuterium Oxide BA- Benzoic acid MW- Molecular weight NAP- Naphthalene TMS- Tetramethylsilane 2NAP- 2-Naphthol/β-Naphthol U.V- Ultra Violet ANTH- Anthracene RT- Room temperature PYR-Pyrene mM-millimolar DFT- Density Functional Theory TGA- Thermogravimetric analysis E.U WFD- European Union water FWHM- Full width half maxima framework Directive λcu – Wavelength of copper U.S EPA- United States Environment Å- Angstrom Protection Agency 3 IR- Infrared LUMO- Lowest unoccupied molecular orbital HOMO- Highest occupied molecular orbital Chapter wise listing of figures and tables Chapter 1 Table 1.1 : Chronological summary on the development of Cyclodextrins. Table 1.2 : List of Chemically modified CDs and their abbreviations. Table 1.3 : Properties of natural cyclodextrins. Table 1.4 : Compilation of the molecular modeling methods used in the study cases. Figure 1.1: Glucopyranose unit. Figure 1.2: Macrocyclic structures with cavity diameters of parent CDs. a) αCD, b) βCD and c) ϒCD. Figure 1.3: Exterior and Interior of the CD cavity. Figure 1.4: Schematic diagram of CD showing the cavity, primary and secondary faces and the distribution of primary and secondary hydroxyl groups on the two CD faces. Figure 1.5: CD Inclusion compounds and Stoichiometry. Figure 1.6 : Views along c axis (right) and b axis (left) of CSD organization in the channel type structure CSD PUKPIU. Guest molecules are willingly hidden. Hydrogen atoms are not represented. Carbon atoms are represented in grey while oxygen atoms are represented in red. Figure 1.7 : Views along b axis (right) and c axis (left) of CDs organization in the herringbone dual nested channel type structure CSD BCDEXD10. Guest molecules are willingly hidden. Hydrogen atoms are not represented. Carbon atoms are represented in grey while oxygen atoms are represented in red. Figure 1.8 : Views along b axis (right) and c axis (left) of CDs organization in the brick dimer type structure CSD BOTBES. Guest molecules are willingly hidden. Hydrogen atoms are not represented. Carbon atoms are represented in grey while oxygen atoms are represented in red. Figure 1.9. Repartition in term of space groups and structural types of the structures involving αCD, βCD and ϒCD available in the CSD version 5.39 update 3 (May 2018). Chapter-2 Table 2.1 : The different mixtures of solution prepared for βCD and linear alcohols. Table 2.2 : The different mixtures of solution prepared for βCD and Aromatic hydrocarbons. Table 2.3 : Experimentally Observed 1H-NMR chemical shifts, (δ ppm), of C-H protons in unsubstituted CDs in D2O. Table 2.4: The position and multiplicity of the proton NMR peak in all alcohols studied. Table 2.5 : Principal structural characteristics of the CSD structures used further as references. Table 2.6 : Simulated X-ray pattern of CSD refcode BCDEXD10 for 4°< 2theta <14°: Dual channel Herringbone structural type. (Cu=1.5405 Å , FWHM = 0.1). Table 2.7: Simulated X-ray pattern of CSD refcode CACPOM for 4°< 2theta < 14° : dual channels made with dimer brick structural type. (Cu=1.5405 Å , FWHM = 0.1). Table 2.8 : Simulated X-ray pattern of CSD refcode PUKPIU for 4°<2theta<14° : Channel structural type. (Cu=1,5406. Å m, FWHM = 0.1). Table 2.9 : Simulated X-ray pattern of CSD refcode POHXUG for 4°<2theta<14° : Channel structural type. (Cu=1.5405 Å, FWHM = 0.1). Table 2.10 : Simulated X-ray pattern of CSD refcode ZUZXOH for 4°<2theta<14°: Channel structural type. (Cu=1.5405 Å , FWHM = 0.1). 4 Table 2.11 : Experimental X-ray pattern of βCD directly out of the box (Wacker) and CSD refcode reference assignment. Table 2.12 : XRD peaks corresponding to different types of βCD Crystals. Table 2.13 : Common characteristic frequencies of organic compounds. Figure 2.1 : Energy levels of a nucleus with spin quantum number. Figure 2.2 : Effect of magnetic field on the energy gap between two possible states adopted by a spinning nucleus. Figure 2.3 : Spinning motion of a nucleus on its axis. Figure 2.4 : Flipping of the magnetic moment on absorption of energy. Figure 2.5 : Experimental setup for NMR. Figure 2.6 : Graphical representation of job’s plot showing (a)1:1 (b) 2:1 and (c) 1:2 complexations respectively. Figure 2.7 : Glucopyranose unit with atoms numbering. Figure 2.8 : Positions of different Hydrogens in a CD molecule. 1 Figure 2.9 : H NMR experimental spectrum of βCD (10mM) solution in D2O. Figure 2.10 : Observed proton NMR spectrum of Hexanol. Figure 2.11 : Schematic of crystal formation at liquid-liquid interface. Figure 2.12 : Power Compensated DSC. Figure 2.13 : Observed DSC thermogram of βCD. Figure 2.14 : Bragg’s Law reflection. Figure 2.15 : Types of diffraction patterns obtained by different style arrangements of βCD while forming an inclusion complex. Simulation done with the Mercury software (Cu=1.5405 Å, FWHM = 0.1). Figure 2.16 comparison of diffraction patterns of experimentally observed and simulated herringbone structure (BCDEXD10) from literature of βCD. The CSD reference are BCDEXD10 and ZUZXOH. The experimentally observed βCD pattern can be seen to show peaks corresponding to both these structures. Figure 2.17 : Observed powder XRD pattern of βCD co-precipitated in presence of octanol in comparision with the powder xray simulated pattern from 4° to 14° in 2theta for CSD CACPOM exhibiting a brick type dimers structural type. Figure 2.18 : "Jablonski" style diagram of energetic transitions involved in Raman scattering. Rayleigh scattering is elastic; the incident photon is of the same energy as the scattered photon. Raman scattering is inelastic; in Stokes scattering, the incident photon is of greater energy than the scattered photon, while in anti-Stokes scattering, the incident photon is of lower energy.