University of Groningen
Photoresponsive supramolecular soft materials in aqueous media
Chen, Shaoyu
DOI:
10.33612/diss.107818650
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Publication date: 2019
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Citation for published version (APA):
Chen, S. (2019). Photoresponsive supramolecular soft materials in aqueous media. Rijksuniversiteit Groningen. https://doi.org/10.33612/diss.107818650
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202
Appendix-Section A
Appendix-Section A
Materials and Methods
General Materials: All commercial reagents were purchased from Sinopharm,
Aladdin, Aldrich, Acros, TCI, Fluka or Merck and were used as received unless otherwise stated. For aqueous solutions, deionized water was used. All reactions were performed under inert atmosphere (Nitrogen). The reaction progress was monitored by Thin-layer chromatography (TLC). Analytical TLC was performed with Merck silica gel 60 F254 plates and visualization was accomplished by UV light (λ = 254 nm or λ = 365 nm). Flash chromatography was carried out using Merck silica gel 60 (230-400 mesh ASTM). Solvents for spectroscopic studies were of spectrophotometric grade (UVASOL Merck).
General information: NMR spectra were recorded at 25 °C on Varian AMX400 (1H:
400 MHz, 13C: 100 MHz) or Varian Unity Plus (1H: 500 MHz, 13C: 125 MHz)
spectrometers, unless otherwise stated. The deuterated solvents (CD2Cl2 and CDCl3)
were treated with Na2CO3, molecular sieves (4Å) and degassed by argon prior to use.
Chemical shifts (δ) are expressed relative to the resonances of the residual non-deuterated solvent for 1H [CDCl
3: 1H(δ) = 7.26 ppm, CD2Cl2: 1H(δ) = 5.32 ppm,
CD3OD: 1H(δ) = 3.31 ppm] and 13C [CDCl3: 13C(δ) = 78.0 ppm, CD2Cl2: 13C(δ) =
53.84 ppm]. Absolute values of the coupling constants are given in Hertz (Hz), regardless of their sign. Multiplicities are abbreviated as singlet (s), doublet (d), doublet of doublets (dd), triplet (t), multiplet (m), and broad (br). High-resolution mass spectrometry (ESIMS) was performed on an LTQ Orbitrap XL spectrometer. Infrared spectrum was recorded for solid samples on a Thermo Finnigan, Nicolet.is10, (USA) FT-IR spectrometer. UV-vis measurements were performed on an Hewlet-Packard HP 8543 Diode Array Photospectrometer UV-vis Spectrophotometer or a Cary 50 ultraviolet spectrophotometer in a 1 cm path length quartz cuvette. Temperature-control was exerted through a Peltier based temperature-controlled cuvette holder (QuantumNorthwest).
General light source information: Light sources for irradiation have been
purchased from commercial suppliers. Details of light sources are summarized in Table A1.
Appendix-Section A
Table A1 Details of light sources
Entry λ(nm) Type Supplier Chapter
1 365 Intelli-ray 600 Uvitron International Inc. 2-5
2 400 – 780 YG(B)982X Wenzhou Darong Textile
Instrument Co., Ltd. 2-5
3 254 EF-260C Spectroline 6
4 312 ENB-280C Spectroline 6
5 365 ENB-280C Spectroline 6
7 365 M365F1 ThorLabs 7
Foamabililty and Foam Stability Measurements:1–3
Foamability and foam stability were determined by the foaming ratio (R) and foam half-life (t1/2), unless stated otherwise. The foaming ratio (R) was calculated from the equation R = Vfoam / Vliquid in which Vfoam and Vliquid referred to the foam volume and the original liquid volume to prepare foams, respectively. A higher foaming ratio represented better foamability. The half-life (t1/2) was defined as the time required for one-half of the liquid in the initial foam to separate out by self-drainage. A longer half-life meant that the foam was more stable. All the measurements were performed in triplicate.
References
(1) Dawson, T. L. Foam Dyeing and Printing of Carpets. J. Soc. Dye. Colour. 1981, 97 (6), 262–274.
(2) Jin, H.; Zhou, W.; Cao, J.; Stoyanov, S. D.; Blijdenstein, T. B. J.; De Groot, P. W. N.; Arnaudov, L. N.; Pelan, E. G. Super Stable Foams Stabilized by Colloidal Ethyl Cellulose Particles. Soft Matter 2012, 8 (7), 2194–2205.
(3) Yu, H.; Wang, Y.; Zhong, Y.; Mao, Z.; Tan, S. Foam Properties and Application in Dyeing Cotton Fabrics with Reactive Dyes. Color. Technol. 2014, 130 (4), 266–272.
204
Appendix-Section B
Appendix-Section B
Photo-Decomposition of the Molecular Motor Amphiphile in
Aqueous Media in Chapter 6
B.1 Identification of the decomposition compound of stable trans-MA
To identify the photo-decomposition compound of stable trans-MA in aqueous media, a stable trans-MA solution (2 mM) was degassed by bubbling argon for 30 min prior to photoirradiation. After irradiating the solution with 254 nm light for 45 min, the resulting solution was investigated using the liquid chromatography–mass spectrometry (LC-MS). The LC-MS analysis was performed without the addition of formic acid to eliminate the effect of acid on the decomposition of stable trans-MA. A major peak at m/z 364.30 in the photoirradiated stable trans-MA solution was observed in the ESI-MS spectra (Figure B1, top spectrum), indicating that compound
7 maybe the major decomposition compound. The identical stable trans-MA
solution irradiated with 254 nm light for 45 min was also studied by the high-resolution ESI mass spectrometry (HRMS). The calculated m/z for compound 7 is 364.2482, and m/z of 364.2475 was found in the HRMS spectrum of the irradiated stable trans-MA solution, further indicating that compound 7 could be the photo-decomposition compound of stable trans-MA in water.
Figure B1 ESI-MS spectra of stable trans-MA solution before (bottom, green) and
after (top, red) 254 nm light irradiation for 45 min.
B.2 Synthesis of compound 7
The synthesis of compound 7 is summarized in Scheme B.1. Compound 5 and 1,2-bis(2-bromoethoxy)-ethane (3) were prepared according to reported procedures1,2.
1,2-Appendix-Section B
bis(2-bromoethoxy)-ethane (3) and Cs2CO3 in DMF. Subsequent reaction of 6 with
trimethylamine gave the corresponding compound 7.
Scheme B1 Synthesis of compound 7.
The detailed procedures of the synthesis and the structures of compound 6 and 7, confirmed by 1H, 13C NMR, and high-resolution ESI mass spectrometry, are
provided below:
Compound 6:
A mixture of 5 (200 mg, 1.05 mmol), 3 (580 mg, 2.10 mmol) and cesium carbonate (1.03 g, 3.15 mmol) in DMF/MeCN (4 mL/14 mL) was heated at 80 oC for 16 h. The
reaction mixture was allowed to cool to room temperature and then washed with water (50 mL) and ethyl acetate (30 mL). The combined organic layers were washed with brine and dried over Na2SO4. The solvent was removed by rotary evaporation.
The residue was successively purified by column chromatography on SiO2 (ethyl
acetate/pentane; v/v = 1/4, Rf = 0.5) to yield 6 (292 mg, 0.76 mmol, 72% yield) as a colorless oil. 1H NMR (400 MHz, CDCl 3) δ (ppm) 6.94 (s, 1H), 4.13 (t, J = 4.9 Hz, 2H), 3.98 (t, J = 4.9 Hz, 2H), 3.82 (t, J = 6.3 Hz, 2H), 3.78 – 3.73 (m, 2H), 3.73 – 3.68 (m, 2H), 3.46 (t, J = 6.3 Hz, 2H), 3.16 (dd, J = 16.7, 8.0 Hz, 1H), 2.72 – 2.61 (m, 1H), 2.51 (s, 3H), 2.46 (dd, J = 16.7, 4.0 Hz, 1H), 2.28 (s, 3H), 1.29 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl 3) δ (ppm) 212.0, 157.2, 146.1, 135.2, 133.7, 125.6, 120.8, 72.2, 71.9, 71.6, 71.0, 70.2, 43.7, 33.5, 31.2, 18.8, 17.5, 10.8. HRMS (ESI) calculated for C18H25BrO4 is 385.1009, found 385.1010.
Compound 7:
A mixture of 6 (292 mg, 0.76 mmol) and a 4.3 M NMe3 solution in ethanol (4 mL)
was stirred in a pressure tube at 50 oC for 24 h. After cooling to room temperature,
the solvent was removed in vacuum and the residue was washed with diethyl ether (2 mL) and Pentane (20 mL). The precipitate was filtered off to provide 7 (304 mg; 0.68 mmol, 90% yield) as a white solid.
206 Appendix-Section B 1H NMR (400 MHz, CDCl 3) δ (ppm) 6.80 (s, 1H), 3.96 (t, J = 4.6 Hz, 2H), 3.84 (t, J = 5.5 Hz, 4H), 3.69 (t, J = 4.6 Hz, 2H), 3.58 (s, 4H), 3.35 (s, 9H), 3.02 (dd, J = 16.8, 8.0 Hz, 1H), 2.50 (m, 1H), 2.38 – 2.26 (m, 4H), 2.14 (s, 3H), 1.12 (d, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl 3) δ (ppm) 211. 7, 156.7, 145.9, 134.8, 133.7, 124.7, 120.5, 71.1, 71.1, 70.5, 69.8, 66.2, 65.8, 43.4, 33.1, 32.1, 18.5, 17.1, 10.6. HRMS (ESI) calculated for C21H34NO4 is 364.2482, found 364.2481.
B.3 Macroscopic foam properties of stable trans-MA solution doped with compound 7
To investigate the effects of compound 7 on the macroscopic foam properties of a
MA solution, freshly prepared buffer solutions (0.4 mL) of stable trans-MA doped
with different concentration of compound 7 were used to generate macroscopic foams by bubbling with a flow of argon gas (10 cm3 min–1 for 8 min). The foamability
was determined by foaming ratios. The foaming ratio (R) was calculated from the equation R=Vfoam/Vliquid, in which Vfoam and Vliquid referred to the foam volume and the original liquid volume to prepare foams, respectively. A higher foaming ratio indicated a higher foamability. The solutions show good foamability with foaming ratios of ~13.8 and the obtained foams remain stable over 20 min (Figure B3), despite the doping of compound 7 at different concentrations. The results clearly demonstrate that compound 7 shows no significate effects on the macroscopic foams properties prepared from the stable trans-MA solutions, indicating that the macroscopic photoresponsive foams prepared from the stable trans-MA solutions (in chapter 6) is attributed to the photoisomerization of MA.
Figure B3 Foamability and foam stability of foams prepared from Tris-EDTA buffer
solutions (0.4 mL) containing (a) stable trans-MA (2 mM), (b) stable trans-MA (1.9 mM) and compound 7 (0.1 mA), and (c) stable trans-MA (1.6 mM) and compound 7 (0.4 mA).
Appendix-Section B
References
(1) Li, Y.; Dong, J.; Xun, Z.; Zeng, Y.; Yu, T.; Han, Y.; Chen, J.; Li, Y. Y.; Yang, G. A Versatile and Robust Vesicle Based on a Photocleavable Surfactant for Two-Photon-Tuned Release. Chem. Eur. J. 2013, 19 (24), 7931–7936.
(2) van Leeuwen, T.; Gan, J.; Kistemaker, J. C. M.; Pizzolato, S. F.; Chang, M. C.; Feringa, B. L. Enantiopure Functional Molecular Motors Obtained by a Switchable Chiral-Resolution Process. Chem. Eur. J. 2016, 22 (21), 7054–7058.
208
Appendix-Acknowledgements
Appendix-Section C
Acknowledgements
The journey of pursuing a PhD has both fun and difficulty. I have enjoyed the fascinating scenery during this journey. I am so lucky to meet a lot of very nice people, who give me support and encouragement. At the end of this thesis, I would like to express my gratefulness and best wishes sincerely to all of you.
First and foremost, I would like to pay my greatest gratitude and respect to my primary promotor Prof. Ben L. Feringa. Dear Ben, thank you very much for offering me the opportunity to carry out research under your guidance. I really like the working atmosphere here as well as the life in the Netherlands. I am so grateful to have worked in such a high-level team that you have created. These two years have meant a lot to me, and have completely changed my life. Although you are very busy, you always manage to participate our subgroup meetings and offer constructive and thoughtful suggestions. Your passion and thoughtful attitude to science deeply impress me. You always say “we can make it” with a smile, which is infectious and give me lots of confidences. I do really appreciate all your supports and helps. Many thanks to my co-promotors, Prof. Chaoxia Wang and Dr. S. J. Wezenberg.
Dear Prof. Wang, thank you for supporting my application for doing research
abroad as a joint-PhD student. You always spend lots of time to keep us on track,
e.g., weekly meeting, monthly report etc. In addition to your concern in our scientific
research, you also care for our daily lives. We have many group activities (hiking, badminton match), helping us to relieve pressure. I really appreciate all your help and guidance in these years. Dear Sander, I would like to thank you for all your guidance and discussions. You always ask us about the progress of our research and give insightful advice. I wish you many successes in your future research. I’m sure you will be a great supervisor and have an excellent group in Leiden University.
Dear Franco, I am extremely grateful to have you as my daily supervisor as well as
our (Qian and me) best friend. Whenever I'm in trouble, you always encourage me and offer guidance. I have learnt a lot from you, e.g., how to manage projects, how to solve experimental problems, how to organize papers, how to work efficiently etc. I can safely say that this thesis would not have looked nearly this good without you. You have not only helped me to correct every chapter, but also taught me how to improve my writing skills. You have now formed your own group in the Hong Kong
Appendix-Acknowledgements
Polytechnic University. For sure, you are an excellent chemist and will be a great supervisor. I wish you and your family all the best in the future.
Thanks to my collaborator Dr. P. van Rijn Group: Dear Patrick, thank you for every meeting and discussion. You always listen to our research progress reports patiently and give us constructive, professional comments and suggestions from the views of organic chemistry and biology. Dear Liang, thank you for the cell cultures in chapter 7. You taught me how to do the biological experiments. Also, thank you for helping me to book the experimental equipment every time.
I would like to thank the members of the Assessment Committee (Prof. E. J. R.
Sudhölter, Prof. P. Rudolf, Prof. W.R. Browne and Prof. P. Ma) for reading my
thesis and providing swift corrections and comments.
Many thanks to Tineke and Inge. Dear Tineke, you always give us kind reminders in time and arrange everything in good order. Whenever we need help, you are always there – offering your helping hand warmly and patiently. Dear Inge, thank you for helping us to arrange appointments with Ben and answering all our questions patiently. We are lucky to have both of you as our group secretaries. I am extremely grateful for all supports and helps from both of you when I met a problem about the examining committee and fortunately, we finally solved the problem. :)
To Jiawen: Dear Jiawen, I still remember the moment when you replied my email two years ago, which was like a beam of sunlight for me at that time. On my first day in Groningen, you picked me up at the train station and helped me to settle down. I am very grateful for all of your help. I wish you and your family all the best in Guangzhou!
To Anouk: Dear Anouk, thank you for helping me to correct the summary and the Dutch translations. When I began to write my thesis, I am very grateful that you told me: “If you need any help, just come to me”. Also, I would like to thank you for arranging things in our group, such as subgroup meetings, lab rules etc., to create a good working environment for us.
To my paranymphs Yuchen and Henrieke: Dear Yuchen, you are a very nice friend with integrity and goodness. Thank you very much for your patience whenever I ask for your help. I am very happy to discuss scientific questions with you, as well as dance, play super Mario games and sing Chinese nursery rhymes. I am surprised to find that there is one man who can sing as many nursery rhymes as I can. Unbelievable! Don't forget, we still have an unfinished competition of singing Chinese nursery rhymes. :) Dear Henrieke, I am very grateful to have a friend like you here. I really appreciate for your invitation of joining the coffee break, the lunch and the drawing course as well as for your help of the Dutch translations.
210
Appendix-Acknowledgements
Additionally, the experience of being an actress in Jinling’s PhD movie was really fun! It’s my big screen debut, you are a good director and my acting is not bad, right? :) Both of you will defend soon, best wishes for the defence and for the future! To Wojtek: Dear Wojtek, Due to the unforeseen problem of my examining committee, it is a pity that I am not defend on the same day with you as planned! But I need to say that you are a very good teammate. We had pleasantly and efficiently discussed the arrangements of reception, dinner and party. I also would like to thank you for every synthetic suggestion. I wish you all the best in the future! Last but not least, I need to say that you are a very cute guy! :)
To all the people providing technical and characterization supports as well as secretarial supports: many thanks to Marc, Pieter and Johan, Monique and Renze,
Léon. I do really appreciate for your kind and patient training and explaining so
many things to me! Many thanks to Gaël for his kind and thoughtful helps!
To other members and former members in Feringa Group: Wiktor, José, Lukas,
Greg, Ruth, Jaime, Jeffrey, Romain, Michael, Niklas, Simon, Nadja, Stefano, Brian, Jana, Fan, Jinyu, Youxin, Cosima, Daisy, Marco, Anirban, Sven, Carlijn, Filippo, Albert, George, Friederike, Dusan, Tobias, Hugo, Piermichele, Mark, Vanda, Bianka, Paco, Thomas, John, Tom, Dorus, Michael, Jinling, Diederik, Mickel, et al. Thank you for creating a harmonious and pleasant working
environment. I have enjoyed working with all of you in the group and I appreciate all of your help. Best wishes!
I also would like to thanks other friends in Groningen. At this moment, many names come to my mind. I am extremely grateful to have met all of you and I cherish the times we had. I like Groningen very much because of the nice environment, especially because of all the nice people. I will not list all of my other friends here, but all of you are in my mind. Cheers to our friendship!
Great thanks to my family: parents, uncles, aunts, brothers, sisters and nieces. 特别
感谢我的父母，舅舅舅妈、阿姨姑姑等长辈、哥哥姐姐们一直以来对我的关心、 照顾和支持！感谢父母：感谢爸妈对我的养育和教导，你们是最棒的父母，为 我遮风挡雨，在我的成长中给我充分的信任、支持、鼓励和自由，让我相信我 能成为更好的自己！感谢公公婆婆对我的支持和理解！你们的孩子已经慢慢长 大，愿以后能替你们分担生活的烦恼，让你们少些操心和担忧，希望你们健康 快乐！！感谢我的哥哥：虽然小时候吵吵闹闹，但我一直都知道你疼我爱我， 从小到大，你一直都把好的东西跟我分享、留给我。曾经我的朋友们羡慕我有 一个特别帅气的哥哥，争着想来我们家玩，但更值得羡慕的是我有一个从心里 疼我爱我的哥哥。感谢哥哥嫂子、姐姐姐夫给予的理解和支持，以及在我们不 在家里的时候对父母的关心和陪伴！感谢家里的长辈们、哥哥姐姐嫂嫂们从小
Appendix-Acknowledgements 到大给我的关心和爱护，我们是一个有爱的大家庭！还有我的小侄女们：感谢 你们的到来，给家里增添很多欢乐。我的小侄女Blue，一个特别乖巧懂事的小 女孩，当你还是一个小小婴儿的时候，我抱你在怀里，看你熟睡的样子，那一 刻我意识到我有责任和义务关心你呵护你；看着你一点一点慢慢长大，今天你 也开启了你的求知之路，希望你今后在漫漫的求学道路上勇敢、坚强，最重要 的是快乐！还有可可，机灵淘气的小女孩，愿你们快乐健康成长！
Finally, I would like to give my great thanks to my husband: Qian Wang! Dear Qian, I am so lucky to have met a person as excellent as you. You are wise, creative and insightful. Thank you very much for giving me everything. You see, you have spoiled me with your love and your care! Whatever you want to do, you always can make it, such as drawing, singing, playing guitar and cooking. I know you have your dream and you make efforts for it. Never give up, I believe that your dream will come true one day! 最后，我要特别感谢我的先生王潜。很幸运遇到你，感谢你一直以来 的陪伴、关心、包容、付出和无微不至的照顾，特别在荷兰这两年，如果没有 你，可能今天这个论文还没有完成。你聪明睿智，很多事只要你想去做，你都 能做好，我知道你一直也有你的理想和追求并为之努力；永远不要放弃理想， 我坚信总有一天会实现，不管怎么样，至少还有我们携手相伴：愿有岁月可回 首，且以深情共白头！
PS：Thanks to my husband, Qian, for designing and drawing the cover, bookmark and illustrations of this thesis! (感谢我的先生王潜为本论文设计封面和插画！)
Shaoyu Chen 陈少瑜
