Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations
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Ohio University / OhioLINK
2013
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| Online Access: | http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1377319288 |
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ndltd-OhioLink-oai-etd.ohiolink.edu-ohiou13773192882021-08-03T06:19:24Z Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations Ling, Xiaoxi Chemistry Organic Chemistry Cucurbiturils Supramolecular chemistry Thermodynamic Kinetic Macrocycle Molecular machine Self-assembling Cucurbit[n]urils (CB[n]s) are a family of pumpkin-shaped macrocycles that have shown great potential in numerous studies. One field of interest is their application in self-assembling molecular devices. In this dissertation, we describe the study of their behaviors from both thermodynamic and kinetic respectively.Firstly, we investigated the thermodynamic trend of CB[7] binding with a group of trimethylsilylmethyl ammonium guests with different N-benzyl substituents. The resonance effects and field effects from the substituents were discovered to have independent contributions to the binding and a functional linear free-energy relationship between the two was validated.Second, we designed a three component self-sorting system consisting of CB[6], CB[7], and a spermine derivative. The system has a well-defined, kinetically favored sequence at room temperature but can undergo a reorganization toward a more stable structure upon thermally induced scrambling.Next, we studied the slippage of CB[6] along a polyaminated axle. The translation rate was highly dependent on even minor sterical alterations of the guest. The slippage pathway is also described as a three-step process of deprotonation, threading, and reprotonation.Finally, we discovered that CB[7] slippage over benzo-15-crown-5 could be enhanced by metallic and organic cations by up to 500 times. The highest energy transition state of the dethreading process is likely stabilized by cations which interact with both crown ether and CB[7]. 2013 English text Ohio University / OhioLINK http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1377319288 http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1377319288 unrestricted This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws. |
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NDLTD |
| language |
English |
| sources |
NDLTD |
| topic |
Chemistry Organic Chemistry Cucurbiturils Supramolecular chemistry Thermodynamic Kinetic Macrocycle Molecular machine Self-assembling |
| spellingShingle |
Chemistry Organic Chemistry Cucurbiturils Supramolecular chemistry Thermodynamic Kinetic Macrocycle Molecular machine Self-assembling Ling, Xiaoxi Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| author |
Ling, Xiaoxi |
| author_facet |
Ling, Xiaoxi |
| author_sort |
Ling, Xiaoxi |
| title |
Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| title_short |
Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| title_full |
Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| title_fullStr |
Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| title_full_unstemmed |
Cucurbit[n]urils in Self-Assembling Molecular Devices: Thermodynamic and Kinetic Considerations |
| title_sort |
cucurbit[n]urils in self-assembling molecular devices: thermodynamic and kinetic considerations |
| publisher |
Ohio University / OhioLINK |
| publishDate |
2013 |
| url |
http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1377319288 |
| work_keys_str_mv |
AT lingxiaoxi cucurbitnurilsinselfassemblingmoleculardevicesthermodynamicandkineticconsiderations |
| _version_ |
1719434644938555392 |