1. Supramolecular polymers
Introduction to polymer science
Supramolecular polymers
超分子聚合物
四川大学化学学院

2. Basic of the Supramolecular

3. Supramolecular polymer
A supramolecular polymer is a polymer whose monomer repeat units are held together by noncovalent bonds.
Non-covalent forces that hold supramolecular polymers together include coordination, π-π interactions, and hydrogen bonding. O P OH
H2C N H HO
CH2
CH3
腺嘌呤
胸腺嘧啶
鸟嘌呤
胞嘧啶

4. Supramolecular polymer
Colloid
Early 20th century
Supramolecular polymer
from 1997
Linear polymer
from 1930
Jean-Marie Lehn
Donald J. Cram
Charles J. Pedersen

5. Definition of Supramolecular polymer
Polymeric arrays of monomeric units that are brought together by reversible and highly directional secondary interactions, resulting in polymeric properties in dilute and concentrated solutions, as well as in the bulk.
molecular chemistry
atom + atom → molecular（covalent）
supramolecular chemistry
molecular + molecular → supramolecular（noncovalent）

6. Intermolecular Interactions
“Supramolecular Chemistry is the chemistry of the intermolecular bond, concerning the structure and functions of the entities formed by the association of two or more chemical species.” (by Jean-Marie Lehn)
Covalent bond
C-O bond 340kJ / mol C-C bond 360kJ / mol
C-H bond 430kJ / mol C=C bond 600kJ / mol
C=O bond 690kJ / mol
Driving Force for the Formation of Supramolecular Structures
Hydrophobic interaction < 40 kJ/mol
Electrostatic interaction kJ/mol
Hydrogen bond interaction ~30 kJ/mol
Van der Waals interaction kJ/mol
Cation-π interaction kJ/mol
π-π interaction kJ/mol
Coordination interaction (Host-guest interaction)

7. van der Waals Interaction: Sticky Secrets of the Gecko
The toes of the gecko have a special adaptation that allows them to adhere to most surfaces without the use of liquids or surface tension.
the attractive forces that hold geckos to surfaces are van der Waals interactions between the finely divided setae and the surfaces themselves.
Every square millimeter of a gecko's footpad contains about 14,000 hair-like setae. Each seta has a diameter of 5 micrometers.

8. Hydrophobic interaction
Hydrophobic molecules tend to be non-polar and thus prefer other neutral molecules and non-polar solvents.
Hydrophobic molecules in water often cluster together forming micelles. Water on hydrophobic surfaces will exhibit a high contact angle.

9. Hydrogen bond
A hydrogen bond is the attractive interaction of a hydrogen atom with an electronegative atom, like nitrogen, oxygen or fluorine.
The hydrogen must be covalently bonded to another electronegative atom to create the bond.
These bonds can occur between molecules (intermolecularly), or within different parts of a single molecule (intramolecularly).
The Hydrogen bonds can vary in strength from very weak (1-2 kJ/mol) to extremely strong (>155 kJ/mol), Typical values include:
F—H... :F (155 kJ/mol or 40 kcal/mol)
O—H... :N (29 kJ/mol or 6.9 kcal/mol)
O—H... :O (21 kJ/mol or 5.0 kcal/mol)
N—H... :N (13 kJ/mol or 3.1 kcal/mol)
N—H... :O (8 kJ/mol or 1.9 kcal/mol)

10. π-π stacking
π-π stacking (aromatic interaction). Weak electrostatic interaction between aromatic rings. There are two general types: face-to-face and edge-to-face:
Face-to-face π-stacking interactions are responsible for the slippery feel of graphite. Similar π-stacking interactions help stabilize DNA double helix.
Face-to-face
edge-to-face
π-π stacking are caused by intermolecular overlapping of p-orbitals in π-conjugated systems, so they become stronger as the number of π-electrons increases.
π-π stacking interactions act strongly on flat polycyclic aromatic hydrocarbons such as anthracene, triphenylene, and coronene because of the many delocalized π- electrons.

12. Self-assembly
Self-assembly is a term used to describe processes in which a disordered system of pre-existing components forms an organized structure or pattern as a consequence of specific, local interactions among the components themselves, without external direction. That is without guidance or management from an outside source (other than to provide a suitable environment).
components
device
molecule components
supramolecular

13. Self-assembly
Self-assembly can be classified as either static or dynamic. In static self-assembly, the ordered state forms as a system approaches equilibrium, reducing its free energy.
However in dynamic self-assembly, patterns of pre-existing components organized by specific local interactions are not commonly described as "self-assembled" but "self-organized".

14. Unit of the Supramolecular

15. Unit of Supramolecular
Based on hydrogen-bonding
Based on π-π stacking
Based on coordination (Host-guest)
Based on miscellaneous interactions

16. Based on hydrogen-bonding
Liquid Crystalline supramolecular developed by Lehn, based on triple hydrogen bonds

17. Based on hydrogen-bonding

18. Based on hydrogen-bonding
Diblock copolymer
Tautomerization
Homodimerization
Heterodimerization
UPy-Napy
UPy-UPy
Ureidopyrimidinones
1,8-naphthyridine

19. Based on π-π stacking RO OR triphenylenes
R = C5H11, C9H19, C11H23, C6H13
R = C3H7CH(CH3)C3H6CH(CH3)2
R = (C2H4O)2CH3

20. Based on π-π stacking a-Hemolysin Heptamer
溶血素
Stacking of Macrocycles via Noncovalent Interaction

21. Based on coordination Metal IonAr Cu
[Cu(CH3CN)4]+PF6-
Metal Ion
Bifunctional metal complexating and its mode of polymerization upon addition of Cu+.
PF6-
PF6-
PF6-

22. Based on miscellaneous interactions

23. Characteristics of the Supramoleculars
Facile and economic synthesis
Self-assembly involves the aggregation of molecules and macromolecules to thermodynamically stable structures which are held together by weak noncovalent interactions.
Reversibility and Self-repairing
Reversible aggregates that can break and recombine on experimental time scales
Environmental responsive
The noncovalent interactions are sensitive to environment change, such as solvent, temperature, pH, etc.

24. Characterization of the Supramolecular

25. Characterization of the Supramolecular
Detection of surface:
AFM, SEM, STM, etc.
Characterization of chemical structure
FTIR, 1H-NMR,MS (MALDI-TOF), etc.
Determination of molecular weight
GPC
Representation of viscosity
Ubbelohde viscometer

26. SPM: Scanning Probe Microscopy
Detector and feedback electronics
Photodiode
Laser
Sample Surface
Cantilever
& Tip
PZT Scanner
STM: scanning tunneling microscope
tunneling of electrons between probe and surface
AFM: atomic force microscope
measuring of the force on the probe
MFM: magnetic force microscope
AFM with magnetical probe
AFM tip

27. Microscopy Investigating the assembly morphology of the supramolecular
a) POM (polarizing optical microscopy); b) SEM (Scanning electron microscope);
c) TEM (Transmission Electron Microscope); d) AFM

28. 1H-NMR

29. MALDI-TOF-MS
Matrix-assisted laser desorption/ionization (MALDI) is a soft ionization technique used in mass spectrometry, allowing the analysis of biomolecules (biopolymers such as proteins, peptides and sugars) and large organic molecules (such as polymers, dendrimers and other macromolecules), which tend to be fragile and fragment when ionized by more conventional ionization methods.
The ionization is triggered by a laser beam (normally a nitrogen laser). A matrix is used to protect the biomolecule from being destroyed by direct laser beam and to facilitate vaporization and ionization.
Time of flight (TOF) describes a methods that measure the time that it takes for an object, particle or acoustic, electromagnetic or other wave to travel a distance through a medium.

30. MALDI-TOF-MS Spectrum

31. Application of the Supramolecular

32. Application of the Supramolecular
Molecular tubes for ion channel
作为离子通道的分子管
Liquid crystal materials
液晶材料
Molecular films for separation
用于分离的分子膜
Micro reaction chamber for catalysis
用于催化的微反应器
Drug release and delivery
药物缓释和传递

33. Preparation of copolymer
Yang, X. W.; Hua, F. J.; Yamato, K.; Ruckenstein, E.; Gong, B.; Kim, W.; Ryu, C. Y.
Angew. Chem., Intl. Ed. 2004, 43, 6471.

34. Nanotube

35. Self-healing Contact Recovery of Cut for 180 min initial strength
Leibler, L. Nature, 2008, 51, 977–980
Aida, T. Nature, 2008, 451, 895–896