Post on 04-Jan-2016
SupramoleculaSupramolecular polymersr polymers
四川大学化学学院
超分子聚合物超分子聚合物
Introduction to polymer scienceIntroduction to polymer science
Basic of the Supramolecular
Supramolecular polymerSupramolecular 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.
OPO OHO
OH2CN
O
N
N H
NN H
HOP OHO
O
O
CH2
N
N
N
O
OP OHOO
O CH2
H
H
O
PO OHO
OH2CN
N
N
N
N
N N
O
CH3
O
HH腺嘌呤
胸腺嘧啶
鸟嘌呤
胞嘧啶
H
Supramolecular polymerSupramolecular polymer
Jean-Marie Lehn
ColloidEarly 20th century
Linear polymerfrom 1930
Supramolecular polymerfrom 1997
Donald J. Cram Charles J. Pedersen
Definition of Supramolecular polymerDefinition 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 chemistrymolecular chemistryatom + atom → molecular ( covalent )
supramolecular chemistrysupramolecular chemistrymolecular + molecular → supramolecular
( noncovalent )
Intermolecular InteractionsIntermolecular 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 bondC-O bond 340kJ / mol C-C bond 360kJ / molC-H bond 430kJ / mol C=C bond600kJ / molC=O bond 690kJ / molDriving Force for the Formation of Supramolecular Structures Hydrophobic interaction < 40 kJ/molElectrostatic interaction - 20 kJ/molHydrogen bond interaction 12~30 kJ/molVan der Waals interaction 0.4-4 kJ/molCation-π interaction 5-80 kJ/molπ-π interaction 0-50 kJ/molCoordination interaction (Host-guest interaction)
van der Waals Interaction:van der Waals Interaction:Sticky Secrets of the Gecko 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.
Hydrophobic interactionHydrophobic 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.
Hydrogen bondHydrogen 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)
ππ--π π stackingstacking
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.
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
Self-assemblySelf-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).
molecule components supramolecular
devicecomponents
Self-assemblySelf-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".
Unit of the Supramolecular
Unit of SupramolecularUnit of Supramolecular
Based on hydrogen-bonding
Based on π-π stacking
Based on coordination (Host-guest)
Based on miscellaneous interactions
Based on hydrogen-bondingBased on hydrogen-bonding
Liquid Crystalline supramolecular developed by Lehn, based on triple hydrogen bonds
Based on hydrogen-bondingBased on hydrogen-bonding
Based on hydrogen-bondingBased on hydrogen-bonding Diblock copolymer
Tautomerization
Homodimerization Heterodimerization
UPy-UPy UPy-Napy1,8-naphthyridineUreidopyrimidinones
Based on π-π stacking Based on π-π stacking
triphenylenes
R = C5H11, C9H19, C11H23, C6H13
R = C3H7CH(CH3)C3H6CH(CH3)2
R = (C2H4O)2CH3
RO
RO
OR
OR
RO OR
Based on π-π stackingBased on π-π stacking
Stacking of Macrocycles via Noncovalent Interaction
a-Hemolysin Heptamera-Hemolysin Heptamer溶血素溶血素
Based on coordinationBased on coordination
NN
R NN
RR
R
NN
R NN
RR
RN
N
R
NN
Ar NN
RR
R
NN
R
CuCu
Cu
+ [Cu(CH3CN)4]+PF6-
Metal IonMetal Ion
PF6-
PF6-
PF6-
Bifunctional metal complexating and its mode of polymerization upon addition of Cu+.
Based on miscellaneous interactionsBased on miscellaneous interactions
Characteristics of the Supramoleculars 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 scalesEnvironmental responsive The noncovalent interactions are sensitive to environment change, such as solvent,
temperature, pH, etc.
Characterization of the Supramolecular
Characterization of the SupramolecularCharacterization 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
SPM: SPM: Scanning Probe MicroscopyScanning Probe Microscopy 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
Detector and Detector and feedback feedback electronicselectronics
Detector and Detector and feedback feedback electronicselectronics
PhotodiodePhotodiode
LaserLaser
Sample SurfaceSample Surface
CantileverCantilever& Tip& Tip
PZT ScannerPZT Scanner
MicroscopyMicroscopy
a) POM (polarizing optical microscopy); b) SEM (Scanning electron microscope);
c) TEM (Transmission Electron Microscope); d) AFM
Investigating the assembly morphology of the supramolecular
11H-NMRH-NMR
MALDI-TOF-MSMALDI-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.
MALDI-TOF-MS SpectrumMALDI-TOF-MS Spectrum
Application of the Supramolecular
Application of the SupramolecularApplication 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
Preparation of copolymerPreparation of copolymer
Angew. Chem., Intl. Ed. 2004, 43, 6471.
Yang, X. W.; Hua, F. J.; Yamato, K.; Ruckenstein, E.; Gong, B.; Kim, W.; Ryu, C. Y.
NanotubeNanotube
Leibler, L. Nature, 2008, 51, 977–980Aida, T. Nature, 2008, 451, 895–896
Cut Contact for 180 min
Recovery of initial strength
Self-healingSelf-healing