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ASSIGNMENT
MOLECULAR IMPRINTING
ANISHA
INT.MTECH, 9th sem
DEFINITIONS
Molecular
imprinting
Molecularly
imprinted
polymer (MIP
)
Molecular imprinting is a technique to create
template-shaped cavities in polymer
matrices with predetermined selectivity and
high affinity. This technique is based on the
system used by enzymes for substrate
recognition, which is called the "lock and key"
model
MIP
A molecularly imprinted polymer (MIP) is a polymer that has been
processed using the molecular imprinting technique which leaves cavities
in the polymer matrix with an affinity for a chosen "template" molecule.
HISTORY & CONCEPT
▪ Allows tailor-made polymeric materials to be
obtained with memory.
▪ 1940: Emerged from Linus Pauling's theory about the
formation of antibodies
▪ It states that;
“Antigen molecules act as templates around
which serum proteins assemble to form antibodies”
▪ In molecular imprinting method, the imprint molecule (template) is
added along with functional monomer and high proportions of cross-
linker, which are polymerized under appropriate conditions.
▪ During the reaction, polymeric chains self-organize around the
imprint molecules through functional group interactions.
▪ The imprint molecules can be removed or washed from the polymer
matrix, which results in the development of highly adapted binding
pockets with a complementary geometrical and chemical fitting
structure.
▪ These pockets are capable of reversibly interacting with target
molecules.
▪ The high percentage of cross-linker provides the necessary stability
to polymer chains that are not collapsed after template release.
PRINCIPLE OF MOLECULAR IMPRINTING
❑ Approach by Pauling's disciple Dickey
❑ Sidney Bernhard
❑ Günter Wulff's research group 1972
❑ Shea and Thompson in 1978
❑ Noncovalent approach by Klaus
Mosbach et al. in 1988.
M.E. Díaz-GarcíaA. Fernández-González, in Encyclopedia of Analytical
Science (Second Edition), 2005
Adnan Mujahid, Franz L. Dickert, in Molecularly Imprinted
Catalysts 2016
COMPONENTS
O A number of catalytic
molecularly imprinted
polymers (MIPs) have
been developed in
recent years for
mimicking different
types of natural
enzymes, such as
carboxypeptidase A,
aldolase, peroxidase,
lipase, and
phosphotriesterase.
O Template molecules
can be metal ions,
complex, organic
molecules, amino
acids and their
derivatives, proteins,
etc
Non-covalent
Covalent
Ionic/Metallic
▪ TYPES OF MOLECULAR
IMPRINTING
▪ Covalent
The template molecule is covalently bonded to the functional monomers that
are then polymerized together.
STEPS INVOLVED IN MOLECULAR IMPRINTING
⮚ After polymerization, the polymer matrix cleaved from the template
molecule, leavE a cavity shaped called template.
⮚ During rebinding with the original molecule binding sites interacts with the
target molecule and reestablis the covalent bonds.
⮚ During this reestablishment, kinetics associated with bond binding and bond
breakage are obtained back.
⮚ The imprinted molecule is then released from the template, in which it
would then rebind with the target molecule, forming the same covalent
bonds that were formed before polymerization.
Shah, Nasrullah (2012). "A Brief Overview of Molecularly Imprinted
Polymers: From Basics to Applications". Journal of Pharmacy
Research. 5: 3309
Non covalent
Interaction forces between template molecule and functional
monomer are same as the interaction forces between the polymer
matrix and analyte.
FORCES
1. Hydrogen bonds
2. Dipole dipole interactions
3. Induced dipole
forces
Ionic/Metallic
Involves metal ions to enhance template
molecule and functional monomer
interaction in water.
⮚ Metal ions are mediator .
⮚ Cross-linking polymers form a matrix that
is capable of metal binding
Two main strategies employed for MIP
technology
O Self-assembling
approach
O Uses non-covalent
forces, hydrogen
bonds, van der
waals forces, ion or
hydrophobic
interaction and
metal-
coordinations;
O Preorganized
approach
O Covalent reversible
bonds and reducing
the non-specific
sites.
O To remove the
template from the
polymer matrix, it is
necessary to cleave
the covalent bounds.
❑ FACTORS AFFECTING THE MOLECULAR
IMPRINTING:
❑Template
❑ Functional monomer
❑Cross-linking monomers
❑Solvent/ Porogen
❑Initiator
❑ Temperature
APPLICATIONS
⮚ Affinity-based separations for biomedical, environmental,
and food analysis.
⮚ Use of molecularly imprinted materials as chemical and
biological sensors.
⮚ In fluorescence sensing, electrochemical sensing,
chemiluminescence sensing, and UV-visible sensing.
⮚ Drug delivery and biotechnology.
⮚ Pharmaceutical applications include selective drug delivery
and control drug release systems
⮚ In catalysis and solid phase extraction
⮚ MIPs in Separation Techniques
MIP for Solid-phase extraction
MOLECULAR IMPRINTING
O ADVANTAGES
O High selectivity and
affinity for the target
O Protein biomarker
detection
O high sensitivity and
selectivity of fluorescence
detection
O Selective adsorption, strong
affinity, simple preparation
O High physical resistance
O DISADVANTAGES
O Difficulty in the
accessibility of the binding
site sculpt in the three
dimensional polymer
networks
O Trapped template slowly
leaching out
O Poor mass transport
O Heterogeneity in binding
affinities
https://www.researchgate.net/figure/Advantages-and-disadvantages-of-
polymerization-methods-for-MIP-synthesis_tbl2_323254620
▪ https://doi.org/10.1002/jssc.201800945
▪ https://en.wikipedia.org/wiki/Molecular_imprinting
▪ Wulff, G.; Sarhan, A. "The use of polymers with
enzyme-analogous structures for the resolution of
racemates". Angew. Chem. Int. (11): 341–346
▪ https://doi.org/10.1016/S0165-9936(98)00092-2
▪ https://www.researchgate.net/figure/Advantages-
and-disadvantages-of-polymerization-methods-for-
MIP-synthesis_tbl2_323254620
▪ WIKIPEDIA
REFERENCES
FROM: ANISHA

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MOLECULAR IMPRINTING TECHNIQUE

  • 3. Molecular imprinting is a technique to create template-shaped cavities in polymer matrices with predetermined selectivity and high affinity. This technique is based on the system used by enzymes for substrate recognition, which is called the "lock and key" model
  • 4. MIP A molecularly imprinted polymer (MIP) is a polymer that has been processed using the molecular imprinting technique which leaves cavities in the polymer matrix with an affinity for a chosen "template" molecule.
  • 5. HISTORY & CONCEPT ▪ Allows tailor-made polymeric materials to be obtained with memory. ▪ 1940: Emerged from Linus Pauling's theory about the formation of antibodies ▪ It states that; “Antigen molecules act as templates around which serum proteins assemble to form antibodies”
  • 6. ▪ In molecular imprinting method, the imprint molecule (template) is added along with functional monomer and high proportions of cross- linker, which are polymerized under appropriate conditions. ▪ During the reaction, polymeric chains self-organize around the imprint molecules through functional group interactions. ▪ The imprint molecules can be removed or washed from the polymer matrix, which results in the development of highly adapted binding pockets with a complementary geometrical and chemical fitting structure. ▪ These pockets are capable of reversibly interacting with target molecules. ▪ The high percentage of cross-linker provides the necessary stability to polymer chains that are not collapsed after template release. PRINCIPLE OF MOLECULAR IMPRINTING
  • 7. ❑ Approach by Pauling's disciple Dickey ❑ Sidney Bernhard ❑ Günter Wulff's research group 1972 ❑ Shea and Thompson in 1978 ❑ Noncovalent approach by Klaus Mosbach et al. in 1988. M.E. Díaz-GarcíaA. Fernández-González, in Encyclopedia of Analytical Science (Second Edition), 2005
  • 8. Adnan Mujahid, Franz L. Dickert, in Molecularly Imprinted Catalysts 2016
  • 9. COMPONENTS O A number of catalytic molecularly imprinted polymers (MIPs) have been developed in recent years for mimicking different types of natural enzymes, such as carboxypeptidase A, aldolase, peroxidase, lipase, and phosphotriesterase. O Template molecules can be metal ions, complex, organic molecules, amino acids and their derivatives, proteins, etc
  • 11. ▪ Covalent The template molecule is covalently bonded to the functional monomers that are then polymerized together. STEPS INVOLVED IN MOLECULAR IMPRINTING ⮚ After polymerization, the polymer matrix cleaved from the template molecule, leavE a cavity shaped called template. ⮚ During rebinding with the original molecule binding sites interacts with the target molecule and reestablis the covalent bonds. ⮚ During this reestablishment, kinetics associated with bond binding and bond breakage are obtained back. ⮚ The imprinted molecule is then released from the template, in which it would then rebind with the target molecule, forming the same covalent bonds that were formed before polymerization. Shah, Nasrullah (2012). "A Brief Overview of Molecularly Imprinted Polymers: From Basics to Applications". Journal of Pharmacy Research. 5: 3309
  • 12. Non covalent Interaction forces between template molecule and functional monomer are same as the interaction forces between the polymer matrix and analyte. FORCES 1. Hydrogen bonds 2. Dipole dipole interactions 3. Induced dipole forces
  • 13.
  • 14. Ionic/Metallic Involves metal ions to enhance template molecule and functional monomer interaction in water. ⮚ Metal ions are mediator . ⮚ Cross-linking polymers form a matrix that is capable of metal binding
  • 15.
  • 16.
  • 17. Two main strategies employed for MIP technology O Self-assembling approach O Uses non-covalent forces, hydrogen bonds, van der waals forces, ion or hydrophobic interaction and metal- coordinations; O Preorganized approach O Covalent reversible bonds and reducing the non-specific sites. O To remove the template from the polymer matrix, it is necessary to cleave the covalent bounds.
  • 18. ❑ FACTORS AFFECTING THE MOLECULAR IMPRINTING: ❑Template ❑ Functional monomer ❑Cross-linking monomers ❑Solvent/ Porogen ❑Initiator ❑ Temperature
  • 19. APPLICATIONS ⮚ Affinity-based separations for biomedical, environmental, and food analysis. ⮚ Use of molecularly imprinted materials as chemical and biological sensors. ⮚ In fluorescence sensing, electrochemical sensing, chemiluminescence sensing, and UV-visible sensing. ⮚ Drug delivery and biotechnology. ⮚ Pharmaceutical applications include selective drug delivery and control drug release systems ⮚ In catalysis and solid phase extraction ⮚ MIPs in Separation Techniques
  • 20. MIP for Solid-phase extraction
  • 21. MOLECULAR IMPRINTING O ADVANTAGES O High selectivity and affinity for the target O Protein biomarker detection O high sensitivity and selectivity of fluorescence detection O Selective adsorption, strong affinity, simple preparation O High physical resistance O DISADVANTAGES O Difficulty in the accessibility of the binding site sculpt in the three dimensional polymer networks O Trapped template slowly leaching out O Poor mass transport O Heterogeneity in binding affinities
  • 23. ▪ https://doi.org/10.1002/jssc.201800945 ▪ https://en.wikipedia.org/wiki/Molecular_imprinting ▪ Wulff, G.; Sarhan, A. "The use of polymers with enzyme-analogous structures for the resolution of racemates". Angew. Chem. Int. (11): 341–346 ▪ https://doi.org/10.1016/S0165-9936(98)00092-2 ▪ https://www.researchgate.net/figure/Advantages- and-disadvantages-of-polymerization-methods-for- MIP-synthesis_tbl2_323254620 ▪ WIKIPEDIA REFERENCES