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Questions and Answers
Which of these options is the MOST likely reason to modify a biomaterial surface?
Which of these options is the MOST likely reason to modify a biomaterial surface?
What is a primary concern when considering physical adsorption for modifying biomaterial surfaces?
What is a primary concern when considering physical adsorption for modifying biomaterial surfaces?
Which of the following best describes the mechanism of a self-assembled monolayer (SAM) when employed for surface passivation?
Which of the following best describes the mechanism of a self-assembled monolayer (SAM) when employed for surface passivation?
If bioinspired functionalization is used, its main strategy is to copy a mechanism which could be commonly found where?
If bioinspired functionalization is used, its main strategy is to copy a mechanism which could be commonly found where?
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Which of the following strategies is primarily aimed at preventing unwanted protein adsorption on a biomaterial surface?
Which of the following strategies is primarily aimed at preventing unwanted protein adsorption on a biomaterial surface?
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What property primarily contributes to the passivating characteristics of supported lipid bilayers (SLB)?
What property primarily contributes to the passivating characteristics of supported lipid bilayers (SLB)?
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Which option describes a method used for bioactive surface functionalization?
Which option describes a method used for bioactive surface functionalization?
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Which condition is essential for maintaining the lateral mobility of lipids in a supported lipid bilayer?
Which condition is essential for maintaining the lateral mobility of lipids in a supported lipid bilayer?
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What factor does NOT contribute to the stability of self-assembled monolayers (SAM)?
What factor does NOT contribute to the stability of self-assembled monolayers (SAM)?
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In the context of self-assembled monolayers (SAM), which characteristic allows for compatibility with patterning methods?
In the context of self-assembled monolayers (SAM), which characteristic allows for compatibility with patterning methods?
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What is a major disadvantage of the covalent coupling of biomolecules to materials?
What is a major disadvantage of the covalent coupling of biomolecules to materials?
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Which functional group is NOT mentioned as relevant in bioconjugation chemistry?
Which functional group is NOT mentioned as relevant in bioconjugation chemistry?
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Which method is used to create reactive groups on surfaces?
Which method is used to create reactive groups on surfaces?
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What is a characteristic of silanization in biomaterials?
What is a characteristic of silanization in biomaterials?
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Which of the following is a drawback of covalent immobilization of biomolecules?
Which of the following is a drawback of covalent immobilization of biomolecules?
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Which characteristic is associated with ideal non-fouling, biopassive surfaces?
Which characteristic is associated with ideal non-fouling, biopassive surfaces?
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What effect does surface passivation have on protein adsorption?
What effect does surface passivation have on protein adsorption?
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Which method is NOT typically used for achieving anti-fouling surfaces?
Which method is NOT typically used for achieving anti-fouling surfaces?
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How can entropic penalties be added to surfaces to discourage protein adsorption?
How can entropic penalties be added to surfaces to discourage protein adsorption?
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What common feature do hydrogels possess that contributes to their non-fouling characteristics?
What common feature do hydrogels possess that contributes to their non-fouling characteristics?
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Study Notes
Biocompatible Materials - Surface Modification
- Course: 376-1714-00L, Biocompatible Materials
- Date: 13.11.2024
- Lecturer: Prof. Dr. Katharina Maniura, Empa
Teaching Objectives
- Students will learn different techniques to control biomolecule/protein adsorption to biomaterials.
- Students will understand the advantages and disadvantages of physical adsorption compared to covalent protein coupling.
- Students will be able to identify various chemical pathways and functional groups for biomolecule conjugation.
- Students will grasp the basic degradation mechanisms of biomaterial surface coatings.
Surface Modifications - Key Parameters
- Density: Crucial for the amount of biomolecules or proteins on the surface.
- Stability: The longevity of biomolecule adhesion on the surface.
- Specificity: The selectivity of biomolecule interactions with the surface.
- Activity: The biological activity of the adsorbed biomolecules.
- Chemical Binding: Defines the specificity of interactions with biomolecules.
- Physical Adsorption: Defines the specific response of implanted materials (e.g., tissue growth).
Bioactive Surface Functionalization
- Physical Adsorption: Includes the diffusion, adsorption, and adhesion processes of biomolecules.
- Chemical Conjugation: Combining biomolecules to the surface via chemical reactions, like forming covalent bonds.
- Bioinspired Functionalization: Mimicking natural systems (e.g., biological surfaces) to adjust surface properties for specific biomolecule interactions.
Passivation: Anti-fouling Surfaces
- Self-assembled Monolayers (SAMs): Organized molecular layers forming on surfaces.
- Supported Lipid Bilayers (SLBs): Mimic cell membranes with two lipid layers.
- Polymer Brushes: Polymer chains extending from the surface.
Stability and Degradability
- Surface stability is a key factor in biomaterial design.
- Degradation of surfaces can be passive (e.g., water-induced cleavage) or active (e.g., biological processes).
- Control over degradation can be achieved by introducing cleavable bonds.
Physical Adsorption of Biomolecules - Electrostatic Interactions
- Electrostatic interactions are influenced by introducing charges to surfaces (e.g., plasma treatment).
- Oxidizing agents (e.g., Piranha solution) modify surfaces (e.g., hydroxylating them).
- Plasma treatment acts as a "molecular sandblast".
- Reactions involving radicals are key.
- Surfaces become more hydrophilic.
Physical Adsorption of Biomolecules - Types of Interactions
- Relevant interactions are:
- Hydrophobic interactions.
- Electrostatic/Coulomb interactions.
- Van der Waals interactions.
- π−π interactions.
- Ion bridging.
Control of Physical Adsorption
- Electrostatic Interactions: Introducing charges to the surface (e.g., plasma treatment).
- Hydrophobic Interactions: Modifying materials to become hydrophobic or adjusting the entropic interactions between biomolecules and water.
- Affinity Recognition: Adding relevant end groups (e.g., biotin-streptavidin) to allow for specific binding and recognition.
Physical Adsorption - Plasma Treatment
- Plasma is a partially ionized gas at high temperatures.
- It creates a means for surface modification via ionization of gas atoms as "molecular sandblast".
- Molecular processes are triggered at the surface including bond-breaking and activation/chemical reaction.
- Surfaces become more energetic and charged (increasing hydrophilicity).
Physical Adsorption - Electrostatic Interactions
-
Coating with a charged polymer (e.g., Poly-L-Lysine):
- A polymer comprised of repeating amino acid units is used.
- Positively charged amino groups bind to negatively charged residues.
- The surface is modified and made more attractive to negatively charged molecules.
Control of Physical Adsorption - Summary
- Electrostatic interactions are affected by introducing charges using various methods like plasma treatment or applying charged molecules.
- Hydrophobic interactions can be manipulated by altering hydrophobicity or regulating protein mobility.
- Affinity recognition leverages specific interactions (such as biotin-streptavidin) to target bonding.
Limitations of Physical Adsorption
- Stability: Interactions are typically weak and reversible.
- Specificity: Different molecules can adsorb depending on the surrounding environment (e.g., different solutions).
- Activity: The orientation of adsorbed biomolecules is frequently random.
- Enhanced control via covalent conjugation of biomolecules is necessary as this allows controlled orientation and better stability.
Covalent Coupling of Biomolecules
- Advantages:
- Stable and specific immobilization.
- Applicable to small molecules.
- Controlled orientation is feasible.
- Disadvantages:
- Requires specific functional groups on both surfaces.
- Can be more expensive with lower throughput.
(Bio-)Conjugation Chemistry - Functional Groups
- Hydroxyl (OH): Polar, hydrophilic.
- Amino (NH₂): Polar, basic.
- Carbonyl (CO, CHO): Polar, can be acidic.
- Carboxyl (COOH): Polar, acidic.
- Thiol (SH): Polar.
- Phosphate (PO₄): Polar, acidic, charged.
- Vinyl (CH₂CH): Hydrophobic or hydrophilic depending on the attached groups.
Methods to Create Reactive Groups on Surfaces
- Ionizing Radiation
- Plasma Activation
- Photochemistry
- Ozone Grafting
- Chemical Derivatization
- Polymeric Adlayers (e.g., PLL)
- CVD/PVD
- Silanization
Silanization of Biomaterials
- Coupling of silanes to hydroxylated surfaces is common.
- Common substrates are rich in hydroxyl groups (e.g., glass, silica, PDMS, etc.).
- Various silane linkers allow diverse functionalities.
- The process is straightforward, fast, and cost-effective.
Surface Coupling of Biomolecules Using a Spacer
- Bioreactive end groups are crucial for coupling to surfaces.
- Covalent bonding enables attachment.
- Advantages include: steric freedom, accessibility, modularity, and tunable degradability.
- PEG linkers (of varying lengths) are typical spacers.
Comparison of Surface Immobilization Strategies
- Physical Adsorption: Simpler, but less stable, weaker and unspecific binding. Lower cost.
- Chemical Bonding: More complex, stronger and specific binding. Higher cost.
Example: Albumin
- Illustrates both physical adsorption (hydrophobic, electrostatic interactions) and covalent tethering methods.
Bioinspired Strategies: Using Attraction
- Mimicking nacre (mother-of-pearl) for creating 3D structures via alternating deposition of layers.
Bioinspired Strategies: Mussel Adhesion and DOPA
- Shows bioinspired strategies employing natural adhesive mechanisms like mussel adhesion and dopamine-based (DOPA) materials to attach different surfaces.
Surface Passivation - Facts
- Ideal non-fouling surfaces resist protein adsorption.
- Low protein adsorption leads to reduced cell adhesion on the surface.
- Hydrogels are generally non-fouling while hydrophobic surfaces are prone to fouling.
- Non-fouling surfaces typically have strong water interactions that shield surface charges.
How to Avoid Protein Adsorption
- Reduce enthalpic interactions (electrostatic, van der Waals, ionic).
- Add an entropic penalty to the surface (e.g., using hydrophobic interactions).
Summary on Surface Passivation
- Crucial to consider enthalpic and entropic contributions to bioadhesion and interaction with a solvent.
- PEG is a prime example of an anti-fouling polymer.
- Self-assembled monolayers (SAMs) are a popular technique for controlling molecular organization and chemical properties on surfaces.
- Supported lipid bilayers (SLBs) mimic cell membranes and provide anti-fouling properties.
- Polymer brushes offer a readily-tunable technique with versatile functionality.
Stability of Functionalized Surfaces
- Passive: Typically involves desorption (e.g. water-induced cleavage).
- Active: Includes cellular adhesion, and enzymatic degradation of bonds on the surface.
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Description
Test your knowledge on biomaterial surface modification techniques. This quiz covers topics such as self-assembled monolayers, physical adsorption, and bioinspired functionalization strategies. Explore the mechanisms and properties that influence the interaction of biomaterials with their environment.