nanoparticles - Carbon Nanotubes and Graphene

Lecture 6: Carbon Nanotubes and Graphene

Overview of Nanoparticles in Biomedicine

  • Types of Nanoparticles:
      - Organic Nanomedicines:
        - Liposome
        - Carbon Nanotube
        - Polymer-based nanoparticles
      - Inorganic Nanomedicines:
        - Gold Nanoparticle
        - Iron Oxide Nanoparticle
        - Quantum Dots
        - Nonporous Silica Nanoparticle

  • Conjugates:
      - Drug-Polymer Conjugate
      - Protein-Polymer Conjugate
      - Dendrimers
      - Micelles
      - Hollow/Porous Nanoparticles

  • Applications:
      - Chemotherapeutic or diagnostic probes
      - References: Tang L, Cheng J (2013) Nonporous Silica Nanoparticles for Nanomedicine Application. Nano Today.

Carbon Nanotubes (CNTs)

Definition and Characteristics
  • What are Carbon Nanotubes?
      - Long, thin cylinders of carbon discovered by Japanese scientist S. Iijima in 1991.
      - Unique properties include:
        - High electrical conductivity, up to 100 times more conductive than copper over distances around a micron.
        - Thermal conductivity that matches diamond.
        - Very high melting temperature (~3600 °C).
        - Chemically inert but can be functionalized to modify characteristics.
        - Approximately 100 times stronger than steel.

  • Types of Carbon Nanotubes:
      - Single-Wall Carbon Nanotubes (SWCNTs):
        - Composed of a single layer of graphene.
        - Require a catalyst for synthesis.
        - Bulk synthesis is difficult.
        - Higher defects during functionalization.
        - Purity is generally poor.
        - Less accumulation in the body, easier characterization.
        - Twisting is easy.
      - Multi-Wall Carbon Nanotubes (MWCNTs):
        - Composed of multiple layers of graphene.
        - Can be produced without a catalyst.
        - Bulk synthesis is easier.
        - Fewer defects, difficult to improve purity.
        - More accumulation in the body, difficult characterization and evaluation.
        - Difficult to twist.

Functionalization of Carbon Nanotubes
  • Methods:   - Non-covalent functionalization:
        - Proteins anchored on the surface using pyrene π–π stacking.
          - Visual example: Transmission Electron Microscopy (TEM) image of SWNT conjugated with proteins.
        - Single-stranded DNA can coat SWNTs via similar π–π stacking.
        - SWNT functionalized with PEGylated phospholipids, using both linear and branched PEG.

  • π–π stacking:
      - Noncovalent attractive force between two aromatic rings due to electrostatic interactions.

Applications in Biomedicine
  • Main applications include:
      - Dispersion & Surface Coating: Enhances material stability in biological systems.
      - Composite Materials: Improves mechanical and physical properties.
      - In Vivo Imaging: Offers visual cues in biological systems.
      - Drug & Gene Delivery: Facilitates the transfer of therapeutic agents to target sites.
      - Hyperthermia Treatment: Utilizes near-infrared radiation (NIR) for heat-based therapies.
      - Tissue Engineering: Acts as growth substrates and scaffolds for cells.
      - Examples from literature: Elena Heister et al. (2013) ACS Appl. Mater. Interfaces 5(6): pp. 1870-1891.

Challenges with Carbon Nanotubes
  • Production Issues:
      - Limited control over growth and connections between nanotubes.

  • High Cost:
      - Market pricing poses barriers to widespread use.

  • Manipulation Difficulties:
      - Challenges arise due to insolubility in many solvents.

  • Efficacy Concerns:
      - Uncertain advantages over established therapies.

  • Risks:
      - Potential for long-term accumulation and toxicity associated with structural similarities to asbestos fibers.
      - Long-term deposits may result in side effects.

Graphene

Definition and Characteristics
  • What is Graphene?
      - A single atom-thick sheet of carbon atoms arranged in a honeycomb lattice structure.

  • Unique Properties:
      - Enhanced electrical conductivity.
      - High mechanical strength and thermal conductivity.
      - High impermeability to gases and optical transparency.

  • Historical Context:
      - First isolated in 2004; Nobel Prize awarded in Physics to Geim and Novoselov in 2010.

Synthesis of Graphene
  • Key Intermediates:
      - Graphite oxide significantly facilitates production, primarily via oxidative treatment that increases interlayer distances.
      - Top-down synthesis allows for large-scale production through exfoliation of graphite sheets.

Functionalization of Graphene
  • Target Functionalizations Include:**
      - Biotin-avidin interactions, nucleic acids, proteins, peptides, small molecules, and bacteria through both physical and chemical conjugation.

  • Report Link: Trends in Biotechnology, Volume 29, Issue 5 (2011).

Applications in Biomedicine
  • Overview of Applications:
      - Drug and gene delivery.
      - Cancer therapies.
      - Biosensing and bioimaging capabilities.
      - Graphene oxide (GO)-based antibacterial materials and scaffolds for cell culture.

  • Reference: Sheng-Tao Yang et al. (2012) for pharmacokinetics, metabolism, and toxicity investigations.

Comparison of Graphene and Carbon Nanotubes
  1. Surface Area:
       - Graphene sheets have a larger surface area compared to single-walled carbon nanotubes (SWCNTs).

  2. Efficacy in Tumor Targeting:
       - 2D graphene has a more effective passive tumor target compared to 1D SWCNTs.

  3. Complexity in Functionalization:
       - 2D graphene sheets allow for easy complexation with various nanoparticles, unlike 1D nanotubes, which have complex modifications.

  4. Biosensing:
       - Graphene devices showcase better reproducibility compared to those made from SWCNTs due to uniform structural characteristics.

Future Perspectives and Considerations
  • Variability in Properties:
      - Different forms and modifications of graphene yield various biological effects.

  • Toxicology Paradigms:
      - Graphene's flat structure might not trigger adverse inflammatory responses similar to fibrous materials like asbestos, but research is ongoing regarding biodegradability and toxicity.

  • Biodegradability Evidence:
      - Some graphene types may be enzymatically degraded through specific biological processes.