Colloids 4 (stability of colloids) Flashcards

1
Q

Brownian motion of colloidal particles lead to?

A

> Permanent contact of particles: coagulation.

  • Eventually large aggregates can be formed and sedimentation occurs.

> Temporary contact of particles: flocculation.

  • Particles remain a small distance apart in an open structure. They may rebound and remain freely dispersed.
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2
Q

Define the following terms

A) Aggregation

B) Coagulation

C) Flocculation

A

A)

  • Aggregation: collection of particles into groups.

B)

  • Coagulation: particles are closely aggregated and impossible to redisperse.

C)

  • Flocculation: particles are loosely grouped. Aggregates have an open structure in which the particles remain a small distance apart from each other.
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3
Q

What are some forces that influence the stability against coagulation or flocculation? (dependent on the interaction between particles)

A
  • Van der Waals’ forces or electromagnetic forces of attraction
  • Electrostatic forces of repulsion (zeta potential)
  • Forces arising from solvation (ie particle-solvent affinity)
  • Steric forces (geometry & conformation of molecules at particle surface).
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4
Q

How to stabilize lyophobic colloids?

A

Only stabilised by electrostatic repulsion

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5
Q

How does repulsion arise in colloidal systems?

A
  1. Osmotic effect produced by the increased number of charged species on the overlap of the diffuse regions of EDLs (electrical double layers) of two particles;

> The like charges on the surface of particles (charged particles repel each other)

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6
Q

How does attraction arise in colloidal systems?

A
  • Van der Waals’ forces
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7
Q

Provide a diagram of a potential energy curve and describe its properties

A
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8
Q

Provide a diagram of a potential energy curve and describe its properties (continue)

A
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9
Q

What does the size of Vmax (primary maximum) depend on? What does reduction of Vmax lead to?

A

Depends on zeta potential which itself is dependent on”

  • Ψ0 (Nernst potential)
  • Electrolyte concentration (which affects length of EDL on magnitude of ζ)

Reduction of Vmax ultimately leads to instability and coagulation of hydrophobic colloid

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10
Q

What is done to achieve controlled flocculation?

A

Addition of electrolytes to compress the EDL and reduce the zeta potential: lowers the primary maximum (Vmax) and deepens the secondary minimum, resulting in an increased tendency for particles to flocculate in the secondary minimum (in suspensions more so)

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11
Q

What does the specific adsoprtion of ionic surfctants lead to?

A

Reduced zeta potential but does not compress the electric double layer

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12
Q

How are lyophobic colloids stabilised? What are they very sensitive to?

A

Lyophobic colloids are stabilized entirely by electric charges on their surfaces.

Very sensitive to added electrolytes

  • Schulze-Hardy Rule: For ions having charge opposite to that of particles, the precipitation (coagulation) power increases rapidly with the valence or charge of the ions.
  • Al+++> Ca++> Na+ (0.13 : 1.6 : 100)
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13
Q

How does concentration of electrolytes affect zeta potential

A

At a particular concentration, accumulation of counter-ions reduces zeta potential below its critical value (decreases Vmax), resulting in aggregation.

Mixing of oppositely charged colloidal particles –> mutual precipitation

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14
Q

How are lyophilic colloids stabilized? Is it affected by adding electrolytes?

A

Stabilized by the combination of electrical double layer interaction and solvation

  • Unaffected by a small amount of added electrolytes; When conc. of electrolytes is high, salting out occurs.
  • “Salting out” effect: Colloidal material loses its water of solvation to those electrolytes or ions which have strong hydration capacity/power, resulting in coacervation.
  • Lyotropic series: order of increasing hydration eg Cs+ < Rb+ < NH4+ < Na+ < Li+
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15
Q

What is coacervation? What are some applications of coacervation in pharmaceutical formulation?

A

Coacervation: the separation of lyophilic colloid into two liquid layers (one is rich in colloidal aggregates) on the addition of another substance.

  • The bottom layer is a colloid-rich layer - known as coacervate. The upper layer is colloid-poor with low viscosity
  • Coacervation indicates the physical incompatibility of colloid with added substance.
  • Coacervation can be induced by the addition of electrolytes, non-solvent or oppositely charged lyophilic colloids.

Application of coacervation in pharmaceutical formulation (deliberate):

  • Microencapsulation
  • Gelation
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16
Q

Mixing hydrophilic colloids with solvents such as acetone and alcohol turns hydrophilic colloids into lyophobic colloids. What effect will have this on the sensitivity of the hydrophilic colloid to electrolytes?

A

Would become more sensitive. Wouldnt have solvation protecting it anymore and makes it unstable in the presence of electrolytes. Accumulation of ions and decreases zeta potential which will cause coagulation and precipitation of colloids.

17
Q

What is the effect of adding hydrophilic macromolecular material to lyophobic colloidal systems? Provide some examples and applications.

A
  1. moderate amounts of polyelectrolyte or polymer are added, a structured floc forms.

Application: removal of colloidal materials, water purification

  1. When large amounts of polymer (enough to cover the surface of particles) are added, lyophobic colloids will be stabilized by steric stabilization or protective colloid effect.

Particles with adsorbed polymers:

  • steric interaction & osmotic effect –> repulsion.
  • two particles do not approach each other closer than twice the thickness of the adsorbed layer –> no primary minimum (ie no strong attractive forces)
  • Modified DLVO theory: VT= VA+VR +Vs (Vs: potential energy for steric stabilisation)
18
Q

What is the equation for free energy changes during the interaction between two particles covered with polymers?

A

ΔG = ΔH - TΔS : Gibbs-Helmholtz equation (2nd law of thermodynamics)

  • ΔG : change of free energy
  • ΔH: change of enthalpy (heat absorbed or released during an interaction)
  • ΔS: change of entropy (change in the randomness or disorder)

> ΔG negative: indicating that particles have aggregated.

> ΔG positive: particles are dispersed

  • When both ΔH & ΔS are negative and TΔS > ΔH. ΔG is positive, dispersion is stable – entropic stabilization (entropic stabilization occurs in non-aqueous dispersion). As polymer strands start to interlock, entropy would be reduced (become more ordered) –> particles remain separated as ΔG is positive.
  • When both ΔH & ΔS are positive and ΔH >TΔS. ΔG is positive, dispersion is stable – enthalpic stabilization (enthalpic stabilization is common with aqueous dispersion). Eg paticles stabilised with polyoxyethylene chains.
19
Q

Describe how enthalpic stabilization is used to stabilize particles in polyoxyethylene chains (aquoeus dispersion)?

A

See attached image

20
Q

What does the steric effect depend on?

A
  • The hydrophilic polymer chain length
  • The interaction of the solvent with the chain
  • The number of chains per unit area of interaction surface
21
Q

How can the stability of colloids be controlled?

A
  • Charge properties of colloidal particles
  • pH and ionic condition of liquid
  • Steric effects (attaching polymers or surfactants to particles)
22
Q

What are some pharmaceutical applications of colloidal systems?

A
  1. Fat emulsions – micro or nanoemulsion (eg Intralipid)

> O/W emulsion of fatty acids with droplets in the range of 0.3-0.5μm

> Lyophobic colloid

>Parenteral nutrition

  1. Technetium (99mTc) Colloidal Sulphur Injection Ph. Eur. Radioactive Tc-labelled sulfur colloid for medical imaging. This is a hydrophobic colloid, stabilised by

> Buffers may contribute to the potential instability of colloids by forming insoluble salts with metallic ions. eg. phosphate buffers

> Insoluble phosphate salt precipitates from a colloidal dispersion. This may co-precipitate the colloidal particles

> Use chelating agents or use non-phosphate buffers.

  1. Blood substitutes and plasma expanders

> For replacing and maintaining blood volume

> Colloids: dextran, gelatin and starch derivatives

  • Retained in blood vessels because of large size
  • colloidal osmotic effect – draws water into vessels (higher MW dextrans)
  • Enhancing blood flow by inhibiting aggregation of red blood cells (low MW dextrans), ie via coating of red blood cells

Advantage: low viscosity, reduce risk of transmission of infection

Disadvantage: risk of hypersensitivity reactions and high cost (dextran 40)

  1. Stabilizing, suspending and gelling agents

> lyophilic and lyophobic colloids

> increasing viscosity of the solution when dissolved or dispersed

> Lyophilic colloids: acacia, sodium alginate hydroxyethylcellulose (artificial tears)

> “Lyophobic” colloids: Bentonite

> Therapeutic example: alginic acid and sodium alginate

23
Q

What are some examples of mucilages and gels? How are they used in the real world? (lyophilic colloids)

A
  • Calcium or sodium alginates are used in wound dressings –Ca Alg swells and Na Alg dissolves or gels in the wound bed. Both highly absorbent (20 times their weight) and calcium alginate has haemostatic properties.

> Used for wounds with moderate or heavy exudate. The alginate dressing and fluid from the wound forms a gel on the wound surface – easy to remove. Haemostasis: can be used to stop bleeding. Some contain silver compound - antimicrobial protection for infection prone wound

  • Artificial tears (preparations contain carboxymethyl cellulose, polyvinyl alcohol, hydroxypropyl methylcellulose (aka. HPMC or hypromellose), hydroxypropyl cellulose and hyaluronic acid (aka. hyaluronan, HA)
  • Gels (gaviscon dual action). Viscous gel of Alginic acid is formed on contact with gastric acid, CO2 is produced by a reaction between acid and bicarbonate –> entrapment in gel and gel floats. Gel strengthened by calcium ions.