Intro to Oral Solids
How do we choose between so many choices of the same drug product?
Tune the release kinetics (input) to target a certain pharmacokinetic profile
Modify the release (input kinetics) to tailor the plasma concentration vs time profile (pharmacokinetics) for a specific effect
Kinetic barriers to drug absorption for oral solids
Processes of disintegration and dissolution are kinetic processes that affect how long it takes for the drug molecule to enter the blood circulation
These kinetics processes directly influence the pharmacokinetics of a drug
Mainly concerned with
How quickly a pharmacological effect is initiated
For how long is the pharmacological effect maintained (affects dosing frequency)
Both solubility and permeability affect tmax
This is one reason why BCS classification system is built on interplay of these two properties
Modifying the surface area term
Size of particles can be reduced through milling
Caveat
Absorption is influenced by 2 kinetic properties: dissolution and permeation
IF absorption is permeation-limited, strategies to enhance dissolution rate (particle size reduction) will not provide a significant improvement in bioavailability
IF the dissolution is rate-limiting, particle size reduction can improve bioavailability
Modifying the solubility term
Beginning with the "solid" in oral solids, there are a variety if forms or solids phases that may be selected for the active pharmaceutical ingredient (API)
Everything in a drug product is deliberately included (from API to secondary packaging)
Selecting the appropriate solid form, main considerations are:
Solubility
Stability
Processability
Crystalline solids
Unique property of crystalline solids is periodicity
One building block (unit cell) may be repeated in space (3-dimensions) to create the entire solid
Polymorphism
Changing the arrangement yields a different polymorph, and changes directly the physical properties of the solid drug: dissolution, compaction, kinetics, bioavailability, etc.
Its not the chemical identity that's changing, it's the crystalline structure and the intermolecular interactions
Controlling polymorphism is a multi-billion-dollar challenge to the pharmaceutical industry
Solubility of different polymorphic forms
Since intermolecular interactions are different in different polymorphic forms of a solid, they typically have different solubility values
Why?
For a solid crystal to be soluble --> lattice needs to be broken apart
Energy required to break the lattice apart is different for different polymorphs, which translates into different solubility values
Stability of different polymorphic forms
By convention, stabilizing energies are represented as a negative value
A more stable lattice (think stronger intermolecular interactions) has a more negative lattice energy
From solubility perspective, that means the more stable a polymorph, the more energy you have to put in to break the lattice apart
More stable = less soluble
More stable lattice = higher melting point = less soluble
Amorphous Form
Amorphous is a unique solid form that has no long-range order
No periodicity
This is a notoriously unstable (high energy) solid form
Less stable than the most unstable crystalline polymorph
However, the "advantage" of being so unstable is that amorphous materials can display a significant solubility advantage
Amorphous solids
An amorphous form could be prepared from a crystalline drug through different techniques
Milling
Primarily used to reduce particle size, but during the process you introduce defects (imperfections) in a crystal
Continue to add more and more defects, you reduce the long-range order to the point you get an amorphous
Stability is the main drawback to formulating amorphous solids (hygroscopicity concern)
Melting/quench cooling
Crystalline solids can be heated above their melting points and quickly quenched and cooled
Example of amorphous solid prepared via melt/cool method:
Glass (quartz sand heated to >3090F) and cooled
Amorphous solid dispersion
Role of the polymer
Stabilize the amorphous drug during storage
Prevents conversion back to crystal form
Stabilize the amorphous drug in solution to maintain the solubility advantage
Enhance the drug dissolution rate during dissolution
Related to bioavailability
Marketed amorphous solid dispersion products
Prior to 2005, there were a few ASDs but they have continued to emerge at a faster rate, in part because many emerging drug candidates are a BCS II or IV
This trend is going to continue as more drugs in the development pipeline have more aqueous solubility
Co-crystal
Been around for 100 years but only recently have demonstrated significant working potential
Co-crystal - a solid that is crystalline single-phase material composed of two or more different molecular ionic compounds in a stoichiometric ratio which is neither a solvate or simple salt WORKING DEFINITION
To be considered a co-crystal
Components (API and co-former(s)) are in a fixed stoichiometric ratio (1:1, 1:2, 1:2:1)
API and co-former(s) are separately solids at room temperature
This is what distinguishes a co-crystal from a solvate
Benefit of co-crystals is that even the most stable phase can still display a 1000x solubility advantage
Limitation is what co-former you choose
To improve solubility, one hypothesis is to use a water soluble co-former
We're re-arranging the intermolecular interactions (like polymorphs or amorphous forms), but now also introducing another species
Heat of solvation may be affected too
Higher co-former solubility = higher co-crystal solubility (relative to pure drug)
Marketed co-crystal products
Lexapro
Escitalopram + oxalic acid
Approved: 2002
Indication: major depression and anxiety
Entresto
Sucabitril + valsartan
Approved: 2015
Indication: heart failure
Steglatro
Ertugliflozin + L-pyroglutamic acid
Approved: 2017
Indication: type 2 diabetes
Drug product quality control
A consistent theme in FPS is drug product design and ensuring the product manufactured is:
Stable - at least to the expiration date listed on the drug product
Accurately and precisely dosed
Identifiable - debossing, color coating, branding logo
Consistent in release profile - in vitro and in vivo
Tamper-resistant
To prove that a given drug product has achieved these goals, a list of product performance characteristics are defined and tested
Guidelines for testing are provided by the United States Pharmacopeia (USP)
Product performance characterization for oral solids
Appearance
Content uniformity
Disintegration and dissolution
Moisture content
Organic impurities
Capsule closure. - for hard capsule shells
Friability
Hardness
Packaging and storage
Testing is done using validated analytical methods to meet the drug product's specifications
A "validated" method provides documented evidence of suitability of a given application
Uniformity of dosage units
Weight variation (WV)
Used for most dosage units (tablet) with a dose of ≥ 25 mg API and ≥25% ratio of API weight to total drug product weight
Content uniformity (CU)
Assaying individual units using an appropriate analytical method
Used when a dosage unit doesn't qualify for the weight variation or when desired
Relative to WV, CU is a superior test because it provides an actual measure of drug content per dosage unit
Challenge of low-dose drug formulations
Synthroid is available in multiple different doses
Levothyroxine has a narrow therapeutic index
Patient is titrated to the right dosage amount
Need to have exceptional control on the manufacturing to ensure the patient is getting the right dose
Importance of compliance to tests
For establishing "uniformity of dosage units" the following critical elements must be demonstrated:
For each batch product, the mean content of API must lie between specified limit (typically 90-110% of label) throughout the shelf life of the product
There is a statistically defined limit to the spread in the individual content values of the tested dosage units
For products requiring USP uniformity of Dosage Units test, failure of this test means the batch of product cannot be legally solid in the US
Characterization tests
Tablet friability
Tablet breaking force
Disintegration time (tablet/capsule)
Dissolution
Loss on drying
Moisture sensitivity/uptake
Stability testing
Applied to all solid dosage forms, but there is no one specific test for stability because the requirements for each API are too specific
Intrinsic stability of the API is determined as a function of
Temperature
Thermal degradation
Humidity
Hydrolysis, crystallization
Light
Photodegradation, photo-oxidation
This is tested against different formulation components as well as different container/closure systems
Foil blister packaging
Amber bottle
Accelerated stability tests (stress testing) are performed on formulations in the proposed packaging to determine the appropriate storage conditions and estimate the product's shelf life
Most used guideline for stability testing is International Council for Harmonization (ICH) Guideline