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114 Cards in this Set

  • Front
  • Back
Polymers do not have _______ phase
Vapor
Addition Polymerization includes these 3 steps
Initiation
Propagation
Termination
Degree of Polymerization
number of mers

monomer (1)
dimer (2)
Trimer (3)
etc.
Mono-dispersed
vs
Poly-dispersed
same size chains

different size chains

smaller chains dissolve quickest
Topology
Linear
Branched
Crosslinked
Stereoisomerism:
Isotactic
Syndiotactic
Atactic
same direction
alternating direction
randome direction
Order of repeating units:
Homopolymer
Random Copolymer
Alternate Copolymer
Block Copolymer
Graft Copolymer
Homopolymer: ------------------
Random Copolymer -=-----=--=-
Alternate Copolymer -=-=-=-=-
Block Copolymer --------=====I
Graft Copolymer --------
=====
Temperature at which a glassy polymer softens into a viscous liquid or rubbery phase
Glass transition Temperature (Tg)
Temperature at which the ordered regions of crustalline polymer melt
Melting Temperature (Tm)
Temperature above which ploymer degrades
Decomposition Temperature (Td)
Thermal Transitions of Polymers
Td> Tm> Tg
Thermal transitions DeltaH

Shift in base line
endothermic
exothermic
Tg
Tm
Td
1st and 2nd order transitions
1st order- volume change is sudden/significant

2nd order- volume change is not sudden/significant
which has more crystal or more amorphous

temp 70-115

temp 220
temp 70-115= amouphous

temp 220= crystal
Tg and crosslinking

Linear Polymer
Lightly-crosslinked polymer
Highly-crosslinked polymer
Linear Polymer= low Tg
Lightly-crosslinked polymer= highTg
Highly-crosslinked polymer= no Tg
Number Average
vs.
Weight Average
deals with number of molecules

deals with size of molecules
Polydispersity
Mw/Mn >1

the closer the pulydispersity is to 1, the more similar each measurement is
Elastic Properties of Polymers

Fibers
Tough Plastics
AUC=?
Fibers= high modulus (strength)
Tough Plastics= low modulus (strength)

AUC= toughness
Rubbers
Drug Degrations includes
1. Reducing bioavailability and therapeutic effect
2. Producing toxics
3. Changing the physical form of a drug
4. Excipient degradation
The expected potency of a drug usually should not fall below _____
90%
Problem with Rotigotine( Neupro)
active ingredients may crystallize in the patch
Stability Triangle Includes
Purity
Identity
Potency
Hydrolysis:

Ester
Lactone
Amide
Lactam
Anhydride
Ester= -OH with COOH
Lactone=-OH with COOH in ring
Amide= COOH with NH2
Lactam= COOH with NH2 ring
Anhydride= two COOH
Hydrolysis Facts
-Anhydrides are more reactive than acids
-ester hydrolysis to acid and alcohol is reversible under acidic condition
-Amides are more stable than esters
-rate of OH catalyzed hydrolysis of amides is greater than H-catalyzed hydrolysis of amides
De-amination occurs in:
asparagine
glutamine
insulin
recombinant human growth
Hydrolysis degradation is affected by:
pH
buffer salts and ionic stregth
temperature
moisture
co-solvents
complexing agents
surfactants
Specific acid-base catalysis

general acid-base catalysis
catalysis by H+ or OH

catalysis by buffer ions like acetate or citrate
Antioxidants:
-Primary
-Secondary
-Tertiary
Primary= Free radical scavengers provide electrons to free radicals

Secondary= oxygen scavengers under auto oxidation by consuming oxygen

Tertiary= ion scavengers ; chelating agens react with ions responsible for initiating oxidation reactions
Drugs with absorption greater than ______ nm may decompose in sunlight
280 nm
Light degradation in dilute solution is _____ order

more concentrated solutions show a _______ order reaction
first

pseudo-zero
Photostability Test

stable vs. unstable

constant intense light source
pH 7.4
room temperature
stable if half-life is >5 hrs

unstable if half life is <5 hrs
undergoes spontaneus racemization
chlorthalidone
_______ degrades faster than ________
solutions
suspensions
Have high vapor pressure
ketones
aldehydes
esters
low molecular weight alcohols
crystals are generally more stable than amourphous except with_______
Insulin is more stable in amorphous form, not crystal form
Expiration Date became law in
1979

date may range over 12 months to 60 months
Factors affecting Reaction Rate
Temperature
Catalyst
Reactant Concentration
Surface area
Pressure
Maxwell-Boltzmann Distribution
For a reaction to happen, particles must collide with energies > or = to Ea for the reaction
Effect of Temperature
Ea remains same
Number of molecules with energy > or = Ea increases
Assumptions of Arrhenius
calculates rate constants at different temperatures

Ea is always positive

Ea is constant over a given temperature

Ea is reduced by catalyst

Ea is increase by inhibitors
The Arrhenius equation
this equation is valid as long as the reaction mechanism does not change over the temperature range studies. If not linear, reaction mechanism changes with heat.

k=Ae ^ (Ea/RT)
Effect of catalyst
Ea is reduced

number of particles with sufficient energy is the same
Homogeneous catalysis

Heterogeneous catalysis

Autocatalysis
Catalyst and reactant are in a same phase; everything will be in a gas or in a single liquid phase

Catalyst and reactants are in different phases; a solid catalyst with the reactants as either liquid or gases

Reaction is catalyzed by one of its products
pH effect
Kobs= k1 [H+] +k2 + k3[OH-]
would increase the rate of reaction between similarly charged ions

would decrease the rate of reaction between oppositely charged ions
Increased Ionic strength
Studies mechanism by which a chemical process or reaction reaches to its final state from its initial state and the rate at which this process or reaction proceeds
chemical kinetics

used to know the stabalization of drug products and predicting shelf life
Thermodynamics
vs
Kinetics
if a reaction takes place

speed a reaction takes place
Different 1st order reactions
Reversible
Parallel
Consecutive
A0-A1=kt
Zero Order
A0/2k
Zero order half life
A0/10k
Zero order t 0.90
linear with negative slop

half lives are decreasing
Zero Order
At=A0 e^-kt
First Order

straight line on when using Y=ln At X= time
t1/2= 0.693/k
No concentration involved

First order half life
t0.9= 0.105/k
no concentration involved

First order shelf life
Half lives are constant
independent of [A]

first order
1/At=1/A0 + kt
Second order

positive slope

Y=1/At
X=time
t1/2=1/kA0
Second order t1/2

t 1/2 are increasing
0.11/kA0
t 0.9 second order
observed when a reactant reacts with itself or when the reaction rate depends on the concentration of more than one component
Second order kinetics
most compounds that degrade in solution follow ________ order reaction
pseudo-first order reaction

since water in excess, rate of drug decomposition dependent on drug concentration and not water
Rate constant Units

zero

first

second
zero= Mt-1

first= t-1

Second= M-1t-1
Rate

k

kA

KA2
zero

first

second
At=A0-kt

At=A0e^(e-kt)

1/At=1/A0 + kt
Zero

First

Second
________ is matter resistance to flow
Viscosity
______ is the science studying the flow properties of a matter
Rheology
When ever a fluid is physically moved or disturbed, as in pouring, spreading, spraying, mixing, etc
Shear
Shear Stress =
Shear Stress = Force/ Area
Poise
shear stress of one dyne per square centimeter per second
Fluidity
reciprocal of viscosity
Factors affecting viscosity
Temperature
Shear Rate
Measuring Condition
time
Pressure
Composition and Additives
Viscosity of Newtonian fluids _____ sharply with increasing temperature
decrease
Most fluids lose their viscosity or their resistance to flow if temperature increases
Thermo-thinning
Some fluids will be more reluctant to flow as temperature rises
Thermo-thickening
At a given temperature, the viscosity is ________ of the shear rate
independent
Non-Newtonian Fluids
-Shear rate varies, viscosity varies
-Shear rate varies, but shear stress is not proportional
-Viscosity is called apparent viscosity
-it depends on temperature, speed, spindle, rate of mixing, rate of spraying, rate of pumping
Viscosity decreases as shear rate increases (Shear thinning)

ex. ketchup
Pseudoplastics
Viscosity increases as shear rate increases (Shear thickening)

ex. whipping cream
Dilatant
Viscosity decreases with time under constant shear rate
Thixotropy
Viscosity increases with time under constant shear rate
Rheopexy
fluids which do not move until certain force is applied on their structure

viscosity decreases as shear rate increases
Plastic

no flow occurs in response to stress until certain point, slope after yeild is plastic velocity
Movement of one layer of fluid past another with no transfer of matter from one to another
Laminar Flow
when layers move, matter can also move from one layer to another
Turbulent Flow
behave like solid if stress application is short, they behave like liquids if stress application is long
Viscoelastic
application of constant stress to monitor deformation with time
creep
Deborah Number
De= tmaterial/tprocess

De<<1 material behaves as viscous liquid

De>>1 material behaves as elastic solid
immediate recovery after deformation
elastic solid
infinite flow of a fluid
wetting
Spring
Dashpot
Maxwell
Voigt
know grafts for them
Poiseuille's Law
Formula for Liquid flow through a pipe (volume of rate flow)

Factors include:

Viscosity
pipe radius
pipe length
pressure differences between two ends
Capillary Viscometer
for dilute solutions and suspensions
_______ is dependent on the flow time and the fluid density
Viscosity
A piston forces the test fluid from a reservoir through a capillary at constant rate. Pressure drops as fluid passes the capillary. By measuring pressure drop across the capillaries of different diameters, viscosity will be determined as function of shear rate
Extrusion Viscometer
Solution dosage forms are _______
Newtonian
Suspensions and emulsions are ____________
non-newtonian
Viscosity of blood is ________
Thixotropic

viscosity decreases with increase in shear rate

Plasma is newtonian and pseudoplastic
concentration of a solution at saturation
solubility
small vs large particles
reach same solubility

different rates of dissolution
measure of the medium influence on the energy needed to seperate two oppositely charged bodies
Dielectric constant

Polar solvent >15
non-polar <15
delta H<0

delta H>0
for soulte to dissolve, heat must be releases. Inceasing temperature of solvent will decrease the solubility

for the solute to dissolve, heat must be given; increasing temperature will increase solubility
love to be mixed wtih a liquid because they obtain more freedom and entropy, so increase in temperature will help them to reach their goal
solids
they hate to be mixed with a liquid as they have to give up their freedom and entropy, so increase in temperature will decrease their solubility
gases
pH <pka

pH > pka
ion-diopole decreases

ion-dipole increase
pH below which a drug precipitates from the solution as an undissociated acid
pHp
ph has no effect on solubility of _____ substance
non-ionizable
amphipathic having both polar and non-polar groups
Surfactants
ratio of concentrations of un-ionized compound between octanol and water
Particion Coefficient
ratio of the sume of the concentrations of all forms of the compound (ionized and unionized) in octanol and water
Distribution Coefficient
high vs low partition coefficient
high lipid solubility/ high permeability

high aqueous solubility/ low permeability
Partition coefficient formula
concentration in ether/ concentration in water
Partition Coefficient of Electrolytes

Log P= 5
Log P= -2
5= drug is 100,000 times more soluble in organic solvent

-2= drug is 100 times more soluble in water
compounds with P values 1-3

compounds with Pvalues greater than 6 or lower than 3
good absorption

poor transport characteristics
amount of particles crossing a unit area in a unit time
Flux
not constant, depends on temperature, pressure, and concentration
Diffusion coefficient