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123 Cards in this Set
- Front
- Back
Pi Bonds vs Sigma Bonds
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- Pi easier to break
- Pi easier to excite - Pi much stiffer - Pi help promote LRO |
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Excitation Energy Equation
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E_exc ~ 1/lambda_exc
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Fluorescence
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Provide energy in form of light to excite valence electron
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UV-vis spectroscopy used for?
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Monitor peak intensity of absorption events for solution of molecules & macromolecules
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Relative Absorbance
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1 - I_x/I_o
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Absorbance equation
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A = (le)*c
l = path length (dim. of cuvette) e = molar absorption coefficient @ lambda_char absorption c = concentration |
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Coordination Number (CN)
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Number ratio of one reference atom to all its nearest neighboring atom
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Lattice Point
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Individual point (or atom) within a crystalline lattice. Each lattice point is surrounded by identical arrangement of neighboring points.
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Basis
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Refers to a group of atoms associated with an individual lattice point.
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Unit cell
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smallest group of lattice points that completely describe the structural arrangement of atoms in a crystal or crystalline lattice.
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Close-packed planes & directions
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Easiest to move during plastic deformation
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Atomic Packing Factor
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Volume of atoms in unit cell / Total volume of unit cell
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Ceramic unit cells
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Ionic Solids
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NaCl Unit Cell
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Interpenetrating FCC unit cells
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CsCl Unit Cell
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Interpenetrating SC Cells
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Defect
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Disruption in the periodicity of a crystal
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Point Defect
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Disruption of a single lattice point or interstitial position
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Vacancy
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Missing an atom in a normally occupied position
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Interstitial
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Smaller atom that occupies an available space between lattice points
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Substitutional Atom
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Impurity atom that replaces an atom normally positioned at a lattice point
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Frenkel Defect
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Atom moves from one space within the lattice to another
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Schottky Defect
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Two atoms of opposite charge are removed from the lattice entirely
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Hume-Rothery Rules
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(1) Similar Size (<= 15% difference)
(2) Similar/identical crystal structure (3) Similar electronegativity values (4) Similar valency |
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Diffusion Equation
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D = D_o * exp(-Q/(R*T))
D = Diffusivity (cm^2/s) D_o = material constant (cm^2/s) Q = Activation barrier (J) R = gas constant (J/mol*K) T = temperature (K) |
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Diffusion requires:
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1) Free space
2) Activation energy (thermal energy) |
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Flux
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Net # of atoms moving across the interface / unit time
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Fick's 1st Law:
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J = -(dC/dx) * D
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Polymerization Routes:
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1) Form new covalent bonds b/w different functional groups on monomers
2) Break pi bonds in UNSATURATED monomers to form new covalent bonds in polymer |
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polyEthylene uses & Structure
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-joint implants
-flexible tubing (IV) -(-CH2CH2-)n- |
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Oligomer
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2-10 monomers
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Conformation
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Overall shape & structural attributes of polymer chain that can be changed through bond rotation
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Configuration
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Structural attributes of a polymer that can be altered by breaking covalent bonds
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"neat" or "melt" polymer
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100 wt% -- no solvent
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Stereoisomers
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Placement of side groups
1) Isotactic - identical arrangement of R 2) Syndiotactic - alternating R placement 3) Atactic - random R placement |
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Steric Effects
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Size, chemical composition
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Edge dislocation
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Extra half-plane ends, causing a virtual line
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Burger's vector
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The extra vector required to close a box around a defect.
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Screw Dislocation
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Burger's vector parallel to dislocation line.
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Plastic deformation occurs through 2 routes:
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1) Creation of new dislocations
2) Movement of existing dislocations |
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Dislocation glide
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movement of a dislocation line from the center of a material to the surface or edge
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Surface Tension
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planar defect on surface caused by unbonded atoms
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Grain boundary
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interface between crystals
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Void
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3D aggregates of vacancies
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Precipitate
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Cluster of substitutional or interstitial impurities
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Porogen
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chemical which promotes creation of voids
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platelets
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non-nucleated fragments of megakaryocytes
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platelet functions
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1. initially arrest bleeding by adhering to exposed collagen
2. conformational changes to integrin receptors on platelets: a) further strengthens platelet adhesion to collagen b) promotes platelet-platelet aggregation |
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mediators of platelet adhesion to collagen:
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-GPVI (receptor on platelet)
-Von willebrand factor (ligand on collagen) |
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Hemostasis Steps (5):
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1. Injury occurs - damages blood vessel & surrounding tissue
2. Platelets migrate to wound area & become activated by binding to exposed collagen 3. Activated platelets release granular content containing chemoattractants that recuruit & activate other platelets & recruit key molecules (e.g. fibrinogen monomers) 4. Fibrin Network forms 5. Platelet Plug fills the wound & serves as scaffold for repair. |
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Fibrin Network Formation:
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Fibrinogen (unactive monomer precursor) --thrombin (secreted by activated platelets)--> fibrin monomer (active) --(Factor XIIIa + Ca++ allows formation of covalent bonds to form cross-linked fibrin polymer network)-->fibrin polymer network --(plasmin causes fibrinolysis)--> fibrin degredation products
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Hallmarks of Adaptive/Acquired Immune Response
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1. Specific
2. Diverse (genetic rearrangement) 3. Self & Non-Self 4. Memory |
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Antibody (draw)
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1. Hinge Region
2. Binding pockets 3. disulfide bonds 4. Fab = antigen-binding region 5. Fc = crystallizable region (serves as ligand to bind to particular cell receptors) 6. IgM --> pentamer structure 7. IgA --> dimer structure |
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Antibody Memory
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Naive T or B cell --> effector T or B or plasma cells --> clonal population --> regulation of effector cells --> leaves behind memory lymphocytes in case identical foreign invaders return to host
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Humoral Immune Response
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- Can be conferred to "non-immune" individuals
- B cells have Ig or Ab: 1. Immobilized on cell membrane 2. Secreted |
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Role of Humoral Immune Response
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1. Ab binds to Ag to prevent Ag from binding to & invading host cells
2. Ab binds to Ag to mark it for phagocytosis by macrophages 3. Ab binds to Ag & then activates the complement system |
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Complement System
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involves a complex mixture of different proteins that self-assemble on surface of foreign invader to membrane attack complex that results in a punctured hole
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Naive
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unactivated & has not yet been exposed to foreign Ag
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Epitope
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Binding domain of Ab which recognizes the Ag
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Types of T cells
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1. Helper T Cells
2. Cytotoxic T Cells |
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Types of Helper T Cells
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TH1 - helps mediate plasma cell response
TH2 - helps mediate the Tc response |
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Role of Cytotoxic T Cells
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recognize & kill non-self cells (e.g. infected host cells)
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3 types of primary bonds
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1. Metallic (delocalized electrons)
2. Covalent (sharing of electrons) 3. Ionic (electron donation) |
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Electron subshells
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s - 2
p - 6 d - 10 f - 14 |
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UV-vis spectroscopy vs Fluorescence
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Antibonding & Bonding instead of Excited & ground state.
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PVC uses
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-less flexible tubing
-plasticizers often added to lubricate chain sliding |
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Polyethylene oxide OR polyethylene glycol structure
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-(-CH2CH2O-)n-
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Polymethylmethacrylate (PMMA) structure
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-(-CH2CCH3COOCH3-)n-
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General structures of polymer chains (3)
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1. Linear
2. Branched 3. Network |
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Network polymer junction sites
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formed either through bonding (more likely) or physical entanglement
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Crosslinking
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involves formation of new covalent bonds at junction sites aka crosslinking sites
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Hydrogel
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network polymer which is hydrophilic (as many network polymers are).
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BIS
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common crosslinker.
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Polyvinyl alcohol (PVA) structure
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-(-CH2CHOH-)n-
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Copolymer
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1. random (ABBABAAA...)
2. Alternating (ABABAB...) 3. Block (AAAABBBB...) (most common) Example: PLGA = poly(lactic-co-glycolic acid) - often used in drug delivery applications due to its biodegradability |
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Step polymerization
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-polymer chains grow stepwise between any 2 reactive species
-monomers have 2 or more reactive sites -monomer is used up quickly -often has byproducts -continues until no reactive sites are left |
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Chain polymerization
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-monomers are typically unsaturated
-chain grows only by rxn of monomer with growing chain -"break" unsaturated bonds to form new covalent bonds -no byproduct -involves distinct stages |
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stages of chain polymerization
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1. Initiation
2. Propagation 3. Termination |
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chain polymerization initiation
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Create free radical center from initiator species which often contains peroxide or azo bond (draw schematic)
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chain poymerization propagation
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bond monomer to free radical monomer end (draw schematic)
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chain polymerization termination
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a) combination - usually results in head-head orientation
b) disproportionation - involves movement of hydrogen from one monomer end to another draw schematics of each |
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Number average molecular weight
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Mn = sum(Ni*Mi)/sum(Ni)
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Weight average molecular weight
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Mw = sum(Ni*Mi^2)/sum(Ni*Mi)
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Diffusion Time/distance equation
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x=sqrt(D*t)
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Polyacrylamide
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(-CH2CHCONH2-)
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PVC
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CH2CHCl
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Monomer "head" and "tail"
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Head = C connected to side group
Tail = other C |
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Chain Scission via oxidation (propagation and termination)
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See picture
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Homolysis (draw)
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2 r groups with one free radical each
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Heterolysis Initiation (draw)
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2 r groups, one positive, one negative
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Spherulites
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3D aggregate of lamellae (crystalline domain) and amorphous regions that radiate from center
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Lamellae
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crystalline domain of a polymer
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Shear stress equation (liquid)
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t = ns*
n = viscosity s* = strain rate = ds/dt |
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shear stress equation (elastic solid)
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t = Gs
G = elastic modulus s = strain |
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viscoelastic complex modulus
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= G + iG"
G = shear elastic modulus G" = shear loss/viscous modulus |
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Exchange of one adsorbate for another with higher affinity.
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Vroman effect
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method used to separate and identify DNA sequences
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Southern blotting
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EM proteins undergo enzymatic breakdown & rearrangement, aka
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remodeling
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Cells that are completely able to replicate or proliferate
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labile cells
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cells that can be cued to replicate, but not as readily.
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stable cells
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cells that are least liekly to replicate
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permanent cells
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stem cells that are capable of differentiating into any cell phenotype
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totipotent
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stem cells that are capable of differentiating into various blood cell phenotypes
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hematopoietic
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Explain the DVLO theory (forces involved, graph)
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refer to book
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Name transport mechanisms for proteins to arrive at a biomaterials surface
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diffusion, flow, convection
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Name two methods for separating proteins, which results in faster migration of proteins?
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SDS-PAGE & SEC
Faster: SEC |
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Soluble chemical factors secreted by cells to affect the behavior of other cells
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cytokines
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Organelle responsible for post-translational modification
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golgi apparatus
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EM protein which undergoes post-translational modification outside the golgi apparatus
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collagen
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Define biomaterial
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any nonviable material intended to interface with biological systems to evaluate, treat, augment, or replace any tisue, organ or function of the body.
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Different types of RNA
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- mRNA (messenger)
- tRNA (transfer) - rRNA (ribosomal) |
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Different types of cytotoxicity assays
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1) direct contact
2) agar diffusion 3) elution |
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4 steps in neutrophil recruitment to injury site
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1. Rolling (bind briefly to endothelium via selectin-carbohydrate)
2. Activation (chemoattractants IL-8 & MIP-1b) 3. Arrest (integrin binding to endothelium) 4. Migration through endothelium |
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2 routes neutrophils use to destroy foreign material
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1) phagocytosis
2) secretion of reactive o2 & n2 |
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5 stages to normal wound repair following injury
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1) bleeding & clotting
2) inflammation 3) granulation tissue formation 4) foreign body reaction 5) fibrous capsule formation |
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3 Important considerations when dealing with biomaterials
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- Processing
- Properties - Structure/Composition |
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How to denature proteins
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SDS or heat
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how to denature DNA
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heat
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purpose of ELISA
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to identify specific proteins based on their antibody binding
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purpose of Western Blotting
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to separate proteins based on their molecular weight alone
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3 types of cytoskeleton
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- microfibrils
- intermediate filaments - microtubules |
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define physicochemical (in reference to coatings)
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any method of surface coating that is not biological
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Self-Assembled Monolayers (SAMs)
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amphiphilic molecules which contain an attachment group
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Langmuir-Blodgett film
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refer to book pg 239
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