Industrial Organic Chemistry

1

• ??????2009
• (Functional Polymers)-2.18.2009
• ???
• ????????????????????
• (?????????????)?
• ???????
• ??????????????????? (functional
  groups)????????????????????
• Polymer Structures ? Properties ? Functions ?
  Applications
• ???? attachment 1 (Lin ??????????)
• ???? 1. ??lectures ?,????,???
• 2. ?????????homework?
• 3. Literature searching,
  reading and reporting

2

• Introduction (2.18.2009)
• Structure ? property ? function ? application
• Ethylene oxide vs. propylene oxide
• Ethylene vs. propylene
• Structure correctness
• Block copolymer or tri-block vs. homopolymer
• Hydrophilic vs. hydrophobic property
• Crystalline (e.g., PEG of 800 Mw) vs. amorphous
• Nanosize segregation in polymer domain (hard vs.
  soft segments)
• --------------------------------------------------
  ---------------------
• Industrial applications such as polymer on
  silicate glass,
• film formation for optoelectronic devices
• e.g., epoxy-glass fiber lamination, adhesion
  and
• role-to-role manufacturing process

3
??????

• (????)
• ????? (Commodity Chemicals)gasoline,
• pigment, paint(formulation)
• (B) ????? (Polymers) PE, PET fiber
• (C) ????? (Specialty Chemicals) dispersant..
• (D) ???? (Biotechnology and Biomedical Materials)
  DNA carrier for therapy
• (E) ???? (Optoelectronics) Lens (PMMA)
• (F) ????? (Micro-electro-materials) Sensors,
  robots (integration)

4
Functional polymers (part 1)

• An introduction and examples of the functional
  polymers

5
Example How much information hidden in this
equation?
6

• 1. Reaction type? (step-growth or
  chain-growthliving?)
• 2. the way of drawing the scheme
• 3. s-BuLi
• 4. benzene vs. cyclohexanesolvent effect?
• 5. EO applications?
• 6. dibromide selectivity ? (wrong structure!)
• 7. why to draw two types of reaction in one
  scheme (by abbreviation)
• 8. PS-b-PAN is still living.
• 9. Structural meanings
• (functionalities?)
• 10. stoichiometric vs. catalytic
• 11. x and y (meaning of the ratio) 12.
  end group Br?
• 13. other critiques or mistakes (structural
  drawing) ?
• How about
  functions?

7
Tips for attending this class and doing research
(after learning technique data, meanings,
presentation)

• Memorization vs. Reasoning (connection and
  convergent/divergent ways of thinkinglogical
  approach)
• (learning without thinking is useless thinking
  without learning is unstable)
• The way of questioning, answering and
  reasoning---(to the point)---to be precise and to
  be concise (try to answer any question by less
  than three sentences)

8
Polymers (basic concepts)

• 1. Polymer is a soft material (what is hard
  material?)
• 2. Random coils, worm-like, rod-like, lamellar,
• core-shell (micelle)
• importance of the geometric
  shape!functions
• 3. In solution (with solvent), in bulk, in film
• 4. solvent parameteramphiphilic property
• e.g., PE, PS and Polyamide (structure and
  property?)

9
Polymeric Materials--issues

• Chemicals (e.g., additive to polymers monomers
  inorganic nanoscale particles.)
• Reactions polymerization and modification
• Chemical structure and meanings
• Process (reaction types)
• Performances (many different areas, including
  electronic conductance and light emitting)
• New developments including concepts such as shape
  selective, supra-molecule, self-assembly, etc.

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? ? ? ? ?
1???(Soft) vs. ??(hard) self-assembly
micelle vs. inorganic array 2?????(??),???(??
), Carbon nanotube C60 DNA (20 A),
cyclodextrin (pore size 4.9 to 7.9 A),
Cylinder Linear etc. 3?Entanglement vs.
Crystalline Property vs. Amorphous 4????0.5-2
µm diameter (?? vs. ???) 5????m gt mm gt µm gt
nm gt pico- gt Femto-
11
? ? ? ? ? ? ?
1??????Cu??,??????? vs. electrolyte
2???????PC?PMMA? EPOXY 3??????? (photoresist
lithography????? 4??????(e.g., NaOH???)
(Solubility) 5????(Compatibility
biocompatibility) (1) ?????
(2)????/???? 6?Dissolve vs. Solubilize
(amphiphilic copolymer in one solvent or in
two solvent system.micelle-like?) 7?polar vs.
nonpolar vs. solvophilicity (solvation?)
12
? ? (versatility in sizes)
1. Cyclodextrin-modified gold nanoparticles 2.
Conjugated polymers as light emitting diodes 3.
Fullerene-based surfactants 4. Clay and DNA 5.
Graft copolymers 6. Light-induced amphiphilic
surfaces 7. (Crown ethers and chelating sizes)
vs. PEG
13
Specific Examples of Polymer Uses and
Basic Concepts Involved

• examples for explaining the concepts of
  diversification of polymer applications

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Example 1 ????? (???,??????,19, 3, 137,
1996) ? ?????,?Commodity Chemical
(?????)? ? ???????,???,???,Emission? ? ?
? MTBE(715),?????,???,
???(anti-knocking),????,???,
????,???,???? (de-hazer),???,
??(Biocides)?? ?? (Specialty Chemicals)
specialty polymers? ???????s?Commodity. Commodi
ty Polymers vs. Specialty Polymers vs. High
Performance Polymers vs. Functional Polymers
15
Patented structure (synthesis)
Note poly(isobutylene)-amine vs.
poly(ethylene)imine or poly(ethyleneglycol)-amine

• ????,??????,????,???????
• ??????,????????????????,???
• 200300 ppm added in gasoline ???,Differentiate
  ????
• ???(???,????)
• CE News (2007)---Biomedical or Drug Development
  
• (3 billions research for one single drug)----
• me-too vs. invention, research vs. marketing
  

16
Example 2 OXO Process (hydroformylation) for
Specialty Chemicals Polyurethane,Polycarbonate
film ????,?????? US Patent 5,434,309(1995)
5,294,675(1994) to Monsanto
17
??????? What is patent?novelty and uses claims
18
Example 3 ????? ??????purpose is to stop the
hydrocarbon oxidation ???3o gt 2o gt 1o
??????(PE vs. PP vs. PS stability?)
??????? (compatibility)?
????????????? ?? extractable?
FDA ?????Regulation and FDA approval ?
??Phenol (??) PP, HDPE, LLDPE, LDPE,
Styrenics,
ABS, HIPS, Phenolic resin, PVC, SBS,

Polybutadiene, EPDM? 0.10.5wt
0.020.1 0.21
Amine (??) (specialty ??)
alkyl or aromatics

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Anionic, cationic, free radical and catalyst
20
free radical generationtertiary C oxidation
and
decomposition !
21
(Butylated hydroxytoluene)
isobutylene
What is the R group?
Michael addition!
Butylatedalkylation via carbonium ion mechanism
and by Fridel Craft Reaction with Lewis Acid
catalystother reactions such as nonylphenol
22
AIBN azo-di-isobutylnitrile
23
free radical generationHC oxidation to peroxide
and decomposition to free
radical ! Secondary vs. Primary
antioxidant
24
Imine formation and hydrogenation
25
Examples of functional polymers

• In the above three examples,
• how much do you know already?

26
Glycidyl ether vs. glycidyl alcohol vs. glycerine
Multiple arms ? geometric shape Mw ? property and
function In solvent, in bulk or in
film--- tentacles or polyvalent functions
27
Key words-1

• What is patent? ---novelty and uses!
• Synthesis and functions of PIB-ethylenediamine.
  Working principle?
• Soft materialsshape changeable and reactive by
  shape changing
• Antioxidant additivesfree radical scavenger vs.
  free radical polymerization
• Polyvalent polymers functions by geometric
  shape with reactive sites e.g., solid catalyst
  and biological function

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Example Polymeric Materials and ?????? 1.
Diversity or Versatility (???) 2. ??? (???)
3. ??? (Chemistry as the central science)
4. Polymers for electronic (e.g., LCD, color
filter..) and biomedical (e.g., biocide,
antimicrobial, drug delivery..) applications

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• Crystal or molecules or quantum dots
• 366 nm irradiation ? red emission
• gt450 nm ? colorless
• For 10,000 cycles of coloration/discoloration
• The red is stable up to 120oC
• (can be erased with visible light)

30

1. Multivalent cluster effect!
2. Micelles shape
3. Sizesmolecular
4. Role of polymer techniques

31
The Revolution in Chemistry (and the trend to
nano scale)

• Converting naturally abundant substances into
  chemically useful building blocks (e.g.,
  chitosan?)
• Developing the art of reaction or process without
  solvents--(ionic liquids in the prior arts?)
• Understanding the properties of compounds of
  intermediate (1-100 nm) size--nanotechnology
• Creating molecules that self-assemblingmicelles
  
• Mastering the chemistry of caged spaces that
  response to the introduction of chemical,
  magnetic or electric field in entrapped an
  appropriate host (e.g., hybrids and organoclays)
• In connecting chemistry with engineering,
  material science, physics, biology, environmental
  (green chemistry), computer and etc.

32
Inorganic nanomaterials in polymers

• ??SiO2?????(?)????,??????????????????????????,????
  ????????????????
• ??SiO2?????499nm??????????7080,????????????????
  (conventional antioxidants)
• 298400nm???????????????????,?????????SiO2?????TiO
  2 Al2O3?ZnO ?????????????
• ??ZnO???????????????,???????????
• Can you design Novel functional material
  (according to the above ideas)?(homework-1)

33
Example 4 Nanotechnology (new trend)

• According to the IUPAC definition porous
  materials can be classified into three groups.
• Microporous pore diameters less than 20 A
• Mesoporous from 20-500 A
• Macroporous larger than 500 A
• Microporous materials include amorphous silica
  to crystalline zeolites (aluminosilicates)
• Nano-scale 1-100 nanometer.

34
Some examples of nanoscale materials

• 1. A human hair has width of 1 micro-meter which
  
• is 1000 nanometers. (conventional materials!!!)
• 2. Micelle is a nano-particle, which can be 20
  nm.
• 3. Microelectronics rests on 100 nanometers or
  less

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• Fabrication top-down and bottom-up
• 1. Patterns generated on a larger scale and
  reduce to
• smaller dimension.
• 2. Bottom-up (easily to be 2-10 nm)
• Two prominent methods are nanotubes
  and quantum dots. Quantum dots are crystals
  containing only a few hundred atoms. The
  electrons are confined to widely separated energy
  levels, the dot emits one wavelength of light
  when it is excited.

36
Soft and Hard Materials

• Hard materials have a controllable shape such as
  zeolite, clay, buckyball, crystalline polymers,
  etc.
• Soft materials are flexible, most time, they are
  in sphere particle shape, such as amorphous
  polymer molecules (random coil) micelle polymer
  crosslinked particles..

37

• Nano Definition
• One of three dimensions in 1100 nm (nm 10 -9
  m)
• Area/weight m2/g Aspect ratio
• Geometric shape
• Functions and Applications heat, physical
  properties, eg mp, heat distortion temp.
• Quantum effect (electron dot)
• eg. Color, electric
  conductivity
• (bulk vs. surface atoms)

38
Nanotechnology and Polymers

• Nano-materials, -technology and science
• (examplesconducting polymer)
• e.g., surface active agent, micelle ..
• Lotus effect (phenomenon, principle and
  applications)
• EMI (electromagnetic shielding insulation)
  Polymer blend, crystalline material
• Inorganic/polymer composites
• Inorganics (powder..)
• Biomaterials (DNA, protein,.) Biosenser

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Nanomaterialsmeanings

• Miniaturize (nanoscale size)
• Surface
• Shape
• Functions (applicationsnovelty)
• Diversity (including Biomaterials)

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There is plenty of room at the bottom
bottom-up vs. top-down

• 1959?,(Richard Feynman),
• ????????????????????,???????????????
• ????????????????????????????????????????????????
  ????????
• ???????????(observing the process!!)

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Size Comparison of Nanomaterials
water
Glucose
Antibody
Virus
Bacteria
Cancer cell
A period
Tennis ball
107
10-1
1
103
104
105
106
108
10
102
-------------- NSP
1 meter
Nanodevices
Nanometers
dendrimer
Nano Silicate Platelet (NSP) Size, Geometric and
Charge Interactions
quantum dots
Nano tubes
Nano shells
42
http//pubs.acs.org/email/cen/html/031706212813.ht
ml
43
Homework 2

• With the concepts of soft/hard material and
  nanosize effect in mind, can you derive an
  equation to correlate surface to dimension of a
  particle (particle size?), a tube (cross-section
  and length?) and a platelet (thickness and disc
  shape?), assuming three materials have an
  identical weight ?

44
Key words

• 1. Micelle (critical micelle concentration CMC)
• vs. (critical aggregation concentration CAC)
• 2. Bottom-up
• 3. Soft-hard materials
• 4. Nano scale in the Nature

45
Is DNA a soft or hard material ?

• DNA ??????????
• 1953?Watson,Crick.
• DNA??????2nm, ???????3.4nm?
• 10???????360oC,????????

46

• 1982?,IBN???????
• (Scanning Tunneling Microscope, STM)
• 1986?,?????
• (Atomic Force Microscopy, AFM)
• STM? AFM ?????SPM
• (Scanning
  Probe Microscopy)

47
Functional Polymers (part 2) (3-19-08)

• Properties vs. structures ? (e.g., polar vs
  nonpolar)
• Applications or Functions (CNT conductivity
  -gt EMI)
• From primary to secondary structure.
• From one-dimensional to two-dimensional films
• Self-assembly to supramolecules from copolymers

48
nitration!
Nylon 6,6!
PI!
49
All the sulfonated samples having
high-molecular-weights (Mn, 74,100109,500) were
soluble in some polar aprotic solvents such as
DMF, DMSO and DMAc, and they could be easily
formed into tough and flexible films via solution
casting. (why film?) The films presented good
thermal stabilities (T5 gt 453 C), and
mechanical properties (high storage moduli and
glass-transition temperatures (Tg gt 220 C), as
well as tensile strengths of about 95 MPa) and
swelling degrees lower than 12. (cf. methyl
cellulose)
50
Chemistry (beyond covalent bonding and structure)
Molecules (covalent bonds)
Supramolecules (non-covalent bonds)

Geometric/Physical Functions (e.g.
1. Protein tertiary structure 2. Nano-materials
3. swelling crosslinking network )
51
Serendipity!!! Surfactant? Water/oil?
Water/ethanol? Water on glass? Dispersion
(RBG,CB or sand) vs. solution? On water surface?
Surface or interfacial tension energy?
Anti-surfactant?
52
Crown Ether chelating, guest/host
interaction---geometric effect
53
Morphology of Nanomaterialsin different shapes
or dimensions
rod- or fiber-like Layered Spherical
e.g., Carbon Nanotubes e.g., montmorillonite, LDH e.g., SiO2
54
Polymersbulk (crystalline vs.
amorphous)solution (solubility, coil and
amphiphilic)film (OLED, color filter from bulk
polymers ? and nanoscale manipulation
?)self-assembly into three dimensional
materials (self-assembling process or
kinetics and self-assembled arrays or
supramolecules or ordered aggregates)
55
Block Copolymers as Surfactants and their
Applications (amphiphilic!)

• Diblock, triblock and multiple block (such as
  octa-block)
• Poly(styrene)-b-poly(butadiene)-b-poly(styrene)
• Graft copolymersPP-g-MA (how to make it?)
• Note synthetic approach vs. structural designa.
  EG-initiated EO/PO block vs. glycerin-initiated
  EO/PO vs. SBS terminated with CBr4

56
Polymeric Nanoparticles

• (Acc, Chem. Res. 2001, 34, 249)
• Concept e.g., emulsion polymerization of
  polystyrene with anionic surfactant, sodium
• dodecyl sulfate (1.8 w), to form up to 40 w
• PS (as low as 60 nm nanoparticle)
• vs.
• polymeric copolymer as surfactant.
• That is, non-extractable surfactant.
• (surfactants as templates polymers are
  nano-particles..)

57
Polymeric Nanoparticles (contd)

• Polymeric nanoparticles block copolymers and
  ionomers can self-assemble in a selective solvent
  to be nanoparticlesamphiphilic copolymers--- at
  least two different blockssolvation differently
  by a solvent. (solvophilic or solvent-selective!)
• Size 100 to 1000 nm current technology it is
  hard to achieve 10-100 nm and stable in water.
• Cf. inorganic nanoparticles 5-100 nm (but it is
  challenging to have 5-10 nm metal particles with
  good dispersity) (nanotechnology)

58
Polymers are soft particles while metal (and
metal oxide) are hard ones

• Degree of flexibility
• Different shapes or conformations (conformational
  entropy)
• Approximately spherical coil shape
• The conformation entropy gives the coil a certain
  elastic resistance to deformation such as
  squeezing and stretching. (three dimensional
  materials)

59
Amphiphilic Block ABA Copolymers as Polymeric
Surfactants

• Summary
• 1. Non-ionic and cationic structuresamphoteri
  c
• 2. Temperature-sensitive (up to 39 C due to
  biological
• functions )
• 3. pH-sensitive (from 10 to 5 to 2)
• 4. Micellar self-assembly and phase inversion
• 5. Self-assembly in bulk (phase separation as
  in SBS)

60
(3-26-08) review
1. The aggregation changes in different
environments 2. Non-covalent bonding forces 3.
geometric shapes and for templates 4.
hierarchical transformation or kinetic vs.
thermodynamic changes
61
Polymer for Self-assembly (secondary and
tertiary structures)(bulk and film from
one-dimensional to two-dimension) (what is
three-dimensional ?)
62

• Ultra-thin organic films vs. Conventional coating
  
• a. wet process
• Self-assembly monolayer (SAM)
• Langmuir-Blodgett (LB)
• Synthetic lipid bimolecular layer
• Electrodeposition
• Layer-by-layer
• b. dry process
• (vacuum) vapor deposition (by sublimation or
• bulk material ablation) (note logo!)

63
Ultra-thin organic films

• Organic electroluminescent (OEL) or light
  emitting diodes (LED) display device using vacuum
  deposited thin films (about 50 nm thick) have
  been achieved.
• Organic Light Emitting Diodes (OLED)
• PLED (polymer LED)

64
The chemical structures of 8-hydroxyquinoline
derivative-metal complexes
65
The chemical structure of BeBq2, ZnBq2
and ZnAC2
66
Chemical structure of ZnBTZ
67
Chemical structure of azomethine-metal
complexes (imine structure)
68
The chemical structure of Zn-porphyrin
69
The chemical structure of Eu(TTA)3(phen)
70
Polymer LED Science, 285 , 233 (1999)

• Dispersing 5-nm particles of silica (SiO2) in
  poly(p-phenylenevinylene) (PPV), whose refractive
  index be tailored from 1.6 to 2.7

71
Optoelectronics

• Organic Light-emitting Diode (OLED)
• 
  Bright Blue Light
• 
  
• 
  JACS 120, 2987 (1998)

72
OLED Red Light
73
OLED Green Light
74
OLED Blue Light
75
3-Layer Device
76
Key words

• 1. LED?OLED?PLED (polymer light emitting diodes)
  
• 2. Thin film process
• 3. Nanoparticles (micelle-like, shape-changing,
  responsible to forces, temp, pH, light,
  magnetic. ? functions)

77
Molecular Orientation of ClAl Phthalocyanine in
Vapor Deposition Process on MoS2 Substrate
78
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79
Dendrimers with Self Assembling Property and
Their Superstructures
80
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Two Dimensional Polymer System Using Xanthate
Modified Dendrimer
SAMs of inorganic-organic two-layer polymers,
which are laminar metal hydroxides with mercapto
groups made by sol-gel reaction.
82
Chelating or tethering or non-covalent bonding to
fix the geometric shapes
83
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84
Summary 1 Polymer chemistry is the fundamental
knowledge

• Fundamentals polymer synthesis, structure and
  property
• 5 noncovalent bonding forces (science)
• Supramolecule and self-assembly (technology)
• Biopolymers (naturally occurring)
• Hydrophilic polymers (polyacrylic acid, PVP etc)
  vs. hydrophobic polymers
• EO-PO copolymers is one of important classes
• molecular architectures by precision
  polymerization
• Others (1. epoxy for advanced materials
  attachment A)

85
Epoxy Chemistry and Nanotechnologysupplementary
A
86
Biopolymers (or biological macromolecules) (in
Nature, there are materials in nanoscale size
and biological process through self-assembling

• Primary structure (covalent bonds)
• Secondary and tertiary structure (noncovalent
  bonds)
• The primary structure of many biopolymers (e.g.,
  sugar, protein,
• DNA, etc.) is linearly architected.
• 2. The complex and specific behaviors behind the
  simple
• structure are caused by their secondary and
  tertiary structures
• (e.g., biological functions of a protein)

87
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88
Chemical structure of a C60 molecule. With 60
atoms the molecule can be regarded as a
mini-solid. The molecule has a diameter of 7.1
A?
89
Two-dimensional view of a fullerene crystal. The
C60 molecules in interact only by weak van der
Waals forces.
90
??(1)???????? (2)????(Surfactancy)
?/???/???/? (3)???(Pigments, Nano-scale clays,
Inorganic Mg/Ca, Cuo/ Ago) ????
(1)????????? (emulsification, solubilization)
(2)Pigment Dispersants for Color filter
(3)???,???? (4)???
(water-borne) (5)?????? (compatibilizer)
(6)????
(7)pH Sensitive ???? (8) OLED/polymers
(8) Nano-scale materials
91
Emulsion of hexane/water by Cm-BO at 1600 Mw at
1.5g/4.0g/4.0g (magnification, 500x)
92
Emulsion by SEBS-g-MA/ED6000 (3.75 in toluene)
in Toluene/Water (500 X)
93
Structures beyond the primary
94
Self-assembly, Self-organization,
Self-synthesis Self-assembly involves the
aggregation of molecules and macromolecules to
thermodynamically stable structures which are
held together by weak concovalent interactions,
including hydrogen bonding, pei-pei interaction,
electrostatic and van der Waals forces, and
hydrophobic and hydrophilic interactions.
The self-assembly process offers considerable
advantages over stepwise bond formation in the
construction of large supramolecular
assembles.
95

• Self-organization is a higher order of
  self-assembly in which the non-covalent
  interactions usually more specific and more
  directional.
• Self-synthesis embraces not only self-assembly
  and self-organization, but also self-replication
  and template-type polymerization or
  autocatalysis. (mimicking to the Nature)

96
Key words

• Dentritic shapeDendrimer having different
  hemispheres and surfactant properties
• Surfactantsself-assembling properties which have
  different shape of arrays (highly ordered
  structures)
• (micelle-like, shape-changing, responsible to
  forces, temp, pH, light, magnetic, functions)
• Thiol compoundswhat is the function?

97
Science, 287, 1245 (2000)
Self-assembling amphiphilic peptides from
marine bacteria
micelles
Spherical particles at 140 - 180 nm
Biological function can be derived from a
self-assembly !
Fe(III)-Marinobactins
98
ABA Triblock Copolymers first example of
self-assembly
(rubbery)
(Microphase separation)
ABA
99
Supramolecules via metal coordination(CE News,
June 8, 1998)

• designing and creating molecules to spontaneously
  organize themselves into larger supramolecular
  assemblies
• (by H-bonding or metal coordination)
• 
  Chem. Eur. J, 3, 99
  (1997)

100
Polymeric Electrolytes(Salts Dissolved in Solid
Polymers)(Re-changeable Lithium Ion Batteries)

• Poly(ethylene oxide) (PEO) / lithium
  hexafluroarsenate (LiAsF6) 6 1
  
• The duel polymer chains interlock to form
  nonhelical cylinders. The lithium ions line up in
  rows within the polymer cylinders, far removed
  from the anions that stack up outside, for ions
  free to zip about.
• cf . Helical or a stretched zig-zag
  conformation .
• 
  
  
• 
  
  
• 
  
  
• 
  Nature, 398, 792
  (1999)
  
• Cf. crown ether?

101
Vapor-phase assembly of multilayered structure
102
50 or more layers inter- planar p- stacking
of aromatics Stable to heat up 300oC and to
most organic solvents and acids Has
fabricated organic LEDs as tiny as 3 nm thick for
a four layer device


CE News, April 13 (1998)
P.44
103
An Amphiphilic Copolymer that Undergoes Folding
and Irreversible Conformational Change
D electron - donor
A electron-acceptor
D
A
A
A
D
D
-OOC
COO-
COO-
COO-
104
An Amphiphilic Copolymer that Undergoes Folding
and Irreversible Conformational Change (Contd)

• a deep-red solution in water at RT
• Folding inter-molecularly
• becoming a pale-pink gel (tangled aggregation)
  at 80oC (irreversible at RT)
• 
  JACS, 121, 2639 (1999)

105
Room Temperature
80OC
106
Intermolecular link stabilizes self-assembled
peptide cylinder CE News, Jan.15 (1996), p.18
Self-assembly into nanotubes (13 A in diameter)
which aggregate into 200-300 microns
107
Cy cyclohexyl
108
Cell-surface Engineering

• Carbohydratebased drug delivery
• Modification of tumor cells to increase the
• drug uptakes
• (CE New, May 5, 1997)
• (CE New, Feb 2, 1998 )

109
Synthetic polymers recognize all four base pairs
in DNA(Nature, 391, 468, 1998)

• Polyamide consisting imidazole, hydroxy pyrrole
• and pyrrole units
• Wraps around segment of double strained DNA,
• through hydrogen bonding to thymine (T),
• guamine (G), adenine (A)

110
Planar-support solid-phase synthetic
technique CE News, July 3 (2000), p.
26 Biopolymers, 47, 397 (1998)
Chemical reactions are carried out in small
spots on functionalized planar supports made of
paper, cloth, or polymer.
111
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112
Review

• Polymers vs. Copolymers
• Interacting with nanoscale inorganics
• Secondary structureself-assembly
• Two-dimensional devicesfilm
• Property vs. Applications

113
Required Reading Advanced functional polymer
membranes by Mathias Ulbricht Polymer 47
(2006) 22172262 (www.elsevier.com/locate/pol
ymer)

• Oral reports
• Synthesis and chemical structures
• Experimental procedureshow to do the experiments
  
• Property/Performance
• Critiques and comments Meaning of data,
  significance, uniqueness and contribution to this
  area of research
• Powerpoint presentationhow to prepare

114
Suggested Topics for Oral Reports (2008)

• 1. sol-gel reactions and polymers (2 students)
• 2. Free-radical living polymerizationprocess or
  polymer structure or applications (3-4)
• 3. AgNP, AuNP, Fe3O4, .nanoparticlessynthesis/fu
  nction/application----biomedical and magnetic
  property, etc.
• 4. self-assembly (and nanoarrays) (2)
• 5. amphiphilic copolymers (2)
• 6. self-assembly, self-organization and
  self-synthesis
• 7. polymeric electrolytes (new development) (1)

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Literature example 1 Discussion on (1)
homo-polymers vs. copolymers (2) Starting
material sources (3) extension or prediction
amine functionality and how to make it and
property different pH sensitive (4) carboxylic
acid ? (5) New knowledge and new proposalaverage
or innovative proposal?
By varying the polymer structure, its function is
changed.
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Unique Properties Among these polymers, one of
the most representative examples is
poly(N-isopropylacrylamide), which is hydrophilic
and exists in a random coil in water below 31 C.
The copolymer corresponds to a lower critical
solution temperature (LCST). Above the LCST, it
becomes hydrophobic and changes its conformation
from a random coil to a globule, then aggregates
due to the hydrophobic interaction among the
isopropyl groups. It has potential uses to
immobilize bioactive molecules, such as peptides
and proteins. The polymer is temperature-respons
ive but unaffected by the pH.
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Quiz 1 redraw the following reaction scheme!
118

• Quiz 2 draw the synthetic schemes
• Poly(styrene)-b-poly(butadiene)-b-poly(styrene)
• a triblock copolymer
• 2. EG-initiated EO/PO triblock copolymer

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Homework

• Do a literature search or use your imagination to
  illustrate an example of dispersion. hint
  what is being dispersed? in what medium? by what
  dispersant (a copolymer)?
• And explain the principle and uses.

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Key words

• 1. Sulfonation SO3H in imidazole- linking
  polymer film
• 2. Crown ether Planar ? Crystalline ? Solubility
  (insoluble in methanol but soluble in
  NaOH/methanol)? Geometric size? Metal complex
  (softhard material)? functions (i.e., metal
  salt into organic matrix! Interface!)
• 3. Surpamolecules by self-assemblyanti-surfactant
  ?

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Quiz 1 ( )

• 1. what is anti-surfactant?
• 2. elaborate the meanings of 18-crown-6
  structure
• 3. elaborate the meanings of PIB-ethylene-diamine
  structure.

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Key words 2

• Oxo process hydroformylation synthesis gas
• Anti-oxidant Mechanism vs. olefin polymerization
• Amine synthesisaromatic and aliphatic amine
  (Isophorone diamine?)
• Polyvalent interaction for drug design
• New Chemical Developments (???????)
• Nanoscalemeaning