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Cyclodextrins!
A powerpoint presentation- 4-05-05:evening
Presenting-Addison CarterAdvisor- Dr David Kammler
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Cyclodextrins:
α-cyclodextrin- 5 sugar moleculesβ-cyclo-dextrin- 6 sugar moleculesγ-cyclodextrin- 7 sugar molecules
Simply cyclized α-d-1,4-glucopyranose sugar
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Utility to HumansCentered in the Torus shaped form, differing interior sizes allow for encapsulation of many target compounds.
β-cyclo-dextrin
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Nonpolar centralcavity
Secondary Hydroxyl rim
Primary Hydroxyl Rim
An ether-like central section creates ideal conditions forpreferential spacial arrangement of non-polar compoundsin the central section
The exterior wall retains polar (hydrophilic) sugar-likecharacter which allows for solubility of the cyclodextrin molecule both with and without a guest molecule
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Bacillus CirculansCyclodextrin glucosyltransferase- Extracted v. in situ
In reaction vats at pH 6.0-7.0 at 35-40 °C.
The source of cyclodextrins
Within starch producing plants
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Targets:
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Real World AppsDrugs
-solubility-photostability-oxidation prevention-ease of handling
Synthesis-site-selective binding-chiral selectivity-general protecting group
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Real World Apps II Environmental Problems
-well water contamination-hypothetically use for heavy metal contamination
Chemical Analysis with HPLC-selective complexation with different target substrates allows for different flow rates for the various target substrates
Enzyme Mimicry?
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Polymerization
Terephthalic acid polymerization
Methyl MethacrylatePolymerization
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Phase Typed Polymerization
Bulk Solution
Emulsion Dispersion
One Phase
Two Phase
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Trouble with polymerization
Surfactants-used in emulsion polymerization, one of the main modes of plastic production-phosphate/sulphate anion base
The problem: Not many readily available natural break down paths
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Alternative Mode to Emulsion PolymerizationDispersion Polymerization:
Non-polar Polar
Some small number of monomericunits move into the aqueous phaseto be polymerized.
-rate-polydispersity-phase separation
Essentially this is the question of how much monomer will transverse the interstitial zone between the oiland water layers
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A Potential Solution: Cyclodextrins as Phase
Transfer Agents
Non-Polar
Polar
Complexation
Polymerization
InitiatorIn this the cyclodextrin modulates the transverse activity of the monomer.
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So then, what's the next Question, Considering:-dispersion polymerization is well documented
-with many substrates-in many solvent pairs-with some phase transfer catalysts
-only one person will be working on this project as a four credit class over the course of a semester
-numbers on the equilibria of substrates/substrate-cyclodextrin pairs is not readily available
-we do not have an NMR available to examine complexation
however,
-we do have a Ultraviolet-Visible spectrophotometric machine -cyclodextrin doesn't absorb UV-Vis spectrum light
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Thus,
-We can find concentrations of photo responsive chemicals in solution
-in the aqueous layer (as well as the organic layer)with and without Cyclodextrin for each of our targetmolecules
-partition coefficients for those solvated chemicals
AbsorptionMolar AbsorptionConstant
Length of Absorbing sample
Concentrationof absorbing sample
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Substrate Choice
- UV-active- polymerizable- soluble- complexable- available from the local stock of chemicals
All these are either mono- or di- substitutedbenzene rings which are known to be quiteUV-active. They are also cheap and polymerizable
Styrene Terephthalic acid p-aminobenzoic acid
p-pentylstyrene
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Para-amino benzoic acid(PABA)
-Locally available-PABA is very UV active-soluble in water-soluble in ethyl acetate
The problem
-Too UV active in Ether, Ethyl Acetate, Water, 1-Octanol.1 M?.01 M?.001 M?.0001 M?
Dilution to this level allowed for a scale within machine detection limits.- Not an effective use of time considering the interest was to study partitioning with an eye toward polymerization which would be served via other routes
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Terephthalic Acid, the First alternateProblem:Solubility
.1 M
.01 M
.001 M
Styrene, the Second Alternative
Unfortunately past this molarity the accuracy of the scale would be called into question for the amount of solvent that was acceptable.
Problem: Time-Only preliminary testing at .01 M was conducted however absorbance was within the detection envelope for the instrument.-Much lower prep time would result in larger volume of data
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AKA: The 1.5 month time warp
AnInterlude
Concerning the Repair of a Certain Piece of Instrumentation
Vital!to the Continuation of Senior Project
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Epsilon Values of PABA in Four SolventsDetermined at .0001M PABA in named solvent
E In Ether
EEE In Ethyl Acetate
In Water
In 1-octanol
20180 at 275 nm
11970 at 284 nm
15650 at 275 nm
13480 at 266 nm
Values taken at the most convenient location along the graph of absorptivity, λ max.
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Partitioning Behavior Compared With and without cyclodextrin
.264 at 273nm
.268 at 273nm1 M equivalent CD
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Amount of Cyclodextrin the issue?
.202 at 276nm
10 Molar equivalents of cyclodextrin presentyields lower absorbancethan the previous 1 Molar equivalent system
-instead of complexing with the PABA the peak shifting right may be a sign of ethyl acetate complexation
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The Road from here:Choice in substrate
-late found resources have recipes in which pure substrate is used as the non-polar phase
example:styrene ON aqueous cyclodextrin mixed -mono-substituted benzene rings-biphenyl
Time to mix-late found materials point to time scale of days for complexation
Substituted cyclodextrin-better match