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Advanced Materials and Coatings

John Texter
School of Engineering Technology, Eastern Michigan University,
Ypsilanti, MI 48197, USA

22 February 2011
Antimicrobial Anionic Surfactants and
Vectors for Delivering Silver Ion

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Use of Reverse-Micelle Forming Anionic Surfactants as
Vectors for Ag+ Delivery into Hydrophobic Coatings

AOT or S1

Na+ easily ion


exchanged with
Ag+

22 February 2011
Application of E. coli to AgAOT (AgS1) containing
polyurethane coatings

μmol
a
% weight Ag in CFU/ml of E. coli at 12 h CFU/ml of E. coli at 24 h
Ag/cm² Coating

0 0 5.8 x 105 , 2.9 x 105, 4.1 x 105 6.8 x 106 , 3.4 x 105, 1.2 x 105
0.00310 0.0012 6.5 x 104 , 4.2 x 104, 1.21 x 105 1.1 x 105, 1.0 x 10³, 3.0 x 10³

0.00737 0.0031 1.4 x 105, 1.3 x 105, 5.8 x 104 1.5 x 10³, 0, 3.0 x 10³
0.00131 0.0061 5.0 x 10², 1.1 x 104, 3.0 x 104 0, 1.7 x 104, 0
0.00250 0.012 5.5 x 104, 9.5 x 10³, 3.5 x 104 0, 0, 0

0.00597 0.031 0, 0, 0 0, 0, 0
0.0122 0.061 0, 0, 0 0, 0, 0
0.0261 0.122 0, 0, 0 0, 0, 0

22 February 2011
Application of P. aeruginosa to AgAOT (AgS1)
containing polyurethane coatings
μmol
a
% weight Ag CFU/ml of P. aeruginosa at 12 h CFU/ml of P. aeruginosa at 24 h
Ag/cm² in Coating

0 0 5.5 x 104, 3.3 x 105, 1.0 x 105 5.0 x 104 , 3.2 x 105, 2.2 x 105

0.00310 0.0012 3.0 x 104, 9.5 x 105 , 2.6 x 104 0, 0, 0

0.00737 0.0031 1.1 x 104, 1.2 x 105, 3.3 x 104 0, 0, 7.5 x 10²

0.00131 0.0061 4.8 x 10³, 2.5 x 10², 6.3 x 10³ 0, 0, 0

0.00250 0.012 1.5 x 10³, 1.5 x 10³, 3.8 x 10³ 6.3 x 10³, 0, 5.0 x 10²

0.00597 0.031 0, 0, 0 0, 0, 0

0.0122 0.061 0, 0, 0 0, 0, 0

0.0261 0.122 0, 0, 0 0, 0, 0

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Serendipity
Contact (h) CFU/ml

B. subtilis S. aureus

0 3.6x104 2.0x105
12 0 0
24 0 0

0 1.6x104 5.1x105
12 0 0
24 0 0

Initial tests of polyurethane coatings on glass slides showed that


sodium surfactant controls, comprising S1 (AOT) at 30% by
weight, killed all of the B. subtilis and S. aureus after 12 and 24 h
exposure.

22 February 2011
Serendipity
Broth Test (TSB)
An initial broth test with (AOT) S1 showed that growth of the
bacteria was inhibited in the broth containing S1, but growth
was sustained in the broth free of S1.
This broth test was then repeated at S1 levels of 1%, 0.5%,
0.25%, 0.12%, and 0.063% with B. subtilis, S. aureus, E. coli,
and P. aerugenosa. After incubation the broths were plated
onto TSA plates and again incubated. No effect on E. coli and
P. aerugenosa, but all the B. subtilis was killed at every
dilution, and only a very few colonies were observed for S.
aureus at the two lowest dilution levels.

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Staphylococcus aureus
Bacillus subtilis
ATCC6538
ATCC33
Pos
Pos Panel of 23
Escherichia coli
Pseudomonas aeruginosa
ATCC11229
ATCC15442
Neg
Neg Bacteria and
Klebsiella pneumoniae
Enterobacteria aerogenes
EM22/ATCC13883
EM25
Neg
Neg Yeast Strains
Escherichia coli
Salmonella typhimurium
EM55
EM56/AA2202
Neg
Neg Investigated
Serratia marcescens EM6 Neg
Streptococcus viridans EM8 Pos
Escherichia coli EM2 Neg
Staphylococcus aureus EM24/ATCC25923 Pos
Streptococcus bovis EM12 Pos
Enterococcus fecalis EM19 Pos
Enterococcus fecalis EM19 Pos
Staphylococcus epidermidis EM3/ATCC12228 Pos
TSB Only

Streptococcus pyogenes EM14 Pos


Streptococcus agalactiae EM13 Pos
Candida tropicalis EM23 Yeast
Bacillus subtilis EM27 Pos
Micrococcus luteus EM17 Pos
Salmonella typhimurium EM57 Neg
Salmonella typhimurium EM38 Neg

22 February 2011
Anionic Surfactants Evaluated

S1

S2

S3
S4

S5

22 February 2011
Plate Tests With Surfactants
S1, S2, S3, S4, and S5

All Anionic

No Effect on Gram Negative Species!

22 February 2011
Plate Tests

1010 organisms spotted onto each plate; growth


assessed after 18-24 h; P ~ intermediate result

22 February 2011
Plate Tests

1010 organisms spotted onto each plate; growth


assessed after 18-24 h; P ~ intermediate result

22 February 2011
Plate Tests
No Gram-negative activity.
S1 & S2 active against all Gram-positives tested.
All S’s active against S. bovis.
Relative activity
S1 ~ S2 > S3 > S4 ~ S5

Hydrophobicity (clogP)
S1(2.5) > S2(1.3) > S3(0.7) ~ S4(0.7) > S5(0)

Activity probably stems from tendency to partition into membrane


and disrupt membrane function.

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Membrane Poration Hypothesis

22 February 2011
Membrane Poration Hypothesis

Glycerol monooleate vesicles are porated by equilibrium adsorption of


surfactant (C16 TAC). These cryo-TEMs represent CTAC/GMO ratios of 1,
1.7, 2.3 (left, right, lower); the scale bar is 100 nm.
(M Kadi, P Hansson, M Almgren. J Phys Chem B (2004) 108:7344-7351; Determination of isotherms for
binding of surfactants to vesicles using a surfactant-selective electrode.)

22 February 2011
Membrane Poration Hypothesis

Oil soluble surfactants will preferentially partition into the


membrane bilayer to form reverse micelles, thereby forming de
facto pores. A structural model of a reverse AOT micelle depicts
such a hypothetical structure. The reverse micelle was produced
by Abel et al.2 in an extensive modeling study.

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
MIC for S1
Optical Density vs. Log AOT Concentration
% AOT(S1) Absorbance S. aureus
0.65

0 .0 0 0
by wt (CFU/mL)

0 .0 0 0

0 .0 0 0
0 .0 0 0

0 .0 0
0.6

0 .0 0

000
0.55 0.45 0.376 0

0000
000

000
00
00
0.5 0.23 0.218 0
Optical Density (ODU)

0.45 0.11 0.103 0


0.4
0 .0 0

0.35 0.057 0.034 0

0.3 0.028 0.031 0


0 .0 0

0.25 0.014 0.012 0


0.2
0.0071 0.017 150, 200
0.15
0 .0 0

0.1
0 .0 0

0.0039 0.552 Confluent Growth


0 .0 0

0 .0 0

0 .0 0

0.05 0.00195 0.559 Confluent Growth


0
0

0
00

0.000975 0.549 Confluent Growth


1 -0.05 0.1 0.01 0.001 0.0001 0.000485 0.54 Confluent Growth
Log00 AOT Con. (%) 0.000244 0.59 Confluent Growth
0.000244 0.59 Confluent Growth

MIC = 0.01% S1 → 0.000122 0.547 Confluent Growth


0 0.573 Confluent Growth

MIC = 100 μg S1/mL Blank (TSB) 0 0

22 February 2011
MIC for Ampicillin AMP Absorbance S. aureus
Optical Density vs. Log Ampicillin Concentration (μg/mL) (CFU/mL)
64 0.008 0

0.0313
0.6 32 -0.001 0
0.55 16 -0.006 10,10
0.5
Optical Density (ODU)

0.125
8 -0.004 30,18

0.0157
0.45
0.4 4 0.006 10,12

0.06125
0.35

0.25
2 0.012 2,2
0.3
0.25 1 -0.01 3,10
0.2 0.5 0.016 CG
0.15
0.1 0.25 0.257 CG
0.5
64

16

0.05
32

0.125 0.34 CG
4
8

0
0.06125 0.402 CG
100 10 1 -0.05 0.1 0.01
0.0313 0.482 CG
Log10 Amp. Con (mg/uL) 0.0157 0.514 CG
0 0.542 CG

MIC = 1 μg/mL
MIC = 32 μg/mL Blank (TSB +
AMP)
0 0

22 February 2011
MICs

S1 appears 1/3 as effective


as Ampicillin!

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Application to PU for Catheters
TDI/PPG PU doped with AgAOT and contacted with
E. coli for 24 hours.
Doping CFU/mL at 24 hours of E. coli

1st 2nd
3% AOT 2.3x106 2.7x106
1% AOT 8.5x105 5.0x105
0% AgAOT/AOT 2.6x106 1.90x106
0.01% AgAOT 3.7x106 2.0x106
0.03% AgAOT 2.5x106 2.4x106
0.1% AgAOT 1.7x105 1.9x105
0.3%AgAOT 0 0
1% AgAOT 0 0
3% AgAOT 0 0

22 February 2011
Application to PU for Catheters
TDI/PPG PU doped with AgAOT and contacted with
S. aureus for 24 hours.
Doping CFU/mL at 24 hours of S. aureus

1st 2nd
3% AOT 0 0
1% AOT 0 0
0% AgAOT/AOT 1.0x105 1.0x105
0.01% AgAOT 9.0x104 1.0x105
0.03% AgAOT 1.2x105 1.0x105
0.1% AgAOT 1.4x105 1.2x105
0.3%AgAOT 0 0
1% AgAOT 0 0
3% AgAOT 0 0

22 February 2011
Such reverse micelle forming
surfactants make adding silver ion
to PU coating and bulk
formulations a simple “drop in”
reformulation.

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Application to Fabrics
A series of commercially available fabrics were
obtained as substrates upon which to test AgAOT
and AOT.
The commercially available fabrics are cotton, jute,
linen, silk, polyester, acetate, rayon, and nylon.
AgAOT or AOT solution was sprayed on a
rectangular area of fabric in a spray booth, dried,
weighed to check deposition, and then sterilized in
an autoclave. The swatches were then cut up into
smaller pieces for repeat testing.

22 February 2011
Application to Fabrics

22 February 2011
Application to Fabrics

22 February 2011
Application to Fabrics

22 February 2011
Application to Fabrics

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Application to Household Surfaces
A series of commercially available indoor household
materials were obtained as substrates upon which to
test AgAOT and AOT.
These materials are window treatment/shade,
polyacrylate sheet, polycarbonate sheet, aluminum
sheet, ceramic tile, metal plate (light switch box
cover), wall paper, and vinyl tile. Samples were cut
into 2cm x 5cm coupons for testing and were
sterilized after coating with AgAOT or AOT by
spraying.

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Application to Household Surfaces

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Toxicology
In ophthalmological formulations, concentrations
greater than 0.1% may cause conjunctival irritation;
repeated use my delay healing of corneal lesions.

22 February 2011
Toxicology
Toxic dose in humans is unknown.
S1 (AOT) used extensively in mineral oil laxative
formulations and as a stool softener.
Toxicity following acute ingestion of excessive
amounts of laxatives is generally minimal and
limited to the gastrointestinal tract.
Hypothesis: Beneficent Gram positive flora killed on
ingestion may lead to intestinal distress.

22 February 2011
Toxicology
As a laxative and a stool softener -

In existing formulations/preparations, S1 is supplied


as 50, 60, and 100 mg capsules and tablets, as 250
& 300 mg capsules, in solution for oral
administration at 10 and 50 mg/mL and as syrup at
4 mg/mL.

22 February 2011
Toxicology
In animals large doses of S1 produce anorexia,
vomiting, and diarrhea.
Even in chronic feeding tests, fatally poisoned
animals show only diarrhea and intestinal bloating,
with no gross lesions outside of gastrointestinal
tract.
Docusate salts (S1) can occasionally cause
diarrhea.
Morphological damage to the intestines has been
observed in rats.
May be hepatotoxic (liver).

22 February 2011
Silver as an Antimicrobial Agent
Serendipity
Plate Tests
Membrane Poration Hypothesis
MICs
Foley Catheter PU Doping
Fabrics
Household Surfaces
Toxicology
Proposed Applications
22 February 2011
Proposed Applications

Develop prophylactic spray for surgeons to use


before closing.
Develop spray treatments for hospital, school, and
public building treatments.
Develop spray for topical burn treatment.
Develop cleanser for acne treatment.
Develop household prophylactic spray.

22 February 2011
Summary
Family of anionic surfactants appear lethal to
Gram-positive bacteria and to some other
microbes.
MICs competitive with known antibiotic.
Preliminary fabric spray tests look promising.
Many new cleaning and prophylactic product
applications to consider.
Adding our surfactant technology to existing
cleansers produces a prophylactic long-acting
product.
Now is the time to capitalize on MRSA hysteria!

22 February 2011
Carbon Nanotube Membranes and
Coatings

22 February 2011
Reactive Ionic Liquid Surfactants

Such reactive monomers found to produce


interesting new copolymers:
Ultrastable nanolatexes
Reversibly porating membranes
Ionic liquid polyelectrolytes
Di-stimuli responsive diblocks

22 February 2011
Microporous Materials From Polymerized
Microemulsion Gels

22 February 2011
Nanolatex Primers
Latexes 20-28 nm diameter produced by
microemulsion polymerization

22 February 2011
Nanolatex Primers
Comparison with commercially available
latexes.
These nanolatexes form robust films.
Particle
Young's
Latex type Size Monomers
Modulus (MPa)
(nm)
Nanolatex 50.5 ± 1.8 25 IL-Br/MMA
Commercial
1.41 ± 0.03 297 Vinyl/Acrylic
Latex 1
Commercial
Latex 2 4.0 ± 1.8 322 Vinyl/Acrylic
Commercial
Latex 3 2.0 ± 0.6 256 Vinyl/Acrylic
Commercial Styrene, Butyl
1.4 ± 0.2 237
Latex 4 Acrylate/Acrylonitrile
Styrene, Butyl
Commercial
140 ± 16 990 Acrylate/Styrenated
Latex 5
Polymer/Polyalkylene Glycol

22 February 2011
Nanolatexes Are Good Film Formers

Transparent Latex Films Treated with Aqueous KPF6

22 February 2011
Nanolatex Primers
Pores can be generated in latex films by soaking in
aqueous KPF6.

22 February 2011
Nanolatex Primers
Topcoat cross-cut adhesion/thickness (µ m)
results for nanolatex-based pigmented primer

22 February 2011
Summary
Nanolatexes ultrastable
Nanolatex films 10x-35x tougher than
commercial latex films
Excellent adhesion on aluminum, plastic and
wood

22 February 2011
Nanolatex Dispersions of SWCNT
Equivalent optical density (average absorbance
over 600-400 nm)

16,000 OD/wt
fraction

22 February 2011
Latex SuperPrimers
Equivalent optical density (average absorbance
over 600-400 nm)

22 February 2011
Proposed Exfoliation Mechanism

22 February 2011
MWCNT Unwinding by Nanolatex
Stabiization

22 February 2011
MWCNT Electrical Conductivity(Through
Plane)

22 February 2011
MWCNT Thermal Diffusivity
(Through Plane)

1.1 mm2/s
(in plane)
SWCNT

22 February 2011
MWCNT Dispersions
How Concentrated?

wt% OD/wt fraction


0.476 55,210
1 56,500
2 57,115
3 60,333
4 59,205

22 February 2011
MWCNT Dispersions
How much needed for complete
exfoliation?

22 February 2011
MWCNT Dispersions
How much needed for complete exfoliation?

0.5-4% MWCNT – Critical amount of nanolatex varies


from 0.23 to 0.31 weight fraction of MWCNT

22 February 2011
MWCNT Dispersions
Latex film dried and pyrolyzed @ 800°C

22 February 2011
Saturation Adsorption of Nanolatex on MWCNT

22 February 2011
Templated Coatings

22 February 2011
Templated Coatings

3 mg MWCNT/cm2
Carbon Fiber Paper

λ|| ~ 1,600-2,000 mm2/s λ|| ~ 46 mm2/s

λ⊥ ~ 0.7-1.0 mm2/s λ⊥ ~ 5 mm2/s


λ|| ~ 4,600 mm2/s – aligned CNT array

Xie, Cai, & Wang, Phys Lett A 369 (2007) 120-123


22 February 2011
Templated Coatings

One of our experimental


coatings of Baytubes (3
mg/cm2) out of aqueous
dispersion

Graphite, pyrolytic graphite, Ag


foil, and carbon fiber paper
controls; linear regression line
extrapolates 900%

22 February 2011
Templated Coatings

Cp~ 0.75 J/g/K


λ|| ~ 1,600-2,000 + k ~ 0.84-1.05


mm2/s ρ ~ 0.7 g/cm3 kW/m/K

22 February 2011
Biomass Hydrothermal Carbon
Dispersions – Antonietti/Titrici (MPIKG)

22 February 2011
Nanolatex Dispersion of WC

22 February 2011
Nanolatex Dispersion of WC

22 February 2011
Nanolatex Dispersion of WC

22 February 2011
Solvent-Free Nanofluids and Resins

22 February 2011
Summary
Imidazolium-based nanolatexes efficiently disperse CNTs
in water, particularly MWCNT (up to 17% w/w).
As is dispersions suitable for printing conductors.
Simple coating produces MWCNT membranes suitable for
electrodes and membranes for various applications.
The use of nano-WC/nanolatexes for stabilizing MWCNT
should produce a practical fuel cell electrode for the ORR.
New and effective heat transfer elements suitable for
flexible electronics should derive from the presently
illustrated examples.

22 February 2011
Solvent-Free Nanoparticle Nanofluids

A¯ =
R(OCH2CH2)7O(CH2)3SO3¯
R = C13 -C15 alkyl
N+ = (–O)3-x (CH3O)xSi(CH2)3N+(CH3)(C10 H21 )2

A.B. Bourlinos, R. Herrara, N. Chalkia, D.D. Jiang, Q.


Zhang, L.A. Archer, E.P. Giannelis, Adv. Mater. 2005, 17,
234-237; DOI: 10/1002/adma.200401060

22 February 2011
Basic Nanofluid from “7 nm” Silica
Cl- N+
Cl-
+
N

SiO2 (CH3O)3Si(CH2)3N(CH3)(C10H21)2Cl SiO2

N+
Cl-
+
N
Cl-

A- N+
A-
C9H19 +
N
C9H19
SiO2 A=
KO3S O -20 -
O3S O -20
+
N
A-
N+
A-

22 February 2011
Amino Sulfonate
SiO2 (CH3O)3Si(CH2)3N(CH3)(C10H21)2Cl + (CH3O)3Si(CH2)3NH2
+

N+
N+

H2N SiO2 NH2


N+
Cl
N+

N+
N+
C9H19
H2N SiO2 NH2 O
N+
+ S O -20
Cl KO O
N+

N+
N+ C9H19
SiO2 NH2 O
H2N
S O -20
N+ O O
N+

22 February 2011
“Core-Free” Nanofluid

22 February 2011
“Core-Free” Nanofluid

22 February 2011
Isothiocyanate Sulfonate

NH2 NCS
A- N+ A- N+
A- A-
N+ +
N

SiO2 CSCl2 SiO2


N+ - N+
A A-
+ +
N N
NH2 NCS
A- A-

C9H19
A- =
-
O3S O -20

22 February 2011
Air Curing PU Clearcoats
NCO
NCO

CH3
H3C CH2 NHCOO CH2 CH O CH CH OOCHN CH2
6 2 CH3
CH3 CH3 + CH3

~ 1 di-NCO/NCS
44% rh; 24ºC
~ 20% MEK
22 February 2011
Air Curing PU Clearcoats

Cured at 50% rh and 25°C.

22 February 2011
Air Curing PU Clearcoats
TDI/nanofluid Physical State
0- 0.3 Powdery to Hard and Opaque
0.4 – 0.81 “Hard” and Clear
0.82 – 0.95 Tacky and Clear

0 0.1 0.3 0.4 0.5 0.8

22 February 2011
Air Curing PU Clearcoats

22 February 2011
Solvent-Free Acrylate UV Clearcoats
O

O
N+
N+
SiO2 C2 H2 2
+
N A- =
-
O2 S O -2 2
N+

+
O

SR494

Acrylate,SR494 at weight ratios of 50:50 (a50), 60:40 (a60), 80:20 (a80),


and 0:100 (SR)
A photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, was used at 1%
(by weight of total reagents)

22 February 2011
Solvent-Free Acrylate UV Clearcoats

Na
Modulus
increasing
vs Displ
5 0.25
nanofluid
a50 a6
4.5

4 0.2
Modulus Hardness
3.5 property decreases with increasing
Each
nanofluid GPa)
Pa)

3 0.15
22 February 2011
Solvent-Free Acrylate UV Clearcoats

Storage modului by nanoindentation of SR494-SiO2-acrylate resins as a function of


nanofluid content at various penetration depths; (left) after curing for several weeks;
(right) after curing for 10 months.

22 February 2011
Solvent-Free Acrylate UV Clearcoats

Storage modulus by nanoindentation of SR494-SiO2


nanocomposite resins as a function of silica content at
various penetration depths.
22 February 2011
Summary
New approach to non-chipping clearcoats
Reactive nanofluids for new resin classes
New cross-linking materials
Composites become more flexible rather than
brittle

22 February 2011
Advanced Materials and Coatings

John Texter
School of Engineering Technology, Eastern Michigan University,
Ypsilanti, MI 48197, USA

22 February 2011