Soft Electronic Organic Materials - UMass...
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Soft Electronic Organic Materials
Sanjeev K. ManoharAssociate Professor
Department of Chemical EngineeringEngineering 106
www.frontiermaterials.net
BMEBT – introduction to materials
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Outline
Introduction to electronic materials (nano/bio)
Biomedical applications using electronic materials
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What is a nano-material?
A material consisting of a substance or structure which exhibits at least one dimension < 100 nm.
For comparison, a human hair is ~50,000 nm; visible light, ~ 400 - 700 nm.
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Selected Examples of Technological Applications of Nano-structured Materials
• Light-Emitting Devices (LEDs)
• Anti-static coating on photographic
film
• Corrosion prevention of metals
• Energy Storage (batteries, capacitors)
• Electromagnetic interference (EMI)
shielding
• Anti-static floor tiles, carpets, shoe
soles, etc.
• Hydrogen storage
• Transparent electrodes in liquid
crystal displays
• Non-linear (NLO) devices
• Stealth (e.g., radar) avoidance systems
• Gas separation membranes
• Biochemical sensors (e.g., for glucose)
• Sensors for volatile organics (VOCs)
• Solar cells
• Drug releasing polymers
• “Plastic chips”
• Inexpensive, “throw-away” electronic
devices (with possibly smaller
efficiency, precision, lifetime, etc.)
than conventional electronic devices
• All-plastic electronic motors
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Electronic Organic Polymers (plastics that conduct electricity)
Carbon Nanotubes
Graphene
Endotoxin detector
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Introduction to Plastics that Conduct Electricity
Synthetic MetalsIntrinsically conducting polymersElectronic organic polymersInherently conductive polymersElectronic plastics ‘Dirty metals’
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Conducting Polymers“Synthetic Metals”
• Electronic, Magnetic, Optical Properties of a Metal.
• Mechanical Properties, Processability, etc., of a conventional polymer.
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106
104
102
100
10-2
10-4
10-6
10-8
10-10
10-12
10-14
10-16
Ag, CuFeMg
In, Sn
Ge
Si
AgBr
Glass
Diamond
Nylon
Quartz
INSU
LATO
RS
SEM
ICO
ND
UC
TOR
SM
ETA
LS
INC
REA
SIN
G D
OPI
NG
LEV
ELS
Conductivity increases with increased doping
Doped trans-(CH)x[105 S/cm]
Doped polyaniline [103 S/cm]
trans-(CH)x[10-5 S/cm]
Polyaniline[10-10 S/cm]
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Conductivity is the Flow of Charge
It depends on:
what is flowing ?how many ?how easily ?
σ = e x Ν x μ
Electron Charge
Number of charge carriers (flow)
Carrier mobility (flow)
charge
flow
flow
What is Conductivity?
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Current in pathway
Current out
Simple model for metal conduction
Metal
Metals are good conductors
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Pathway blocked
Plastic
Current in
Plastics as Insulators
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Why are plastics good insulators?
1. They don’t have a pathway to carry current.
2. They don’t have any charge to carry current
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Modification of PlasticsMake a pathwayCreate current carriers
no pathwayno carriers
pathway
pathwayno carriers
pathwaycarriers
carriers
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The Idea
Benzene3 single bonds3 double bonds
Now, how do you introduce charge?
HCCH
CHCH
HC
HC
HCCH
HC
CH
HC
CH
HCCH
HC
CH
HC
CH
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HC
CH
HC
CH
HC
CH
HC
CH
HC
CH
HC
CH
HCCH
+
Electricity travels along the chain
Remove an electron
Idea…creating charge in the plastic
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HC CH
HC
CH
HC
CH
HC
CH
HC
CH
+
Flow, or pathway
charge
World’s first conductive plastic! 1977
Conductivity: 34 S/cm (1977); 150,0000 S/cm (2004)
Welding gas, acetylene
“Poly” acetylene insulating
“Poly” acetylene…. conducting
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Y2K Nobel Prize in Chemistry
Alan Heeger Alan MacDiarmid Hideki Shirakawa
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Electronic (Organic) Polymers
Non-Doped: Semiconductors/Insulators
Doped: “Metals”(Conducting Polymers: “Synthetic Metals”)
“de-dope”dope”
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• Organic Polymers
- Electrically Insulating- Electrically conducting
• The Concept of Doping of an Organic Polymer(to increase its conductivity to the metallic regime)
• Redox Doping
- p-doping-- chemical--electrochemical
- n-doping-- chemical-- electrochemical
• Non-redox Doping: The Polyanilines
• Technological Applications
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Concept of Doping of Organic Polymers
• Doping:- The unique, central, underlying and unifying theme in conducting
polymers
• Controlled addition of known, small (<10%), non-stochiometric quantities of chemical species results in dramatic changes in electronic, optical, and structural properties of the polymer
• Doping is reversible (No degradation of the polymer “backbone”)
• Doping and undoping by either chemical or electrochemical methods
• ALSO:
•“Photo-doping” (Transitory: no chemical species added)•“Charge Injection Doping” (Transitory: no chemical species added)
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Polyacetylene* “The Prototype Conducting Polymer”
0.5x HCΞCH cis- (CH)xSilvery films
(semiconductor)
trans- (CH)xSilvery films
(semiconductor)
~150 oC
* H. Shirakawa and S. Ikada, Polym. J., 2, 231 (1971).
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Redox Doping*(Increase or decrease number of electrons on the polymer backbone)
trans- (CH)x 3/2(xy) I2+ [(CH+y)(I3-)y]x
Chemical Doping
*Shirakawa, et al., J. Chem Soc., Chem. Comm., 578 (1977); Phys.\ Rev. Lett., 39, 1098 (1977).
σ ~ 10 -5 S/cm σ ~ 10 5 S/cmy ≤ ~0.1
HC
CH
HC
C
HC
CH
HC
C
HC
CH
HC
CH
CH
HCδ+
δ+ δ+δ+δ+
I3-
A positive soliton (~15 CH units)
Electrochemical Doping
trans- (CH)x (xy) (ClO4) - [(CH+y) (ClO4)y xy) e -+ - (+ y ≤ ~0.1
σ ~ 10 -5 S/cm σ ~ 10 3 S/cm
p-Doping (partial oxidation of the π-system)
Polyacetylene (The prototype conducting polymer)
Anode
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Redox Doping (cont’d)
trans- (CH)x (xy) Na/Hg+
Chemical Doping
σ ~ 10 -5 S/cm σ ~ 10 3 S/cmy ≤ ~0.1
Electrochemical Doping
trans- (CH)x (xy) Li++ [(CH+y) (ClO4)y- y ≤ ~0.1
σ ~ 10 -5 S/cm σ ~ 10 3 S/cm
n-Doping (partial reduction of the π-system)
Polyacetylene
[Nay+(CH-y)] x
Cathode
+ (xy) e -
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Redox Doping (cont’d)
Other examples of redox-dopable polymers(chemical and/or electrochemical)
x
C
Cx
H
H
Z x Z CC
xH
H
Z = NH, NR, S, O, etc.
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Carbon Nanotubes
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What are Carbon Nanotubes?
Diamond, sp3
Graphite, sp2 Fullerene, C60, sp2
Nanotubes, sp2
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What are Carbon Nanotubes?
• A graphene sheet rolled up into a cylinder…..
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Single vs. Multi Walled Carbon Nanotubes
Single-wall carbon nanotube: Tubes closed at the ends by half-fullerenes
Multi-walled carbon nanotube: A concentric arrangement of many tubes
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Metallic and Semiconducting SWNTs
Burghard, M. et al., Small; 2005; 2; 180-192
review1fig002
n - m = 3q (q: integer): metallicn - m ≠ 3q (q: integer): semiconductor
Metallic tubes: Optoelectronic displays, transparent conductors, and chemiresistors
Semiconducting tubes: Switching devices like transistors, diodes and sensors (chem-FETs)
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(0,0)Ch = (10,0)
Wrapping (10,0) SWNT (zigzag)
a1a2 x
y
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(0,0)Ch = (10,0)
Wrapping (10,0) SWNT (zigzag)
a1a2 x
y
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(0,0)
Ch = (10,10)
Wrapping (10,10) SWNT (armchair)
a1a2 x
y
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(0,0)
Ch = (10,10)
Wrapping (10,10) SWNT (armchair)
a1a2 x
y
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(0,0)
Ch = (10,5)
Wrapping (10,5) SWNT (chiral)
a1a2 x
y
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(0,0)
Ch = (10,5)
Wrapping (10,5) SWNT (chiral)
a1a2 x
y
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Interesting Properties of Carbon Nanotubes
Ajayan M et al., Chem.. Rev.; 1999; 2; 180
1nm in diameter, up to 1cm in length, aspect ratio of 107
1 defect in 1012 C atoms => ballistic conduction
High melting point ~3800oC
High young’s modulus 1TPa (103 times diamond)
High electronic current carrying capacity (109A/cm2) ~103 times higher than that of the noble metals
Thermal conductivity 6600W/mK at room temperature is twice the maximum known bulk thermal conductor, isotropically pure diamond = 3320W/mK
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Potential Applications of Carbon Nanotubes
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Sanjeev Manohar - UML CONFIDENTIAL
Graphene oxide and reduced graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
Isolation of single layer graphene sheet (2004)
Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A., Electric Field Effect in Atomically Thin Carbon Films. Science 2004, 306, 666-69
Mechanical exfoliation - (repeated peeling) of highly ordered graphite using scotch tape
Limited yield……Chemical methods……..
Graphite (3D)
Graphene (2D) (2004)
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Sanjeev Manohar - UML CONFIDENTIAL
Synthesis of reduced graphene oxide from graphite
Oxidation
1) Hummers2) Brodie3) Staudenmaier 1) N2H4, NaBH4
2) Thermal3) Radiation
Graphene oxide
Reduction
Park, S.; Ruoff, R. S., Chemical Methods for the Production of Graphenes. Nature Nanotechnology 2009, 4, 217-24
Graphite
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Hummers, W. S., Jr.; Offeman, R. E., Preparation of Graphitic Oxide. Journal of the American Chemical Society 1958, 80, 1339Staudenmaier, L., Preparation of Graphitic Acid. Berichte der Deutschen Chemischen Gesellschaft 1898, 31, 1481-70
Reduced graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
Synthesis of graphene oxide (Hummers method)*
Graphite Nanoplatelets (2g) NaNO3 (1g)
50 mlconc. H2SO4
KMnO4 (6g)5 ml H2O2
Graphene Oxide
Graphene oxide dispersion
H2O
Sonication
Strong acids and oxidants!
*Hummers, W. S., Jr.; Offeman, R. E., Preparation of Graphitic Oxide. Journal of the American Chemical Society 1958, 80, 1339
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Sanjeev Manohar - UML CONFIDENTIAL
Graphene oxide is readily inkjet printed on PET, paper, etc., using commercial printers
Graphene oxide dispersion in water
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1. Empty inkjet commercial cartridge2. Fill cartridge with graphene oxide dispersion
Inkjet print using commercial printer on paper or plastic
Graphene oxide film on PET Inkjet print using commercial printer
on paper or plastic
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Sanjeev Manohar - UML CONFIDENTIAL
Free Free-standing films of inkjet printed graphene oxide lift off a PET substrate
~700 nm
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Graphene oxide film on PET
Immerse in water
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Sanjeev Manohar - UML CONFIDENTIAL
Ascorbic acid readily converts graphene oxide to reduced graphene oxide
RGOAscorbic acid (Reduced)
Ascorbic acid (Oxidized)
∆
Pressed pellet conductivity 15 S/cmVitamin C reduced is similar to hydrazine reduced graphene
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Graphene oxide Reduced graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
Free-standing film of reduced graphene oxide readily obtained by ascorbic acid treatment
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Sanjeev Manohar - UML CONFIDENTIAL
XPS: Fewer defects observed using ascorbic acid as the reducing agent
RGOAscorbic acid (Reduced)
Ascorbic acid (Oxidized)
∆
Graphene oxide Reduced graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
TGA: Reduced graphene oxide powder obtained by ascorbic acid and hydrazine reduction are similar
0 200 400 600 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (oC)
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Vitamin C reduced graphene is similar to hydrazine reduced graphene
Reduced graphene oxide
Graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
An electronic ink of reduced graphene oxide is readily obtained as an aqueous surfactant supported dispersion
Reduced graphene oxide (10 mg) in water
Bath sonicate (20 min)Probe sonicate (5x5 min)
Triton-X-100; n = 9-10
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+
Reduced graphene oxide dispersion
Reduced graphene oxide
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Sanjeev Manohar - UML CONFIDENTIAL
Reduced graphene oxide is readily inkjet printed on PET
1. Empty inkjet commercial cartridge2. Fill cartridge with graphene oxide dispersion
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Inkjet print using commercial printer on paper or plastic
Inkjet print using commercial printer on paper or plastic
Reduced graphene oxide dispersion
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Rapid Endotoxin Detector for the Global Industrial Microbiological Market
VALUE PROPOSITION:
An inexpensive, easy‐to‐use, hand‐held instantaneous endotoxin detection system for industrial and medical applications that requires little to no pre‐treatment of samples
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Testing for endotoxins is now mandatory for every medical device
Global industrial microbiological market ‐ 1.5 B tests (~$4.5 B)
― Beverage, food processing, pharma, personal care, industrial processes & environmental
Endotoxins also cause septicemia (sepsis) –
2 million/yr lives lost in the US ‐ ~$17 billion
No direct test to detect endotoxins in blood
Existing test is based on using blood from horseshoe crab (LAL test)
Slow, cumbersome (takes days for a single test)
Costly (1 quart of horseshoe crab blood ~$15,000, revenues ~$100 million)
Horseshoe crab blood population declining
Urgent and unmet market need
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Urgent and unmet market need
Urgent need for a fast, low cost, endotoxin detection system
Current revenues from rapid microbiology test systems ~$200 million/yr
Customers‐ US Pharma (USP), US FDA, DHS and the entire industrial microbiological sector
End‐users ‐ Amgen, Genentech, Genzyme, Biogen Idec (& others), Homeland Security, Hospitals
Potential licensees ‐ Lonza Group, Charles River, Bio Test, BioDtech (BDTI) and Associates of Cape Cod (ACC)
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Our new technology Identified novel chemistry between endotoxins and antifungals:
Antifungals ‐ large class of polyene macrolides
Instantaneous complex formed between endotoxins can antifungals
53Endotoxins
Antifungal – amphotericin‐B
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Our new technology….cont’d Interrogate this novel chemistry in 3 different ways:
Optical (instantaneous 1ppt level detection)
Electrical (using carbon nanotubes)
Electrochemical (using conducting polymers)
Provisional patent application filed 02/09/2011 covering all 3 detection methods
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A B
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Our new technology….cont’d
Signal change is near instantaneous (optical), or within 2‐5 min ‐significant advantage vs. horseshoe crab blood test (takes days)
Signal is very selective to endotoxins ‐ significant advantage vs. horseshoe crab blood test (sensitive to interferents)
Detection limit is at 0.001 EU/ml (parity with horseshoe crab blood test) with potential to be lowered even further
VALUE PROPOSITION:
An inexpensive, easy‐to‐use, hand‐held instantaneous endotoxin detection system for industrial and medical applications that requires little to no pre‐treatment of samples
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Maturity of our technology
Validated in laboratory environment (all 3 detection methods)
Both optical detection methods already at 0.001 EU/ml (best of class)
Electrical detection using carbon nanotubes at 2‐10 EU/ml (lower using UML’s inkjet printing technology)
Electrochemical detection using conducting polymers at 0.5 EU/ml(lower using UML’s oligomer synthesis methodology)
Tolerates a wide range of potential interferents
PROOF‐OF CONCEPT:
Established. Need to lower detection limits further for electrical & electrochemical methods (use of seed fund)
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Benchmarking vs. competition
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Desired Properties
LAL1 Charles River2 Dimer-AmB Electrochemical
r-GO-AmB Chemiresistor
Optical
Toxin Response Excellent Excellent Good Excellent Excellent
Sensitivity3 0.005EU/ml 0.02EU/ml 0.5EU/ml 0.05Eu/ml 0.001EU/ml
Interferents Excellent
Response time 72hrs 15min 1 min 45 sec 5min
Startup time Poor <1min < 1 min <1min <1min
Portable No Yes Yes Yes Yes
Operator skills High Skills On/Off On/Off On/Off On/Off
Environments Clean room Robust Robust Robust
Unit cost Expensive Expensive <$200 <$20
1Horseshoe crab assay, the industry standard. It is costly, time consuming and cumbersome (but very sensitive). 2New fluorescence based commercial detector (2009). 31EU/ml=100 pg/ml.
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Endotoxin detection platform technology
FIRST MARKET (INDUSTRIAL): Manufacturing Quality Control (1‐3 Yrs)Pharmaceutical, medical device, food, and beverage industries all require endotoxin testing for safety of their products.
UML Solution: Inexpensive, hand‐held sensors that can be taken to the manufacturing site for instant readings without need for sterileprocedure or sample preparation. In‐line sensors for water supply systems with alarms
SECOND MARKET (CLINICAL): Diagnostics (3‐6 years)There are over 750,000 cases of sepsis each year in the United States with 28‐50% being fatal
UML Solution: Array detector that can detect sepsis‐causing endotoxins in whole blood and determine organism responsible, allowing proper drugs to be administered
$25K SEED FUNDING WILL BE USED TO:Increase the sensitivity of the 2 electrical methodsMake a breadboard demonstratorAttract a licensee for industrial applicationsFrom the basis of a second product (clinical)
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Technology transfer planFY 2011 FY 2012 FY 2013 FY 2014
Level‐I funding
(industrial)
Level II funding (industrial + clinical)
$100K $500K $2MM $25K (CVIP)
Improve sensitivity for nanotube/polyaniline sensorDemonstrate discrimination between endotoxinsTesting under real‐world conditionsPattern recognition (single sensors)
Couple with parallel LPS detection testing (e‐nose)
Test, validate and produce multinode detector cassette ‐ breadboard
Usability analysis, manufacturing study, initiate new “family of point detector” study
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Development team
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Members Affiliation Function
Sanjeev K. Manohar UMass LowellChemical Engineering
Improve sensitivity of electrical and electrochem methodsImprove selectivity using wider range of antifungals (sensor array)
Dr. Stephen Heard UMass Medical CenterAnesthesiology
Validation under realistic conditionsTest for detector fouling
Dr. Steve TelloUMass LowellCollege of
ManagementPrepare the technology for the “Venture Project”
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Rapid Endotoxin Detector for the Global Industrial Microbiological Market
Dr. Sanjeev K. ManoharAssociate ProfessorChemical Engineering
UMass Lowell
VALUE PROPOSITION:
An inexpensive, easy‐to‐use, hand‐held instantaneous endotoxindetection system for industrial and medical applications that requires little to no pre‐treatment of samples
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