Smart Electrochemical Sensors: From Advanced Materials To .
Nanosensors:Transitioning Nanosensors from the laboratoryto the marketplace:Challenges and Lessons learnedWunmi SadikDepartment of ChemistryState University of NewYork-BinghamtonNNI Nanosensor WorkshopSeptember 11-12th, 2014,Washington, DC
Science –to –Technology (S2T) A vast amount of nanosensors havebeen developed, tried and testedbiosensors electrochemical capacitors batteries, fuel cells, novel membranesystems and many more There are many roadblocks in bridgingthe gap between academic research andthe market place2
Highlights Operational definitionsCategory 1 nanosensor Category 2 nanosensor Case studiesUltra-sensitive Portable Capillary Sensor (UPAC ) CeO2, Fe2O3, TiO2, ZnO, and fullerenes Testbeds and performance metrics Bridging the gap a proposal for moving forward
How do you bridge the gap betweenresearch and commercialization?Answer the two key questions ofsuccessful innovation: Can you make a product?Can you get anyone to buy it?4
Trivia Questions Who was:The first innovator of electrochemistryinstruments? The person who founded ShockleySemiconductor Laboratory creating SiliconValley and electronics innovation?
Answer Arnold Orville Beckman (April 10, 1900 – May 18,2004) was an American chemist who founded BeckmanInstruments based on his 1934 invention of the pHmeter, a device for measuring acidity. He also fundedthe first transistor company, thus giving rise to SiliconValley.
Beckman’s pH meterBeckman's first pH meter - predecessor of Model G.This is a picture of original model made in 1934 and patented.Picture courtesy of Beckman Coulter, Inc“maybeModel G pH meter.Device was closed in wooden box 12"wide by 8" deep by 9" high. - was hardlyportable, weighting almost 8 kilograms.you want to call it entrepreneurship or invention, I don’tknow. But anyway, I thought, well, heck, lets make a completeinstrument then. Get rid of the stuff spread on the desktop and makeit a compact unit”.
Nanosensor Classification Type 1 Nanosensors:Nanotechnology-enabled sensors orsensors that are themselves nanoscaleor have nanoscale materials orcomponents Type 2 Nanosensors:Nanoproperty-quantifiable sensors thatare used to measure nanoscalepropertiesSadik et al, Journal of EnvironmentalMonitoring, 11, 25, echnology-whitepaper-0207.pdf
Category 1 Nanosensors Hundreds of research articles using nanomaterials for chemical &biosensors have been published. There are dozens of reviewsavailable which partly deal with use of nanomaterials forelectrochemical nanobiosensorsNanoparticles Nanowires Nanoneedles Nanosheets Nanotubes Nanorods Biosensors & Bioelectronics, 24, 2749-2765, 2009.
Metal-Enhanced Electrochemical Detection(MED)Kowino I., Agarwal R., Sadik O. A., Langmuir 19, 4344-4350, 2003
UPAC BiosensorSUNY-Binghamton scientists and engineers havedeveloped a portable, fully autonomous, and remotelyoperated sensing device, called Ultra-SensitivePortable Capillary Sensor (U-PAC )1. Sadik. O., Karasinski, J, “Ultra-Sensitive, Portable Capillary Sensor”, U.S. Patent No. 8,414,844 B2, April 9, 2013.2. Sadik. O., Karasinski, J, “Ultra-Sensitive, Portable Capillary Sensor”, U.S. Patent No. 7,708,944, May 5, 2010.3. Sadik, O., Wang Q., Blythe, P., US Provisional Application No. 32291/1310 (RB-347), “Capillary Biosensoand its Method of Use”, April 19, 20105. Analytical Chemistry, 74,713-719, 20026. Guide 101-10, March 2007, US Department of Homeland Security, Preparedness Directorate,Office of Grants and Training Systems Support Division, Washington DC.
UPAC instrumentBench-top System(Developed by SadikGroup in conjunctionwith the Naval ResearchLab1,2)Use provenimmobilization andfluorescentchemistry to studyand optimize thecapillary geometry1. Ligler F., Breimer M., Golfen J., Sadik O. A. Anal Chem., 74., 713, 20022. Breimer M., Gelfand G., Sadik O. A., Biosens. Bioelectronics, 14, 779, 20033. Sadik O. A., Karasinski J., U.S. Patent No. 7,708,944"Ultra-Sensitive, Portable Capillary Sensor, May 5, 2010.
Performance CharacteristicsTechniqueLODUPAC 00spores/mlStandard ELISAStandard PCROptical Leaky CladwaveguidebiosensorDOXQualitativeResponseTime30 minSample Preparation6hrsExtensive12 hrs40 minExtensive (PCRextraction)Autonomous30 minMinimalMinimal
Category-1:Nanoscale PropertiesFew sensors exist to measure nanoscaleproperties including mechanical, electronic,photonic, and magnetic properties ROS production Characterization methods Not high-throughput Not mass quantitativeElectron microscopy Size, shape, compositionCrystallinity XRD, XPS, RamanSize in liquid DLS(Auffan et al., 2009)14
Conventional and emerging tools forcharactering engineered nanoparticlesSP-ICP-MS Single Particle Inductively Coupled Mass Spectrometer,FFF-ICP-MS Fluid Flow Fractionation Inductively Coupled Mass Spectrometer,EC-TFF Electro-Chemical Tangential Fluid Flow, DOX-EC Dissolved oxygen Sensor15coupled with Electrochemical technique, DLS Dynamic Light Scattering.
Category 2:Size-exclusive Nanosensors forQuantitative Analysis of FullerenesSADIK et al, ES&T 2011, 45, 5294 – 5294A single-use quantity of cosmetic (0.5 g) may contain up to 0.6µg of C60 and demonstrates a pathway for human exposure toengineered fullerenesBenn et al., Environ. Poll. (2011)
Nanosensor ResponsesDose dependentresponse Active sensing electrode surface area of 0.196 cm2, an equivalent of2.02 x1012 beta-CDs should fit on the QCM sensor At low concentrations, the ratio of beta-CD/C60 molecules was 1.12C60/cavity which, is consistent with the host-guest chemistry of beta-CD-C601:1 inclusion chemistryES&T 2011, 45, 5294 – 5294.
Category 2:Capture and Detection of AerosolNanoparticles using Poly (amic)acid, Phase-inverted Membranes1SUNY-BINGHAMTON,NY2 HARVARD SCHOOL OF PUBLIC HEALTH, MA, Sadik, Demokritou et al,J. Hazardous Materials, 2014(In press), Nanoletters 201418
Harvard’s VENGESNew Platform for pulmonary and cardiovascular toxicologicalcharacterization of inhaled ENMsNanotoxicology, 2011; Early Online, 1–1119
Surface Characterization20
Proposal for Going Forward Develop the necessary calibrationand validation toolsDevelop SRMs and the analyticalquality control toolsDevelop acceptable standardstestbeds & charactization centers
Overcoming Present Challenges Develop acceptable Depends on testbedsSRMs Calibration/validationtools Standardization and TestingCenters Develop training manuals & SOPs Define measures of success
23
Test beds depend on theapplication Health Food Pharmaceutical Process Environmental Defense& Security
Testbed Specifications Environmental sensor should be sensitive,specific, provide fast response, must bereliable, flexible and capable of rapid anddirect detection of toxic compounds. Additionally, there should be no need forsample preparation steps when analyzingenvironmental matrices or point-of-carebiomedical samples. The sensor should be capable of convenientsignal processing that will allow immediateremedial actions to be taken after detection25
Environmental and Clinical Requirements Precision,accuracy,measurement range, total error Interference Reference Response time Calibration Manufacturing Single use Vs. multi-use
Nanosensor PerformanceMetrics-EPA QA/QC Data quality parameters Method Determination Method positive control, matrix spike, negative control(buffers,blanks, reagent water)Frequency Precision, accuracy, LOD, robustness etcWith every field sample, 1/batch or 20 samples, 10% of fieldsamples, all standards, blanks, samplesQuality objective & Comparability % RSD, MDL, intended use of data Designated Analytical Levels. Sadik et. al, Journal of Environmental Monitoring, 6,513-522, 2004; US-EPA (1995) and revisions. TestMethods for Evaluating Solid Waste & Emergency Response, Washington DC.27
Performance Metrics Experimental variables should be definedSensitivity should be defined Selectivity and reliability (false positives andfalse negatives) should be assessed usingSOPs. Optimization of experimental variablesinfluencing sensor selectivity and sensitivity aswell as the transfer to manufacturing platforms. Comparable to standard EPA, AOAC or FDAmethods.28
Conclusions -Needs of the Community) Manufacturing must produce stable sensors withuniform and non-distortable signals acrosssensing area Sensor layers must be mounted with a suitabletransducer that does not distort them Unpreventable calibration errors in the devicesmust be reduced to an acceptable level Developing QC for the sensor industry requiresthe collaboration between the manufacturing,government, and research laboratories
Wunmi Sadik Department of Chemistry State University of New York-Binghamton . NNI Nanosensor Workshop . September 11-12th, 201
Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton-electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface.
Xu, X. 2019. Interface Studies for Gold-based Electrochemical DNA Sensors. Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 1882. 83 pp. Uppsala: Acta Universitatis Upsaliensis. ISBN 978-91-513-0824-1. Gold based label-free electrochemical DNA sensors have been widely studied for biomarker .
Other examples of sensors Heart monitoring sensors "Managing Care Through the Air" » IEEE Spectrum Dec 2004 Rain sensors for wiper control High-end autos Pressure sensors Touch pads/screens Proximity sensors Collision avoidance Vibration sensors Smoke sensors Based on the diffraction of light waves
Sensors 2008, 8 1404 for the increased use of electrochemical sensors to characterize biointerfaces. Emerging devices for electrochemical biosensors inspired by advances in microelectronics and nanotechnology like the bio-field effect transistors, nanowires and other "near-molecular scale devices" will be introduced. The last
1. Understand the relation between work and free energy in an electrochemical cell. 2. Use experimental data to derive thermodynamic quantities for an electrochemical reaction. 3. Understand the correspondence between theoretical expressions and graphical methods of data analysis. 4. Distinguish energy, work and power in an electrochemical system.
CHAPTER 21,Electrochemistry (continued) 10. Circle the letter of each sentence that is true about electrochemical cells. a. An electrochemical cell either produces an electric current or uses an electric current to produce a chemical change. b. Redox reactions occur in electrochemical cells. c.
material covered in the class, or can be explained using electrochemical concepts covered in the class. Journal of the Electrochemical Society Nano Letters, ACS Nano, Chemistry of Materials Electrochemical and Solid State Letters Journal of the American Che
spectroscopy has been used and morphological study was done using field emission scanng in electron microscope(FE-SEM) technique. Electrochemical properties were studied by electrochemical impedance spectroscopy (EIS). The electrochemical properties of polyaniline thin
