Valeriu Ciocan, AMS 2020

Supervisor Raivo Jaaniso ,PhD

Gas phase detection of camphor using molecularly imprinted polymer on

a plasma treated graphene film (MSc project)

The presentation provides a brief overview of MIPs and describes a master’s

project goals and hypotheses for designing a sensor for volatile
organic compounds with a graphene transducer and a MIP receptor.
 Content
• Aims and objectives
• Introduction
• Graphene treatment
• MIP
• Optimization
• References
 Aim and Objectives
To integrate Camphor (CMP) imprinted polymer film (CMP-MIP) with graphene
transducer for the detection of CMP and study the performance of the resulting
CMP-MIP/Graphene in terms of sensitivity to and selectivity towards CMP;

1. Selection of a suitable Electropolymerisable monomer;

2. Plasma treatment of the graphene film.
3. Optimization of synthesis parameters for preparation of CMP imprinted
polymer on the working electrode

4. Removal of CMP from the polymer in an appropriate washing out solvent to

generate CMP-MIP ;

5. Characterization of CMP-MIP in terms of template selectivity and limit of

detection.
Problem: Air quality and air pollutants
 Air quality

 The air we breathe contains emissions from motor vehicles, industry,

heating and commercial sources, as well as tobacco smoke and household fuels.

 Air pollution harms human health, particularly in those already vulnerable because of
their age or existing health problems [1]
Example time series trends in air pollution levels. A) National emissions of oxidized nitrogen (NOx)
and sulfur dioxide (SO2) throughout the U.S. from U.S. EPA’s National Emissions Inventory. B)
Annual wet deposition of sulfur (S) and nitrogen (N) since 1979 as measured by the National
Atmospheric Deposition Program at Huntington Forest, NY and total (wet plus dry) deposition
estimated by Schwede and Lear (2014) since 2000 at Big Moose Lake, NY
Global and regional emissions of NH3 and NMVOC between 1750 and 2010.
This graph shows surface ozone concentrations in 2010
The Stockholm Convention on Persistent Organic Pollutants:dioxine, TCDD

LD50 in animals at 0.6 ug/kg

Chronic Toxicity

Effects on Reproductive Function

Mutagenic

Carcinogenic 

Other Systemic Effects

https://www.cdc.gov
Dummy template: (S)-Camphor

-Sublimes at RT

-Safe while considered air pollutant

-Soluble DCM

-Racemic
 Graphene

 2D material, carbon allotrope

 The high electron density and surface area, excellent conductive properties:
dramatic response to the presence of molecules adsorbed on its surface [3]
 can be functionalized to create recognition sites for sensor applications [4]
- spatial distribution of these functional sites on the graphene surface and resulting materials
are difficult to replicate
- material becomes hydrophilic, while drastically diminishing its conductivity.
 A strong demand exists for a method of graphene processing with simple steps and robust results.
Thus, we have considered the plasma enhanced amination
Surface Functionalization of Graphene

 we need to functionalize the Graphene surface with domains capable to selectively

capture and recognize analytes.

 For recognition of gas molecules, we must take advantage of polymer pore size and
use the polymer to block nonspecific interactions with the graphene film [5]

 Graphene doped with Nitrogen functionalities is investigated for its catalytic activities,
however its usually formed via graphene oxide and later reduction, leaving high oxygen
content and poor crystallinity hampering its catalytic activity and reducing its
operation life [6]
Step 1:Plasma functionalisation
1

2
Polymerization:
Monomer selection
The monomer must form a taught, robust, and inert polymer film,
preferably non interacting with the template outside the recognition zones
in the MIP. One important characteristic of the monomer selection is its
solubility in organic solvents which also dissolve the analyte

Conductive polymers, commonly referred to as synthetic metals, they

presented as a macromolecule consisting of repeating structural units with
current conducting properties due to presence of delocalized electron
clouds and/or electrons from the resonance structures

One important interferent is atmospheric water and it

competes for the imprinted areas with the template as shown
in previous work, where nanoparticle MIPs would recognize
formaldehyde gas only in absence of air humidity
Step 4: Electropolymerization
Molecularly Imprinting Step 1. Mixture

17
Molecularly Imprinting Step 2. Attachment
Molecularly Imprinting Step 3.

1
 Molecularly Imprinting Step 4.
2

1
Molecularly Imprinting Step 5.
 Molecularly Imprinting Step 5.1
H2O H2O

H2O
H2O
Ideal response – room temperature/RH%
Thank you

QA
References

 [1] https://www.euro.who.int/en/health-topics/environment-and-health/air-quality
 [2] https://www.eea.europa.eu/data-and-maps/indicators/exceedances-of-air-quality-objectives-7/assessment-2
[3] Baraket, M. et al. Aminated graphene for DNA attachment produced via plasma functionalization. Applied Physics
Letters 100, 233123 (2012).
[4] Nam, K. B. et al. Fabrication of extreme ultraviolet lithography pellicle with nanometer-thick graphite film by
sublimation of camphor supporting layer. Nanotechnology 32, (2021).
[5] Béraud, A. et al. Graphene field-effect transistors as bioanalytical sensors: Design, operation and performance.
Analyst vol. 146 403–428 (2021).
[6] Zhang, C., Hao, R., Liao, H. & Hou, Y. Synthesis of amino-functionalized graphene as metal-free catalyst and
exploration of the roles of various nitrogen states in oxygen reduction reaction. Nano Energy 2, 88–97 (2013).
Figures

Slide 5: https://doi.org/10.1016/j.envsci.2018.02.016

Slide 6: https://doi.org/10.1098/rsta.2019.0314

Slide 24: https://www.als-japan.com/1398.html