Surfactant Detection with Surface Enhanced Raman Spectroscopy

Meghan Zuelke ,
1 Ian Bruzas ,
3 William Lum ,
3 Ariel Lebron ,
2 and Laura Sagle3
1Department of Engineering, University of Cincinnati; 2Procter and Gamble; 3Department of Chemistry, University of Cincinnati
Introduction Results Future Work
Surface Enhanced Raman Spectroscopy (SERS) is Dried Samples Improve reproducibility or confine the sample
a technique that uses light scattering to detect A. Uncapped Colloids Dried on a Surface - 633nm Laser B. Uncapped Colloids With and Without CTAB C. Uncapped Nanostars Dried on a Surface - 633nm Laser D. Uncapped Nanostars With and Without CTAB
to a hot spot to increase signal
types of vibrations between atoms within a
50000
SDS Control

Reduce number of extraneous peaks

SDS Control
CTAB Control CTAB Control 20000 CTAB Control 25000 CTAB Control
20000
Uncapped Colloids Control Uncapped Colloids Control Nanostars Control Nanostars Control
Colloids/SDS Colloids/NaCl Nanostars/NaCl

molecule. Nanoparticles made of noble metals

40000 Nanostars/SDS
Colloids/CTAB Colloids/CTAB/NaCl

Determine origin of peaks due to colloids and

Nanostars/CTAB 20000 Nanostars/CTAB/NaCl

Intensity (a.u.)

Intensity (a.u.)

Intensity (a.u.)
Intensity (a.u.)
15000 15000

enhance SERS signal of molecules.1 The shape of

30000

nanostars
15000

10000 10000

the nanoparticles used in SERS can affect the

20000
10000

5000 5000 Determine how the surface shifts peaks

signal produced through different
10000 5000

0 0 Modify substrate to increase surfactant

enhancements. This is in part due to hotspots
0 0
500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500 500 nm
adsorption
500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500
-1 -1 -1
Raman Shift (cm-1) Raman Shift (cm ) Raman Shift (cm ) Raman Shift (cm )

created by sharp edges or other features of Concentrations for all dried solutions: ~2.5uM surfactant, ~180mM NaCl. A. Colloids enhance the signal of a compound that is not SDS or CTAB. B. No unique peaks
Improve limit of detection on substrates
are produced by the CTAB. Significant signal is detected from colloids with NaCl. C. Signal is enhanced by nanostars, though not due to surfactant.
nanoparticles. Various other sample
2 D. Nonaggregated nanostars have no signal, whereas aggregated nanostars show the same signal with or without CTAB on the surface.
Test different substrate shapes
preparations affect signal intensity, including Test with silver particles
capping agent removal, drying the samples on a Solutions Particle Slurries Test charged polymers
metal surface, suspending in solution or A. Colloid/SDS Solutions - 633nm Laser B. Nanostar/SDS Solutions - 633nm Laser Nanostar and Colloid Slurries with CTAB - 633nm

fabricating particles on glass. Conclusions

15000
250000
200000

Solution in H2O
Colloid Slurry
Solution in H2O

Surfactants are used in everyday detergents

Solution in H2O/NaCl 200000 Nanostar Slurry
Solution in H2O/NaCl

Intensity (a.u.)
Uncapped Colloid Slurry
Intensity (a.u.)

150000 Uncapped Solution in H2O Uncapped Solution in H2O

Intensity (a.u.)
Uncapped Nanostar Slurry

Surfactant cannot be detected on gold

Uncapped Solution in H2O/NaCl Uncapped Solution in H2O/NaCl 10000

soaps, shampoos, laundry and dish detergents.

150000

nanoparticles using SERS, whether dried or

100000

During the manufacturing process, it is

100000

5000

suspended in solution
50000
50000

important to be able to determine the final

Sodium chloride aggregates particles and
0 0

concentration of surfactant to ensure quality. 500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500 0
-1 500 1000 1500 2000 2500 3000 3500
Raman Shift (cm-1) Raman Shift (cm )
Raman Shift (cm-1)
enhances an impurity on both colloids and
Methods Concentrations for all solutions: ~2.5uM SDS, ~180mM NaCl. A. Colloidal
solutions with SDS do not produce signal, whether capped or uncapped. Concentrations: ~2.5x10-7 M CTAB, 180mM NaCl. Some signal is detected in the nanostars
300cm-1 region, though it is weak.
Nanostar Synthesis
B. Nanostar solutions with SDS do not produce signal, whether capped or
uncapped. Highly concentrated particle slurries are an
ineffective method to detect surfactant
Substrates/CTAB - Varied Concentrations Nanofabricated solid substrates are more
Nanofabricated Solid Substrates
effective at detecting surfactant vs colloids
47 nm
Solid Substrate LSPR
35000
Nanofabricated solid substrates enhance
1.0

665nm CTAB Control

30000 Substrate Control
signal down to micromolar concentrations
Absorbance (a.u.)

Transmission Electron
Microscopy Image of CTAB 5x10-3
Intensity (a.u.)

Nanostars
0.5
CTAB 5x10-4
25000
CTAB 5x10-5
Colloids Purchased from BBI International 20000
CTAB 5x10-6
CTAB 5x10-7
References
Nanofabricated Solid Substrates 0.0
400 500 600 700
Wavenumber (nm)
800 900 1000 1100
500 nm
The Localized Surface Plasmon
15000 1.Sharma, Bhavya, Renee R. Frontiera, Anne-
Resonance (LSPR) of the solid
substrates in air is 665nm, Atomic Force Microscopy image of
0 nm
10000
Isabelle Henry, Emilie Ringe, and Richard P.
indicating a 633nm laser should
allow SERS signal to be
fabricated Substrates Van Duyne. "SERS: Materials, Applications, and
produced. 5000 the Future." MaterialsToday 15 (2012): 16-25.
0 2.Schlcker, Sebastian. "Surface Enhance Raman
A. The 760cm-1 peak is indicative of a
trimethylammonium group. As the concentration of
500 1000 1500 2000 2500 3000 3500 Spectroscopy: Concepts and Chemical
Cetyltrimethylammonium
CTAB increases, the intensity of the 760cm-1
increases, supporting the conclusion that CTAB is
Raman Shift (cm-1) Applications." Angewandte Reviews (2014): n.
Each spectra for the various concentrations of CTAB is the measured spectra with
bromide (CTAB) being detected down to micromolar concentrations. the greatest intensity. The intensity is dependent on the location on the sample at pag.
+ B. The CTAB peaks at ~1440cm-1 and ~1450cm-1 which the measurement is taken. While some extraneous peaks appear, there is
indicate CH2 bending, though they appear as a consistency in the appearance of the peaks at ~760cm-1 and ~1440cm-1 , both of
broader peak between 1440 and 1450cm-1 . In
Capping Agent Removal which can be attributed to CTAB.

3x 100uL washes of 75mM NaBH4 shake for 10

general, as concentration increases, intensity
increases. This supports that the peak is due to
A. Calibration of 760cm-1 Peak B. Calibration of 1445cm-1 Peak Calibration of 3000cm-1 Region
Acknowledgements
CTAB on the substrates. C. The peaks in the 2800- 1000
2000
3000

minutes after each addition 3000cm-1 region are due to CH stretching.

2500 Procter and Gamble
Dried Solutions Slurries
Average 1500
Intensity (a.u.)

Average
Intensity (a.u.)

Protg Undergraduate Research Program

Intensity (a.u.)

Intensity was calculated from the peak height of a 2000

Lorenz fit of the baseline corrected spectra. The 500 1000

average was calculated using the heights from the

University of Cincinnati Chemistry
1500

ten spectra for each concentration. Standard 500

Department
1000
deviation was also calculated from these ten spectra.
Graph C. is a calibration of the most intense spectra 0 500

The Sagle Group

0
as chosen for the above Varied Concentrations
1:1 Surfactant Solution:Nanoparticles by volume
5E(-7) 5E(-6) 5E(-5) 5E(-4) 5E(-3) 5E(-7) 5E(-6) 5E(-5) 5E(-4) 5E(-3) 5E(-7) 5E(-6) 5E(-5) 5E(-4) 5E(-3)

graph. Concentration (M) Concentration (M) Concentration (M)