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Spectroscopic Detection of Metal Ions using Nanoparticles

Spectroscopic Detection of Metal Ions using Nanoparticles

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An essay for the 2011 Undergraduate Awards (Ireland) Competition by James Flanagan. Originally submitted for Chemistry (MSci) (UCAS Code F105) at Queen University Belfast, with lecturer Dr Nick Fletcher in the category of Chemistry
An essay for the 2011 Undergraduate Awards (Ireland) Competition by James Flanagan. Originally submitted for Chemistry (MSci) (UCAS Code F105) at Queen University Belfast, with lecturer Dr Nick Fletcher in the category of Chemistry

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Published by: Undergraduate Awards on Aug 31, 2012
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10/27/2013

 
- 1 -
Spectroscopic Detection of Metal Ions using Nanoparticles
 A synthesis of the compound 7-(9-methyl-1,10-phenanthrolin-2-yl)heptane-1-thiol, using key starting materialsof neocuproine, 1,6-dibromohexane, and thiourea, is reported. The overall yield was 15%. It was apparent thatthe product mixture contained some impurities, most likely as the result of the inability to find an eluent whichgave very good separation in (column and thin layer) chromatography of the intermediate bromo productmixture. 7-(9-methyl-1,10-phenanthrolin-2-yl)heptane-1-thiol made was found to be a good ligand for complexation to Cu
2+
ions, as detected by the use of surface enhanced resonance Raman spectroscopy(SERRS) using silver nanoparticles. It was found not to complex as well to Al
3+
, Cd
2+
, Fe
2+
, Fe
3+
, Ni
2+
, and Sn
2+
 ions in solution. The potential for 7-(9-methyl-1,10-phenanthrolin-2-yl)heptane-1-thiol to act as a component in ahighly sensitive sensor for the detection of Cu
2+
ions in solution is also described.
 
1. Introduction
Raman spectroscopy provides a techniqueof studying vibrational and rotational modes in asystem, and is used to assist in the identification(and quantification) of many substances.
1
Thebasic Raman process relies on the scattering of asingle frequency of incident electromagneticradiation (photons) directed onto a sample using alaser. Most photons are elastically scattered(negligible change in energy). However, C.V.Raman, in 1928, was able to experimentally showthat a very small proportion are inelasticallyscattered
2
: they distort the electron cloud (polarisethe molecule) and are promoted to a ‘virtual’energy state, but return to an energy level which isdifferent to its original level by one energyvibrational energy level. It is this change in energyis what is measured in Raman spectroscopy.However, for a molecule to be ‘Raman active’, theelectromagnetic radiation must induce a change inthe magnitude or direction of polarisability of themolecule. This basic selection rule results inRaman spectroscopy often yieldingcomplementary information to infraredspectroscopy – for example, since symmetricvibrations often have a large change inpolarisability yet no very little change in dipolethey are often Raman and not infrared active (andasymmetric vibrations often vice-versa).
3
 One of the key limitations of ‘traditional’Raman spectroscopy is the lack of sensitivity withsamples in solution.
1
There are two main reasonsfor this: Firstly, it is estimated that only one in 10
6
 10
7
incident photons which hits a samplemolecule is actually Raman scattered
4
(i.e. thescattered photon has a different energy to theincident photon by one vibrational energy level).Secondly, the target molecules are further apart ina solution (relative to the solid state), and so asignificant proportion of incident photons will missthe target molecules completely, not even having achance to be Raman scattered. Therefore there isscope for a Raman technique which allowsanalysis of solutions with increased sensitivity.Such a technique is available in the form surfaceenhanced resonance Raman scattering (SERRS).SERRS is essentially a combination of twokinds of Raman technique: resonance Ramanspectroscopy and surface enhanced Ramanspectroscopy (SERS).
5
In resonance Ramanspectroscopy, the laser used for excitation ischosen to be as close as possible in energy to theenergy between the first vibration state of theground electronic state and the first or secondvibrational state of the excited electronic state(Figure 1). The lifetime spent in the excitedelectronic state is of crucial importance and canlead to a large increase in polarisability
1
, as
 
- 2 -
described by the Kramer-Heisenberg-Diracexpression (which can found on page 87 of Reference 1). Enhancements of up to 10
3
times the‘traditional’ Raman signal can be achieved withthis method.
5
 Resonance Raman spectroscopy has somedrawbacks in that it frequently encountersproblems with sample degradation
7
andfluorescence.
4
SERS has less of these problems,encompassing a wider range of molecules, andgives bigger enhancements of up to 10
6
timestraditional Raman spectroscopy.
1
The key featureof SERS is the bringing of the sample moleculeclose to a roughed metal surface (such asaggregated colloidal suspensions, electrodes andmodified metal films).
7
The metal used is typicallysilver or gold (although lithium and sodium havealso been shown to work).
8
To understand SERS,the nature of the metal surfaces needs to beexamined. These surfaces are covered withelectrons, the electron density extending beyondthe surface. Light can interact with these electronsand cause them to oscillate as a group (of ‘surfaceplasmons’). Silver and gold plasmons happen tooscillate at frequencies at which Raman is typicallyrecorded (visible, near-infrared). The roughedsurface provides a component of the oscillationsperpendicular to the surface (which would beabsent on a smooth surface), and the Ramanscattering occurs from this perpendicularcomponent
1
(Figure 2).When the sample molecule comes close to theroughened surface, it can be held in closeproximity, adsorbed, or chemically bond with thesurface. The resulting enhancement is described bytwo different theories: electromagneticenhancement (requiring only adsorption) andcharge transfer (or chemical enhancement,requiring a chemical bond to form between samplemolecule and surface).
9
Electromagneticenhancement can be loosely described as aninteraction between the cloud of plasmons and theelectrons on the adsorbed analyte, whichintensifies polarisation around the analyte.Chemical enhancement can be described as themovement of charge (either electrons or holes)from the metal surface to the sample molecule.This newly formed surface species will cause greatpolarisability of the sample molecule, as chargehas been introduced onto it.The enhancement of the Raman signal of amolecule with the ability to bind to the metalsurface in SER(R)S described above can beexploited in the creation of ‘sensors’ for specieswhich can bind to that molecule. For example,thiols have been used extensively to modify silversurfaces for SERS.
7,10
The Ag-S bond is a strongcovalent bond (average bond enthalpy 217.1 kJmol
-1
)
11
and it is likely that a charge transfermechanism for signal enhancement is operating. If a species (such as a metal ion in solution) cancoordinate to this thiol (and the thiol in turn bindsto the Ag surface), then an examination of SERRSspectra can could show up this coordination and soprovide a method of detecting very minuteamounts of a species.The aim of this experiment is to synthesise7-(9-methyl-1,10-phenanthrolin-2-yl)heptane-1-thiol (Figure 3), a thiol based on 1,10-phenanthroline (neocuproine), a well known ligandfor its complexation to copper.
12
 
Figure 3. 7-(9-methyl-1,10-phenanthrolin-2- yl)heptane-1-thiol
SN NCH
3
HHH HHHHabcd e
 
fghi jklmno
Virtual energy statesStokes Anti-StokesGroundelectronicstateExcitedelectronicstateResonance RamanRamanRayleighRaman
Figure 1. Normal and Resonance Raman SpectroscopyFigure 2. Oscillations leading to SERS 
 
Surface plasmons locatedin valleys and releasedfrom peaksRoughened metalsurface
 
- 3 -
The synthesis of the thiol firstly requiresthe synthesis of the analogous bromo compound2-(7-bromoheptyl)-9-methyl-1,10-phenanthroline(Figure 4).
Figure 4. 2-(7-bromoheptyl)-9-methyl-1,10- phenanthroline
The synthesised thiol will then be testedfor complexation with a range of metal ions insolution by recording SERRS spectra. A noticeableenhancement or change from the spectrum of theblank thiol is good evidence for complexation, andfurther SERRS spectra will be recorded of promising thiol-metal combinations with a view toinvestigating the suitability of the technique for thedetection of small amounts of that metal ion.
2. Experimental
 Materials
Lithium diisopropylamide 2.0 M in cyclohexane(LDA; Aldrich), 2,9-dimethyl-1,10-phenanthroline
 
(Aldrich) and 1,6-dibromohexane (Aldrich) wereused as received without further purificationLaboratory grade solvents were used unlessotherwise specified. Dry tetrahydrofuran wasobtained by distillation under N
2
from sodium withbenzophenone as indicator.
 Instrumentation
1
H NMR spectra were recorded on a Bruker DPX300 and DRX500 using the solvent as an internalreference. Raman spectra were recorded on aRamanStation (Avalon Instruments). CHN analysisand E.I mass spectroscopy were performed byA.S.E.P., The School of Chemistry, The Queen'sUniversity of Belfast.
Synthesis of 2-(7-bromoheptyl)-9-methyl-1,10- phenanthroline
5,13,14
 
2,9-dimethyl-1,10-phenanthroline (0.500g, 2.401 mmol) was added to dry tetrahydrofuran(20 ml) under a nitrogen atmosphere and cooled to-78 °C. Lithium diisopropylamide (1.60 ml, 1.8 M,2.882 mmol) was added dropwise and the mixturestirred for 2 hours. After this time, 1,6-dibromohexane (5.828 g, 24.01 mmol) was addedquickly to the mixture, and stirred for a further 20hours. Water (3 ml) was added to the mixture(turning it from brown to bright yellow in colour),and the mixture removed from the nitrogenatmosphere. The crude product was extracted usingdichloromethane (2 x 10 ml). The organic layerswere combined and dried over anhydrousmagnesium sulfate. The mixture was thenevaporated at 40
o
C.The mixture was separated using flashchromatography with a 6:4:1 petroleum ether:ethyl acetate : triethylamine eluent. Fractions wereanalysed by thin layer chromatography (TLC). Thefractions identified as the required monobromoproduct were combined and evaporated to leave adark yellow liquid.Yield 296 mg; 33.2%.
δ
H
(500 MHz,CDCl
3
): 8.12–8.15 (2H, m, H
c
, H
), 7.71 (2H, s, H
d,
H
e
), 7.52 (2H, m, H
b
, H
g
), 7.27 (CHCl
3
), 3.42 (7H,m,
impurity from 1,6-dibromohexane
), 3.27 (2H,m, H
n
), 2.95 (3H
 ,
s
 ,
H
a
), 2.18 (25H
 ,
m
 , impurity
),1.88 (9H, m, H
h
+
impurity
), 1.65 (6H, s,
impurity
),1.46-1.49 (12H
 ,
m, includes H
i
, H
 j
, H
, H
l
, H
m
). Rf of required fractions 0.6-0.8 using 6:4:1 petroleumether: ethyl acetate : triethylamine solvent.
Synthesis of 7-(9-methyl-1,10-phenanthrolin-2- yl)heptane-1-thiol 
15
 
The substance prepared above (thought to be2-(7-bromoheptyl)-9-methyl-1,10-phenanthroline)(0.2960 g, 0.797 mmol) was placed in a roundbottomed flask equipped with stirrer andcondenser. Ethanol (10 ml) and thiourea (0.0631 g,0.797) was added to the flask and the mixturestirred and heated under reflux for 20 hours. Themixture was cooled to room temperature andpotassium hydroxide solution (1.43 M, (0.08 gpellet dissolved in 1 cm
3
water)) was added. Theresulting mixture was heated under reflux for 2hours. The organic layer was separated andretained. The remaining aqueous layer wasacidified with sulfuric acid (0.6 cm
3
, 2M) and thenextracted with hexane (2 x 10 cm
3
). The organic
BrN NCH
3
HHH HHHabcd e
 
fghi jklmn

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