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Using gold nanoparticles in spectrophotometry

Article  in  Journal of Analytical Chemistry · January 2014

DOI: 10.1134/S1061934814010031

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ISSN 10619348, Journal of Analytical Chemistry, 2014, Vol. 69, No. 1, pp. 1–11. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © V.V. Apyari, V.V. Arkhipova, S.G. Dmitrienko, Yu.A. Zolotov, 2014, published in Zhurnal Analiticheskoi Khimii, 2014, Vol. 69, No. 1, pp. 4–15.

REWIEVS

Using Gold Nanoparticles in Spectrophotometry

V. V. Apyari, V. V. Arkhipova, S. G. Dmitrienko, and Yu. A. Zolotov
Department of Chemistry, Moscow State University, Moscow, 119992 Russia
Received March 13, 2013; in final form, May 22, 2013

Abstract—Published data on the use of gold nanoparticles in spectrophotometry are summarized. Data on
methods for preparing gold nanoparticles and their optical properties are presented. The main approaches on
which spectrophotometic methods of substance determination using gold nanoparticles are based are dis
cussed. Examples of determining of metal ions, anions, and organic compounds are presented.

Keywords: gold nanoparticles, surface plasmon resonance, spectrophotometry

DOI: 10.1134/S1061934814010031

The number of publications on the synthesis, study
of properties, and application of gold nanoparticles
(NPs) increases every year. This is indicative of the
considerable interest of researchers working in various
branches of science to these nanoobjects (Fig. 1).
Abundant information on the methods of preparing
and use of gold NPs in biochemistry and biomedicine
can be found in monograph [1] and reviews [2–10].
Data on the application of gold NPs to electrochemi
cal and bioelectrochemical analysis [11, 12], chro
matographic and electrophoretic methods [13, 14], to
the creation of chemical and immunosensors [15–19]
have also be summarized. The study of the properties
of metal NPs, including gold ones, and corresponding
analytical methods were the subject of review [20].
In this review we summarized data on the use of
gold nanoparticles for spectrophotometic and visual
colorimetric determinations of metal ions, anions,
and organic compounds published mainly from 2007
till 2012.
In spectrophotometic and visual colorimetric
determinations of metal ions, anions, and organic
compounds, analysts use spherical gold NPs of an
average diameter of 10–50 nm, synthesized by the
chemical reduction chloroauric acid. The reductants
are most often sodium citrate and sodium borane;
other reductants are used rarely.
The formation of NPs proceeds through a number
of consecutive stages: formation of individual atoms;
nucleation and formation of an initial atomic cluster;
cluster growth to a certain size; and the stabilization of
NPs (Fig. 2). The sizes and dispersity of the formed
NPs and also their stability in time are regulated by
varying the nature of the stabilizer and its amount. The
stabilizers in the synthesis of monodisperse gold NPs
3000
2500
Number of publications

GENERAL DATA ON METHODS

FOR THE PREPARATION OF GOLD 2000
NANOPARTICLES AND THEIR OPTICAL
PROPERTIES
1500
Though the first article devoted to methods of syn
thesis and properties of colloidal gold was published by
Michael Faraday as early as in 1857, this direction has 1000
not lost its importance nowadays. The main efforts of
researchers today are directed to the preparation of 500
gold nanoparticles of different sizes and shapes with
narrow size distribution; to the search for new sub
stances favoring their stabilization; to the revelation of 0
1998
2099

2006

2009

12
1996
1997

2002

2005
2001

2007

2010
1995

2000

2003
2004

2008

2011

correlations between the size, shape, and properties of

19

nanoparticles and the chosen reductants, stabilizers, Year

and synthesis conditions. The data on the methods of
synthesis of gold NPs were summarized in a number of Fig. 1. Number of publications in the Scopus database with
reviews [1, 2, 5, 8, 16, 21, 22]. titles containing prefix nano and the word gold.

1
2 APYARI et al.
HAuCl4 + reductant
Au atoms
Stabilizer
Nonstabilized Au NP
Fig. 2. Scheme of synthesis of gold nanoparticles.
are excess reductants and also specially added sub
stances: ionogenic surfactants, for example, sodium
dodecyl sulfate or lauryltrimethylammonium chlo
ride; ionic liquids; or synthetic and natural polymers:
polyvinyl pyrrolidone, polyethyleneglycol, cyclodex
trins, chitosan, etc. [2].
The most often used method for the preparation of
gold NPs is the Turkevich method, based on the
reduction of chloroauric acid by sodium citrate, and
also its various modifications. The size of the NPs can
be controlled in the range from 10 to 150 nm by vary
ing the ratio between the concentration sodium citrate
(in this case it is both the reductant and the stabilizer)
and chloroauric acid. To prepare NPs, an aqueous
solution of HAuCl4 is heated to boiling and then
sodium citrate is added. The formation of nanoparti
cles begins with the stage of rapid nucleation and is
followed by diffusion growth [5]. The average diameter
of the particles synthesized by the citrate method
decreases with increasing citrate concentration in the
reaction mixture [23, 24].
An interesting possibility of controlling the size of
gold NPs and obtaining of their narrower size distribu
tion is provided by the seedmediated growth tech
nique. It consists in the preliminary growth of small
gold nanoparticles, which are then used as seeds for
the growth of larger particles upon their introduction
into a mixture of HAuCl4 with a reductant. A system
atic study of the growth of NPs on seeds was per
formed in [25]. It was found that the dependences of
the growth rate and of the size of the synthesized NPs
on the concentration of HAuCl4 are nonmonotonic.
At low concentrations of HAuCl4, the growth of NPs
on seeds is accelerated and their average size increases
JOURNAL OF ANALYTICAL CHEMISTRY
Au clusters
Stabilized Au NP
with increasing concentration of HAuCl4 in the solu
tion. At high concentrations of HAuCl4, a rapid for
mation of seeds was observed, because of which the
average diameter of the NPs decreased and their poly
dispersity increased. Thus, the regularities of the
growth of gold NPs do not contradict the classical the
ory of deposit formation.
The unique optical properties of gold NPs are
determined by the phenomenon of surface plasmon
resonance (SPR) (as applied to nanoparticles, SPR is
sometimes named local or localized surface plasmon
resonance) [1, 2, 8, 21, 22]. This phenomenon is due
to the collective behavior of delocalized conductivity
electrons on the surface of a particle, appearing in
their interaction with external electromagnetic fields.
This leads to the presence of maxima in absorption
spectra due to resonance on the coincidence of the fre
quency of electromagnetic radiation with the intrinsic
frequency of the oscillation of surface plasmons. Such
oscillations are named plasmons and the resonance,
surface plasmon resonance.
The concentration of surface atoms in the NPs is
high; therefore, the position and shape of an SPR band
strongly depends on the local dielectric permeability
of the medium near the surface. As a result, any
change in the particle environment (surface modifica
tion, aggregation, change of refraction index of the
medium, etc.) changes their optical properties [26].
For example, if particles form aggregates, the SPR
band shifts towards longer wavelengths and broadens
as a result of dipole–dipole interactions (Fig. 3). For
spherical gold nanoparticles in an aqueous solution,
the SPR bands lie in the visible spectrum region. The
position of the band maximum depends on the average
size of the NPs and shifts to longer wavelengths with
Vol. 69 No. 1 2014
 USING GOLD NANOPARTICLES IN SPECTROPHOTOMETRY 3

A utilizing gold NPs and spectrophotometic techniques

0.25 1 2 are based on changes in the degree of aggregation.
Two types of aggregation with the participation of
gold NPs can be distinguished, i.e., crosslinking
0.20 aggregation and noncrosslinking aggregation
(Fig. 5). In the first case, analyte molecules are bound
to modifiers on the surface of two or more nanoparti
cles, which results in the crosslinking and aggregation
0.15 of NPs. In the second case, an analyte removes or dis
places the modifier from the surface nanoparticles,
thus destabilizing the colloidal system (Fig. 5).
0.10 The major factors favoring the application gold
NPs to spectrophotometry are the simplicity of NP
preparation; high molar absorption coefficients; and
0.05 also almost unlimited possibility of regulating the
spectral properties of NPs by varying their size, shape,
and chemical environment.
0 The main difference between gold NPs and the tra
400 500 600 700 800 ditional spectrophotometic reagents for which the
λ, nm color change is the consequence of a change in the
electronic state of a reagent or an analyte upon their
Fig. 3. Typical absorption spectra of gold NPs (1) and (2) direct interaction consists in the possibility of varying
their aggregates. the optical properties of NPs due to only their aggre
gation in the presence of an analyte. To put this in
other words, the chromophore properties of the mod
increasing particle diameter [21, 27] (Fig. 4). Differ ifier, analyte, and products of their interaction are of
ent methods for estimating the geometrical parame no importance. The possibility of functionalizing the
ters of NPs from absorption spectra of their solutions surface of NPs with modifiers of various nature and
are based on the effects of NP size and shape on their chemical properties and the absence of requirements
optical properties [28]. to their chromophore properties ensures the synthesis
of sensitive and selective reagents based on NPs for
The SPR band of gold NPs is most strongly affected determining a wide range of compounds. Using such
by the aggregate state of the NP. The aggregation of reagents in the determination of compounds that do
gold NPs leads to a contrast color change of solutions not bear chromophore groups or whose colored deriv
from rubyred to violet or dark blue (depending on the atives can hardly be synthesized seems to be most
NP size). Most of optical sensors known by now and expedient.

(а) (b)
I, arb. units λmax, nm
1.2 580
30 nm 100 nm
1.0
560
0.8

0.6 540
0.4
520
0.2

0
500
400 500 600 700 800 0 20 40 60 80 100
λmax, nm Diameter of nanoparticles, nm

Fig. 4. (a) Normalized absorption spectra of gold NP of various sizes and (b) the dependence of the wavelength of absorption max
imum on the diameter of NPs [27].

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 69 No. 1 2014

4 APYARI et al.
(а)
(b)
Fig. 5. Scheme of aggregation of gold nanoparticles by (a) crosslinking and (b) without crosslinking.
The strategy of using gold NPs in spectropho
tometic analysis in most cases is reduced to the follow
ing: a certain amount of preliminarily synthesized gold
NPs is added to an analyte solution and changes in the
optical properties of the test solutions are recorded by
spectrophotometry or visually. In spectrophotometic
determinations, analysts usually record a change in
absorbance at the wavelength of the absorption maxi
mum of individual NPs (520–530 nm) or their aggre
gates (600–800 nm) or calculate the ratio of these val
ues, which characterizes the degree of NP aggrega
tion.
Using gold NPs, analysts can determine metal
ions, anions, and organic compounds. We will con
sider principles on which procedures of this type are
based.
DETERMINATION OF METAL IONS
Gold NPs were used for the spectrophotometic
determination of mercury [29–62], lead [29, 38, 47,
54, 63–69], chromium [70–75], copper [54, 76–80],
silver [31, 45, 47, 81], calcium [82–84], arsenic [85–
87], magnesium [84], aluminum [88], potassium [89],
iron [90], cobalt [29], cadmium [91], platinum and
palladium [29], lanthanides [92], and uranium [93].
In most cases the determination was based on the
formation of coordination compounds between the
metal ions and NP modifiers. Therefore, the choice of
a modifier is important for regulating the sensitivity
and selectivity of the determination. The interaction
of a metal ion with modifier molecules on the surface
of gold NPs most often causes the crosslinking of the
JOURNAL OF ANALYTICAL CHEMISTRY
NPs, leading to NP aggregation. In most cases metal
ions are determined using gold NPs modified with
DNA [37, 53, 80, 81], peptides [29, 64, 82, 88], and
thiols [37, 70, 75, 85, 86, 91]. Nanoparticles modified
with peptide were used for the determination of metal
ions in [29]. Note that the observed change in the color
of gold NPs from the initial ruby depends on the metal
ion. Thus, in the presence of mercury, the system
becomes blueviolet; lead, bluegreen; cobalt, brown;
palladium, cherry; and platinum, dirtyviolet.
The limits of detection for metals are at a level of 20–
200 nM.
Among the metals whose determination was
described in the literature, the greatest attention was
given to mercury and lead. The interest to these metals
is in many respects due to not only the urgency of their
determination in trace amounts, but also to their high
affinity to the modifier molecules, because of which
the aggregation gold NPs is observed at low concentra
tions of these ions. Procedures for the spectropho
tometic determination of mercury using gold NP
modified with DNA were described; the limits of
detection for mercury were 100–1000 nM [56–58].
Mercury ions participate in the formation of com
pounds between thymine DNA bases on the surface of
two different NPs; this leads to their binding and an
increase in the temperature of the decomposition of
aggregates; therefore, NPs remain in the aggregated
state, whereas in the absence of mercury aggregates at
the same temperature NPs already decompose. The
advantage of the procedures is their high selectivity
due to complementary interactions and their disad
vantages are the necessity of precise temperature con
Vol. 69 No. 1 2014
 USING GOLD NANOPARTICLES IN SPECTROPHOTOMETRY
trol and also difficulties in the work with DNA and its
rather high cost.
A number of methods for determining mercury
based on the aggregation of NPs modified with DNA
without their crosslinking was described. Nanoparti
cles are usually modified by shortchain single or
doublestraight DNA molecules adsorbed on the sur
face NPs and stabilizing them through electrostatic
repulsion. Mercury cations, being bound to thymine
DNA bases, cause the removal (desorption) of DNA
molecules from the surface of NPs and the aggregation
of the NPs [59–62]. The method ensures the determi
nation of mercury at a level of several nanomoles per
liter. One more example is provided by the application
of positively charged gold NPs modified by (11mer
captoundecyl)trimethylammonium chloride [48].
The introduction of mercury ions into a solution con
taining such NPs favors the break of Au–S bonds
between surface gold atoms and the modifier, the des
orption of the modifier, and the aggregation of the
NPs. It was found that the reaction is accelerated by
light. The limit of detection for mercury is 30 nM. The
method was used to determine mercury in potable
water.
In some cases the interaction of metal ions with
modifier molecules on the surface of gold NPs causes
an effect reverse to aggregation, peptization or “anti
aggregation” of the NPs due to their additional stabi
lization. Lead was determined using NPs modified
with DNA; analysts added molecules of another DNA
to the system, which bore sites complementary to
those in the modifying DNA and also “break sites,”
i.e., mutations, capable of easily breaking in the pres
ence of lead ions [63]. The break of DNA molecules in
the sites of mutations prevented the aggregation of
gold NPs with the formation of doublestraight struc
tures due to complementary interactions. Therefore,
in the presence of lead ions, NPs upon heating
changed from the aggregated state to free ones much
easier than in their absence. The color of their solution
thus changed from dark blue to rubyred, thus offering
a possibility of lead determination. By this method
lead could be determined with a limit of detection of
100 nM [63].
More comprehensive data on methods for deter
mining mercury, lead, and copper ions can be found in
review [54]. Other examples of using gold NPs for
determining metal ions are presented in Table 1.
DETERMINATION OF ANIONS
Spectrophotometic and visual colorimetric proce
dures using gold NPs were proposed for determining
dihydrogen [94, 95] and hydrogen phosphate [96], flu
oride [97, 98], cyanide [99], nitrite [100], sulfate
[101], sulfide [102], and hypochlorite [103] ions. The
characteristics of methods for anion determination
using gold NPs are presented in Table 2. In the major
ity of the described procedures, the interaction of
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 69
5
anions with NP modifiers caused aggregation.
Depending on the nature of the modifier and analyte,
the interaction can proceed either by an ionexchange
or by an donor–acceptor or a redox mechanism.
Thus, ion exchange between hydrophilic and
hydrophobic anions was used to detect fluoride ions
after their transfer into trifluorophenylborate
ones [98]. Nanoparticles stabilized by isothiouronium
bromide [bis(5(N(2(2metoxiethoxi)ethyl)N
methylSizothiouronio)pentyl)disulfide] were used.
Upon the exchange of bromide and triphenylborate
ions, analysts observed the hydrophobization of NPs
followed by their aggregation.
An interesting method for determining nitrite ions
was described in [100]. A mixture of NPs of two types,
functionalized by aniline and naphthylamine frag
ments, was used. In the presence of nitrite ions, a
Griess reaction proceeded, which led to the formation
of an azo compound acting as a covalent linkage
between the NPs. The method is characterized by
good selectivity and ensures the determination of
nitrite ions with a limit of detection of 22 µM. The
method was used to determine nitrite ions in natural
waters.
One more approach to the determination of anions
was described in [94]. Dihydrogen phosphate ions
were determined using gold NPs modified by pheny
lurea. In the case under consideration, NH groups of
phenylurea act as proton donors, while dihydrogen
phosphate ions were their acceptors. The interaction
of the anion with the NPs prevents the formation of
hydrogen bonds between the NPs, which causes the
antiaggregation of the NPs and increased the inten
sity of the SPR band at 510 nm. Because of the hydro
phobicity of the functionalized NPs, this method is
inapplicable to the analysis of aqueous solutions, but
offers promise for the determination of dihydrogen
phosphate in nonpolar media.
A spectrophotometic method for determining
dichromate ions was based on a redox reaction [75].
The determination was based on the oxidation of thiol
groups in the modifier molecules, dithiothreitol, by
dichromate ions with the formation of disulfide bonds
between individual nanoparticles. In this case the
anion does not participate in the formation of com
pounds between gold NPs and only creates conditions
for their formation. The detection limit for dichro
mate is 20 nM. The method is suitable for the determi
nation of dichromate in natural waters.
DETERMINATIONOF LOWMOLECULAR
ORGANIC COMPOUNDS
Unlike metal ions and anions, organic compounds
are often determined using gold NPs stabilized by cit
rate ions (these are also named unmodified, label
free). The determination is based on the fact that an
organic analyte, being adsorbed on such NPs, reduces
the negative charge of their surface and causes aggre
No. 1 2014
6 APYARI et al.

Table 1. Examples spectrophotometic (SF) and visual colorimetric (VC) determinations of metal ions in various samples
with the use of gold NPs

Ion Test sample Method of NP synthesis (modifier) ñmin Method References

Hg(II) Ground waters Citrate (oligonucleotide) 10 nM SF [52]

Natural waters Citrate (DNA) 10 nM SF [37], [53]
Aqueous solutions Borohydride, (dithiadiazo2[3(2aminoet 35 nM SF [37]
hylsulfanyl)propylsulfanyl]ethylamine)
Pb(II) Aqueous solutions Citrate (peptide) 242 nM VC [29]
Seawater, urine, blood Citrate (bovine serum albumin) 50 nM VC [64]
Cd(II) Lake water Citrate (6mercaptonicotinic acid and L 100 nM SF [91]
cystain
Co(II) Aqueous solutions Citrate (peptide) 190 nM VC [29]
Cu(II) Aqueous solutions Citrate (DNA) 5 µM VC [80]
Pd(II), Aqueous solutions Citrate (peptide) 31 nM VC [29]
Pt(IV) 23 nM
K(I) Aqueous solutions Citrate 1 µM SF, VC [89]
Ca(II) Blood plasma Citrate (calsequestrin) 1 µM SF, VC [82]
As(III) Ground waters Citrate (glutathione, dithiothreitol, and cys 0.13 nM SF, VC [85], [86]
teine)
Cr(III) Aqueous solutions Citrate (5,5’dithiobis 1.8 µM SF, VC [70]
(2nitrobenzoic acid)
River water 5− 100 nM VC [72]
(Borohydride (tripolyphosphate P3O10 )
Al(III) Surface of cervical Citrate (pentapeptide) 0.2 µM SF, VC [88]
tumor cells
Ag(I) Aqueous solutions Citrate (pentapeptide) 0.59 nM SF, VC [81]

gation. Thus, a method for the semiquantitative deter
mination of cationic surfactants was described in
[104]. The authors suppose that surfactants in concen
trations lower than CCM are adsorbed on negatively
charged NPs and cause their hydrophobization and
aggregation, which leads to color change from ruby to
blueviolet. At concentrations higher than CCM, the
ruby color of the solution restored, which was related
to the formation of micelles in which the NPs were on
hydrophilic surfaces. However, it seems to us that the
formation of similar structures is unlikely because of
the high weights and big sizes of gold NPs. In our opin
ion, a more adequate mechanism of the restoration of
the optical properties of solutions involves the encap
sulation of hydrophobized gold NPs into nonpolar
cavities of surfactant micelles and, as a consequence, a
change in their charge. The described approach is
based on the use of two types of interactions, electro
static and hydrophobic, which makes it universal for
determining various cationic surfactants and the
assessment of their total amounts. Note that nonionic
and anionic surfactants do not cause the aggregation
of gold NPs.
One more example of the visual colorimetric deter
mination using unmodified gold NPs for detecting
thiolcontaining amino acids was described in [105].
The proposed approach consists in the displacement
of citrate ions by molecules of thiolcontaining amino
acids because of stronger interactions of the sulfur
atom of the thiol group with gold atoms on the surface
of NPs, leading to the reduction of the charge of the
NPs and their aggregation. By replacing the thiol
group in a homocystein molecule with the hydroxyl
group, researchers proved that the formation of a
strong bond with the surface of a gold NP is due to just
the thiol group (when NPs of the hydroxylsubstituted
derivative were introduced into the solution, no
changes in the optical properties of the system were
observed). The key difference of this example from
that considered above is in the replacement of citrate
ions on the gold surface. In essence, in the last case the
analyte and a gold NP come into specific interactions
with the formation of a covalent bond with the surface
of the NP, which, on one hand, makes the approach
more selective for compounds containing no sulfur,

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 69 No. 1 2014

 USING GOLD NANOPARTICLES IN SPECTROPHOTOMETRY 7

Table 2. Examples spectrophotometic (SF) and visual colorimetric (VC) determinations of anions in various samples with
the use of gold NPs

Anion Test sample Method of NP synthesis (modifier) cmin Method References

Model system based on

H2PO4− Borohydride (phenylurea) 10 µM SF [94]
dichloromethane

PO34− River water Citrate (mercaptoacetic acid and Eu3+) 76 nM SF [95]

Oxo anions
2− Aqueous solutions Borohydride (isothiouronium) 100 µM SF, VC [96]
(HPO4 )
F– Aqueous solutions Reduction by thioglucose (thioglucose) 20 mM VC [97]

Citrate (aniline and naphthylamine

NO2
− Natural waters 22 µM VC [100]
derivatives)

CN– Aqueous solutions Citrate (adenosine triphosphate) 14 µM SF, VC [99]

SO24− Aqueous solutions Borohydride (cysteamine) 50 µg/L VC [101]

S2– Waste water Citrate (calix[4]arene) 10 nM SF, VC [102]

ClO– Tap water Citrate (mercaptoundecanoic acid 1.5 µM VC [103]

Cr2O7
2− Natural waters Citrate (dithiothreitol) 20 μM SF [75]

and, on the other hand, imposes some restrictions on
the range of determined compounds.
There are evidences that the mechanism based on
the direct interaction of analyte functional groups with
gold is implemented not only for thiolcontaining
compounds. Guo et al. [106] believed that, because of
specific interactions of melamine amino groups with
surface gold atoms, citrate ions are also replaced from
the surface of NPs, which reduces the stability of their
aggregates. The proposed method ensures the deter
mination of melamine in milk and baby food with a
limit of detection of 1.0 µg/mL in the visual colorim
etry version and 0.15 µg/mL in the spectrophotometry
version [106].
In addition to the above examples, gold NPs stabi
lized by citrate ions were used to determine cysteam
ine [107], cysteine [108], cocaine [109], dopamine
[110], adenosine triphosphate [111], glucose [112,
113], and ascorbic acid [114]. Among the advantages
of the proposed methods is the relative simplicity of
preparing NPs and among the drawbacks, a strong
interference with positively charged compounds or
ions. For the elimination of the effect of alkalineearth
and heavy metal cations on the determination cys
teamine, we proposed using the EDTA disodium salt
[107]. Ethylenediamine tetraacetic acid masks cations
by transferring them into negatively charged chelates,
which cannot neutralize the charge of the NPs and
cause their aggregation.
In some cases using gold NPs modified by other
compounds was more efficient for the determination
of organic compounds. The modifiers were (analyte in
given in the parentheses) surfactants (cysteine) [115],
thioamines (trinitrotoluene, melamine) [116, 117],
crown ethers (melamine) [118], thioacids (streptomy
cin) [119], thiolcontaining amino acids (trinitrotolu
ene) [120] and their derivatives (tyrosine) [121], anti
genes (cortisol) [122], DNA (theophyllin, melamine)
[123, 124], luminophores (melamine, pesticides)
[125, 126], and polymers (cysteine) [127]. The princi
ples of analyte interaction with the modified NPs
remain the same as for metal ions and anions. This, a
method for determining trinitrotoluene is based on the
donor–acceptor interaction of this compound with
cysteine, modifier of NPs [120]. The method ensures
the determination of trinitrotoluene on a picomolar
level.
Other examples of spectrophotometic and visual
colorimetric determinations of lowmolecular organic
compounds are listed in Table 3.
Thus, we can note that, in the last five years, the
number of publications on the use gold NPs in spec
trophotometry has substantially increased. The use of
gold NPs in spectrophotometry is based on the effect
of surface plasmon resonance, which manifests itself
as the appearance of an intense absorption band in the
visible spectrum region. This effect was used to elabo
rate procedures for determining metal ions, anions,
and organic compounds. The main facts favoring the

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 69 No. 1 2014

8 APYARI et al.

Table 3. Examples spectrophotometic (SF) and visual colorimetric (VC) determinations of lowmolecular organic com
pounds in various samples with the use of gold NPs

Method of NP
Compound Test sample cmin Method References
synthesis (modifier)

Cationic surfac Hair conditioner Citrate – VC [104]

tants

Cysteine Aqueous solutions The same 1 µM SF [108]

Urine Citrate (fluorinecontaining 0.8 µM SF, VC [115]

surfactant)

Aqueous solutions Citrate 10 nM VC [128]

Melamine Milk, baby food The same 0.15 µg/L SF; VC [106]

Milk Citrate (polythymine) 0.02 µM SF, VC [124]

Aqueous solutions Borohydride (riboflavin) 0.25–0.5 µM SF [125]

Milk Citrate (cysteamine) 1 mg/L SF [117]

Thiolcontaining Aqueous solutions Citrate 3 µM VC [105]

amino acids

Cysteamine Urine, hair curling prepa The same 0.01 µg/L SF [107]
ration

Cocaine Aqueous solutions '' 2 µM VC [109]

Dopamine Aqueous solutions '' 0.03 µM SF, VC [110]

Adenosine Aqueous solutions '' 0.6 µM SF, VC [111]

triphosphate

Glucose Mouse brain '' 1 mM SF, VC [112]

microdialysate

Blood serum '' 10 nM SF [113]

Ascorbic acid Fruit juce '' 3 nM VC [114]

Trinitrotoluene Natural waters Citrate (cysteamine) 0.5 pM SF, VC [116]

Streptomycin Milk Citrate (mercaptoacetic acid) 50 µg/L SF [119]

Cortisol Blood serum Citrate (antigene*) 30 ng/mL VC [122]

Theophyllin Aqueous solutions Citrate (DNA) 200 µM SF [123]

Organophospho River water Citrate (rhodamine C) 0.1–1 µg/L SF [126]

rous pesticides and
carbamates

Thiols Aqueous solutions Citrate (disulfide) 1 µM VC [129]

* Cortisol3carboxymethyloxime–adipic acid dihydrazide–bull serum albumin.

JOURNAL OF ANALYTICAL CHEMISTRY Vol. 69 No. 1 2014

 USING GOLD NANOPARTICLES IN SPECTROPHOTOMETRY
application of gold NPs to spectrophotometry are the
relative simplicity of NP preparation, high molar
absorptivities, and also almost unlimited possibility of
regulating the spectral and chemical properties of NPs
by varying their size, shape, and chemical environ
ment. The procedures for spectrophotometic determi
nation based on using gold NPs differ by simplicity
and rapidity. Because of the contrast color change of
solutions they can also be implemented in the test ver
sion.
A number of problems remain unsolved in the
practice of using gold NPs in spectrophotometry for
the analysis of real samples. Real samples, such as, for
example, biological fluids (blood, urine), foodstuffs,
or environmental objects, contain various salts or
other substances capable of causing aggregation of
NPs also in the absence of analytes. The data on the
use of masking agents for the elimination of such
interferences are scanty. In addition, the sensitivity of
the developed procedures for spectrophotometic
determination are not always adequate for the real
(lower) concentrations of analytes.
ACKNOWLEDGMENTS
This work was supported by the Russian Founda
tion for Basic Research, project no 130300100.
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Translated by E. Rykova
No. 1 2014