Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану
The stable colloidal solutions of monometallic and bimetallic gold and silver nanoparticles (NPs) have been obtained in the presence of amino acid tryptophan. For the synthesis of bimetallic composition the metals were used in a molar ratio of Ag:Au = 3:1, 1:1 and 1:3. The only one plasmon resonance...
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Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine
2016
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| author | Vityuk, N. Mukha, Iu. Grodzyuk, G. Eremenko, A. |
| author_facet | Vityuk, N. Mukha, Iu. Grodzyuk, G. Eremenko, A. |
| author_institution_txt_mv | [
{
"author": "N. Vityuk",
"institution": "Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України"
},
{
"author": "Iu. Mukha",
"institution": "Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України"
},
{
"author": "G. Grodzyuk",
"institution": "Інститут фізичної хімії ім. Л.В. Писаржевського НАН України \/ ТОВ НаноМедТех"
},
{
"author": "A. Eremenko",
"institution": "Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України"
}
] |
| author_sort | Vityuk, N. |
| baseUrl_str | |
| collection | OJS |
| datestamp_date | 2019-02-11T09:36:14Z |
| description | The stable colloidal solutions of monometallic and bimetallic gold and silver nanoparticles (NPs) have been obtained in the presence of amino acid tryptophan. For the synthesis of bimetallic composition the metals were used in a molar ratio of Ag:Au = 3:1, 1:1 and 1:3. The only one plasmon resonance band in absorption spectra was located between the bands inherent to the individual metals and it was characteristic for “alloy” type bimetallic AgAu NPs. The position of its maximum strongly depends on the Ag:Au molar ratio. The surface of all synthesized nanoparticles carries a negative charge due to the stabilizing shell consisted of amino acid. In the paper we usedUV/visible spectroscopy and dynamic light scattering method to analyze the effect of experimental procedure on the properties of obtained NPs. |
| doi_str_mv | 10.15407/Surface.2016.08.118 |
| first_indexed | 2025-07-22T19:34:32Z |
| format | Article |
| fulltext |
Поверхность. 2016. Вып. 8(23). С. 118–122 118
UDC 546.57 + 546.59 + 544.77 + 577.112.387.4
BIMETALLIC GOLD/SILVER ALLOY NANOPARTICLES
PREPARED IN THE PRESENCE OF TRYPTOPHAN
N. Vityuk1, Iu. Mukha1, G. Grodzyuk2,3, A. Eremenko1
1Chuiko Institute of Surface Chemistry of National Academy of Sciences of Ukraine,
17 General Naumov Str. Kyiv, 03164, Ukraine
2L.V. Pisarzhevskii Institute of the Physical Chemistry, NASU, 31 Nauki Ave., Kyiv 03028, Ukraine
3NanoMedTeсh LLC, 68 Gorkogo str., Kyiv 03150, Ukraine.
The stable colloidal solutions of monometallic and bimetallic gold and silver nanoparticles
(NPs) have been obtained in the presence of amino acid tryptophan. For the synthesis of bimetallic
composition the metals were used in a molar ratio of Ag:Au = 3:1, 1:1 and 1:3. The only one plasmon
resonance band in absorption spectra was located between the bands inherent to the individual metals
and it was characteristic for “alloy” type bimetallic AgAu NPs. The position of its maximum strongly
depends on the Ag:Au molar ratio. The surface of all synthesized nanoparticles carries a negative
charge due to the stabilizing shell consisted of amino acid. In the paper we usedUV/visible
spectroscopy and dynamic light scattering method to analyze the effect of experimental procedure on
the properties of obtained NPs.
Introduction
Gold and silver nanoparticles (NPs) can be applied as well or in combination with
other objects for targeting, imaging and therapy[1-4]. Their bimetallic composition could act
more effectively in cancer treatment due to synergetic effect. Also, the toxicity of bimetallic
NPs can be greatly decreased through the use of essential amino acid as reducing and
stabilizing agent [5]. Here we used tryptophan for reduction of metal ions and also for
stabilization of NPs in the colloid.
The formation of gold and silver NPs in the presence of tryptophan is strongly
influenced by the acidity of initial components as we showed earlier [6, 7]. Based on the
previous study here we used initial reagents with the best combination of pH for the synthesis
of stable bimetallic “alloy” AgAuNPs. The aim was to analyze the influence of experimental
procedure on final properties of colloids synthesized in three series using the same
concentrations and metal ratios of the components.
Experimental
Colloidal solutions of mono- and bimetallic silver and gold NPs were obtained via
chemical reduction of silver nitrate and tetrachlorauratic acid (AgNO3 and HAuCl4, Merck,
Germany) with amino acid tryptophan (Trp, SC12-20120713, China). The components
interacted in a molar ratio M : Trp =1:1. The concentrations in the resulting solution used
were C(M) = 10-4M. The initial metal molar ratios in bimetallic composition were 3:1, 1:1 and
1:3. For all colloids, the initial solutions of the components were adjusted to required pH that
was 4 for gold and 10 for silver. Amino acid was used in an anionic state that exists in
alkaline medium. Initial solutions of the components of 2x10-4M were mixed in equal
volumes when stirred and heated continuously to boiling. The series of samples obtained
when (I) metals were injected into the heated solution of Trp one by one, silver before gold,
(II) metals were injected simultaneously into heated solution of Trp, (III) metals were heated
and injected simultaneously into heated solution of Trp.
The pH measurements were performed using a pH-meter I-160MI. As a working
electrode, a glass electrode was used. Silver chloride electrode served as a reference one.
The absorption spectra of the colloidal solutions of Ag (Au) NPs were recorded in the
UV-visible region with a spectrophotometer Lambda 35 (Perkin-Elmer, United States) in 1
cm quartz cells.
119
The particle size distribution function and zeta potential measurement were studied by
a laser correlation spectrometer Zeta Sizer Nano S (Malvern, UK) equipped with a correlator
(multi-computing correlator type 7032 ce) by the method based on the scattering of light on
any micro-objects. The information signal from the random movement of nanoparticles was
analyzed by multi-channel spectrum analyzer and colorimeters. 1 ml of studied suspension
was placed in a cylindrical optical glass cell with a diameter of 10 mm located in the
thermostatted sample holder of the laser correlation spectrometer. Registration and statistical
processing of the scattered laser light at 173° from the suspension (helium-neon laser LGN–
111 was used with a power output of 25 mW and wavelength of 633 nm) were performed
three times for 120 seconds at 25°C. The resulting autocorrelation function was treated with
standard computer programs PCS–Size mode v 1.61.
Results and discussion
The phenomenon of localized surface plasmon resonance (LSPR) causes a bright red
color of gold nanoparticles (NPs)[8]. Colloids of monometallic nanosized gold obtained in the
presence of the amino acid tryptophan (Trp) were also red colored. In UV-vis spectra,
absorption band maxima of Au NPs were located near 525 nm. Meanwhile, silver NPs with
intrinsic yellow coloration had LSPR band near 420 nm. Three series of samples of bimetallic
AgAu NPs synthesized with the same content of reagents but with some difference in
experimental procedure are indicated as (I), (II) and (III) as described above.
Zeta potential measurements of all tryptophan-capped Ag, Au and AgAu NPs showed
that surface of synthesized nanoparticles carried a negative charge (Table 1). It led to the
stability of colloids during a year even when stored light at room temperature.
In absorption spectra, the only one band maximum is characteristic for “alloy” type
NPs when Ag+ and [AuCl4]
- ions are simultaneously reduced. It is located between the
maxima inherent to the bands of individual metals and depends on the composition of the
particle [9]. It is shifted from silver to gold gradually according to decreasing Ag:Au molar
ratio (Table 1). The coloration of colloids also changed from yellow, then orange to red.
Table 1. Positions of absorption band maxima and zeta potentials of synthesized
nanoparticles
λ max, nm zeta potential, mV N
Sample,
C = 10-4M
І ІІ ІІІ І ІІ ІІІ
1 Ag NPs 417 425 416 -27 -21 -23
2 AgAu (3:1) 441 434 438 -21 -26 -26
3 AgAu (1:1) 494 469 464 -13 -29 -26
4 AgAu (1:3) 508 498 496 -25 -11 -21
5 Au NPs 526 523 527 -20 -21 -15
No significant difference was observed between λ max positions of bimetallic AgAu
NPs when initial solutions of metals injected simultaneously to the reaction mixture both
previously heated (III) and not heated (II). But adding solutions of HAuCl4 after AgNO3 to
the mixture (I) caused the red shift of λ max for all three ratios compare to (II) and (III).
Moreover, for (I) a long-wavelength shoulder appeared, the most prominent for the ratio
Ag : Au = 3:1 (Fig. 1a). Despite the reduction by tryptophan is not immediate and can take a
long time (few days with heating), the possible explanation of this phenomenon can be the
formation of NPs of core-shell type because metals were added sequentially[10]. Also, the
longitudinal LSRP absorption [11] of aggregated particles influenced on the interpretation of
UV/vis spectra.
120
a b
Fig. 1. Optical spectra of colloidal solutions of monometallic NPs and bimetallic composition
with different metal molar ratios (a), where different series are indicated as (I) dash-dot
line, (II) dash line and (III) solid line; polydispersity in colloidal solutions reflected as
the particle size distribution by intensity basis (b), where different series are indicated as
(I) square, (II)circle and (III) triangle.
Broad LSPR bands in the spectra of all nanoparticles with different metal ratios
indicated polydispersity in colloidal solutions. We suggest that it can be the aggregation of
small NPs occurring due to cross-linking of particles through tryptophan during the synthesis.
The existence of small particles is confirmed by the characteristic position of LSPR band.
Polydispersity in colloids was evidenced by the dynamic light scattering (DLS) data. Intensity
basis suggested the formation of a wide range of structures up to several hundreds of
nanometers for all bimetallic AgAu NPs (Fig. 1b).
For colloids obtained from all previously heated initial solutions (III), LSPR
absorption bands were the narrowest and the most symmetrical, as well as the size distribution
of particles by intensity indicated the smallest particles among other series (Table 2). One
121
more finding is that according to DLS, the more content of gold in bimetallic composition, the
smaller aggregates formed.
Table 2. Size distribution of bimetallic nanoparticles by DLS
d, nm (more than 60%) d, nm (more than 30%) N
Ag:Au
molar ratio І ІІ ІІІ І ІІ ІІІ
2 3:1 140-300 100-250 70-220 160-220 140-190 100-160
3 1:1 60-220 50-250 50-220 100-190 100-190 80-140
4 1:3 40-250 50-220 20-120 90-160 90-140 30-80
The properties of bimetallic NPs with different metal ratios are affected by the
mechanism of reduction for two metals. Probably higher red-ox potential of gold caused faster
oxidation of amino acid (reduction of metal) and thus smaller particle formation. However,
donor-acceptor complex formation with amino acid plays a key role because in aqueous
solution adjusted to high pH Trp exists in anionic form and has a nonbonding pair of electrons
on the nitrogen atom of the amino group and deprotonated carboxylic group -COO-. Thus, the
whole process is very complicated. Donor-acceptor complex with metal on the surface of one
NP is formed simultaneously with the charge-transfer complex one with indole moiety on the
surface of another NP causing the aggregation in the system.
Conclusions
Reduction of the noble metal with tryptophan leads to the formation of large
aggregates of NPs in the system for both mono- and bimetallic NPs. The heating of all initial
solutions, as well as simultaneous injection of metal to the reaction mixture, causes the
formation of the smallest aggregates of bimetallic NPs.
References
1. J. Conde, G. Doria, P. Baptista, Noble Metal nanoparticles applications in cancer // J.
Drug Deliv. – 2012. – doi: 10.1155/2012/751075.
2. Babu, A. K. Templeton, A. Munshi, R. Ramesh. Nanoparticle-Based Drug Delivery for
Therapy of Lung Cancer: Progress and Challenges // J.Nanomater. – 2013. –
doi: 10.1155/2013/863951.
3. W. Cai, T. Gao, H. Hong, J. Sun. Applications of gold nanoparticles in cancer
nanotechnology// Nanotechnol. Sci. Appl. – 2008. – V. 1. – P. 17-32.
4. M. Babaei, M. Ganjalikhani. A systematic review of gold nanoparticles as novel cancer
therapeutics // J. Nanomedicine. – 2014. – V.1(4). – P. 211-219.
5. O. Shmarakov, Iu. P. Mukha, V. V. Karavan, O. Yu. Chunikhin, M. M. Marchenko,
N. P. Smirnova, A. M. Eremenko. Tryptophan-assisted synthesis reduces bimetallic
gold/silver nanoparticle cytotoxicity and improves biological activity //
Nanobiomedicine. – 2014. –doi: 10.5772/59684.
6. Iu. Mukha, N. Vityuk, O. Severynovska, A. Eremenko, N. Smirnova.The pH-dependent
stucture and properties of Au and Ag nanoparticles produced by tryptophan reduction //
Nanoscale Res. Let. – 2016. –doi: 10.1186/s11671-016-1318-8
7. Н. В. Вітюк, Ю. П. Муха, С. М. Махно, Г. М. Єременко, Н. П. Смірнова.
Стабілізація наночастинок срібла у присутності триптофану // Поверхность. –
2015. – Вып. 7(22). – С. 222–226
8. Louis, O. Pluchery. Gold nanoparticles for physics, chemistry and biology//Imperial
College Press. 2012: 395 pp.
9. Link S., Wang Z.L., El-Sayed M.A.Alloy Formation of Gold-Silver Nanoparticles and
the Dependence of the PlasmonAbsorption on Their Composition // J. Phys. Chem. B. –
1999.– V. 103. – P. 3529-3533.
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10. Г. Яшан, Ю. Муха, Г. Крилова, Н. Смiрнова, A. Єременко. Спектральні
характеристики біметалічних кластерів Ag/Au (ядро-оболонка та сплав),
одержаних фотохімічним та хімічним шляхами // Всеукраїнська міжнароднa
конференція молодих вчених “Наноматеріали в хімії, біології та медицині”. Київ,
Україна, 15-17 травня, 2007. – С. 137-138.
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БІМЕТАЛЬНІ НАНОЧАСТИНКИ СПЛАВУ ЗОЛОТО/СРІБЛО СИНТЕЗОВАНІ
У ПРИСУТНОСТІ ТРИПТОФАНУ
Н. Вітюк1, Ю. Муха1, Г. Гродзюк2,3, Г. Єременко1
1Інститут хімії поверхні ім. О.О. Чуйка Національної академії наук України,
вул. Генерала Наумова, 17, Київ, 03164, Україна
2Інститут фізичної хімії ім. Л.В. Писаржевського НАН України, просп. Науки 31, м.
Київ,Україна, 03028
3ТОВ НаноМедТех вул. Горького 68, м. Київ, Україна, 03150
Стабільні колоїдні розчини наночастинок (НЧ) срібла та золота та їх
біметалічні композити зі співвідношенням металів Ag:Au = 3:1, 1:1, 1:3 синтезовані у
присутності амінокислоти триптофану. В спектрах поглинання присутня лише одна
смуга поглинання плазмонного резонансу НЧ, характерна для біметальних
наночастинок сплаву AgAu, розташована між смугами індивідуальних металів.
Положення максимуму поглинання дуже залежить від мольного співвідношення Ag:Au.
Поверхня всіх синтезованих наночастинок має негативний заряд за рахунок
стабілізуючою оболонки амінокислоти. Проаналізовано вплив експериментальних
методик на властивості одержаних НЧ за допомогою УФ / видимої спектроскопії і
методу динамічного світлорозсіювання.
БИМЕТАЛЛИЧЕСКИЕ НАНОЧАСТИЦЫ ЗОЛОТО/СЕРЕБРО ТИПА
СПЛАВ, СИНТЕЗИРОВАННЫЕ В ПРИСУТСТВИИ ТРИПТОФАНА
Н. Витюк1, Ю. Муха1, Г. Гродзюк2,3, А. Еременко1
1Институт химии поверхности им. А.А. Чуйко Национальной академии наук Украины,
ул. Генерала Наумова, 17, Киев, 03164, Украина
2Институт физической химииим. Л.В. Писаржевского НАН Украины, просп. Науки 31,
г. Киев, Украина, 03028
3ООО НаноМедТех, ул. Горького 68, г. Киев, Украина, 03150
Стабильные коллоидные растворы наночастиц (НЧ) серебра и золота, а так
же их биметаллические композиты с соотношением металлов Ag:Au = 3:1, 1:1, 1:3
синтезированы в присутствии аминокислоты триптофана. В спектрах поглощения
присутствует только одна полоса плазмонного резонанса НЧ, характерная для
биметаллических наночастиц сплава AgAu, находящаяся между полосами НЧ
отдельных металлов. Положение ее максимума сильно зависит от мольного
соотношения Ag:Au. Поверхность всех синтезированных наночастиц имеет
отрицательный заряд за счёт стабилизирующей оболочки аминокислоты.
Проанализировано влияние экспериментальных методик на свойства полученных НЧ с
помощью УФ/видимой спестроскопии и метода динамического светорассеивания.
|
| id | oai:ojs.pkp.sfu.ca:article-612 |
| institution | Surface |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-03-12T17:16:02Z |
| publishDate | 2016 |
| publisher | Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine |
| record_format | ojs |
| resource_txt_mv | surfacezbircomua/5c/6634f7ffd01e39467db9bc7687facf5c.pdf |
| spelling | oai:ojs.pkp.sfu.ca:article-6122019-02-11T09:36:14Z Bimetallic gold/silver alloy nanoparticles prepared in the presence of tryptophan Биметаллические наночастицы золото/серебро типа сплав, синтезированные в присутствии триптофана Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану Vityuk, N. Mukha, Iu. Grodzyuk, G. Eremenko, A. The stable colloidal solutions of monometallic and bimetallic gold and silver nanoparticles (NPs) have been obtained in the presence of amino acid tryptophan. For the synthesis of bimetallic composition the metals were used in a molar ratio of Ag:Au = 3:1, 1:1 and 1:3. The only one plasmon resonance band in absorption spectra was located between the bands inherent to the individual metals and it was characteristic for “alloy” type bimetallic AgAu NPs. The position of its maximum strongly depends on the Ag:Au molar ratio. The surface of all synthesized nanoparticles carries a negative charge due to the stabilizing shell consisted of amino acid. In the paper we usedUV/visible spectroscopy and dynamic light scattering method to analyze the effect of experimental procedure on the properties of obtained NPs. Стабильные коллоидные растворы наночастиц (НЧ) серебра и золота, а так же их биметаллические композиты  с соотношением металлов Ag:Au = 3:1, 1:1, 1:3 синтезированы в присутствии аминокислоты триптофана. В спектрах поглощения присутствует только одна полоса плазмонного резонанса НЧ, характерная для биметаллических наночастиц сплава AgAu, находящаяся между полосами НЧ отдельных металлов. Положение ее максимума сильно зависит от мольного соотношения Ag:Au. Поверхность всех синтезированных наночастиц имеет отрицательный заряд за счёт стабилизирующей оболочки аминокислоты. Проанализировано влияние экспериментальных методик на свойства полученных НЧ с помощью УФ/видимой спестроскопии и метода динамического светорассеивания. Стабільні колоїдні розчини наночастинок (НЧ) срібла та золота та їх біметалічні композити зі співвідношенням металів Ag:Au = 3:1, 1:1, 1:3 синтезовані у присутності амінокислоти триптофану. В спектрах поглинання присутня лише одна смуга поглинання плазмонного резонансу НЧ, характерна для біметальних наночастинок сплаву AgAu, розташована між смугами індивідуальних металів. Положення максимуму поглинання дуже залежить від мольного співвідношення Ag:Au. Поверхня всіх синтезованих наночастинок має негативний заряд за рахунок стабілізуючою оболонки амінокислоти. Проаналізовано вплив експериментальних методик на властивості одержаних НЧ за допомогою УФ / видимої спектроскопії і методу динамічного світлорозсіювання. Chuiko Institute of Surface Chemistry National Academy of Sciences of Ukraine 2016-10-06 Article Article application/pdf https://surfacezbir.com.ua/index.php/surface/article/view/612 10.15407/Surface.2016.08.118 Surface; No. 8(23) (2016): Surface; 118-122 Поверхность; № 8(23) (2016): Поверхность; 118-122 Поверхня; № 8(23) (2016): Поверхня; 118-122 3154-8091 3154-8083 10.15407/Surface.2016.08 en https://surfacezbir.com.ua/index.php/surface/article/view/612/612 Авторське право (c) 2016 N. Vityuk, Iu. Mukha, G. Grodzyuk, A. Eremenko |
| spellingShingle | Vityuk, N. Mukha, Iu. Grodzyuk, G. Eremenko, A. Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title | Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title_alt | Bimetallic gold/silver alloy nanoparticles prepared in the presence of tryptophan Биметаллические наночастицы золото/серебро типа сплав, синтезированные в присутствии триптофана |
| title_full | Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title_fullStr | Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title_full_unstemmed | Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title_short | Біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| title_sort | біметальні наночастинки сплаву золото/срібло синтезовані у присутності триптофану |
| url | https://surfacezbir.com.ua/index.php/surface/article/view/612 |
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