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AZ9RBAYCAN KIMYA JURNALI № 4 2016
UDC 544.23.02/03;544.25.02/03
SYNTHESIS OF SILVER NANOPARTICLES IN DIFFERENT POLYMERS
ENVIRONMENT
S.F.Humbatova, Sh.Z.Tapdigov, S.M.Mammadova, N.A.Safarov, D.B.Tagiyev, N.A.Zeynalov
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
[email protected] Поступила в редакцию 14.06.2016
Synthesis and stabilization of silver nanoparticles in different reaction conditions have been carried out with gum arabic with an average molecular weight of 200 kDa and 40000 of polyethylene glycol, as well as in 200 kDa chitosan (Cht) condition in the presence of small concentration of NaBH4 and HCOOH aqueous solutions at 293-353 K temperature. The sizes of obtained silver nanoparticles were investiqated by X-ray phase analysis. It was determined that the size of silver nanoparticles stabilized in polyethylene glycol and gum arabic based co-polymers conditions range between 7-9 nm, while the sizes of formed silver nanoparticles range between 8-11 nm when using Cht being natural polysaccharide as the stabilizer.
Keywords: silver nanoparticles, gum arabic, chitosan, polyethylene glycol, nanocomposites, XRD-ray.
Introduction
Recently, studying synthesis, structure, and properties of Cu, Au, Ag, Pt and Pd nanoparticles containing polymer compositions has been the main directions of a scientific community. High optical [1, 2], catalytic [2, 3], conductive [4, 5] and medical [6-8] properties of polymer materials containing metal nanoparticles make their research and a wide range of synthesis more urgent. Sizes of metal nanoparticles in nanocomposites define their direct application areas.
Usage of synthetic polymers containing polar functional groups as a stabilizing agent in these researches, preparation of silver nanopar-ticles, studying their structures and properties are in the focus of interest [9-14]. It is possible to regulate sizes of metal nanoparticles depending on nature of selected stabilizing and reducing agent and process condition. It is known that depending on particle size polymer composites containing silver nanoparticles are widely used in medicine as a carrier for immobilization of bionanocomposites, bionanocatalysts, antibacterial preparations and biologically active compounds [15-20].
The use of some biopolymers as stabilizing agent and different type reducers provides wider effects of obtained nanocomposite. High therapy opportunities and antimicrobial properties of silver nanoparticles were studied by researchers. In some works the use of Ag0 nano-
particles in the treatment of cancer was studied [21]. But the shortcoming is that when using >20 nm of Ag0 nanoparticles freely the healthy cells are also exposed to toxic effects.
In other work, we synthesized 25 nm of silver nanoparticles by using aniline as a reducer and showed their application in the preparation of different preparations [22].
Priya and his colleagues have used Musa balbisiana (banana), Azadirachta indica (neem) and Ocimum tenuiflorum (black tulsi) extracts and carried out "green synthesis" of silver nanoparticles. Antibacterial and toxic properties of 20-25 nm of silver nanoextractants showed positive results [23].
<10 nm of Ag0 and Au0 nanoparticles were prepared by using poly-N-vinylpyrroli-done as both reducer and stabilizer [24]. Synthesized nanocomposites were used in the production of optical and magnetic materials.
In the present work, we synthesized Ag0 by polyethyleneglycol (PEG), gum arabic (GA) and chitosan (Cht).
Experimental part
Materials. GA with average molecular weigth of 200 kDa used as a stabilizer has 97% chemical purity. Chitosan with 84% deacetylation degree and average molecular weight of 200 kDa was purchased from Sigma-Aldrich. Average molecular weight of 97% chemically pure PEG is
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2016
SYNTHESIS OF SILVER NANOPARTICLES IN DIFFERENT POLYMERS 7
40 kDa and was purchased from Fluka. Both polymers were used without purification in experiments. As silver precursor AgNO3 (99.98%) from Mersk (Germany) was taken. All the chemical reagents - natrium boron hydrate 98% (NaBH4), acetic acid (CH3COOH), formic acid (HCOOH), deionized water and precipitants are chemically pure and from Fluka.
Synthesis of Ag colloidal. PEG and GA are dissolved in 2:1 mass ratio in 100 ml of deio-nized water within 2 h, 0.5 g Cht is dissolved in 25 ml of acetic acid by mixing 15 min and 5 ml of 2.5x10 M AgNO3 is added to the solution and mixed at room temperature for 2 h. Then in two parallel experiments, NaBH4 and HCOOH with relevant concentrations are added into the solution and mixed at 293 K. After 15-20 min color of the solution changes from yellow to dark brown and black. The solution is deposited at diethyl ether or acetone, dried after washing 2-3 times with etha-nol and brought into constant mass under atmospheric pressure. To study the impact of different factors on sizes of nanoparticles the reduction process was conducted at 293, 313, 333, 353 K temperatures, in m(PEG):m(GA)=1:1, 1:2, 2:1, as well as (Cht):m(AgNO3) mass ratios, in 5, 10, 20, 30 and 60 min intervals.
Results and Discussion
In experiments PEG and biologically active natural polysaccharide GA are separately used as a soluble unique polymer matrix in the stabilization of metal nanoparticles. It is known that PEG with H(OCH2CH2)„OH formula is soluble in water and is widely used in pharmacology and cosmetic industry. Natural polysaccharide GA contains -OH and -COOH groups
and has wide application areas as an immunomodulator, gastroprotector, antioxidant and carrier in medicine and biotechnology. We compared the reduction of Ag+ ions with NaBH4 and HCOOH and investigated the dimensions of na-noparticles and use of them for biological purposes. It was shown that PEG and GA macro-molecules form a homogeneous system at aqueous medium and their functional groups create a configuration with each other in more favourable form. Ag+ ions are coordinated around -OH and -COOH groups of PEG and GA:
PEG/GA + AgNO3^ PEG/GA/Ag+NO3-.
When adding reducers into the system silver atoms are formed by following chemical conversion:
PEG/GA/Ag+NO3- + NaBH4 + H2O ^ PEG/GA/Ag0 + H2 +B2H6 + NaNO3, PEG/GA/Ag+NO3- + HCOOH ^ PEG/GA/Ag0 + CO2 + HNO3.
In both cases depending on temperature and reaction time, the change in color of solution first to yellow, then to dark brown and black (Figure 1) shows the reduction of silver ions. It is known that X-ray phase analysis is one of the main methods which determines crystal phase. X-ray phase analysis of PEG-GA-Ag0 composite was studied and in Figure 2 X-ray phase spectra of reduction products performed at different temperatures are given.
As is seen from Figure 2, according to results of analysis of polymer composites obtained in PEG:GA=2:1 mass ratio at pH=11 and 293353 K temperature range depending on temperature sizes of silver nanocomposites vary in the range of 7-9 nm.
PEG GA
Fig. 1. Depending on reaction time the change of color of PEG-GA-Ag0 suspension. AZERBAIJAN CHEMICAL JOURNAL № 4 2016
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S.F.HUMBATOVA et al.
Fig. 2. X-ray spectra of PEG/GA/Ag0 composite obtained at different temperatures. The spetra at 353 K given as 24 hours differs from previous examples by the maintenance of for 24 hours a day. In comparison with other examples it shows there are no aggregated Ag-NPs.
In spectrum, we observed 19.230 and 23.340 strong and 13.610, 27.320 weak reflections at angle 20 typical for PEG and GA amorphous system. 37.910, 43.710, 64.060 and 76.980 degree values of Bragg reflection at angle 20 for silver nanoparticles are determined by corresponding (111), (200), (220), (311) crystalline regions. This shows the formation of silver nanoparticles in centered cubic shape. High intensity of the peak corresponding to (111) field justifies the existence of nanoparticles. Average value of dimensions of Ag nanoparticles is calculated by Debye-Scherrer equation:
n =-
p cos 0 ,
where K - Scherrer constant (0.9-1), X - X-ray wavelength (1.5418 A), P1/2 - width of X-ray peak and 0 - Bragg angle. By Scherrer equation, it was determined that average sizes of particles are found to be 7-9 nm depending on the reaction time and temperature.
By parallel experiments, it was determined that the sizes of silver nanoparticles produced at high temperature from 292 to 353 K, increase when PEG/GA is not used. This confirms the stabilizing function of polymer mac-romolecules without any changes in nanosizes of Ag nanoparticles for a long period. At the
high temperature of over 353 K nanosizes of particles increases. This can be explained by high flexibility of polymer macromolecules and aggregation process in silver atoms.
Cht is a biologically active natural polysaccharide P-1,4 connected with deacetylated D-glucosamine residues with N-acetyl-D-glucos-amine residues. High bioconformity, degradation ability, non-toxical property, bioactivity, and multifunctionality caused study of it as a natural cation exchanger biopolymer. From this point many research works are dedicated to the use of chitosan with another synthetic polymer in biomedical purposes, pH sensitive medical preparations and in stabilization of metal nano particles.
Using NaBH4 and HCOOH Ag0 nanoparticles were synthesized with (Cht) and it was determined that Ag+ ions form coordination around -NH2 and -OH groups in Cht. In Cht, medium reduction of silver ions and formation of different color changes occurs similar to PEG:GA systems. It was determined that to stabilize experiments in relatively small sizes in chitosan medium of Ag0 nanoparticles the process should be performed 1 hour in the range of 323-343 K.
In Figure 3 (a, b) obtaining spectra of silver nanoparticles in chitosan medium.
A3EPEAHffAAHC KHH XHMHHECKHH KKYPHAJJ № 4 2016
SYNTHESIS OF SILVER AANOPARTICLES IN DIFFERENT POLYMERS 9
a
Fig. 3. a - X-ray spectrum of chitosan, b - X-ray spectrum of Chitosan-Ag composite
b
As it is seen, peak typical for crystal phase is not observed in X-ray spectrum of (Cht). But in Cht.-Ag0 spectrum in 29 three strong intensiveness is formed typical for silver atoms. These are crystal phases which conform to 37.860, 43.680 and 64.120 values of Bragg reflection in 29 for Ag0 nanoparticles. It was determined that average sizes of nanoparticles are found to be 8-11 nm depending on reaction period and temperature.
Conclusion
We have synthesized colloidal Ag0 nano-particles with PEG/GA and Cht. Results of X-ray analysis show that Ag0 nanoparticles are in centered cubic crystal shape and depending on temperature sizes of particles changes in the range of 7-9 and 8-11 nm corresponding to PEG/GA, Cht medium.
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MUXTЭLiF POLiMERLЭR MUHШNDЭ GUMU§ NANOHiSSЭCiKLЭRlNiN SiNTEZi
S.F.Hйmbэtova, §.&Тарйщоу, S.M.Mэmmэdova, ^Э^ЭГОУ, D.B.Taglyev, ^А.геупа1оу
ОАз то1еки1 kйtlэsi 200 Ша о1ап qummiarabik уэ 40000 о1ап polietilenqlikol elэcэdэ 200 Ша о1ап xitozan mйhitindэ кфк qatlllqll NaBH4 уэ НСООН тэЫиИап ^йгак1 ilэ 293-353 К temperatur intervalmda, mйxtэ1if reaksiya mйddэtindэ Ag0 nanohissэcik1эrinin allnmasl уэ stabi11э§dirilmэsi hэyata кедт^;^. А1тт1§ gйmй§ nanohissэcik1эrin б^Шэп rentgen-faza ana1izi i1э tэdqiq ейПт^йш Мйэууэп olunmu§dur ki, stabiUэ§dirici кш1 po1ieti1enq1iko1 уэ qummiarabik эsasll Ы^э po1imer1эr mйhitindэ formala§an gйmй§ nanohissэcik1эrinin б1дй1эг1 7-9 nm, tэbii po1iaminosaxarid o1an xitozandan istifadэ etdikdэ stabi11э§эn gumй§ nanohissэcik1эrinin бlgйlэri isэ 8-11 nm arallgmda dэyi§ir.
Адаг sдzlэr: gumщ nanohissэciklэr, диттгагаЫк, хН^ап, роНеШепциЫ, папокотро2Мэг, Rentgen-faza апаИ21.
СИНТЕЗ НАНОЧАСТИЦ СЕРЕБРА В РАЗЛИЧНЫХ ПОЛИМЕРНЫХ СРЕДАХ
С.Ф.Гумбатова, Ш.З.Тапдыгов, С.М.Мамедова, Н.А.Сафаров, Д.Б.Тагиев, Н.А.Зейналов
В среде гуммиарабика со средней молекулярной массой 200 кДа, полиэтиленгликоля 40000 и хитозана 200 кДа, с участием растворов низких концентраций NaBH4 и НСООН в температурном интервале 293-353 К и различных временах реакции осуществлены получение и стабилизация наночастиц серебра. Размеры полученных наночастиц серебра исследованы рентгенофазовым анализом. Установлено, что с использованием в качестве стабилизатора сополимера на основе полиэтиленгликоля и гуммиарабика размеры с формированных наночастиц серебра составили 7-9 нм, а в среде природного полиаминосахарида, такого как хитозан, размеры стабилизованных наночастиц серебра меняются в пределах 8-11 нм.
Ключевые слова: наночастицы серебра, гуммиарабик, хитозан, полиэтиленгликоль, нанокомпозиты, Рентген-фазовый анализ.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 4 2016
