CC BY
42
UDC 678.01.,544.23.02/.03;544.25.02/.03
SYNTHESIS OF SILVER NANOPARTICLES IN THE PRESENCE OF NATURAL AND SYNTHETIC POLYMERS AND THE INVESTIGATION OF THEIR MORPHOLOGICAL STRUCTURES
D.B.Tagiyev, N.A.Zeynalov, Sh.Z.Tapdigov, S.F.Humbatova, S.M.Mammadova,
M.Kh.Hasanova
M.Nagiyev Institute of Catalysis and Inorganic Chemistry, NAS of Azerbaijan
shamo.chem.az@gmail.com Received 17.05.2016
The results of works (including also the authors of the given review) in a field of obtaining the stable nanoparticles of silver and study of the mechanism of their f0rmation at reducing Ag ions in aqueous solutions in the presence of the natural and synthetic polymers, as well the influence of different factors on aggregation, size and sustainability nano size metallic particles According to the data obtained in researches it has been established that a form, state and intensity of plasma absorption strip of silver nanoparticles depend on conditions of their receiving. The methods of scanning electronic microscopy, X-ray phase analysis and UV-spectroscopy used in works permit to estimate size, form and distribution of na-noparticles in polymer, as well provide identification of nanoparticles in the metallic state.
Keywords: silver nanoparticles, chitosan, poly-N-vinylpyrrolidone, gum arabic, polyethylene glycol, scanning electron microscope, X-ray.
Introduction
The potential of inorganic nanoparticles has been explored world-wide in nanomedicine, drug delivery and biomedical devices, cosmetics, electronics, energy sector, and environmental protection [1-4]. For over centuries, silver-based compounds were used as nontoxic inorganic antibacterial agents owing to their biocid-al properties in many applications such as wood preservation, water purification in hospitals, in wound or burn dressing, and so forth. The recent advances in the field of nanoparticle synthesis have a strong impact in many scientific areas and the synthesis of silver nanoparticles has also followed this tendency. In fact, silver based compounds are much cheaper than gold based ones, moreover, silver nanoparticles (Ag-NPs) are now considered as an important class of nanomaterials. They are presently mainly used as the catalyst or antibacterial agents [5-7].
Recently, the number of publications on the topic of Ag-NPs has increased rapidly and an increase of 93% in the number of published articles has been observed since 2001-2011. During this period, 247 articles were published in 2001, which it increased to 3603 in 2011. Most of these were published in the field of chemistry, materials science, physics, enginee-
ring, polymer science, spectroscopy, electrochemistry, molecular biochemistry, optics, and spectroscopy [8-12].
Environmentally friendly synthesis methods are becoming more and more popular in chemistry and chemical technologies. This trend has several origins, including the need for greener methods counteracting the higher costs and higher energy requirements of physical and chemical processes. For this reason, scientists search for cheaper methods of synthesis. In order to reduce the environmental impact of na-noparticle synthesis, greener routes have been investigated for over a decade [13-15].
Green chemistry should aim at thwarting waste, minimizing energy use, employing renewable materials, and applying methods that minimize risk. The three main concepts for the preparation of nanoparticles in a green synthesis approach are the choice of the solvent medium, an environmentally friendly reducing agent, and a nontoxic material for the stabilization of the nanoparticles [16-19]. Since vast literature on the Ag-NPs is present in the form of individual research articles that only focuses on the minor application part, we aimed to summarize it in
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
the present review form so that the interested readers may find all recent information ranging from synthetic procedures to application in a single document. This paper aims to summarize the various methods adapted for the synthesis of Ag-NPs and the area in which these Ag-NPs were, now are, and to be used so that it can be easy for common readers who wants to seek information related to these nanoparticles. In this review paper every aspect of Ag-NPs, from synthesis to their application in the fields of environment, science, biology, molecular science, textiles industry, and last but not the least their role inme-dicinal fields, has been briefly explored [20-23].
Synthesis methods of Ag-NPs
Currently, a variety of methods, such as chemical, physical and biological, has been developed for the synthesis of Ag-NPs. Each method has its advantages and disadvantages. The synthetic routes with commonly associated problems, that is, costs, stability, scalability, particle sizes, and size distribution for the Ag-NPs, have been described as follows.
Many research groups and academicians are using these methods to synthesize Ag-NPs in various sizes and shapes. For example, one research group synthesized monodisperse silver nanocubes by simply reducing AgNO3 with ethylene glycol in the presence of polyvinylpyr-rolidone (PVP) polymer the process was called polyol process. In this process, it has been revealed that ethylene glycol is used as both the solvent and the reducing agent. Furthermore, the size and shape of the nanocubes were dependent on the molar ratio of AgNO3 and PVP. In this method, particles with 20 nm or smaller size were prepared [24-31]. Normally, the synthesis of Ag-NPs by chemical method banks on three factors (stages): (a) Ag precursor, (b) reducing agents, and (c) stabilizing agent. Uniform size and monodispersity can be achieved by controlling the nucleation stage and stacking nuclei in which depends on experimental parameters such as precursor, pH, temperature, and reducing agents. More recently there was synthesized Ag-NPs using AgNO3 as precursor and sodium borohydride and trisodiumcitrate as
reducing and stabilizing agent. The size of the Ag-NPs was controlled by optimizing the experimental parameters and was in the range of 5 nm to 100 nm. Furthermore, they elucidated the effect of size and dose-dependent property of the synthesized Ag-NPs. From the analysis of the obtained results, they revealed that Ag-NPs with small size show excellent antibacterial activity as compared with its other counterparts [32-35].
Along with the chemical methods used, various alternative techniques were also accepted by researchers for the synthesis of Ag-NPs. Usually in those techniques, evaporation and condensation processes are implemented for the synthesis of Ag-NPs. As being similar to chemical methods, these ones have their own advantages and disadvantages. One of the most common drawbacks of these methods is the higher energy requirement and time consuming. Therefore, researchers have reported on the numerous alternative physical methods for the synthesis of Ag-NPs instead of implementing conventional condensation and evaporation method. These methods not only reduce the preparation time, but also are energy friendly. In such method, complexation reaction between Ag and oleate at elevated temperature was carried out for the synthesis of Ag-NPs with a particle size less than 10 nm [36, 37]. Recently researchers reported on a unique technique for the physical synthesis of Ag-NPs with uniform geometry and the particle size less than 5 nm along with improved dispersion. The technique was proposed to be an alternative for chemical techniques with the added advantage of saving time. Ag-NPs were also prepared by sputtering metal into the reaction mixture, that is, physical deposition of Ag into glycerol. Physical techniques used for the preparation of Ag-NPs having uniform particle size and shape are mostly governed by the thermal, as power, and arc discharge. By adopting these aforementioned techniques, the bulk amount of Ag-NPs can be synthesized in a single process which will save time and the purity of the Ag-NPs particles will not be compromised. However, the cost is considered to be the main hurdle in adopting such method as it needs expensive equipment [38-42].
It is known that silver nanoparticles are widely used in the preparation of stabilized composites, biosensors, antibacterial preparations in medicine and drug delivery [43-45]. The use of some bio- and synthetic polymers [chi-tosan (Cht.)], chitin, gum arabic (GA), arabino-galactan, polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyacrylamide (PAA) and etc.) as a stabilizing agent leads to wide spectra impact possibilities of obtained nanocomposite. Cht. is a natural polysaccharide which is generated from the P-1,4-compound of glucosamine and N-acetylglucosamine chain [46].
Chitosan is an antimicrobial, antibacterial natural large molecular compound which does not form toxic compounds in human organism when decomposes by the impact of ferments. High therapy possibilities and antimicrobial properties of silver nanoparticles were studied many times by researchers. PVP has attracted considerable interest due to its hydrophilicity, lubricity, anti-adhesive property and excellent biocompatibility. PVP is a vinyl polymer possessing planar and highly polar side groups due to the peptide bond in the lactam ring.
The use of GA having prospective scope among the natural polysaccharides spread rapidly today. Its solubility and polyfunctionality allow its application in medicine and various areas of biotechnology. GA is biologically active natural polysaccharide which has the effect of gastro protector, membrane conductivity, immu-nomodulatory activity. GA's shown characteristics provide the basis to in obtaining drugs, enzymes and the carrier of microelements which is necessary to the human body and as well as metal nanoparticles and in using it both as de-oxidant, as well as stabilizing agents.
Many scientific works on the use of Ag nanoparticles in a treatment of cancer can be found in literature [47-52]. But the disadvantage is that when using >20 nm of free Ag nanoparticles toxic effects are being observedon healthy cells.
Synthesized Ag-NPs with chitosan without using any reducing reagent. The reduction was conducted under 15 psi pressure and at 393 K. Catalytic property of chitosan-Ag0 com-
posite was tested in reduction reaction of 4-nit-rophenol. Antimicrob activity of nanocomposite was tested on Escherichia coli and Micrococcus gluteus and its inhibitor property was determined [53]. Analysis of literature data shows that by using starch, agar-agar, cellulose, gum arabic, arabinogalactan, chitin and other natural polysaccharides obtaining of Ag nanocompo-sites is now one of the promising directions [54, 55]. In our paper, we studied obtaining and structure of Ag-NPs by using NaBH4 as a reducer and chitosan both as a reducer and stabilizing agent.
Literature review shows that each of the conducted research works in Ag-NPs obtaining differ from others in terms of deoxidant agent, stabilizing substance, reduction period, long-term stability and antibacterial, optical etc. characteristics which will show. Despite this research works such as the application of Ag-NPs new stabilization method and the dimensions regulation still does not lose its actuality. From this point of view stabilizing agent plays an important role and its right selection is essential.
Getting nano-bio-composites has the ability to show high antibacterial activity by using chitosan, polyethylene glycol, gum arabic and poly-N-vinylpyrrolidone-based natural and synthetic polymers containing -COOH, -NH2, -OH, >C=O, -O- functional groups in its structure as stabilizing agent and keeping Ag-NPsof different sizes in its structure and the investigation of their structures are given in the submitted article.
Ag-NPs having Cht. composition
High biocompatibility, biodegradation, non-toxicity, bioactivity and multifunctionality of chitosan have been a reason for studying it as a natural cationic biopolymer for many years. From this point of view, many research works can be found in literature data on using chitosan for biomedical purposes, using it with other synthetic polymers for stabilization of pH-sensitive drug carriers. As it was stated our main aim is to study the synthesis and structure of Ag0 ions by NaBH4 as a reducer with
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chitosan. Ag+ ions form coordination around -NH2 and -OH groups in chitosan:
Cht. + AgNOs^ Cht./Ag+ NO3- .
When adding NaBH4 into the system reduction of silver ions goes according to the following chemical equation (Figures 1, 2):
Cht./Ag+NO3"+BH4"+3H2O^Cht./Ag0+3.5H2+ B(OH)3.
As is seen from Figure 1 during reduction process color of the solution changes first to yellow, then to dark brown. This shows the formation of Ag-NPs-containing colloidal solution.
One of the physical research methods which shown a formation of Ag-NPs is UV-spectroscopy. We recorded UV of the samples when nanoparticles are formed in the reduction process. All show a strong peak associated with surface plasmon resonance centered in 410 nm.
This data is agreed to literature, a previous study reported the plasmon resonance peak near 400 nm with Ag-NPs of 12±2 nm. If a maximum peak between 405-418 nm with the Ag-NPs size of 9-30 nm [56].
As is seen in Figure 2 the intensity of peak rises and absorption band forms maximum adsorption due to the full conversion of Ag+ ions to Ag0 atoms within an hour during reduction time. When the reduction process proceeds more than 1 hour, the intensity of peak does not change. 350-450 nm interval of plasmon resonance of Ag-NPs shows that sizes of silver nanoparticles in suspension are distributed in a narrow fraction. The reduction process accelerates the formation of Ag-NPs at 353-363 K temperature. Variation is observed on flexibility of chitosan macromole-cule as increasing the energy of system at 363 K.
Fig. 1. Color variations depending on reduction time of chitosan-Ag0 suspension.
Wavelength(r
Fig. 2. UV-visible spectra of formation of Ag-NPs depending on time with the use of chitosan.
Fig. 3. X-ray phase spectra of chitosan (left) and chitosan-Ag composite (right).
Thus, adsorption of 405 nm intensive peak of Ag-NPs are reduced and the curve becomes wide. According to the researchers in order to stabilize the small size Ag-NPs in chitosan participation the process must be conducted in an hour at 323-343 K. It is known that X-ray diffraction phase analysis is one of the methods which determines crystal phase. X-ray phase spectra of stabilized Ag-NPs containing polymer composite was recorded (Figure 3).
As is seen, the peak of crystal phase in X-ray phase spectra of Cht. is not observed. But in 20 three strong intensities, which belong to silver atoms are formed in Cht.-Ag0spectra . These are crystal phases with (111), (200) and (220) areas which conform to 37.860, 43.680 and 64.120 values of Bragg reflection in 20 for Ag-NPs [57, 58]. Obtained X-ray phase results
show that Ag-NPs exist in the centered cubic form in chitosan. The sizes of Ag-NPs are stabilized in polysaccharide were determined by Debye-Scherrer equation:
«=KX/pcos0,
where K - Scherrer constant (0.9-1), X - X-ray wavelength (1.5418 A), the P1/2 width of X-ray peak and 0 Bragg angle. It was determined that average sizes of nanoparticles make up 14-25 nm depending on reaction time and temperature. The scanning electron microscopy (SEM) study of synthesized Cht.-Ag0 composite was performed. Cht.-Ag0 nanocomposite nanoparticles are stabilized in more oval granules. SEM image of Cht.-Ag0 is presented in Figure 4. The image reveals the surface structure of Cht.-Ag0 nanocomposite.
Fig. 4. SEM image of chitosan-silver nanocomposite. АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
Figure 4 it shows that Ag is nano-spherical between 12 and 23 nm in size. Since Cht. molecules act as reducing agents in the participation of aqueous sodium borohydride, even after drying the chitosan molecules does not allow Ag-NPs to get merge with each other. Thus, in SEM image, these particles appear as nano-sized ones.
Probably, chitosan macromolecules or its -NH2 and -OH functional groups enclose Ag-NPs together with a polymer chain. The interaction between Ag-NPs and chitosan macromolecule was confirmed by FTIR-spectroscopy (Figure 5).
We observed bands in 3354 and 3294 cm-1 region typical for O-H and N-H vibration bonds in FTIR spectra of chitosan. 2876 cm-1 adsorption band shows distorted chemical shift of aliphatic C-H bond, 1643 and 1584 cm-1 show N-H chemical bond, 1419, 1376 and 1318 cm-1 intensities show aliphatic C-H chemical
bond, 1061 and 1026 cm-1 adsorption bands are the peaks which conform to C-O bond [59-61]. As is seen in Cht.-Ag0 spectra marked with the blue line, 1643 and 1584 cm-1 adsorption bands are exposed to chemical shift up to 1635 and 1544 cm 1 correspondingly. In 1544 cm-1 high intensive peak is observed. In 1397 cm-1 distorted bond of Cht.-Ag0 complex characterizes the interaction between Ag-NPs and chitosan. Thus, when amine and hydroxyl groups in chitosan enclose Ag-NPs spheric stabilized (Cht.-Ag0)n system is formed. The interaction or stable state of the system occurs due to electrostatic interaction forces between negatively charged functional groups in basic chitosan and partially positively charged metal nanoparticles and Vander Waals forces [62-64]. According to this, we may show schematic form (Figure 6) of stabilization of Ag-NPs with Cht. macromolecules.
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm'1)
Fig. 5. Structural unit of Cht. macromolecule and FTIR of Cht.-Ag0 composite.
Fig. 6. The suggestetd structural form of A
Ag-NPs having PEG and GA composition
Currently metal nanoparticles are intensely studied in terms of their unique optical, electrical, and catalytic properties. To utilize and optimize the chemico-physical properties of nanosized metal particles, a large spectrum of research has focused on the control of the size and shape, which is crucial in tuning their physical, chemical, and optical properties [65-69]. The numerous kinds of technique, such as
;-NPs which is stabilized by Cht.
chemical reduction, gas condensation, laser irradiation, sonochemical deposition, and nanostructured templates [70-73] have been reported. In most cases, the surface passivation reagents, including surfactant molecules and polymers, are needed to prevent the nanoparti-cles from aggregation [74-78].
Ag-NPs have high therapeutic potential and exhibit good antimicrobial activity. Ag-NPs have a wide range of antimicrobial activities and exhibit high performance even at a very
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
low concentration. Ag-NPs have been identified to possess the good potential for the treatment of cancer. But the major disadvantage of using silver alone is that it is not specific at targeting the cancer cells and also it is toxic to the normal cells when exposed for a longer time when the size of silver used is 20 nm. It is known that polymer compositions depending on particles sizes containing silver nanoparticles are widely used in medicine as a carrier for immobilization of bio-nanocomposites, bionanocatalysts, antibacterial preparations and biologically active compounds [79-84].
The use of different type reducers justifies the direct research area of obtained nano-composite. Using antioxidant Rumex hymeno-sepalus extract we synthesized 2-40 nm silver nanoparticles [85]. It was confirmed by SEM, UV-Vis and FTIR spectroscopy methods that obtained silver nanoparticles centered on the surface having cubic and hexagonal structure and can be used in medicine.
In other work by using aniline as a reducer we synthesized 25 nm Ag-NPs and showed application areas for preparation of different preparations [86]. Priya and his colleagues used Musa balbisiana (banana), Aza-dirachta indica (neem) and Ocimum tenuiflo-rum (black tulsi) extracts and conducted "green synthesis" of Ag-NPs. Antibacterial and toxic properties of obtained 20-25 nm silver nano extractants' showed positive results [87]. Ag and Au nanoparticles with the size of 10 nm or less were obtained by using PVP as both reducer and stabilizing agent [88]. Synthesized nano-composites were used in preparation of optical and magnetic materials.
Generally, different Ag nanocomposites were obtained by using natural and synthetic including PAA [89], heparin [90], Cht. [91], poly-acrylic acid [92], PVP [93], polyvinyl alcohol [94], arabinogalactan [95], polyurethane [96] type polymers as a stabilizing agent in the studies. As it is shown "green synthesis" of metal nanoparticles is one of the widely used methods in this field. This method differs from other physical and chemical reduction methods for its advantages. In this method nanoparticles are ob-
tained cheaply and effectively at mild condition - low temperature and pressure, low energy consumption, and toxic substances are not used.
In the present work by using reducers in the participation of PEG and GA we studied the obtaining and structure of Ag-NPs.
In experiments PEG and biological active natural polysaccharide GA are used as a soluble unique polymer matrix in stabilization of separate metal nanoparticles. It is known that PEG with H(OCH2CH2)«OH formula dissolves in water and is widely in pharmacology and cometic industry. Natural polysaccharide GA contains -OH and -COOH groups and has a wide application areas as an immunomodulator, gastroprotec-tor, antioxidant and carrier in medicine and biotechnology. Comparison of reduction of Ag+ ions by NaBH4 and HCOOH arouses great interest in the sizes of obtained nanoparticles and use of them for biological purposes. PEG and GA mac-rocolecules form 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 inside PEG and GA:
PEG/GA + AgNOs^ PEG/GA/Ag+ NO3- .
When adding reducers into the system the formation of silver atoms occurs according to the following chemical conversion:
PEG/GA/Ag+NO3-+NaBH4+H2O^ PEG/GA/Ag0 + H2 +B2H6 + NaNO3,
PEG/GA/Ag+NO3-+HCOOH ^ PEG/GA/Ag0+CO2+H2O+HNO3.
In both cases the color of solution depending on temperature and reaction period changes into firstly yellow, then to dark brown and black color shows the reduction of silver ions.
It is known that studying the metal nanoparticles by UB spectroscopy is one of the methods which proves their formation. Thus, surface plasm resonance which is specific for metal atoms is observed in spectra with intensive peak. Obtained nanocomposite is deposited in diethyl or ethyl alcohol, dried and its UB are recorded in deionized water (Figure 7).
300 3so too ¿so 600 eso 6oo 6 so 700 Wavelength (nm)
Fig. 7. UV-visible spectra of PEG-GA-Ag colloidal system at different temperatures.
In Figure 2 UV-Vis of reaction solutions at different temperatures were given. All shown adsorption band around typical plasma resonance 410-425 nm which is specific for Ag-NPs. Lack of adsorpdion peak around 335 and 560 nm proves that Ag-NPs are not aggregated. According to literature data [97-99] if maximum adsorption changes in the 405 and 503 nm range for Ag-NPs, sizes of particles are formed at 2100 nm interval. According to the results the presence of high adsorption between 380 and 500 nm leads to the decrease of low-sized nanoparticles in the distribution of particles. When increasing the temperature up to 353-363 K and reaction time to 2 hours, the formation of Ag-NPs accelerates. As a result adsorption peak which is specific for atomic silver is exposed to
chemical-slip 410 nm towards region. According to experiments performed under different conditions for obtaining Ag-NPs with less than 20 nm in PEG/GA system, the process must be carried out within 2 hours at 353 K.
It was shown that when changing PEG and GA mass ratio, many differences occur in sizes and stability of Ag-NPs. Thus, when the mass ratio of GA in the mixture increases, Ag-NPs are obtained in less sizes (12-17 nm), however when the amount of PEG increases the sizes up to 34 nm. This is due to high amount of stabilizing functional groups in GA.
In Figure 8 X-ray diffraction spectra of reduction products is given at different temperatures.
Fig. 8. X-ray diffraction spectra of PEG/GA/Ag composites obtained at different temperatures. АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
As to Figure 8 sizes of Ag-NPs varies at 24-32 nm interval depending on temperature according to X-ray diffraction analysis results of polymer composites which were obtained at PEG:GA=2:1 mass ratio, pH=11 medium and 293-353 K temperature range. In the spectra at 20, we observed 19.230 and 23.340 strong and 13.610, 27.320 weak reflections which are specific for PEG and GA amorphous system. In 20 37.910, 43.710, 64.060 and 76.980 degree values of Bragg reflection for obtained silver na-noparticles are determined by corresponding (111), (200), (220), (311) crystalline areas. This shows the formation of Ag-NPs in centered cubic shape. The high intensity of the peak which corresponds to (111) area justifies the existence of nano particles. It was determined by parallel experiment that when PEG/GA is not used, sizes of Ag-NPs obtained at risen temperature from 293 K to 353 K, increase. This confirms once again stabilizing function of polymer macromolecules without any changes in nano sizes of Ag-NPs for a long period [100104]. When the temperature goes up over 353 K
the size of nanoparticles is growing. This can be explained by the increasing flexibility of polymer macromolecules and aggregation process happening among silver atoms. The spectra at 353 K given as 24 hours Figure 8 differes from previous exampes by the maintenannce of for 24 hours a day. In comparison with other examples it shows there are on aggregated Ag-NPs.
Chemical interaction between Ag-NPs and PEG/GA macromolecule was studied by FT-IR spectroscopy (Figure 9). As is seen intensive adsorption bands are observed at 1730, 1630 and 1007 cm-1 region. 1730 cm-1 peak is specific for >C=O bond of the carboxyl group in GA. 1268, 1007 cm-1 adsorption bands which are specific for C-O and C-O-C groups of C-O bond form wide adsorption bands. Aliphatic C-H bond forms the specific vibrating stress at 1413 and 1344 cm-1.
In Figure 5 wide peaks at 503, 407 and 291 cm-1 regions characterize the bond formed between oxygen of hydroxyl groups in Ag-NPs and PEG macromolecule.
Wavenumber (cm ')
Fig. 9. FTIR of PEG, PEG-GA and PEG-GA-Ag composite.
From the other side 3246 cm-1 adsorption form distorted bands up to -OH, 2901 sm-1 aliphatic C-H bond, 1442, 1374 and 1339 cm-1 C-H bond up to valency vibrations and O-C-H and C-O-H combination bonds form distorted bands from 1442 to 1339 cm-1. Thus, the surface of nanoparticles is positively loaded and hydroxyl groups of PEG surround Ag nanoparticles [105-107]. It can be stated that stabilization of Ag-NPs occurs due to Van der Waals forces which are formed between positively charged inert metal nanoparticles and negatively charged oxygen atoms [108, 109].
There are several types of researches on the drug release process since 1930. For the first time, estrogen was compressed into a tablet and placed under the skin, and its releasing was studied. But now, it is more actually to synthesis metal nanoparticles based on natural and synthetic polymers as reducing and stabilization agent. Then, to use these nanocomposites for immobilization antibiotics, proteins and etc., these nano-biocomposites show prolonged affects [110-115].
Ag-NPs having PVP composition
Getting Ag-NPs in PVPr participation and the investigation of their structures are given in our next research work, where Ag na-nocomposites are considered effective carriers
300
Fig. 11. Powder X-ray diffraction patterns of Ag-NPs stabilized in PVP.
АЗЕРБАЙДЖАНСКИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
for the immobilization of biologically active compounds[116-119]. The typical XRD patterns of the pure PVP and the prepared Ag-NPs are shown in Figure 11. It was observed that, PVP/Ag-NPs showed such strong reflections at 29 (38.1, 44.2, and 64.40) were characteristic to the 111, 200 and 220 planes of the face-centered cubic of Ag-NPs, respectively [120125]. The peaks showed that the main composition of nanoparticles was silver and obvious other peaks, present as impurities, were found in the X-ray patterns.
Previous studies have shown that the spherical Ag-NPs contribute to the absorption bands at around 410 nm in the UV-Vis.
That peaks shows the typical surface plasmon resonance of conducting electrons from the surface of Ag-NPs.
Analysis of FTIR spectra of PVP and PVP/Ag-NPs shows that the strong bands in the regions 1629 and 1637 cm-1 (Figure 12). Instead of two peaks in PVPr, only one peak 1645 cm-1 appears in PVP nano silver matrix [126-129]. The FTIR spectra for pure PVP/Ag-NPs clearly indicate that observed absorption peaks regarding the characteristic chemical bonds presented in PVPr (Figure 13). The peak at 1190 cm-1 represents the functional unit C-N in PVP, and it shifts to 1210 cm-1 after embedding Ag-NPs [130-136].
w 0 -00
500.00 600.00
Wavelength, nm Fig. 12. UV-VIS absorption of PVP/Ag-NPs in different pH.
65 55 45 35 25
15. 4000
3500 3000 2500 2000 1500
Wave number, cm-1
Fig. 13. FTIR of PVP/Ag-NPs pure. Table 1. Influence of pH environment Xmax of PVP/Ag-NPs systems
1000
PVPr/Ag-NPsCPVpr/Ag-NPs=0.08 mg/mL, Amax=410 nm
pH 3 4 5 6 7 8 9 10
Xmax of Ag-NPs 439 473 447 423.5 477.5 422 424.5 422.5
Absorbance 0.876 0.813 0.812 0.831 0.789 0.852 0.830 0.02
Fig. 14. SEM images of PVP-silver nanocomposite.
The SEM images of Ag-NPs depicted in Figure 14. It shows the SEM image of synthesized Ag-NPs by HCOOH which are spherical in shape and have a smooth surface morphology. Ag-NPs show the monodispersed distribution of particle sizes by this method. The average particle sizes of the Ag-NPs were obtained around 30 nm with spherical shape [137-144].
The PVP forms a hydrophobic domain, which surrounds metal particles and protects the particles from agglomeration. The reduction of silver ions in the presenceof PVP leads to the formation of Ag-NPs that are stable in solution.
Conclusion
Ag-NPs have attracted the attention of researchers because of their unique properties and proven applicability in diverse areas such as medicine, catalysis, textile engineering, biotechnology, nanobiotechnology, bioengineering sciences, electronics, optics and water treatment. The flexibility of Ag-NPs synthetic methods and facile incorporation of Ag-NPs into different media have interested researchers to further investigate the mechanistic aspects of antimicrobial, antiviral and anti-inflammatory effects of these nanoparticles. The various chemical, physical and biological synthetic
methods have been developed to obtain Ag-NPs of diverse shapes and sizes, including laser ablation, gamma irradiation, electron irradiation, chemical reduction, photochemical methods, microwave processing, and thermal decomposition of silver nitrate in water and in Cht., GA, PEG, PVP environment. Most of these methods are still in the development stages and the problems experienced involve the stability and aggregation of nanoparticles, control of crystal growth, morphology, size and size distribution, and occasional difficulty in the management of the synthesis, as in the case of the radiolysis technique. By using different reducing agents and stabilizers, the particle size and morphology of Ag-NPs have been controlled.
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ТЭВП УЭ SÍNTETÍK POLÍMERLOR MÜHÍTÍNDO GÜMܧ NANOHISSOCÍKLORÍNÍN SÍNTEZÍ УЭ ONLARIN MORFOLOJÍ QURULU§LARININ TODQÍQÍ
D.B.Tagiyev, N.A.Zeynalov, §.Z.Tapdiqov, S.F.Hümbatova, S.M.Mammadova, M.X.Has3nova
Verilmi§ icmalda tabii va sintetik polimerlar mühitinda gümü§ün davamli nanohissaciklari alinmi§ va gümü§ ionlannin sulu mahlulunda reduksiyasinin formala§ma mexanizmi, eyni zamanda, müxtalif faktorlarin nanoölgülü metal hissac i-klarinin aqreqasiya olunmasina, ölgülarina va davamliligina tasiri öyranilmi§dir Müayyan olunmu§dur ki, gümü§ nano-hissaciklarinin plazma udma zolaginin formasi, vaziyyati va intensivliyi alinma §araitindan asilidir. í§da istifada olunan skanedici elektron mikroskopiya, rentgenfaza analizi va UB-spektroskopiya üsullan nanohissaciklarin polimerda paylanmasim, forma va ölgülarini öyranmaya imkan yaradir, hamginin, nanohissaciklarin metal halinda identifikasiya olunmasini tamin edir.
Agar sözlzr: Gümü§ nanohissacikbr, xitozan, poli-N-vinilpirrolidon, qummiarabik, polietilenqlikol, skanedici elektron mikroskop, rentgen faza analizi.
СИНТЕЗ НАНОЧАСТИЦ СЕРЕБРА В ПРИСУТСТВИИ ПРИРОДНЫХ И СИНТЕТИЧЕСКИХ ПОЛИМЕРОВ И ИССЛЕДОВАНИЕ ИХ МОРФОЛОГИЧЕСКИХ СТРУКТУР
Д.Б.Тагиев, Н.А.Зейналов, Ш.З.Тапдыгов, С.Ф.Гумбатова, С.М.Мамедова, М.Х.Гасанова
Приведены результаты работ (в том числе и авторов данного обзора) в области получения устойчивых наноча-стиц серебра и изучения механизма их формирования при восстановлении ионов Ag в водных растворах в присутствии природных и синтетических полимеров, а также влияния различных факторов на агрегацию, размер и устойчивость наноразмерных металлических частиц. По полученным в исследованиях данным установлено, что форма, положение и интенсивность полосы плазменного поглощения наночастиц серебра зависят от условий их получения. Используемые в работах методы сканирующей электронной микроскопии, рентгенофазового анализа и УФ-спектроскопии позволяют оценить размер, форму и распределение наночастиц в полимере, а также обеспечивают идентификацию наночастиц в металлическом состоянии.
Ключевые слова: наночастицы серебра, хитозан, поли^-винилпирролидон, гуммиарабик, полиэтиленгликоль, сканирующий электронный микроскоп, рентгенофазовый анализ.
AЗЕPБAЙДЖAHCKИЙ ХИМИЧЕСКИЙ ЖУРНАЛ № 3 2016
