Next Article in Journal
Drug Delivery from Hyaluronic Acid–BDDE Injectable Hydrogels for Antibacterial and Anti-Inflammatory Applications
Next Article in Special Issue
Recent Advances in Hydrogel-Based Sensors Responding to Ionizing Radiation
Previous Article in Journal
Aminopolycarboxylic Acids-Functionalized Chitosan-Based Composite Cryogels as Valuable Heavy Metal Ions Sorbents: Fixed-Bed Column Studies and Theoretical Analysis
Previous Article in Special Issue
How Xylenol Orange and Ferrous Ammonium Sulphate Influence the Dosimetric Properties of PVA–GTA Fricke Gel Dosimeters: A Spectrophotometric Study
 
 
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique

1
National Center for Radiation Research and Technology (NCRRT), Egyptian Atomic Energy Authority, Cairo 11787, Egypt
2
Chemistry Department, Faculty of Education, Ain Shams University, Cairo 11566, Egypt
3
Chemistry Department, Faculty of Science, Cairo University, Cairo 12613, Egypt
4
Physics Department, “Aldo Pontremoli” Milano University, 20133 Milan, Italy
*
Author to whom correspondence should be addressed.
Gels 2022, 8(4), 222; https://doi.org/10.3390/gels8040222
Submission received: 28 February 2022 / Revised: 28 March 2022 / Accepted: 31 March 2022 / Published: 5 April 2022
(This article belongs to the Special Issue Gel Dosimetry)

Abstract

:
The dosimetric characteristics of hydrogel dosimeters based on polyacrylamide (PAC) as a capping agent incorporating silver nitrate as a radiation-sensitive material are investigated using UV-Vis spectrophotometry within the dose range 0–100 Gy. Glycerol was used in the hydrogel matrix to promote the dosimetric response and increase the radiation sensitivity. Upon exposing the PAC hydrogel to γ-ray, it exhibits a Surface Plasmon Resonance (SPR) band at 453 nm, and its intensity increases linearly with absorbed doses up to 100 Gy. The results are compared with the silver nitrate gel dosimeter. Glycerol of 15% in the hydrogel matrix enhances the radiation sensitivity by about 30%. PAC hydrogel dosimeter can be considered a near water equivalent material in the 400 keV–20 MeV photon energy range. At doses less than 15 Gy, the PAC hydrogel dosimeter retains higher radiation sensitivity than the gel dosimeter. The total uncertainty (2σ) of the dose estimated using this hydrogel is about 4%. These results may support the validity of using this hydrogel as a dosimeter to verify radiotherapy techniques and dose monitoring during blood irradiation.

1. Introduction

Gel dosimeters can measure radiation dose distributions in three dimensions (3D), making them excellent dosimetric tools for external beam radiotherapy. These dosimeters are important for dose verifications of radiotherapy and the establishment of treatment planning systems as they have a good spatial resolution property [1,2]. Hydrogels are nearly tissue equivalent and can be molded to any desired shape or form [3,4] There are different classes of gel dosimeters, particularly the Fricke gel and polymer gels [4]. Fricke gel (FG) systems are based mainly on ferrous ions (Fe2+) in a gel matrix. The interaction of ionizing radiation with the molecules of the hydrogel, and the consequent free-radicals formation, activate different chemical routes that lead to the oxidation of ferrous ions (Fe2+) to ferric ions (Fe3+) with oxidation yield proportional to the absorbed dose. This variation is detectable by Nuclear Magnetic Resonance (NMR) and Magnetic Resonance Imaging (MRI) [5,6]. Furthermore, adding a suitable metallic-ion indicator to the FG dosimeters makes these systems capable of being analyzed by optical techniques [7,8,9,10,11]. These gels are simple to prepare and less expensive, and different gel matrices such as gelatin, agarose, and poly(vinyl-alcohol) (PVA) were largely studied [3,4,7,12,13,14]. The major drawback of FG dosimeters is the diffusion of ferrous and ferric ions, which leads to a gradual blurring of the dose pattern with time after irradiation. [15,16,17]. The diffusion limitation of the FG can be overcome by using a different radiochromic gel called leucocrystal violet micelle gel (LCV gel) [17,18].
Researchers are currently working on improving gel dosimeter sensitivity and efficiency and finding new dosimeters of suitable properties for radiation technology applications. Nanoparticles such as gold, bismuth, platinum, and silver can be incorporated into the gel to enhance the sensitivity and efficiency for a lower dose range [19,20,21]. Moreover, radiation-induced AgNPs in silver nitrate solutions could be successfully applied for radiation detection and dosimetry [22,23] and dose enhancement in radiotherapy applications [19,24,25,26]. AgNPs are an exciting alternative for dose enhancement in radiation therapy due to their inexpensive cost compared to gold nanoparticles [25] and antitumor activity [27,28]. The silver nitrate dosimeter features a linear response and good measurements reproducibility [22]. The influence of γ-rays on AgNO3 solution had been examined [29,30,31,32,33,34]. A liquid detector based on silver nitrate and 1% sodium citrate is introduced, where the ionizing radiation induces the formation of spherical AgNPs as recognized by the appearance of a sharp peak around 410 nm in the absorbance spectrum of the colloidal solution [35]. However, this study did not address most of the dosimetric characteristics [35].
The radiation-sensitive silver nitrate was mixed with gelatin (8%) as a stabilizing agent to minimize the agglomeration of the formed AgNPs [23]. This gel exhibits an SPR band at 450 nm related to AgNPs formed upon irradiation. This dosimeter has a linear dose–response function up to 100 Gy. The increase in Ag+ ion concentrations in the gel considerably improves the radiation dose sensitivity. The overall uncertainty (2σ) of dose estimation in the range of 5–100 Gy was found to be ≈4.65%; thus, it can be applicable for radiotherapy dose measurements and blood irradiation. The response of irradiated AgNO3 gel displays good stability over a month after irradiation when kept at 6 °C. In contrast, it shows poor stability and considerable response growth when stored in the dark or light after irradiation. The gel response has a temperature coefficient of ~0.339% per 1 °C [23]. Recently, Tadros et al. [36] improved the sensitivity of this gel dosimeter by using isopropanol in the gel matrix and decreasing the gel content to 4% instead of the 8% previously used [23].
The present investigation aims to develop a radiochromic hydrogel dosimeter for silver nitrate using polyacrylamide (PAC), as a new capping agent for preventing aggregation of Ag [37,38,39,40], and to study the suitability of its use in low-dose dosimetry applications (radiotherapy and blood irradiation). The γ-rays induced AgNPs in the PAC hydrogel dosimeter, the effect of silver nitrate concentration, the glycerol content on the dosimeter response, and the dose–response functions were investigated using a UV-Vis spectrometric technique. The overall combined uncertainties (at 2σ) associated with the calibration and the energy dependence were calculated. In addition, the effects of temperature during irradiation on the response function and post-irradiation stability were described. Finally, we compared the results of silver nitrate hydrogel dosimeters with the previous results of silver nitrate gel dosimeters [23,36].

2. Results and Discussion

2.1. Absorption Spectra of PAC Hydrogel Dosimeter

The optical absorption spectra of silver nitrate PAC dosimeter (100 and 150 mM) in the 0–100 Gy dose range are shown in Figure 1a,b. The unirradiated AgNO3 gel is colorless and does not have prominent peaks in the visible range. The color of the PAC hydrogel dosimeter turns into a visual yellow color with irradiation, as shown in Table 1. The intensity of the yellow color and optical absorbance increases with the increase in the absorbed doses. A significant main band at 453 nm, corresponding to a band of SPR of AgNPs absorption [23], distinguishes this color. The band intensity increases progressively as the radiation dose increases, with no noticeable shifts in the band position. While, as the absorbed dose increases, the broadening of the peak gradually decreases.
Furthermore, the position of the SPR band is found to be mainly dependent on the size of the formed nanoparticles [41] and the nearby intermediate [42,43]. This indicates that γ-irradiation-induced nucleation of silver nanoparticles is dependent on the absorbed dose [44]. At higher doses around 100 Gy, there is no pronounced shift in the main absorption band with the dose, [41,45]. This suggests that at high irradiation doses below 100 Gy, the nucleation event is more than the total ions. On the other hand, at low doses where the nucleation event is less than the total ions, the radiation produced larger sizes of Ag following aggregation [44].
PAC has a dual function: it acts as a steric stabilizer, preventing agglomeration of gamma-induced AgNPs, and it can form complexes with Ag+ ions via interaction with the amino (–NH2) groups of PAC. This coordination effect can significantly slow the reduction to enable kinetic control [39]. The PAC polymer and AgNPs interact by charge transfer from the metal particles to the nitrogen sites on the polymer side chains, as shown by S Mukherjee and M Mukherjee [40].

2.2. The Effect of Silver Nitrate Concentration on PAC Hydrogel Dosimeter

The dose–response functions of PAC hydrogel dosimeter at various silver nitrate concentrations (20, 50, 100, and 150 mM AgNO3) are shown in Figure 2a. Table 2 shows the radiation sensitivity and the percent variation compared to the standard 20 mM Ag+ concentration. The dose responses are linear, with R2 values of 0.9992, 0.9975, 0.9987, and 0.9973 for silver nitrate concentrations of 20, 50, 100, and 150 mM, respectively.
The response of this dosimeter increases with increasing [Ag+] concentrations up to 100 mM, then the response decreases at 150 mM as investigated in the radiation sensitivity curve shown in Figure 2b. As the concentration of the Ag+ ions increased from 50 to 100 mM, the radiation sensitivity was found to be increased by approximately 33%. As a result, the appropriate composition should be selected based on the dose range required. The 100 mM Ag+ gel dosimeter can be used for doses ranging from 5.0 Gy to 100.0 Gy, as a useful range for blood irradiation and radiotherapy dosimetry.

2.3. The Effect of Glycerol on the Response of PAC Hydrogel Dosimeter

Glycerol is a non-toxic, non-volatile, and biodegradable material. In addition, it can dissolve a wide range of compounds that have poor solubility in water and be a promising candidate as a “green solvent” [46,47]. Thus, it was selected in the preparation of the hydrogel matrices. Recent works have also demonstrated that glycerol can be used as a solvent and reducing agent to generate metal nanoparticles [47,48]. Free radical species are generated for glycerol upon irradiation, as shown in Figure 3. The obtained glycerol radicals can serve as a reducing agent for silver ions [47,48]. In addition, irradiation of glycerol in an aqueous medium produces solvated electrons which serve as a reducing agent for Ag+. Glycerol yields solvated electrons greater than other alcohols [47].
Figure 1 and Figure 4 represent the absorption spectra for the hydrogel dosimeters without and with 15% glycerol, respectively. The spectra of both types have nearly the same peak features, but the absorbance change is highly significant with the absorbed dose in the case of using glycerol in the hydrogel matrix. This result indicates also the reduction of Ag+ ions into Ag NPs as in the case of hydrogel dosimeter without glycerol. Figure 5 shows the dose–response curves for PAC hydrogel dosimeter at different content of glycerol %. The intensity of the absorption band increases linearly with increasing dose up to 100 Gy, with correlation coefficients (R2) of 0.9987, 0.9997, 0.9991, and 0.9968 for glycerol 0, 5, 15, and 25%, respectively, indicating the goodness of linearity. The hydrogel response increased as the glycerol content increased from 0 to 15%. This result indicates that glycerol significantly reduces the Ag+ ions in the hydrogel into AgNPs. The increase in glycerol content in the PAC matrix from 0 to 15% improves the radiation sensitivity by ≈30%, as shown in Figure 6 and Table 3. Then, the steady state is reached at 25% glycerol. Consequently, it is recommended to use 15% glycerol on the hydrogel matrix to increase the radiation sensitivities in the radiotherapy dose applications.

2.4. Effect of Irradiation Temperature on the Response of PAC Hydrogel Dosimeter

The effect of irradiation temperature on the PAC hydrogel dosimeter (100 mM) response in the range of 8–34 °C was investigated by irradiating the gel dosimeters with γ-rays to an absorbed dose of 50 Gy normalized to response value at 23 °C (see Figure 7). The results reveal that the response of the PAC hydrogel dosimeter increases linearly with irradiation temperature over the range of 8–34 °C. The temperature coefficient is +1.6 ± 0.9% per °C. In comparison, the temperature has a low impact for gel dosimeters containing 15% glycerol in the range of 16–31 °C; the temperature coefficient is +0.69 ± 0.1% per °C. For the silver nitrate PAC hydrogel dosimeter, it is strongly recommended to calibrate it under actual processing conditions, i.e., in-plant calibration, to minimize the errors resulting from temperature rise [49]. Alternatively, correction to temperature effect has to be applied.

2.5. Stability of Silver Nitrate PAC Hydrogel Dosimeter

Figure 8 and Figure 9 illustrate the change of relative response of irradiated hydrogel dosimeter stored in a dark place at different temperatures (6 °C and RT, 23 °C) with time for the hydrogel of 0 and 15% glycerol, respectively. The results demonstrated that both irradiated hydrogel dosimeters stored at 6 °C are nearly stable over 15 days. Under room temperature, the response of both hydrogel dosimeters increased significantly with storage time [23]. However, the rate of increasing responses is higher in the case of using 15% glycerol than the hydrogel of 0% glycerol. Thus, it is recommended to store the dosimeter at 6 °C to minimize the continuous reduction of Ag+ ions with time.

2.6. Effective Atomic Numbers and Water Equivalency of PAC Hydrogel Dosimeter

Table 4 displays the composition and fraction of atoms by weight for the PAC hydrogel dosimeters without and with 15% glycerol, respectively. We used the X-COM program [50] to obtain the fraction by weight for these dosimeters.
Effective atomic numbers (Zeff) at different energies were estimated using the Auto Zeff program [51], as shown in Figure 10. The Zeff values of both PAC hydrogel dosimeters are nearly comparable to pure water for the photon energy above 300 keV. However, for lower energy, the Zeff values of both hydrogel dosimeters are higher than the Zeff of water, which is related to high photoelectric absorptions in the hydrogel dosimeters [52,53].
The maximum Zeff is observed at 25.5 keV, which is the K-edge of Ag [54]. Significant absorption of low-energy X-ray in the case of using heavy elements is obtained due to the increase in the probability of photoelectric absorption, as this interaction is proportional to Z3 [55]. Additionally, the photoelectric interaction is dominant at low energies (kV ranges) [52].
The mass-energy absorption coefficients, (μen/ρ)Hydrogel and (μen/ρ)Gel of the PAC hydrogel dosimeter and the silver nitrate gel dosimeter previously prepared [36], respectively, relative to the same values of water (μen/ρ)W, are plotted in Figure 11 as a function of photon energy from 1 keV to 20 MeV. The mass-energy absorption coefficients were derived from the online NIST physical reference data [56]. Both dosimeters (gel and PAC hydrogel) are considered water equivalent materials in the photon energy range of 400 keV–20 MeV, exhibiting their ability to be used in radiation therapy of high-energy photons without using corrections to energy dependency.

2.7. Uncertainty Assessments

Various parameters can contribute to the uncertainty of absorbed dose measurements, such as calibration of the gamma irradiation cell, uniformity of silver nitrate gel dosimeter (batch homogeneity), stability of dose–response, absorbance measurement, and calibration curve fit. Table 5 lists the uncertainty parameters of the formulated gel dosimeter. The uncertainty components were determined as previously described in detail [49,57,58,59]. The response’s overall uncertainty (2σ, 95% confidence interval) was 4.04%.

2.8. Comparing the Response of PAC Hydrogel Dosimeter with Silver Nitrate Gel Dosimeter

Figure 12 displays the dose–response curves of silver nitrate PAC hydrogel and previously prepared silver nitrate gel [36] dosimeters. It was found that the response or radiation sensitivity of the gel dosimeter is higher than the PAC hydrogel, which indicates the role of gelatin in the reduction of Ag+ ions into Ago metallic NPs and the effect of capping agents on the response of silver nitrate dosimeter solution. However, for the low doses (less than 15 Gy), the change of response of the hydrogel is more significant than the change of response of the gel dosimeter, as shown in Figure 12. These results may indicate the effectiveness of the hydrogel dosimeter within the radio-therapeutic dose range.

3. Conclusions and Remarks

A novel polyacrylamide (PAC) hydrogel dosimeter based on silver nitrate was studied spectrophotometrically in a dose range of 0–100 Gy. Gamma radiation promotes the formation of Ag nanoparticles linearly up to 100 Gy, with R2 values of 0.9996, 0.9987, 0.9995, and 0.9986 for silver nitrate concentrations of 20, 50, 100, and 150 mM, respectively.
The responses of the PAC hydrogel dosimeters are greatly enhanced by the increase in Ag+ ion concentration and glycerol content. This dosimeter has a temperature coefficient of 1.6% per °C.
The Zeff values of these dosimeters are comparable to the Zeff values of water at energies greater than 300 keV. It was found that the PAC hydrogel dosimeter can be considered as a water equivalent material in the photon energy range of 400 keV–20 MeV.
At doses less than 15 Gy, the PAC hydrogel dosimeter exhibits higher radiation sensitivity than the gel dosimeter [36]. The overall uncertainty (2σ) in absorbed dose estimation is approximately 4.04%. These results may support a promising use of this system as a valid dosimeter to quantify the dose both in radiotherapy treatments and in blood irradiation.

4. Materials and Methods

4.1. Sample Preparation

Silver nitrate (99.8%), glycerol (99.5%), polyacrylamide (PAC), with an average molecular weight of about 5.0 × 105 Da were all purchased from Aldrich, Baden-Württemberg Germany.
Aqueous PAC solutions (2% w/v) were prepared and homogenized using a magnetic stirrer at room temperature (≈ 25 °C). These solutions were then mixed with aqueous AgNO3 solutions to obtain dosimeter solutions with concentrations of 20, 50, 100, and 150 mM of AgNO3. After that, the solutions were kept under stirring for an additional hour to obtain homogeneous mixtures. The solutions were then poured slowly into disposable poly(methyl-methacrylate) (PMMA cuvettes (1 × 1 × 3 cm3) and stored in a refrigerator adjusted at 6 °C to form the PAC hydrogels. In addition, the effect of glycerol on the PAC response was investigated by incorporating different glycerol content of 0, 5, 15, and 25% (v/v) into PAC solutions (2% w/v) containing 100 mM of AgNO3. These compositions were prepared at room temperature, similar to the above-mentioned procedures. All formulations of PAC hydrogel dosimeters are shown in Table 6.

4.2. Samples Irradiation and Characterization

A 60Co Gamma Cell (GC) model GC-220 Excel (MDS, Nordion, Canada) was used to irradiate PAC hydrogel dosimeters with absorbed doses of water ranging from 0 Gy to 100 Gy. A specially designed polystyrene holder was utilized to achieve an electronic equilibrium during irradiation. The dose rate as determined by the National Physical Laboratory (NPL) in England was ≈ 1.0 kGy/h. It was measured using alanine dosimeters of the NPL (dose rate is traceable to NPL, a primary laboratory).
The γ-rays unexposed and exposed silver nitrate hydrogel dosimeters were analyzed using a UV-Vis spectrophotometer model Evolution 500 (Thermo Electron Corporation, Winsford, UK.) to various absorbed doses. This spectrophotometer was used to measure the absorptions spectra in the wavelength interval of 350–750 nm with steps of 2 nm. The optical absorbance at a fixed wavelength of 453 nm was chosen to evaluate the optical dose–response of PAC hydrogel dosimeters. Three dosimeters of each set were irradiated for each dose value.
The hydrogel responses are established with optical absorbance variation (net absorbance), ∆A = Ai − A0, where Ai and A0 are the absorbances at 453 nm for the unirradiated and irradiated hydrogel dosimeter, respectively.

Author Contributions

Conceptualization, Y.S.S. and W.B.B.; formal analysis, Y.S.S. and S.M.T.; investigation, S.M.T.; methodology, Y.S.S. and W.B.B.; resources, Y.S.S. and W.B.B.; supervision, Y.S.S., G.R.S., L.I.A. and M.M.N.; validation, S.M.T.; visualization, S.M.T.; writing-original draft, S.M.T.; writing-review & editing, Y.S.S., W.B.B., G.R.S., S.G., L.I.A. and M.M.N. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Silva, N.A.; Nicolucci, P.; Baffa, O. Spatial resolution of magnetic resonance imaging Fricke-gel dosimetry is improved with a honeycomb phantom. Med. Phys. 2003, 30, 17–20. [Google Scholar] [CrossRef] [PubMed]
  2. Oldham, M.; Siewerdsen, J.H.; Shetty, A.; Jaffray, D.A. High resolution gel-dosimetry by optical-CT and MR scanning. Med. Phys. 2001, 28, 1436–1445. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  3. Marrale, M.; D’Errico, F. Hydrogels for Three-Dimensional Ionizing-Radiation Dosimetry. Gels 2021, 7, 74. [Google Scholar] [CrossRef] [PubMed]
  4. Alyani Nezhad, Z.; Geraily, G. A review study on application of gel dosimeters in low energy radiation dosimetry. Appl. Radiat. Isot. 2022, 179, 110015. [Google Scholar] [CrossRef] [PubMed]
  5. Gore, J.C.; Kang, Y.S. Measurement of radiation dose distributions by nuclear magnetic resonance (NMR) imaging. Phys. Med. Biol. 1984, 29, 1189–1197. [Google Scholar] [CrossRef] [PubMed]
  6. Doran, S.J. The history and principles of chemical dosimetry for 3-D radiation fields: Gels, polymers and plastics. Appl. Radiat. Isot. 2009, 67, 393–398. [Google Scholar] [CrossRef] [PubMed]
  7. Schreiner, L.J. Review of Fricke gel dosimeters. J. Phys. Conf. Ser. 2004, 3, 9–21. [Google Scholar] [CrossRef]
  8. Schreiner, L.J. True 3D chemical dosimetry (gels, plastics): Development and clinical role. J. Phys. Conf. Ser. 2015, 573, 012003. [Google Scholar] [CrossRef]
  9. Fathima, K. Study on the Role of Gold Nanoparticles on External Beam Radiation Using Fricke Gel. Int. J. Innov. Sci. Res. Technol. 2019, 4, 173–178. [Google Scholar]
  10. Gambarini, G.; Veronese, I.; Bettinelli, L.; Felisi, M.; Gargano, M.; Ludwig, N.; Lenardi, C.; Carrara, M.; Collura, G.; Gallo, S.; et al. Study of optical absorbance and MR relaxation of Fricke xylenol orange gel dosimeters. Radiat. Meas. 2017, 106, 622–627. [Google Scholar] [CrossRef]
  11. Alves, A.V.S.; de Almeida, W.S.; Sussuchi, E.M.; Lazzeri, L.; D’Errico, F.; de Souza, S.O. Investigation of chelating agents/ligands for Fricke gel dosimeters. Radiat. Phys. Chem. 2018, 150, 151–156. [Google Scholar] [CrossRef]
  12. Gallo, S.; Pasquale, S.; Lenardi, C.; Veronese, I.; Gueli, A.M. Effect of ionizing radiation on the colorimetric properties of PVA-GTA Xylenol Orange Fricke gel dosimeters. Dyes Pigm. 2021, 187, 109141. [Google Scholar] [CrossRef]
  13. Gallo, S.; Lizio, D.; Monti, A.F.; Veronese, I.; Brambilla, M.G.; Lenardi, C.; Torresin, A.; Gambarini, G. Temperature behavior of radiochromic poly(vinyl-alcohol)-glutaraldehyde Fricke gel dosimeters in practice. J. Phys. D Appl. Phys. 2020, 53, 36. [Google Scholar] [CrossRef]
  14. Soliman, Y.S.; El Gohary, M.I.; Abdel Gawad, M.H.; Amin, E.A.; Desouky, O.S. Fricke gel dosimeter as a tool in quality assurance of the radiotherapy treatment plans. Appl. Radiat. Isot. 2017, 120, 126–132. [Google Scholar] [CrossRef]
  15. Baldock, C.; Harris, P.J.; Piercy, A.R.; Healy, B. Experimental determination of the diffusion coefficient in two-dimensions in ferrous sulphate gels using the finite element method. Australas. Phys. Eng. Sci. Med. 2001, 24, 19–30. [Google Scholar] [CrossRef]
  16. Olsson, L.E.; Westrin, B.A.; Fransson, A.; Nordell, B. Diffusion of ferric ions in agarose dosimeter gels. Phys. Med. Biol. 1992, 37, 2243–2252. [Google Scholar] [CrossRef]
  17. Babic, S.; Battista, J.; Jordan, K. Radiochromic leuco dye micelle hydrogels: II. Low diffusion rate leuco crystal violet gel. Phys. Med. Biol. 2009, 54, 6791–6808. [Google Scholar] [CrossRef]
  18. Babic, S.; McNiven, A.; Battista, J.; Jordan, K. Three-dimensional dosimetry of small megavoltage radiation fields using radiochromic gels and optical CT scanning. Phys. Med. Biol. 2009, 54, 2463–2481. [Google Scholar] [CrossRef]
  19. Titus, D.; Samuel, E.J.J.; Mohana Roopan, S. Current scenario of biomedical aspect of metal-based nanoparticles on gel dosimetry. Appl. Microbiol. Biotechnol. 2016, 100, 4803–4816. [Google Scholar] [CrossRef]
  20. Titus, D.; Samuel, E.J.J.; Roopan, S.M. Radiation Dosimetry—A Different Perspective of Polymer Gel. In Gels Horizons: From Science to Smart Materials; Springer: Singapore, 2018; pp. 309–341. [Google Scholar]
  21. Farahani, S.; Riyahi Alam, N.; Haghgoo, S.; Shirazi, A.; Geraily, G.; Gorji, E.; Kavousi, N. The effect of bismuth nanoparticles in kilovoltage and megavoltage radiation therapy using magnetic resonance imaging polymer gel dosimetry. Radiat. Phys. Chem. 2020, 170, 108573. [Google Scholar] [CrossRef]
  22. Funaro, M.; Di Bartolomeo, A.; Pelosi, P.; Sublimi Saponetti, M.; Proto, A. Dosimeter based on silver-nanoparticle precursors for medical applications with linear response over a wide dynamic range. Micro Nano Lett. 2011, 6, 759–762. [Google Scholar] [CrossRef]
  23. Soliman, Y.S. Gamma-radiation induced synthesis of silver nanoparticles in gelatin and its application for radiotherapy dose measurements. Radiat. Phys. Chem. 2014, 102, 60–67. [Google Scholar] [CrossRef]
  24. Vedelago, J.; Mattea, F.; Valente, M. Integration of Fricke gel dosimetry with Ag nanoparticles for experimental dose enhancement determination in theranostics. Appl. Radiat. Isot. 2018, 141, 182–186. [Google Scholar] [CrossRef]
  25. Hassan, M.; Ur Rehman, A.; Waheed, M.M.; Anjum, M.N. Dose of radiation enhancement, using silver nanoparticles in a human tissue equivalent gel dosimeter. J. Pak. Med. Assoc. 2016, 66, 45–48. [Google Scholar]
  26. Guidelli, E.J.; Ramos, A.P.; Baffa, O. Silver nanoparticle films for metal enhanced luminescence: Toward development of plasmonic radiation detectors for medical applications. Sens. Actuators B Chem. 2016, 224, 248–255. [Google Scholar] [CrossRef]
  27. Sriram, M.I.; Kanth, S.B.M.; Kalishwaralal, K.; Gurunathan, S. Antitumor activity of silver nanoparticles in Dalton’s lymphoma ascites tumor model. Int. J. Nanomed. 2010, 5, 753–762. [Google Scholar] [CrossRef] [Green Version]
  28. Franco-Molina, M.A.; Mendoza-Gamboa, E.; Sierra-Rivera, C.A.; Gómez-Flores, R.A.; Zapata-Benavides, P.; Castillo-Tello, P.; Alcocer-González, J.M.; Miranda-Hernández, D.F.; Tamez-Guerra, R.S.; Rodríguez-Padilla, C. Antitumor activity of colloidal silver on MCF-7 human breast cancer cells. J. Exp. Clin. Cancer Res. 2010, 29, 148. [Google Scholar] [CrossRef] [Green Version]
  29. Chen, P.; Song, L.; Liu, Y.; Fang, Y.e. Synthesis of silver nanoparticles by γ-ray irradiation in acetic water solution containing chitosan. Radiat. Phys. Chem. 2007, 76, 1165–1168. [Google Scholar] [CrossRef]
  30. Van Phu, D.; Lang, V.T.K.; Kim Lan, N.T.; Duy, N.N.; Chau, N.D.; Du, B.D.; Cam, B.D.; Hien, N.Q. Synthesis and antimicrobial effects of colloidal silver nanoparticles in chitosan by γ-irradiation. J. Exp. Nanosci. 2010, 5, 169–179. [Google Scholar] [CrossRef] [Green Version]
  31. Hettiarachchi, M.A.; Wickramarachchi, P.A.S.R. Synthesis of chitosan stabilized silver nanoparticles using gamma ray irradiation and characterization. J. Sci. Univ. Kelaniya Sri Lanka 2012, 6, 65. [Google Scholar] [CrossRef] [Green Version]
  32. Bin Ahmad, M.; Lim, J.J.; Shameli, K.; Ibrahim, N.A.; Tay, M.Y. Synthesis of silver nanoparticles in chitosan, gelatin and chitosan/gelatin bionanocomposites by a chemical reducing agent and their characterization. Molecules 2011, 16, 7237–7248. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  33. Darroudi, M.; Ahmad, M.B.; Hakimi, M.; Zamiri, R.; Zak, A.K.; Hosseini, H.A.; Zargar, M. Preparation, characterization, and antibacterial activity of γ-irradiated silver nanoparticles in aqueous gelatin. Int. J. Miner. Metall. Mater. 2013, 20, 403–409. [Google Scholar] [CrossRef] [Green Version]
  34. Temgire, M.K.; Joshi, S.S. Optical and structural studies of silver nanoparticles. Radiat. Phys. Chem. 2004, 71, 1039–1044. [Google Scholar] [CrossRef]
  35. Puišo, J.; Laurikaitiene, J.; Adliene, D.; Prosyčevas, I. Liquid radiation detectors based on nanosilver surface plasmon resonance phenomena. Radiat. Prot. Dosim. 2010, 139, 353–356. [Google Scholar] [CrossRef]
  36. Tadros, S.M.; Soliman, Y.S.; Beshir, W.B.; Saad, G.R.; Ali, L. Dosimetric investigations on radiation-induced Ag nanoparticles in a gel dosimeter. J. Radioanal. Nucl. Chem. 2021, 329, 463–473. [Google Scholar] [CrossRef]
  37. Salaheldin, H.I.; Almalki, M.H.K.; Hezma, A.E.M.; Osman, G.E.H. Facile synthesis of silver nanoparticles mediated by polyacrylamide-reduction approach to antibacterial application. IET Nanobiotechnol. 2017, 11, 448–453. [Google Scholar] [CrossRef]
  38. Rabilloud, T.; Vuillard, L.; Gilly, C.; Lawrence, J.J. Silver-staining of proteins in polyacrylamide gels: A general overview. Cell. Mol. Biol. 2009, 40, 57–75. [Google Scholar] [CrossRef]
  39. Xiong, Y.; Siekkinen, A.R.; Wang, J.; Yin, Y.; Kim, M.J.; Xia, Y. Synthesis of silver nanoplates at high yields by slowing down the polyol reduction of silver nitrate with polyacrylamide. J. Mater. Chem. 2007, 17, 2600–2602. [Google Scholar] [CrossRef]
  40. Mukherjee, S.; Mukherjee, M. Nitrogen-mediated interaction in polyacrylamide–silver nanocomposites. J. Phys. Condens. Matter 2006, 18, 11233. [Google Scholar] [CrossRef]
  41. Ramnani, S.P.Ã.; Biswal, J.; Sabharwal, S. Synthesis of silver nanoparticles supported on silica aerogel using gamma radiolysis. Radiat. Phys. Chem. 2007, 76, 1290–1294. [Google Scholar] [CrossRef]
  42. Yiwei, A.; Yunxia, Y.; Shuanglong, Y.; Lihua, D.; Guorong, C. Preparation of spherical silver particles for solar cell electronic paste with gelatin protection. Mater. Chem. Phys. 2007, 104, 158–161. [Google Scholar] [CrossRef]
  43. Xu, X.; Zhou, M. Antimicrobial gelatin nanofibers containing silver nanoparticles. Fibers Polym. 2008, 9, 685–690. [Google Scholar] [CrossRef]
  44. Naghavi, K.; Saion, E.; Rezaee, K.; Yunus, W.M.M. Influence of dose on particle size of colloidal silver nanoparticles synthesized by gamma radiation. Radiat. Phys. Chem. 2010, 79, 1203–1208. [Google Scholar] [CrossRef]
  45. Eid, M. Gamma Radiation Synthesis and Characterization of Starch Based Polyelectrolyte Hydrogels Loaded Silver Nanoparticles. J. Inorg. Organomet. Polym. Mater. 2011, 21, 297–305. [Google Scholar] [CrossRef]
  46. Díaz-Álvarez, A.; Cadierno, V. Glycerol: A promising Green Solvent and Reducing Agent for Metal-Catalyzed Transfer Hydrogenation Reactions and Nanoparticles Formation. Appl. Sci. 2013, 3, 55–69. [Google Scholar] [CrossRef]
  47. Liu, T.; Baek, D.R.; Kim, J.S.; Joo, S.-W.; Lim, J.K. Green Synthesis of Silver Nanoparticles with Size Distribution Depending on Reducing Species in Glycerol at Ambient pH and Temperatures. ACS Omega 2020, 5, 16246–16254. [Google Scholar] [CrossRef]
  48. Kou, J.; Varma, R.S. Speedy fabrication of diameter-controlled Ag nanowires using glycerol under microwave irradiation conditions. Chem. Commun. 2013, 49, 692–694. [Google Scholar] [CrossRef]
  49. Sharpe, P.; Miller, A. Guidelines for the Calibration of Routine Dosimetry Systems for use in Radiation Processing. NPL Report CIRM 29; National Physical Laboratory: Teddington, UK, 2009. [Google Scholar] [CrossRef]
  50. Berger, M.J.; Hubbell, J.H.; Seltzer, S.M.; Chang, J.; Coursey, J.S.; Sukumar, R.; Zucker, D.S.; Olsen, K. XCOM: Photon Cross Section Database (Version 1.5); National Institute of Standards and Technology: Gaithersburg, MD, USA, 2010. Available online: http://physics.nist.gov/xcom (accessed on 2 March 2022).
  51. Taylor, M.L.; Smith, R.L.; Dossing, F.; Franich, R.D. Robust calculation of effective atomic numbers: The Auto- Z eff software. Med. Phys. 2012, 39, 1769–1778. [Google Scholar] [CrossRef]
  52. Smith, C.L.; Ackerly, T.; Best, S.P.; Gagliardi, F.; Kie, K.; Little, P.J.; McCorkell, G.; Sale, C.A.; Tsunei, Y.; Tominaga, T.; et al. Determination of dose enhancement caused by gold-nanoparticles irradiated with proton, X-rays (kV and MV) and electron beams, using alanine/EPR dosimeters. Radiat. Meas. 2015, 82, 122–128. [Google Scholar] [CrossRef]
  53. Sathiyaraj, P.; Samuel, E.J.J.; Valeriano, C.C.S.; Kurudirek, M. Effective atomic number and buildup factor calculations for metal nano particle doped polymer gel. Vacuum 2017, 143, 138–149. [Google Scholar] [CrossRef]
  54. Brennan, S.; Cowan, P.L. A suite of programs for calculating x-ray absorption, reflection, and diffraction performance for a variety of materials at arbitrary wavelengths. Rev. Sci. Instrum. 1992, 63, 850–853. [Google Scholar] [CrossRef]
  55. Gibbons, J.P. Khan’s the Physics of Radiation Therapy, 6th ed.; Wolters Kluwer Health: Philadelphia, PA, USA, 2019; ISBN 9781496397539. [Google Scholar]
  56. Hubbell, J.H.; Seltzer, S.M.; Hubblell, H.J.; Seltzer, M.S. Tables of X-ray Mass Attenuation Coefficients and Mass Energy-Absorption Coefficients (Version 1.4); National Institute of Standards and Technolog: Gaithersburg, MD, USA, 2004. Available online: http://physics.nist.gov/xaamdi (accessed on 2 March 2022).
  57. Abdel-Fattah, A.A.; Abdel-Rehim, F.; Soliman, Y.S. A new label dosimetry system based on pentacosa-diynoic acid monomer for low dose applications. Radiat. Phys. Chem. 2012, 81, 70–76. [Google Scholar] [CrossRef]
  58. Soliman, Y.S.; Beshir, W.B.; Abdelgawad, M.H.; Bräuer-Krisch, E.; Abdel-Fattah, A.A. Pergascript orange-based polymeric solution as a dosimeter for radiotherapy dosimetric validation. Phys. Med. 2019, 57, 169–176. [Google Scholar] [CrossRef]
  59. Abdel-Fattah, A.A.; Beshir, W.B.; Hassan, H.M.; Soliman, Y.S. Radiation-induced coloration of nitro blue tetrazolium gel dosimeter for low dose applications. Radiat. Meas. 2017, 100, 18–26. [Google Scholar] [CrossRef]
Figure 1. Optical absorption spectra of PAC hydrogel dosimeter unirradiated and irradiated at various absorbed dose values up to 100 Gy for PAC dosimeter with 100 mM AgNO3 (a) and PAC dosimeter with 150 mM AgNO3 (b).
Figure 1. Optical absorption spectra of PAC hydrogel dosimeter unirradiated and irradiated at various absorbed dose values up to 100 Gy for PAC dosimeter with 100 mM AgNO3 (a) and PAC dosimeter with 150 mM AgNO3 (b).
Gels 08 00222 g001
Figure 2. (a) illustrates the dose–response curve of silver nitrate PAC hydrogel dosimeter (2% PAC) at different AgNO3 concentrations; net absorbance change at 453 nm as a function of absorbed dose (5–100 Gy). (b) shows the radiation sensitivity of silver nitrate PAC dosimeter as a function of [AgNO3]. The solid red line is a guide for the eye obtained using a basis spline function. The error bars denote the standard deviation of the mean values.
Figure 2. (a) illustrates the dose–response curve of silver nitrate PAC hydrogel dosimeter (2% PAC) at different AgNO3 concentrations; net absorbance change at 453 nm as a function of absorbed dose (5–100 Gy). (b) shows the radiation sensitivity of silver nitrate PAC dosimeter as a function of [AgNO3]. The solid red line is a guide for the eye obtained using a basis spline function. The error bars denote the standard deviation of the mean values.
Gels 08 00222 g002
Figure 3. Represent the free radicals of Glycerol.
Figure 3. Represent the free radicals of Glycerol.
Gels 08 00222 g003
Figure 4. Optical absorption spectra of PAC hydrogel dosimeter (100 mM AgNO3 and 15% glycerol) unirradiated and irradiated at various absorbed doses values up to 100 Gy.
Figure 4. Optical absorption spectra of PAC hydrogel dosimeter (100 mM AgNO3 and 15% glycerol) unirradiated and irradiated at various absorbed doses values up to 100 Gy.
Gels 08 00222 g004
Figure 5. Dose–response curve of PAC hydrogel dosimeter (2% PAC) at different glycerol content, %; net absorbance change at 453 nm as a function of absorbed dose (5–100 Gy for 0, 5, 15, and 15% of Glycerol).
Figure 5. Dose–response curve of PAC hydrogel dosimeter (2% PAC) at different glycerol content, %; net absorbance change at 453 nm as a function of absorbed dose (5–100 Gy for 0, 5, 15, and 15% of Glycerol).
Gels 08 00222 g005
Figure 6. Radiation dose sensitivity of PAC hydrogel dosimeter as a function of glycerol concentration (%). The solid line is a guide for the eye obtained using a basis spline function. The error bars represent the one standard deviation of the mean values.
Figure 6. Radiation dose sensitivity of PAC hydrogel dosimeter as a function of glycerol concentration (%). The solid line is a guide for the eye obtained using a basis spline function. The error bars represent the one standard deviation of the mean values.
Gels 08 00222 g006
Figure 7. Variation of OA at 453 nm normalized to the value at room temperature as a function of irradiation temperature. The solid lines are a guide for the eye obtained using a basis spline function.
Figure 7. Variation of OA at 453 nm normalized to the value at room temperature as a function of irradiation temperature. The solid lines are a guide for the eye obtained using a basis spline function.
Gels 08 00222 g007
Figure 8. Relative response of irradiated hydrogel dosimeter (100 mM AgNO3 and 0% Glycerol) to the response measured immediately after irradiation (zero time) as a function of storage time. The hydrogel dosimeters were irradiated at 50 Gy and then stored in a dark place at different temperatures (6 °C and RT, 23 °C). The solid lines are a guide for the eye obtained using a basis spline function.
Figure 8. Relative response of irradiated hydrogel dosimeter (100 mM AgNO3 and 0% Glycerol) to the response measured immediately after irradiation (zero time) as a function of storage time. The hydrogel dosimeters were irradiated at 50 Gy and then stored in a dark place at different temperatures (6 °C and RT, 23 °C). The solid lines are a guide for the eye obtained using a basis spline function.
Gels 08 00222 g008
Figure 9. Relative response of irradiated hydrogel dosimeter (100 mM AgNO3 and 15% Glycerol) to the response measured immediately after irradiation (zero time) as a function of storage time (days). The hydrogel dosimeters were irradiated at 50 Gy and then stored in a dark place at different temperatures (6 °C and RT, 23 °C). The solid lines are a guide for the eye obtained using a basis spline function.
Figure 9. Relative response of irradiated hydrogel dosimeter (100 mM AgNO3 and 15% Glycerol) to the response measured immediately after irradiation (zero time) as a function of storage time (days). The hydrogel dosimeters were irradiated at 50 Gy and then stored in a dark place at different temperatures (6 °C and RT, 23 °C). The solid lines are a guide for the eye obtained using a basis spline function.
Gels 08 00222 g009
Figure 10. Effective atomic number (Zeff) of PAC hydrogel dosimeter (100 mM Ag+) without and with glycerol and compared with water as a reference material.
Figure 10. Effective atomic number (Zeff) of PAC hydrogel dosimeter (100 mM Ag+) without and with glycerol and compared with water as a reference material.
Gels 08 00222 g010
Figure 11. The mass energy-absorption coefficients of silver nitrate PAC hydrogel dosimeter (100 mM Ag+ ions) and silver nitrate gel dosimeter (100 mM Ag+ ions) relative to (μen/ρ)W of water against photon energy in the range of 0.1–20 MeV and compared with alanine dosimeter and soft tissue.
Figure 11. The mass energy-absorption coefficients of silver nitrate PAC hydrogel dosimeter (100 mM Ag+ ions) and silver nitrate gel dosimeter (100 mM Ag+ ions) relative to (μen/ρ)W of water against photon energy in the range of 0.1–20 MeV and compared with alanine dosimeter and soft tissue.
Gels 08 00222 g011
Figure 12. Response curves of gel dosimeter (100 mM Ag+ ions) at 450 nm [36] and PAC hydrogel dosimeter (100 mM Ag+ ions) at 453 nm.
Figure 12. Response curves of gel dosimeter (100 mM Ag+ ions) at 450 nm [36] and PAC hydrogel dosimeter (100 mM Ag+ ions) at 453 nm.
Gels 08 00222 g012
Table 1. Scanned images of silver nitrate hydrogel dosimeter (4% gelatin and 100 mM Ag) irradiated at different dose levels. An Epson Perfection V850 Pro scanner, made by Seiko Epson Corporation, was used to scan these images.
Table 1. Scanned images of silver nitrate hydrogel dosimeter (4% gelatin and 100 mM Ag) irradiated at different dose levels. An Epson Perfection V850 Pro scanner, made by Seiko Epson Corporation, was used to scan these images.
Absorbed Dose (Gy)Unit
0.0 Gels 08 00222 i001
5.0 Gels 08 00222 i002
15.0 Gels 08 00222 i003
25.0 Gels 08 00222 i004
50.0 Gels 08 00222 i005
75.0 Gels 08 00222 i006
100.0 Gels 08 00222 i007
Table 2. Radiation sensitivity, correlation coefficient (R2), and the percentage variation of response of PAC hydrogel dosimeters prepared using different concentrations of silver nitrate.
Table 2. Radiation sensitivity, correlation coefficient (R2), and the percentage variation of response of PAC hydrogel dosimeters prepared using different concentrations of silver nitrate.
Composition of PAC
Hydrogel Dosimeter
Sensitivity ± S.D., Gy−1cm−1R2∆ (%)
PAC, %[AgNO3], mMGlycerol, %
220-0.00283 ± 0.000030.99920.00
250-0.00360 ± 0.000070.9975+27.21
2100-0.00479 ± 0.000070.9987+69.26
2150-0.00427 ± 0.000090.9973+50.88
Table 3. Radiation sensitivity, correlation coefficient, and the percentage variation of response of PAC hydrogel dosimeters prepared using different glycerol contents.
Table 3. Radiation sensitivity, correlation coefficient, and the percentage variation of response of PAC hydrogel dosimeters prepared using different glycerol contents.
Composition of PAC Hydrogel DosimeterSensitivity ± S.D., Gy−1cm−1R2∆ (%)
PAC, %[AgNO3], mMGlycerol, %
210000.00479 ± 0.000070.99870
210050.00563 ± 0.000040.9997+17.54
2100150.00620 ± 0.000080.9991+29.43
2100250.00613 ± 0.000020.9968+27.97
Table 4. The silver nitrate (100 mM) PAC hydrogel composition without and with 15% glycerol.
Table 4. The silver nitrate (100 mM) PAC hydrogel composition without and with 15% glycerol.
SymbolZ NumberFraction by Weight
(without Glycerol)
Fraction by Weight
(with 15% Glycerol)
H10.1091780.104578
C60.0101390.084087
N70.0053410.005341
O80.8645600.795212
Ag470.0107820.010782
Table 5. Uncertainty budget of PAC hydrogel dosimeter in the dose range up to 100 Gy.
Table 5. Uncertainty budget of PAC hydrogel dosimeter in the dose range up to 100 Gy.
Source of UncertaintyType of
Uncertainty
Standard
Uncertainty (%)
Calibration irradiation dose rateB1.145 a
Irradiation facilityB0.44
Instrumental variationA0.04
Reproducibility of measurementsA0.42
Batch variabilityA1.03
Calibration curve fitA1.1
Post-irradiation stabilityA0.36
Combined standard uncertainty (uc), 1σ 2.02
overall uncertainty (2σ) 4.04
a As quoted from the calibration certificate
Table 6. Different compositions of PAC hydrogel dosimeter.
Table 6. Different compositions of PAC hydrogel dosimeter.
PAC Hydrogel Dosimeter Composition[PAC]
% w/v
[AgNO3]
mM
[Glycerol]
% v/v
12200
22500
321000
421500
521005
6210015
7210025
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Soliman, Y.S.; Tadros, S.M.; Beshir, W.B.; Saad, G.R.; Gallo, S.; Ali, L.I.; Naoum, M.M. Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique. Gels 2022, 8, 222. https://doi.org/10.3390/gels8040222

AMA Style

Soliman YS, Tadros SM, Beshir WB, Saad GR, Gallo S, Ali LI, Naoum MM. Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique. Gels. 2022; 8(4):222. https://doi.org/10.3390/gels8040222

Chicago/Turabian Style

Soliman, Yasser S., Soad M. Tadros, Wafaa B. Beshir, Gamal R. Saad, Salvatore Gallo, Laila I. Ali, and Magdi M. Naoum. 2022. "Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique" Gels 8, no. 4: 222. https://doi.org/10.3390/gels8040222

APA Style

Soliman, Y. S., Tadros, S. M., Beshir, W. B., Saad, G. R., Gallo, S., Ali, L. I., & Naoum, M. M. (2022). Study of Ag Nanoparticles in a Polyacrylamide Hydrogel Dosimeters by Optical Technique. Gels, 8(4), 222. https://doi.org/10.3390/gels8040222

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop