Tribological and Antimicrobial Properties of Two-Component Self-Assembled Monolayers Deposited on Ti-Incorporated Carbon Coatings.

In this work, Ti-incorporated carbon coatings were used as substrates for modification with one- and two-component self-assembled monolayers of organosilane compounds using a polydimethylsiloxane (PDMS) stamp. This enabled the selective functionalization of surfaces with micrometric dimensions. The topography of the modified surfaces was defined using an atomic force microscope (AFM). The effectiveness of the modification was confirmed by measurements of the water contact angle and surface free energy using the Oss and Good method. Using a T-23 microtribometer with counterparts in the shape of balls that were made of steel, silicon nitride (Si3N4), and zirconium dioxide (ZrO2), the tribological properties of the obtained coatings were tested. These investigations showed that modification by using a PDMS stamp makes it possible to produce two-component ultrathin silane layers on Ti-containing carbon substrates. Two-component organosilane layers had higher hydrophobicity, a lower friction coefficient, and a smaller width of wear tracks than the one-component analogs. It was also found that the work of adhesion of the created surfaces had a significant influence on the value of the friction coefficient and the percentage value of the growth inhibition of bacteria.

Human serum albumin as a potential drug delivery system for N-methylated hot spot insulin analogs inhibiting hormone aggregation.

The purpose of this study was to investigate whether Human Serum Albumin (HSA) can bind N-methylated analogs of hot spots of native insulin. Three N-methylated derivatives of the A13-A19 fragment of native insulin were used: L(N-Me)YQLENY (1), LYQ(N-Me)LENY (2), and L(N-Me)YQ(N-Me)LENY (3). The studied N-methylated insulin fragments possess inhibiting potential against hormone aggregation. A variety of research techniques, including spectroscopic methods and microscopy assays, were used to study the interaction of HSA with the N-methylated insulin fragments. Based on spectroscopic measurements with Congo Red and Thioflavin T, all the analyzed N-methylated peptides were able to interact with the HSA surface. The CD spectrum registered for HSA in the presence of L(N-Me)YQLENY showed the smallest content of α-helix conformation, indicating the most compact HSA structure. Based on the results of MST, the dissociation constants (Kd) for complexes of HSA and peptides 1-3 were 19.2 nM (complex 1), 15.6 nM (complex 2), and 8.07 nM (complex 3). Microscopy assays, dynamic light scattering measurements as well as computer simulation of protein-ligand interaction also confirmed the possibility of docking the N-methylated inhibitors within HSA.

The Surface Modification of Papers Using Laser Processing towards Applications.

This work presents the results of paper laser processing. It begins with the selection and examination of the processing parameters, then an examination of the properties of the modified papers and examples of applications of the developed modification method. The properties of laser-modified paper were studied using reflectance spectrophotometry to examine the colour aspects of the modified papers, scanning electron microscopy (SEM) and confocal microscopy for a morphological analysis, and Raman spectroscopy to analyse the papers under the influence of laser light. The influence of laser processing on the wettability of paper and the evenness of unprinted and printed paper was also investigated. The knowledge gained on paper surface modification with laser light was used to propose several applications, such as methods of marking, tactile detection, the controlled removal of optical brightener, ink, and metallised coatings from paper packaging, highlighting the design and aesthetics of paper. The developed laser-assisted method shows a promising, ecological approach to the design of many value-added paper products.

Changes in the Laser-Processed Ti6Al4V Titanium Alloy Surface Observed by Using Raman Spectroscopy.

This works reports on the effects of treating the surface of Ti6Al4V titanium alloy samples with a laser with a wavelength of 1064 nm, operating in a pulsed and continuous mode. The obtained surfaces with different roughness, complexity and wettability were examined by Raman spectroscopy in order to recognize the presence of titanium oxides on the functionalized surface. The layer of titanium oxides on the surface with the identified rutile phase obtained by laser treatment in the continuous wave mode is a reason for a hydrophobic surface that appeared 50 days after the treatment process. In the case of the surface obtained by the pulsed laser process, only local points at which the Raman bands attributed to the metastable phases anatase and brookite of TiO2 can be identified. In this treatment process, complete surface hydrophilicity was observed during 29 days after the functionalization process (maximal contact angle observed during this time was 68.4 deg). For some functionalization processes of different parameters, the contact angle remained immeasurable until 119 days after the functionalization process. In summary, Raman spectroscopy identifies surface changes of Ti6Al4V after laser processing.

Laser Light Trapping Phenomenon in a 3D Radiotherapy Polymer Gel Dosimeter.

This paper aims to explain the phenomenon of laser light trapping (LLT) in a 3D polymer gel dosimeter. A VIC-T polymer gel dosimeter containing 17% N-vinylpyrrolidone, 8% N,N'-methylenebisacrylamide, 12% tert-butyl alcohol, 5% gelatine, 0.02% hydroquinone and 14 mM tetrakis(hydroxymethyl)phosphonium chloride was used in this study. It was exposed to green laser light with a wavelength of 532 nm. A film was recorded during the exposure. After exposure, Raman spectroscopy was used to study the reactions taking place inside the dosimeter. The obtained results were used to explain what the LLT phenomenon is, what are the consequences for the dosimeter in which such a phenomenon occurs, and what dosimeter components play an important role in the occurrence of LLT. In addition, the conditions under which 3D polymer gel dosimeters can be measured using optical computed tomography at short wavelengths of visible laser light are indicated.

Comparison of the Physicochemical Properties of Carboxylic and Phosphonic Acid Self-Assembled Monolayers Created on a Ti-6Al-4V Substrate.

This study compared the tribological properties in nano- and millinewton load ranges of Ti­6Al-4V surfaces that were modified using self-assembled monolayers (SAMs) of carboxylic and phosphonic acids. The effectiveness of the creation of SAMs with the use of the liquid phase deposition (LPD) technique was monitored by the contact angle measurement, the surface free energy (SFE) calculation, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FTIR) measurements. The obtained results indicated that more stable and well-ordered layers, which were characterized by the lowest values of the coefficient of friction, adhesion, and wear rate, were obtained using phosphonic acid as a surface modifier. Based on the obtained results, it was found that the Ti-6Al-4V alloy modified by phosphonic acid would be the most advantageous for practical applications, especially in micro- and nanoelectromechanical systems (MEMS/NEMS).

The Effect of Physicochemical Properties of Perfluoroalkylsilanes Solutions on Microtribological Features of Created Self-Assembled Monolayers.

The presented article shows the influence of concentration of perfluoroalkylsilanes in solutions on tribological properties of self-assembled monolayers (SAMs) deposited on three surfaces with different silicon content in the millinewton load range. The SAMs were created using the liquid phase deposition (LPD) method with 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (FDTS) and (3, 3, 3-trifluoropropyl) trichlorosilane (FPTS) solutions, for which viscosity and surface tension were estimated. Deposited layers were analyzed in terms of thickness, coverage, wettability, structure and coefficient of friction. The obtained results demonstrated that SAMs created on the silicon-incorporated diamond-like carbon (Si-DLC) coatings possess the best microtribological properties. Systems composed of perfluoroalkylsilane SAM structures deposited on Si-DLC coatings are highly promising candidates as material for microelectromechanical applications.

Conjugates of Chitosan and Calcium Alginate with Oligoproline and Oligohydroxyproline Derivatives for Potential Use in Regenerative Medicine.

New materials that are as similar as possible in terms of structure and biology to the extracellular matrix (external environment) of cells are of great interest for regenerative medicine. Oligoproline and oligohydroxyproline derivatives (peptides 2-5) are potential mimetics of collagen fragments. Peptides 2-5 have been shown to be similar to the model collagen fragment (H-Gly-Hyp-Pro-Ala-Hyp-Pro-OH, 1) in terms of both their spatial structure and biological activity. In this study, peptides 2-5 were covalently bound to nonwovens based on chitosan and calcium alginate. Incorporation of the peptides was confirmed by Fourier transform -infrared (FT-IR) and zeta potential measurements. Biological studies (cell metabolic activity by using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test and Live/Dead assay) proved that the obtained peptide-polysaccharide conjugates were not toxic to the endothelial cell line EA.hy 926. In many cases, the conjugates had a highly affirmative influence on cell proliferation. The results of this study show that conjugates of chitosan and calcium alginate with oligoproline and oligohydroxyproline derivatives have potential for use in regenerative medicine.

Microstructures Manufactured in Diamond by Use of Laser Micromachining.

Different microstructures were created on the surface of a polycrystalline diamond plate (obtained by microwave plasma-enhanced chemical vapor deposition-MW PECVD process) by use of a nanosecond pulsed DPSS (diode pumped solid state) laser with a 355 nm wavelength and a galvanometer scanning system. Different average powers (5 to 11 W), scanning speeds (50 to 400 mm/s) and scan line spacings ("hatch spacing") (5 to 20 µm) were applied. The microstructures were then examined using scanning electron microscopy, confocal microscopy and Raman spectroscopy techniques. Microstructures exhibiting excellent geometry were obtained. The precise geometries of the microstructures, exhibiting good perpendicularity, deep channels and smooth surfaces show that the laser microprocessing can be applied in manufacturing diamond microfluidic devices. Raman spectra show small differences depending on the process parameters used. In some cases, the diamond band (at 1332 cm-1) after laser modification of material is only slightly wider and shifted, but with no additional peaks, indicating that the diamond is almost not changed after laser interaction. Some parameters did show that the modification of material had occurred and additional peaks in Raman spectra (typical for low-quality chemical vapor deposition CVD diamond) appeared, indicating the growing disorder of material or manufacturing of the new carbon phase.

Clinical radiotherapy application of N-vinylpyrrolidone-containing 3D polymer gel dosimeters with remote external MR-reading.

PURPOSE: Advanced 3D dosimetry is required for verifications of complex dose distributions in modern radiotherapy. Two 3D polymer gel dosimeters, coupled with magnetic resonance (MR) imaging (3 T MRI) readout and data processing with polyGeVero® software, were tested for the verification of calculated 3D dose distributions by a treatment planning system (TPS) and ArcCHECK®-3DVH®, related to eradication of a lung tumour. METHODS: N-vinylpyrrolidone-containing 3D polymer gel dosimeters were used: VIC (containing ascorbic acid and copper sulfate pentahydrate) and VIC-T (containing tetrakis(hydroxymethyl)phosphonium chloride). Three remote centers were involved in the dosimeters preparation and irradiation (Poland), and MRI (Austria). Cross beam calibration of the dosimeters and verification of a 3D dose distribution calculated with an Eclipse External Beam TPS and ArcCHECK®-3DVH® were performed. The 3D-to-3D comparisons of the VIC and VIC-T with TPS and ArcCHECK®-3DVH® along with ArcCHECK®-3DVH® versus TPS dose matrixes were performed with the aid of the polyGeVero® by analyzing dose profiles, isodoses lines, gamma index, gamma angle, dose difference, and related histograms. RESULTS: The measured MR-relaxation rate (R2 = 1/T2) for the dosimeters relates to the dose, as follows: R2 = 0.0928 ± 0.0008 [Gy-1 s-1] × D [Gy] + 2.985 ± 0.012 [s-1] (VIC) and 0.1839 ± 0.0044 [Gy-1 s-1] × D [Gy] + 2.519 ± 0.053 [s-1] (VIC-T). The 3D-to-3D comparisons revealed a good agreement between the measured and calculated 3D dose distributions. CONCLUSIONS: VIC and VIC-T with 3T MRI readout and polyGeVero® showed potential for verifications of calculated irradiation plans. The results obtained suggest the implementation of the irradiation plan for eradication of the lung tumour.

Impact of Perfluoro and Alkylphosphonic Self-Assembled Monolayers on Tribological and Antimicrobial Properties of Ti-DLC Coatings.

The diamond-like carbon (DLC) coatings containing 1.6%, 5.3% and 9.4 at.% of Ti deposited by the radio frequency plasma enhanced chemical vapor deposition (RF PECVD) method on the silicon substrate were modified by n-decylphosphonic acid (DP) and 1H, 1H, 2H and 2H-perfluorodecylphosphonic acid (PFDP). The presence of perfluoro and alkylphosphonic self-assembled monolayers prepared by the liquid phase deposition (LPD) technique was confirmed by Fourier transform infrared spectroscopy (FTIR). It was shown that DP and PFDP monolayers on the surface of titanium incorporated diamond-like carbon (Ti-DLC) coatings had a huge influence on their wettability, friction properties, stability under phosphate- and tris-buffered saline solutions and on antimicrobial activity. It was also found that the dispersive component of surface free energy (SFE) had a significant influence on the value of the friction coefficient and the percentage value of the growth inhibition of bacteria. The dispersive component of SFE caused a reduction in the growth of bacteria and the friction coefficient in mili- and nano-newton load range. Additionally, both self-assembled monolayers prepared on Ti-DLC coatings strongly reduced bacterial activity by up to 95% compared to the control sample.

Leuco crystal violet-Pluronic F-127 3D radiochromic gel dosimeter.

This work reports results related to the manufacturing and optimisation of a leuco crystal violet (LCV)-Pluronic F-127 radiochromic gel dosimeter suitable for 3D radiotherapy dosimetry. A feature of this gel is that the natural gelatine polymer, which is most often used as a matrix in 3D dosimeters, is substituted with Pluronic F-127 synthetic copolymer (poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide). Pluronic F-127 ensures a higher transparency than gelatine, which may be beneficial for optical computed tomography readout, and improves the thermal properties in the temperature range above ~30 °C at which the gelatine physical gel converts to a solution. The optimal composition obtained comprises 2 mM LCV, 4 mM 4-(1,1,3,3-tetramethylbutyl)phenyl-polyethylene glycol (Triton X-100), 17 mM trichloroacetic acid (TCAA) and 25% Pluronic F-127. Its main dose-response features are 4‒150 Gy linear dose range (150 Gy was the maximal dose applied to gels in this work), 0.0070 Gy-1 cm-1 dose sensitivity (derived from absorbance (600 nm) = f (dose) for 6 MeV electrons, 0.88(3) Gy s-1 and 0.0156 Gy-1 cm-1 derived from optical density (Δµ) = f (dose) for 6 MV x-rays, 0.1010 Gy s-1), low initial colour (initial absorbance = 0.0429) and a diffusion coefficient of crystal violet (CV) in LCV-Pluronic of 0.054 ± 0.023 mm2 h-1. Raman spectroscopy was used to characterize LCV-Pluronic chemical changes after irradiation. Differential scanning calorimetry (DSC) revealed that LCV-Pluronic is stable in temperatures between approximately 11 °C and 56 °C. Irradiation of LCV-Pluronic gel impacts on its first sol-gel transition temperature and the thermal effect of this process-both increased with absorbed dose, which might be related to the degradation of Pluronic. LCV-Pluronic is a promising 3D dosimeter for ionising radiation applications. Further work is needed to improve LCV-Pluronic response in the low dose region, and characterize potential effects of pH, temperature during irradiation, and radiation quality/dose rate on dose response characteristics.

Examination of THPC as an oxygen scavenger impacting VIC dosimeter thermal stability and comparison of NVP-containing polymer gel dosimeters.

This work reports on the impact of tetrakis(hydroxymethyl)phosphonium chloride (THPC) on the properties of a VIC gel dosimeter (VIC is an abbreviated acronym of VIPARCT). THPC was used as a substitute oxygen scavenger in VIC (17% N-vinylpyrrolidone, 8% N,N'-methylenebisacrylamide, 12% tert-butyl alcohol, 7.5% gelatine, 0.02% hydroquinone and an oxygen scavenger of 0.007% ascorbic acid and 0.0008% CuSO4 × 5H2O). THPC reduced the gelation time of VIC from hours to minutes. The best composition (VIC-T) contained 14 mM THPC and a reduced gelatine concentration (5%) with respect to VIC, which allowed for gelation in about 3 min. VIC-T was characterised by the same dose sensitivity (0.176 ± 0.003 Gy-1 s-1 for VIC-T and 0.171 ± 0.002 Gy-1 s-1 for VIC), dose threshold (0.5 Gy) and dynamic dose range (0.5‒50 Gy) as VIC, and a lower linear dose range (20 Gy for VIC-T, 30 Gy for VIC) (0.47 T NMR measurements). VIC-T was stable for at least 10 days after irradiation, and 3D dose distribution was stable for over 4 months after irradiation. The dose response of VIC-T was independent of the radiation dose rate, type and energy of radiation for 6 and 15 MV photons and 12 MeV electrons. This is an improvement with respect to VIC which showed a different dose response for 6 MV photons than for 12 MeV electrons and 15 MV photons. Raman spectroscopy showed similarity in the rate of radiation-induced conversion of monomers in VIC and VIC-T, indicating interaction of THPC with gelatine in VIC-T, and showed ageing of gelatine in both dosimeters. Differential scanning calorimetry showed VIC-T stability at 0 °C-80 °C (VIC: 0 °C‒29.5 °C). The chemical polymerisation and crosslinking of gelatine with THPC is reported, the mechanism of which was analysed in detail. A comparison of N-vinylpyrrolidone-containing dosimeters is presented in this work.

Study on the Materials Formed by Self-Assembling Hydrophobic, Aromatic Peptides Dedicated to Be Used for Regenerative Medicine.

The aims of this study were to identify the short aromatic peptides which are able to form highly ordered amyloid-like structures in self-assembling processes, to test the influence of length of hydrophobic peptides on tendency to aggregation, and to check if aggregated peptides fulfill requirements expected for materials useful for scaffolding. All tested hydrophobic peptides were prepared on solid phase by using DMT/NMM/TsO- as a coupling reagent. The progress of aggregation was studied by set of independent tests. All aggregated peptides were found stable under in vitro conditions. All fibrous material formed by self-assembling of peptides does not show any cytotoxic effects on L929 fibroblast cells. Peptides containing tyrosine and tryptophan residues even effectively accelerated the proliferation and stimulated the activity of L929 fibroblasts.

Orthogonal Functionalization of Nanodiamond Particles after Laser Modification and Treatment with Aromatic Amine Derivatives.

A laser system with a wavelength of 1064 nm was used to generate sp² carbon on the surfaces of nanodiamond particles (NDPs). The modified by microplasma NDPs were analysed using FT-IR and Raman spectroscopy. Raman spectra confirmed that graphitization had occurred on the surfaces of the NDPs. The extent of graphitization depended on the average power used in the laser treatment process. FT-IR analysis revealed that the presence of C=C bonds in all spectra of the laser-modified powder. The characteristic peaks for olefinic bonds were much more intense than in the case of untreated powder and grew in intensity as the average laser power increased. The olefinized nanodiamond powder was further functionalized using aromatic amines via in situ generated diazonium salts. It was also found that isokinetic mixtures of structurally diverse aromatic amines containing different functional groups (acid, amine) could be used to functionalize the surfaces of the laser-modified nanoparticles leading to an amphiphilic carbon nanomaterial. This enables one-step orthogonal functionalization and opens the possibility of selectively incorporating molecules with diverse biological activities on the surfaces of NDPs. Modified NDPs with amphiphilic properties resulting from the presence carboxyl and amine groups were used to incorporate simultaneously folic acid (FA-CONH-(CH2)5-COOH) and 5(6)-carboxyfluorescein (FL-CONH-(CH2)2-NH2) derivatives on the surface of material under biocompatible procedures.

Substituting gelatine with Pluronic F-127 matrix in 3D polymer gel dosimeters can improve nuclear magnetic resonance, thermal and optical properties.

This work discusses the substitution of a gelatine physical gel matrix with a matrix made of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127) in five 3D radiotherapy polymer gel dosimeters: MAGAT, PAGAT, NIPAM, VIPARnd (VIP) and VIPARCT (VIC). The current research outcomes showed that not each polymer gel dosimeter could be manufactured with Pluronic F-127. Two of the polymer gel dosimeters (PAGAT and VIP) containing the Pluronic F-127 matrix allowed for some proper dose response for radiotherapy dosimetry (a response to a dose range of e.g. 0‒50 Gy). The new best performing Pluronic-based polymer gel dosimeters were characterised by improved nuclear magnetic resonance properties, when being compared to gels with gelatine matrix at the same monomer content. These are: (i) a ~33% higher dose sensitivity; (ii) a comparable or slightly higher linear and dynamic dose range and (iii) a lower (new VIP composition, VIP3) or equivocal (new PAGAT composition, PAGAT2-Pluronic) dose threshold. However, there might be optimised gelatine based polymer dosimeters demonstrating even better sensitivity. UV-vis spectrophotometry measurements revealed that Pluronic matrices ensure six-times lower (VIP3-Pluronic) and eight-times lower (PAGAT2-Pluronic) absorbance (at 400 nm) of non-irradiated gels compared to gelatine matrices, which makes the new polymer gel dosimeters optically improved in comparison to their corresponding gelatine-based compositions. The differences in absorption reduce for higher wavelengths. Differential scanning calorimetry measurements revealed the following temperature stability ranges for the gels: (i) VIP with gelatine matrix: 0 °C‒26 °C, (ii) VIP3 with Pluronic matrix: 13.8 °C-55.2 °C, (iii) PAGAT2 with gelatine matrix: 0 °C-80 °C and (iv) PAGAT2 with Pluronic matrix: 21.4 °C-55.2 °C. In conclusion, Pluronic F-127 is an attractive co-polymer to serve as a substitute for the gelatine matrix in some 3D polymer gel dosimeters.

Tetrazolium salts-Pluronic F-127 gels for 3D radiotherapy dosimetry.

This work is a follow-up study for a recently-proposed 3D radiochromic gel dosimeter that contains a tetrazolium salt and a physical gel matrix made of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127). Several tetrazolium salts were examined in this work, including tetrazolium violet, blue tetrazolium chloride, nitro blue tetrazolium chloride (NBT), tetranitro blue tetrazolium chloride (tNBT) and thiazolyl blue tetrazolium bromide (TBTB). The salt-containing gel dosimeters were compared with the first Pluronic gel composition that contained 2,3,5-triphenyltetrazolium chloride (TTC) as the radiation-sensitive component (dose sensitivity of 0.0023 (Gy cm)-1). The Pluronic gels with NBT and tNBT outperformed the other gels, including the TTC-containing gel, with respect to their dose sensitivity and low dose-response. The NBT gels were found to have better stability over time than tNBT gels. Sensitization of the gels to ionizing radiation was examined by addition of tert-butyl alcohol and sodium formate. The best composition was 0.0818% NBT (1 mM), 25% Pluronic F-127 and 0.136 × 10-2% sodium formate. This gel dosimeter was insensitive to changes in dose rate for photons of different energies. The mean dose sensitivity amounted to 0.0047 ± 0.1 × 10-4 (Gy cm)-1. A diversion in the dose-response was observed for the gel irradiated with electrons. Additional characteristics of the NBT gel were a linear-dose range and a dynamic-dose range between <1 and ⩾150 Gy and a dose threshold of <1 Gy. The dose distribution registered for the NBT-Pluronic gel was stable after irradiation for over 7 d with no visible diffusion of the irradiated part, which is analogous to the original TTC-Pluronic gel.

The Method of Coating Fe3O4 with Carbon Nanoparticles to Modify Biological Properties of Oxide Measured in Vitro.

The coating of nanoparticles on materials for medical application [e.g., the coating of Fe3O4 nanopowder (IONP) with a carbon nanolayer] serves to protect and modify the selected biological, physical, and chemical properties of the coated material. Increases in chemical stability, changes in biocompatibility, and a modified surface structure are examples of the effects caused by the formation of carbon coatings. In the current study, Fe3O4 nanoparticles were coated with a carbon nanolayer (IONP@C) in a plasmochemical reactor (using radio-frequency plasma-enhanced chemical vapor deposition methods) under various experimental conditions. Based on data from X-ray diffraction, Raman, and IR spectroscopy, the best processing parameters were determined in order to produce a carbon coating that would not change the structure of the IONP. The materials with the best cover, i.e., a uniform carbon nanolayer, were used in cytotoxic tests to investigate their biological properties using the human HepG2 hepatocarcinoma cell line and chicken embryo red blood cells as an in vitro model. The obtained results proved the low cytotoxicity of Fe3O4 micropowder and IONP in contrast to IONP@C, which reduced cell viability, increased hemolysis, and generally was more toxic than bare Fe3O4.

TTC-Pluronic 3D radiochromic gel dosimetry of ionizing radiation.

This work reports the first results obtained using a new 3D radiochromic gel dosimeter. The dosimeter is an aqueous physical gel matrix made of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (Pluronic F-127, PEO-PPO-PEO) doped with a representative of tetrazolium salts, 2, 3, 5-triphenyltetrazolium chloride (TTC). There were several reasons for the choice of Pluronic as a gel forming substrate: (i) the high degree of transparency and colourlessness; (ii) the possibility of gel dosimeter preparation at both high and low temperatures due to the phase behaviour of Pluronic; (iii) the broad temperature range over which the TTC-Pluronic dosimeter is stable; and (iv) the non-toxicity of Pluronic. A reason for the choice of TTC was its ionising radiation-induced transformation to water-insoluble formazan, which was assumed to impact beneficially on the spatial stability of the dose distribution. If irradiated, the TTC-Pluronic gels become red but transparent in the irradiated part, while the non-irradiated part remains crystal clear. The best obtained composition is characterised by <4 Gy dose threshold, a dose sensitivity of 0.002 31 (Gy × cm)-1, a large linear dose range of >500 Gy and a dynamic dose response much greater than 500 Gy (7.5% TTC, 25% Pluronic F-127, 50 mmol dm-3 tetrakis). Temporal and spatial stability studies revealed that the TTC-Pluronic gels (7.5% TTC, 25% Pluronic F-127) were stable for more than one week. The addition of compounds boosting the gels' dose performance caused deterioration of the gels' temporal stability but did not impact the stability of the 3D dose distribution. The proposed method of preparation allows for the repeatable manufacture of the gels. There were no differences observed between gels irradiated fractionally and non-fractionally. The TTC-Pluronic dose response might be affected by the radiation source dose rate-this, however, requires further examination.

On the development of a VIPARnd radiotherapy 3D polymer gel dosimeter.

This work presents an improvement of the VIPARnd ('nd' stands for 'normoxic, double', or VIP) polymer gel dosimeter. The gel composition was altered by increasing the concentration of the monomeric components, N-vinylpyrrolidone (NVP) and N,N'-methylenebisacrylamide (MBA), in co-solvent solutions. The optimal composition (VIPARCT, where 'CT' stands for computed tomography, or VIC) comprised: 17% NVP, 8% MBA, 12% t-BuOH, 7.5% gelatine, 0.007% ascorbic acid, 0.0008% CuSO4 × 5H2O and 0.02% hydroquinone. The following characteristics of VIC were achieved: (i) linear dose range of 0.9_30 Gy, (ii) saturation for radiation doses of over 50 Gy, (iii) threshold dose of about 0.5 Gy, (iv) dose sensitivity of 0.171 Gy-1 s-1, which is roughly 2.2 times higher than that of VIP (for nuclear magnetic resonance measurements). It was also found that VIC is dose- rate-independent, and its dose response does not alter if the radiation source is changed from electrons to photons for external beam radiotherapy. The gel responded similarly to irradiation with small changes in radiation energy but was sensitive to larger energy changes. The VIC gel retained temporal stability from 20 h until at least 10 d after irradiation, whereas spatial stability was retained from 20 h until at least 6 d after irradiation. The scheme adopted for VIC manufacturing yields repeatable gels in terms of radiation dose response. The VIC was also shown to perform better than VIP using x-ray computed tomography as a readout method; the dose sensitivity of VIC (0.397 HU Gy-1) was 1.5 times higher than that of VIP. Also, the dose resolution of VIC was better than that of VIP in the whole dose range examined.