END-TO-END AUDIT: COMPARISON OF TLD AND LITHIUM FORMATE EPR DOSIMETRY.

The aim of this study was to test two different solid state dosimetry systems for the purpose of end-to-end audits of radiotherapy volumetric modulated arc therapy (VMAT) technique; a lithium formate electron paramagnetic resonance system and a lithium fluoride thermoluminescent dosimetry system. As a complement to the solid state systems, ion chamber measurements were performed. A polystyrene phantom with a planning target volume (PTV) and an organ at risk (OAR) structure was scanned using CT. A VMAT dose plan was optimized to deliver 2 Gy to the target volume and to minimize the dose to the OAR. The different detectors were inserted into the phantom and the planned dose distribution was delivered. The measured doses were compared to the treatment planning system (TPS) calculated doses. Good agreement was found between the TPS calculated and the measured doses, well accepted for the dose determinations in remote dosimetry audits of VMAT treatment technique.

CHARACTERIZATION OF A LITHIUM FORMATE EPR-DOSIMETRY SYSTEM FOR PROTON RADIATION THERAPY.

The specific aim for the characterization of the lithium formate dosimetry system is to determine response and stability in a proton beam. The long-term goal for this investigation is an audit system for proton therapy like the end-to-end dose determinations performed for radiotherapy with photons. For a 150-MeV proton beam, the dose response was found to be linear in the dose interval 0-8.8 Gy. The accuracy of dose reconstruction was controlled in a blind test, in which the dose of 6.63 Gy was measured in samples irradiated with a real dose of 6.70 Gy. The stability was determined by irradiations of sets of four dosimeters every week during 1 month and analyzed at the same day thereafter. The fitting of the fading curve was done with a second-order polynomial resulting in a 6.6% lower value compared to the reference after 31 d.

EPR spin trapping evidence of radical intermediates in the photo-reduction of bicarbonate/CO2 in TiO2 aqueous suspensions.

Using the EPR spin trapping technique, we prove that simultaneous reactions take place in illuminated suspensions of TiO2 in aqueous carbonate solutions (pH ≈ 7). The adsorbed HCO3(-) is reduced to formate as directly made evident by the detection of formate radicals (˙CO2(-)). In addition, the amount of OH˙ radicals from the photo-oxidation of water shows a linear dependence on the concentration of bicarbonate, indicating that electron scavenging by HCO3(-) increases the lifetime of holes. In a weakly alkaline medium, photo-oxidation of HCO3(-)/CO3(2-) to ˙CO3(-) interferes with the oxidation of water. A comparative analysis of different TiO2 samples shows that formation of ˙CO2(-) is influenced by factors related to the nature of the surface, once expected surface area effects are accounted for. Modification of the TiO2 surface with noble metal nanoparticles does not have unequivocal benefits: the overall activity improves with Pd and Rh but not with Ru, which favours HCO3(-) photo-oxidation even at pH = 7. In general, identification of radical intermediates of oxidation and reduction reactions can provide useful mechanistic information that may be used in the development of photocatalytic systems for the reduction of CO2 also stored in the form of carbonates.

Lithium formate for EPR dosimetry: radiation-induced radical trapping at low temperatures.

Radiation-induced primary radicals in lithium formate. A material used in EPR dosimetry have been studied using electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR) and ENDOR-Induced EPR (EIE) techniques. In this study, single crystals were X irradiated at 6-8 K and radical formation at these and higher temperatures were investigated. Periodic density functional theory calculations were used to assist in assigning the radical structures. Mainly two radicals are present at 6 K, the well-known CO2(•-) radical and a protonated electron-gain product. Hyperfine coupling tensors for proton and lithium interactions were obtained for these two radicals and show that the latter radical exists in four conformations with various degrees of bending at the radical center. Pairs of CO2(•-) radicals were also observed and the tensor for the electron-electron dipolar coupling was determined for the strongest coupled pair, which exhibited the largest spectral intensity. Upon warming, both the radical pairs and the reduction product decay, the latter apparently by a transient species. Above 200 K the EPR spectrum was mainly due to the CO2(•-) (mono) radicals, which were previously characterized as the dominant species present at room temperature and which account for the dosimetric EPR signal.

Synthesis and assembly of Pd nanoparticles on graphene for enhanced electrooxidation of formic acid.

Monodisperse 4.5 nm Pd nanoparticles (NPs) were synthesized by solution phase reduction of palladium acetylacetonate with morpholine borane in a mixture of oleylamine and 1-octadecene. These NPs were assembled on graphene uniformly in the form of a monolayer, and showed much enhanced catalysis for electrooxidation of formic acid. The work demonstrates the great potential of graphene as a support to enhance NP catalysis and stability for important chemical oxidation reactions.

Hydrogen production by photoelectrochemically splitting solutions of formic acid.

A TiO2/FTO (FTO=fluorine-doped tin oxide) electrode was prepared by dip-coating FTO in a suspension of TiO2 prepared from a sol-gel method and was used as a photoanode to split an aqueous solution of formic acid to produce hydrogen. The surface of the TiO2/FTO film was covered with assemblies of TiO2 nanoparticles with a diameter of approximately 20 nm. Under irradiation by using a Xe lamp, splitting of formic acid was performed at different applied current densities. Compared to splitting water or utilizing FTO and Pt foil as the anode, the splitting voltage is much lower and can be as low as -0.27 V. The results show that the splitting voltage is related to the concentration of free formate groups. The evolution rate of hydrogen measured by using gas chromatography is 130 µmol h⁻¹ at a current density of 20 mA cm⁻² and the energy-conversion efficiency can be 1.79 %. Photoelectrolysis of formic acid has the potential to be an efficient way to produce hydrogen with a high energy-conversion efficiency.

An environmentally friendly procedure for the reductive alkylation of amines with ammonium formate using supported reagent.

Reductive alkylation of amines with carbonyl compounds is a useful method for the production of N-alkylated amines, a rapid, mild, efficient, inexpensive and environmentally friendly procedure is reported for the reductive alkylation of amines with aromatic aldehydes using ammonium formate and NiCl2/SiO2 with microwave heating.

Products of radiation removal of lead from aqueous solutions.

The influence of typical *OH radical scavengers as potassium formate and isopropanol on the radiation-induced removal of lead was individually studied. The lead can be completely removed from aqueous solutions containing 1x10(-2) mol/L of formate already at the dose of 2.5 kGy. With increasing concentration of formate (5x10(-5)-1x10(-2) mol/L) increases the amount of Pb(formate)(+) species in the solution before irradiation. The radiation product is metallic lead at low concentration of formate to PbCO(3) at higher concentration of scavenger. In the system with 10% isopropanol dominates the species Pb(2+) and the product of radiation reduction is then metallic lead.

Evaluation of a lithium formate EPR dosimetry system for dose measurements around 192Ir brachytherapy sources.

A dosimetry system using lithium formate monohydrate (HCO2Li x H2O) as detector material and electron paramagnetic resonance (EPR) spectroscopy for readout has been used to measure absorbed dose distributions around clinical 192Ir sources. Cylindrical tablets with diameter of 4.5 mm, height of 4.8 mm, and density of 1.26 g/cm3 were manufactured. Homogeneity test and calibration of the dosimeters were performed in a 6 MV photon beam. 192Ir irradiations were performed in a PMMA phantom using two different source models, the GammaMed Plus HDR and the microSelectron PDR-v1 model. Measured absorbed doses to water in the PMMA phantom were converted to the corresponding absorbed doses to water in water phantoms of dimensions used by the treatment planning systems (TPSs) using correction factors explicitly derived for this experiment. Experimentally determined absorbed doses agreed with the absorbed doses to water calculated by the TPS to within +/-2.9%. Relative standard uncertainties in the experimentally determined absorbed doses were estimated to be within the range of 1.7%-1.3% depending on the radial distance from the source, the type of source (HDR or PDR), and the particular absorbed doses used. This work shows that a lithium formate dosimetry system is well suited for measurements of absorbed dose to water around clinical HDR and PDR 192Ir sources. Being less energy dependent than the commonly used thermoluminescent lithium fluoride (LiF) dosimeters, lithium formate monohydrate dosimeters are well suited to measure absorbed doses in situations where the energy dependence cannot easily be accounted for such as in multiple-source irradiations to verify treatment plans. Their wide dynamic range and linear dose response over the dose interval of 0.2-1000 Gy make them suitable for measurements on sources of the strengths used in clinical applications. The dosimeter size needs, however, to be reduced for application to single-source dosimetry.

Irradiated lithium formate and amino acids.

Radiation-induced free radicals in solids show a microwave saturation effect when studied by electron spin resonance. A comparison is made between such effects in lithium formate and amino acids. The relative effectiveness of neutrons against high-energy photons is also considered.

The energy dependence of lithium formate EPR dosimeters for clinical electron beams.

The objective of this study was to investigate the potential of using polycrystalline lithium formate for EPR (electron paramagnetic resonance) dosimetry of clinical electron beams, with the main focus on the dose-to-water energy response. Lithium formate dosimeters were irradiated using (60)Co gamma-rays and 6-20 MeV electrons in a PMMA phantom to doses in the range of 3-9 Gy. A plane-parallel ion chamber was used for water-based absolute dosimetry. In addition, the electron/photon transport was simulated using the EGSnrc Monte Carlo code. From the EPR measurements, the standard deviation of single dosimeter readings was 1.2%. The experimental energy response (the lithium formate dosimeter reading per absorbed dose to water for electrons relative to that for (60)Co gamma rays) was nearly independent of the electron energy and on average 0.99 +/- 0.03. The Monte Carlo calculated energy response was on average 0.5% higher than the experimental energy response, the difference being not significant. Simulations with water and polystyrene as irradiation media indicated that the energy response of lithium formate dosimeters was nearly independent of the phantom materials. In conclusion, lithium formate EPR dosimetry of clinical electron beams provides precise dose measurements with low dependence on the electron energy.

An ESR and ENDOR study of irradiated 6Li-formate.

Lithium formate ((6)LiOOCH.H(2)O), 95% (6)Li enrichment, combined with an exchange of crystallization water with D(2)O was investigated. The ESR spectrum of the radiation induced free radicals stable at room temperature consists of a singlet with a narrow line width, 0.92mT. (6)Li has smaller magnetic moment and nuclear spin, which resulted in the narrower line width accompanied with an increase in peak amplitude. In comparison with lithium formate with natural isotopic composition, (6)Li (7.5%, I=1) and (7)Li (92.5%, I=3/2), the sensitivity was increased by a factor of two. With optimised spectrometer settings (6)Li formate had seven times higher sensitivity compared to alanine. Therefore this material is proposed as a dosimeter material in a dose range down to 0.1Gy. The g and the (13)C-hyperfine (hf) tensors of the CO(2)(-) radical anion, major paramagnetic products, were evaluated to be g=(2.0037, 1.9975, 2.0017), and A((13)C)=(465.5, 447.5, 581.3) MHz for polycrystalline samples at room temperature. Furthermore, the (1)H-hf and (6)Li-hf tensors observed for the surroundings of CO(2)(-) by ENDOR technique were in fairly good agreement with DFT calculations. The CO(2)(-) radicals are found to be so stable that the formate is applicable to the ESR dosimetry, because of fully relaxing in a fully relaxed geometrical structure of the CO(2)(-) component and remaining tight binding with the surroundings after the H atom detachment from HCO(2)(-).

Photocatalytic degradation of pollutants from Elcogas IGCC power station effluents.

The aim of this work is to improve the quality of water effluents coming from Elcogas IGCC power station (Puertollano, Spain) with the purpose of fulfilling future more demanding normative, using heterogeneous photocatalytic oxidation processes (UV/H(2)O(2)/TiO(2) or ZnO). The efficiency of photocatalytic degradation for the different catalysts (TiO(2) and ZnO) was determined from the analysis of the following parameters: cyanides, formates and ammonia content. In a first stage, the influence of two parameters (initial concentration of H(2)O(2) and amount of catalyst) on the degradation kinetics of cyanides and formates was studied based on a factorial experimental design. pH was always kept in a value >9.5 to avoid gaseous HCN formation. The degradation of cyanides and formates was found to follow pseudo-first order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The mathematical model reproduces experimental data within 90% of confidence and allows the simulation of the process for any value of parameters in the experimental range studied. Moreover, a measure of the saliency of the input variables was made based upon the connection weights of the neural networks, allowing the analysis of the relative relevance of each variable with respect to the others. Results showed that the photocatalytic process was effective, being the degradation rate of cyanides about five times higher when compared to removal of formates. Finally, the effect of lowering pH on the degradation of formates was evaluated after complete cyanides destruction was reached (10 min of reaction). Under the optimum conditions (pH 5.2, [H(2)O(2)]=40 g/l; [TiO(2)]=2g/l), 100% of cyanides and 92% of initial NH(3) concentration are degraded after 10 min, whereas 35 min are needed to degrade 98% of formates.

LET effects following neutron irradiation of lithium formate EPR dosimeters.

Lithium formate electron paramagnetic resonance (EPR) dosimeters were irradiated using 60Co gamma-rays or fast neutrons to doses ranging from 5 to 20 Gy and investigated by EPR spectroscopy. Using a polynomial fitting procedure in order to accurately analyze peak-to-peak line widths of first derivative EPR spectra, dosimeters irradiated with neutrons had on average 4.4+/-0.9% broader EPR resonance lines than gamma-irradiated dosimeters. The increase in line width was slightly asymmetrical. Computer simulated first derivative polycrystalline EPR spectra of a *CO2- radical gave very good reconstructions of experimental spectra of irradiated dosimeters. The spectrum simulations could then be used as a tool to investigate the line broadening observed following neutron irradiation. It was shown that an increase in the simulated Lorentzian line width could explain both the observed line broadening and the asymmetrical effect. The ratio of the peak-to-peak amplitude of first derivative EPR spectra obtained at two different microwave powers (20 and 0.5 mW) was 7.8+/-1.2% higher for dosimeters irradiated with neutrons. The dependence of the spectrum amplitude on the microwave power was extensively investigated by fitting observations to an analytical non-linear model incorporating, among others, the spin-lattice (T1) and spin-spin (T2) relaxation times as fitting parameters. Neutron irradiation resulted in a reduction in T(2) in comparison with gamma-irradiation, while a smaller difference in T1 was found. The effects observed indicate increased local radical density following irradiation using high linear energy transfer (LET) neutrons as compared to low LET gamma-irradiation. A fingerprint of the LET may thus be found either by an analysis of the line width or of the dependence of the spectrum amplitude on the microwave power. Lithium formate is therefore a promising material for EPR dosimetry of high LET radiation.

Comparison of catalytic activity of two platinised TiO2 films towards the oxidation of organic pollutants.

Two types of platinised TiO2 films, i.e., Pt-TiO2/ITO and Pt(TiO2)/ITO, were prepared by a procedure of dip-coating and subsequent photo-deposition, and photo-deposition and subsequent dip-coating, respectively. They were well characterized by DRS, XRD spectra, SEM microscopy and photoelectrochemical measurement. Their photocatalytic, dark catalytic and photoelectrocatalytic activities were investigated using formic acid as a model organic pollutants. Compared with pure TiO2/ITO film, the photocatalytic activity of the platinised TiO2 films were apparently improved. However, the improvement was considerably dependent on the preparation method of these films. Pt-TiO2/ITO not only possessed higher photocatalytic activity but also showed a dark catalytic activity towards HCOOH degradation. As a sequence, it was first emphasized that the dark catalytic effect of Pt-TiO2/ITO was partly responsible for degradation of formic acid in the photocatalytic oxidation process. Although the Pt(TiO2)/ITO film does not exhibit the dark catalytic activity, its photocatalytic degradation efficiencies towards HCOOH are higher than that of Pt-TiO2/ITO film. Therefore, in view of enhanced photocatalytic activity, the Pt(TiO2)/ITO was more favored than Pt-TiO2/ITO film.

Formates and dithionates: sensitive EPR-dosimeter materials for radiation therapy.

Polycrystalline formates and dithionates are promising materials for EPR dosimetry, as large yields of radiation induced stable radicals are formed with a linear dose response. Rapid spin relaxation rates were detected in many of the substances, indicating that a high microwave power can be applied during EPR acquisition in order to improve sensitivity. Different techniques used to further improve the sensitivity, such as the replacement of 7Li with 6Li or exchange of protons with deuterons in the corresponding crystalline matrices and metal ion doping are discussed. It is concluded that formates and dithionates may be up to 10 times as sensitive as L-alpha-alanine.

Preparation and photoinduced patterning of azidoformate-terminated self-assembled monolayers.

This paper presents a new method for the patterning of self-assembled monolayers (SAMs) using UV light. Azidoformate-terminated SAMs starting from 18-acetoxy-octadecyltrichlorosilane SAMs on silicon, prepared for the first time, are electrophilic and photosensitive, and can be patterned by UV irradiation through a mask. The resulting structured surfaces are still electrophilic and can be reacted with nucleophilic functions, for example, primary amines.

Electron paramagnetic resonance (EPR) dosimetry using lithium formate in radiotherapy: comparison with thermoluminescence (TL) dosimetry using lithium fluoride rods.

Solid-state radiation dosimetry by electron paramagnetic resonance (EPR) spectroscopy and thermoluminescence (TL) was utilized for the determination of absorbed doses in the range of 0.5-2.5 Gy. The dosimeter materials used were lithium formate and lithium fluoride (TLD-100 rods) for EPR dosimetry and TL dosimetry, respectively. 60Co gamma-rays and 4, 6, 10 and 15 MV x-rays were employed. The main objectives were to compare the variation in dosimeter reading of the respective dosimetry systems and to determine the photon energy dependence of the two dosimeter materials. The EPR dosimeter sensitivity was constant over the dose range in question, while the TL sensitivity increased by more than 5% from 0.5 to 2.5 Gy, thus displaying a supralinear dose response. The average relative standard deviation in the dosimeter reading per dose was 3.0% and 1.2% for the EPR and TL procedures, respectively. For EPR dosimeters, the relative standard deviation declined significantly from 4.3% to 1.1% over the dose range in question. The dose-to-water energy response for the megavoltage x-ray beams relative to 60Co gamma-rays was in the range of 0.990-0.979 and 0.984-0.962 for lithium formate and lithium fluoride, respectively. The results show that EPR dosimetry with lithium formate provides dose estimates with a precision comparable to that of TL dosimetry (using lithium fluoride) for doses above 2 Gy, and that lithium formate is slightly less dependent on megavoltage photon beam energy than lithium fluoride.

Formate ion decomposition in water under UV irradiation at 253.7 nm.

Formate ion (HCO2-) occurs in natural waters as a result of photooxidation of humic substances. Under UV irradiation, as applied in water purification (253.7 nm), formate ion decomposed following split-rate pseudo-zero-order kinetics (k1 and k2 are initial and final rate constants, respectively). In the presence of dissolved oxygen (DO), it was found that (a) k1 < k2, (b) k1 and k2 increased with initial formate ion concentration ([HCO2-]0 = (1.73-38.3) x 10(-5) mol L(-1)) and absorbed UV intensity (Ia = (1.38-3.99) x 10(-6) mol quanta L(-1) s(-1)), and (c) k1 and k2 were relatively insensitive to initial pH (pHo = 5.41-8.97) in buffer-free solutions. Both rate constants decreased with increasing carbonate alkalinity ((0-1.0) x 10(-3) mol L(-1)) and k1 was virtually unchanged in phosphate buffer at pH0 between 5.25 and 9.92. Carbonate buffer lowered the rate of formate ion decay, possibly due to scavenging of OH* radicals. Initial rate constant k1 slightly increased with temperature (15-35 degrees C), while k2 remained unchanged. The reaction pH increased rapidly during irradiation of buffer-free NaHCO2 solution to approach an equilibrium level as [HCO2-] reached the method detection level (MDL). The pH profile of buffer-free formate ion decay was estimated using closed-system equilibrium analysis. DO utilization during UV irradiation was 0.5 mol of O2/mol of HCO2-, while nonpurgeable organic carbon (NPOC) measurements on kinetic samples closely followed the HCO2- profile, thus strongly suggesting the transformation of HCO2- -C to CO2 in the presence of DO. In DO-free water, k1 > k2 was observed. Furthermore, k(1,DO FREE) > k(1,DO) (k(1,DO) = k1) and k(2,DO FREE) < k(2,DO) (k(2,DO) = k2). The effect of dual acid solutions on HCO2- decay was examined in a mixture of NaHCO2 and sodium oxalate (Na2C2O4). HCO2- decomposed readily until [HCO2-] approximately equal to MDL but at a lower rate than in buffer-free HCO2- solutions, while C2O4(2-) remained virtually unchanged. C2O4(2-) decay commenced following near complete conversion of HCO2-.

EPR dosimetric properties of formates.

As a part of a program to develop an electron paramagnetic resonance (EPR) dosimeter suited for clinical use (doses in the cGy range), polycrystalline samples of lithium formate monohydrate (HCO2Li.H2O), magnesium formate dihydrate (C2H2O4Mg.2H2O), and calcium formate (C2H2O4Ca) have been examined. L-Alanine was included for comparison and reference. Samples were irradiated with 60Co gamma-rays and 60-220 kV X-rays. The dosimeter response was assessed using the peak-to-peak amplitude of the first-derivative EPR spectrum. Dose-response curves for the 60Co gamma-irradiated samples were constructed, and the dependences of the response on the photon energy, microwave power, and modulation amplitude were studied. Stability of the irradiation products upon storage (signal fading) was also investigated. Lithium formate monohydrate is by far the best candidate of the tested formates, suitable for measuring doses down to approximately 0.1 Gy. Lithium formate monohydrate is more sensitive than alanine by a factor of 5.6-6.8 in the tested photon energy range, it exhibits no zero-dose signal and shows a linear dose response in the dose range from 0.2 to 1000 Gy. Its EPR signal was found unchanged in shape and intensity 1 week after irradiation to 10 Gy. Various less favorable properties rendered the other formates generally unsuitable, although calcium formate exhibits some interesting EPR dosimetric properties.