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•The fourth stable radical in X-irradiated solid state sucrose has been identified.•It is a fragment molecule with the unpaired electron localized close to the original C5’ atom ...location.•The radical is produced by a double scission of the fructose ring.•MD simulations did not reveal any other stable conformations of the radical.
Identification of radiation-induced radicals in relatively simple molecules is a prerequisite for the understanding of reaction pathways of the radiation chemistry of complex systems. Sucrose presents an additional practical interest as a versatile radiation dosimetric system. In this work, we present a periodic density functional theory study aimed to identify the fourth stable radical species in this carbohydrate. The proposed model is a fragment suspended in the lattice by hydrogen bonds with an unpaired electron at the original C5’ carbon of the fructose unit. It requires a double scission of the ring accompanied by substantial chemical and geometric reorganization.
Defect-engineering of TiO2 can have a major impact on its photocatalytic properties for the degradation of persisting and non-biodegradable pollutants. Herein, a series of intrinsic and extrinsic ...defects are induced by post annealing of crystalline TiO2 under different reducing atmospheres. A detailed optoelectronic characterization sheds light on the key characteristics of the defect-engineered TiO2 nanopowders that are linked to the photocatalytic performance of the prepared photocatalysts. The photodegradation of a model dye, malachite green, as well as the inactivation of bacterial endospores of the Geobacillus stearothermophilus species were studied in the presence of the developed catalysts under visible light illumination. Our results indicate that a combination of certain defects is necessary for the improvement of the photocatalytic process for water purification and disinfection under visible light.
Lund, A., Sagstuen, E., Sanderud, A. and Maruani, J. Relaxation-Time Determination from Continuous-Microwave Saturation of EPR Spectra. Based on the theories of Portis and of Castner 50 years ago, ...different continuous-wave measurement procedures for analyzing the microwave saturation power dependence of inhomogeneously broadened EPR lines were developed. Although these procedures have been refined, they still use only a few selected points on the saturation curve. A non-linear least-squares procedure for analyzing the microwave-power dependence of inhomogeneously broadened lines using all data points on a saturation curve has been developed. This procedure provides a simple alternative method to obtain magnetic relaxation data when the more direct pulse-saturation techniques are not available or are less suitable. The latter includes applications of quantitative EPR such as dosimetry. Then microwave saturation data should be obtained under conditions similar to those used in the quantitative measurements, which are usually made on first derivative spectra recorded using continuous-wave spectrometers. Selected applications to benchmark literature data and within the field of EPR dosimetry are discussed. The results obtained illustrate that relaxation times comparable to those yielded by various pulse-saturation EPR techniques can be obtained. It appears as a systematic feature that, whenever the pulse EPR data are fitted using bi-exponential functions, the shortest relaxation times obtained are those that correspond best to those measured using the current continuous-wave saturation method.
Sagstuen, E., Sanderud, A. and Hole, E. O., The Solid-State Radiation Chemistry of Simple Amino Acids, Revisited. Radiat. Res. 162, 112–119 (2004). The solid-state radiation-induced free radical ...formation in simple amino acids like α-glycine (gly) and l-α-alanine (ala) has been the subject of investigations by EPR spectroscopy since the late 1950s. The EPR spectra from crystals of gly and ala generally are very complex due to the simultaneous trapping of several free radicals regardless of irradiation and observation temperatures. Untangling these complex spectra is necessary for understanding the mechanisms for the solid-state radiation chemistry of amino acids. Recently, radical formation in gly and ala after room-temperature irradiation has been reinvestigated in our laboratories using X-, K- and Q-band EPR and ENDOR spectroscopy, combined with the ENDOR-induced EPR (EIE) techniques as well as single-crystal and powder EPR and ENDOR spectrum simulations. Several new radical products have been detected and characterized, most prominently the gly species H2N − C·H − COOH and the ala species H3+N − C·(CH3) − COO− and H2N − C·(CH3) − COOH. A short description of these radicals is given, and an overview of the solid-state radiation chemistry of the simple amino acids is presented, based on a review of the literature combined with these recent experimental results.
Electron paramagnetic resonance (EPR), electron nuclear double resonance (ENDOR), and ENDOR-induced EPR (EIE) measurements on sucrose single crystals at 10 K after in situ X irradiation at this ...temperature reveal the presence of at least nine different radical species. Nine proton hyperfine coupling tensors were determined from ENDOR angular variations and assigned to six of these species (R1−R6) using EIE. Spectral simulations indicate that four of those (R1−R3 and R6) dominate the EPR absorption. Assisted by periodic density functional theory (DFT) calculations, R1 and R2 are identified as H-abstracted C1- and C5-centered radicals, R3 is tentatively assigned to an H-abstracted C6-centered radical, and R6 is identified as an alkoxy radical where the abstracted hydroxy proton has migrated to a neighboring OH group via intermolecular proton transfer. The latter radical had been characterized and identified in a previous study, but the present DFT calculations provide additional insight into its conformation and particular properties. This study provides the first step in unraveling the formation mechanism of the stable sucrose radicals detected after room-temperature irradiation and contributes to the understanding of the initial stages of radiation damage to solid-state carbohydrates.
Recently, the chemical structure of two of the three major stable radicals (T2 and T3) produced in sucrose single crystals by X-irradiation at room temperature was identified by comparing Density ...Functional Theory (DFT) calculations of Electron Magnetic Resonance parameters with experimental results H. De Cooman, E. Pauwels, H. Vrielinck, E. Sagstuen, F. Callens and M. Waroquier, J. Phys. Chem. B, 2008, 112, 7298-7307. Ambiguities concerning an unusual proton hyperfine coupling (HFC) tensor prevented the identification of the third major stable radical (T1). In the present work, experimental results of continuous wave Electron Nuclear Double Resonance experiments on sucrose single crystals and Hyperfine Sublevel Correlation Spectroscopy experiments on sucrose powder are presented that lift these remaining ambiguities. Using the final set of experimental HFC tensors and employing advanced DFT calculations, the chemical structure of the T1 radical is established: an allylic-type radical with approximately half of the spin density localised on the C2' carbon of the fructose unit, involving glycosidic bond cleavage at the fructose side and a concerted formation of a carbonyl group at the C1' carbon. The electronic structure of the T1 radical is discussed in more detail by means of additional DFT calculations, yielding a better understanding of the peculiar properties of the unusual proton HFC tensor mentioned above.
Electron magnetic resonance analysis of radiation-induced defects in dipotassium glucose-1-phosphate dihydrate single crystals in situ X-irradiated and measured at 77 K shows that at least seven ...different carbon-centered radical species are trapped. Four of these (R1−R4) can be fully or partly characterized in terms of proton hyperfine coupling tensors. The dominant radical (R2) is identified as a C1-centered species, assumedly formed by a scission of the sugar−phosphate junction and the concerted formation of a carbonyl group at the neighboring C2 carbon. This structure is chemically identical to a radical recently identified in irradiated sucrose single crystals. Radical species R1 and R4 most likely are C3- and C6-centered species, respectively, both formed by a net hydrogen abstraction. R3 is suggested to be chemically similar to but geometrically different from R4. Knowledge of the identity of the sugar radicals present at 77 K provides a first step in elucidating the formation mechanism of the phosphoryl radicals previously detected after X-irradiation at 280 K. In paper II, the chemical identity, precise conformation, and possible formation mechanisms of these radical species are investigated by means of DFT calculations and elementary insight into the radiation chemistry of sugar and sugar derivatives is obtained.
Radiation-induced free radical formation in the amino acid l-α-alanine has been studied using powder and single-crystal X-, K-, and Q-band electron paramagnetic resonance (EPR) spectroscopy, X-band ...powder electron−nuclear double resonance (ENDOR), thermal annealing, and EPR spectrum simulations. The spectra obtained after room temperature irradiations are composite, consisting of resonances from mainly three radicals denoted R1, R2, and R3. R1 is the well-known, stable room-temperature species formed by deamination from a protonated alanine anion radical. On the basis of simulations of EPR spectra obtained at X-, K-, and Q-bands, the room-temperature EPR spectrum seems to consist of about 55% of R1. Upon thermal annealing, the R1 resonance disappears faster than those of the other two components. The R2 species is presumably formed in the oxidative chain of radiation-induced events by net H-abstraction from the central alanine carbon atom. Q-band EPR was used to determine the g-tensor of R2. This species contributes about 35% to the resonance recorded at room temperature. Upon thermal annealing this radical decays slower than R1, resulting in the predominance of R2 in spectra obtained after prolonged warming at 480 K. Powder ENDOR was used to verify that the dominating species remaining after thermal annealing at this temperature indeed is R2 and not a successor species of either of the room-temperature radicals. The R3 species was previously assigned to an N-deprotonated version of R2 being additionally protonated at the carboxyl group. Detailed spectral data for this resonance are missing but a set of parameters based on available data and otherwise estimated using literature values for similar products was constructed. Simulations indicated that 5−10% of the room-temperature resonance could be ascribed to R3. R3 is more heat-resistant than the R1 and R2 radicals, and after prolonged annealing at 480K it was estimated that the resulting resonance consisted of about 51% R2 and 43% R3. The remaining part (about 6%) of the resonance was due to R1. These numbers must, however, be considered as tentative because of the lack of precise spectral data for R3.
Polyphenolic molecules have become attractive building blocks for bioinspired materials due to their adhesive characteristics, capacity to complex ions, redox chemistry, and biocompatibility. For the ...formation of tannic acid (TA) surface modifications based on silicate-phenolic networks, a high ionic strength is required. In this study, we investigated the effects of NaCl, KCl, and LiCl on the formation of TA coatings and compared it to the coating formation of pyrogallol (PG) using a quartz-crystal microbalance. We found that the substitution of NaCl with KCl inhibited the TA coating formation through the high affinity of K+ to phenolic groups resulting in complexation of TA. Assessment of the radical formation of TA by electron paramagnetic resonance spectroscopy showed that LiCl resulted in hydrolysis of TA forming gallic acid radicals. Further, we found evidence for interactions of LiCl with the Siaq crosslinker. In contrast, the coating formation of PG was only little affected by the substitution of NaCl with LiCl or KCl. Our results demonstrate the interaction potential between alkali metal salts and phenolic compounds and highlight their importance in the continuous deposition of silicate-phenolic networks. These findings can be taken as guidance for future biomedical applications of silicate-phenolic networks involving monovalent ions.
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•Methods to obtain the g, zerofield and hyperfine coupling tensors.•Compact and transparent MatLab®codes to replace obsolete software.•Correction of crystal misorientation by a ...simplified method.•Functions for analysis of single crystal data of free radicals and triplet states.•Manual and functions at https://old.liu.se/simarc/downloads?l=en.
The analysis of single crystal electron magnetic resonance (EMR) data has traditionally been performed using software in programming languages that are difficult to update, are not easily available, or are obsolete. By using a modern script-language with tools for the analysis and graphical display of the data, three MatLab® codes were prepared to compute the g, zero-field splitting (zfs) and hyperfine coupling (hfc) tensors from roadmaps obtained by EPR or ENDOR measurements in three crystal planes. Schonland’s original method was used to compute the g- and hfc -tensors by a least-squares fit to the experimental data in each plane. The modifications required for the analysis of the zfs of radical pairs with S = 1 were accounted for. A non-linear fit was employed in a second code to obtain the hfc -tensor from EPR measurements, taking the nuclear Zeeman interaction of an I = ½ nucleus into account. A previously developed method to calculate the g- and hfc -tensors by a simultaneous linear fit to all data was used in the third code. The validity of the methods was examined by comparison with results obtained experimentally, and by roadmaps computed by exact diagonalization. The probable errors were estimated using functions for regression analysis available in MatLab. The software will be published at https://doi.org/10.17632/ps24sw95gz.1, Input and output examples presented in this work can also be downloaded from https://old.liu.se/simarc/downloads?l=en.
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