Highly Sensitive Detection of Ionizing Radiations by a Photoluminescent Uranyl Organic Framework

Precise detection of low‐dose X‐ and γ‐radiations remains a challenge and is particularly important for studying biological effects under low‐dose ionizing radiation, safety control in medical radiation treatment, survey of environmental radiation background, and monitoring cosmic radiations. We report here a photoluminescent uranium organic framework, whose photoluminescence intensity can be accurately correlated with the exposure dose of X‐ or γ‐radiations. This allows for precise and instant detection of ionizing radiations down to the level of 10⁻⁴ Gy, representing a significant improvement on the detection limit of approximately two orders of magnitude, compared to other chemical dosimeters reported up to now. The electron paramagnetic resonance analysis suggests that with the exposure to radiations, the carbonyl double bonds break affording oxo‐radicals that can be stabilized within the conjugated uranium oxalate‐carboxylate sheet. This gives rise to a substantially enhanced equatorial bonding of the uranyl(VI) ions as elucidated by the single‐crystal structure of the γ‐ray irradiated material, and subsequently leads to a very effective photoluminescence quenching through phonon‐assisted relaxation. The quenched sample can be easily recovered by heating, enabling recycled detection for multiple runs.     

A review of the radiation stability of ion exchange materials

A comprehensive literature survey on the radiation stability of ion exchangers resulted in the publication of an extensive data compilation on the effects of ionizing radiation on synthetic organic ion exchangers in this journal (Vol. 97, No. 1). This paper is a brief review of the majorfindings of this literature survey along with similar information on synthetic inorganic ion exchangers. The primary goal of this literature survey is to review present knowledge on the effects of ionizing radiations on synthetic ion exchange materials used in radiochemical processing. Although there are gaps in our knowledge of the mechanisms of radiolytic changes in ion exchangers, the information available in the literature shows some general trends and similarities in observed qualitative effects by different types of organic and inorganic ion exchange materials. These trends and observations have been formulated into a set of qualitative and semi-quantitative statements that can be useful to potential users of ion exchange materials in nuclear material processing and radioactive waste management. Present knowledge, of the behavior of ion exchangers under the influence of ionizing radiations is too limited to justify quantitative predictive modeling.     

Construction of polymer skeletons with radiation‐scissile groups at predetermined sites

Polymers that can be cleaved at predetermined sites by ionizing radiations have been synthesized by incorporating benzylic esters into their skeletons. Secondary electrons generated by ionizing radiations are captured by the benzylic esters to dissociate into benzylic radicals and carboxyl anions, so that the polymer skeletons are cleaved at predetermined sites. The γ‐irradiation of a three‐armed star polymer, 1,2,4‐tri‐(2‐polystyrene‐2‐methyl‐propyonyloxymethyl)‐benzene, results in the selective scission of the arms, and the resultant radicals neither combine with each other nor graft to the other polymer skeletons to give larger polymer molecules. The irradiation of poly(methyl methacrylate) crosslinked with 4‐methacryloyloxybenzyl methacrylate results in the selective scission at the crosslinking sites with high radiation‐chemical efficiency of 8.5 scissions per 100 eV radiation energy absorbed. These results indicate that the incorporation of benzylic esters into polymer skeletons opens a new way of constructing radiation resists with high sensitivity to ionizing radiations and high resistivity to plasma etching. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1945–1953, 2008     

Decomposition of halogenated hydrocarbons using intense, penetrating bremsstrahlung

Radiolytic decomposition of chlorinated hydrocarbons and other toxic compounds has been experimentally measured using ionizing radiation produced by electron accelerator and nuclear isotope sources. Decomposition products have been identified. A portable, commercially available electron accelerator was set up at a Superfund site where vapor extraction wells were removing trichloroethylene (TCE) from a spill into the unsaturated soil. The extraction vapor was passed through the accelerator beam to decompose the TCE. On site radiolytic decomposition of TCE vapor using an accelerator is shown to be significantly less expensive than filtration of TCE vapor using activated charcoal.     

Chemical Investigations of the Molecular Origin of Biological Radiation Damage

The radiation damage observed when UV and ionizing radiations react on biological objects is caused in many cases by changes in the nucleic acids. Exposure of these compounds to UV radiation in vitro and in vivo leads, inter alia, to dimerization of the pyrimidine bases with formation of cyclobutane derivatives, and to addition of water to the 5,6-double bond of the pyrimidine bases to form derivatives of the 6-hydroxyhydropyrimidine system. The structure of the irradiation products has been established. The dimerization prevents the reduplication of the DNA, and the addition of water appears to be the cause of UV mutations. Ionizing radiation in aqueous solution results e.g. in addition of H and/or HO radicals to the 5,6-double bond of the pyrimidine bases and cleavage of the imidazole ring of the purine bases. The mutations caused by ionizing radiation are probably also due, in part, to the formation of 6-hydroxydihydropyrimidine derivatives.     

Resveratrol imparts photoprotection of normal cells and enhances the efficacy of radiation therapy in cancer cells

Solar radiation spans a whole range of electromagnetic spectrum including UV radiation, which are potentially harmful to normal cells as well as ionizing radiations which are therapeutically beneficial towards the killing of cancer cells. UV radiation is an established cause of a majority of skin cancers as well as precancerous conditions such as actinic keratosis. However, despite efforts to educate people about the use of sunscreens and protective clothing as preventive strategies, the incidence of skin cancer and other skin-related disorders are on the rise. This has generated an enormous interest towards finding alternative approaches for management of UV-mediated damages. Chemoprevention via nontoxic agents, especially botanical antioxidants, is one such approach that is being considered as a plausible strategy for prevention of photodamages including photocarcinogenesis. In this review, we have discussed the photoprotective effects of resveratrol, an antioxidant found in grapes and red wine, against UVB exposure-mediated damages in vitro and in vivo. In addition, we have also discussed studies showing that resveratrol can act as a sensitizer to enhance the therapeutic effects of ionizing radiation against cancer cells. Based on available literature, we suggest that resveratrol may be useful for (1) prevention of UVB-mediated damages including skin cancer and (2) enhancing the response of radiation therapies against hyperproliferative, precancerous and neoplastic conditions.     

Initiating nuclear-chemical transformations in native systems: Phenomenology

A possible mechanism of nuclear transformations in biological systems in vivo is proposed. Reasons why there is no ionizing radiation that could be detrimental to native systems during the corresponding nuclear reactions are given. It is established that the initial stage of these processes is associated with that of ATP hydrolysis, which initiates the action of the inner-shell electron of an atom participating in the reaction on its nucleus according to the mechanism of weak nuclear interaction. This results in the formation of a nucleus in a metastable state with a disturbed nucleon structure and a charge one unit lower than that of the initial nucleus. It is also assumed that the atom participating in the reaction is adsorbed near the mouth of one of the transport ATPases in the cell’s cytoplasmic membrane, and the reason for the initiating impact the electron has on the nucleus is due to the emergence of a local electric field formed during ATP hydrolysis near the ion channel of a donor–acceptor pair of charges that is opposite to the direction of the average membrane field. It is concluded that as a result of the key role of weak nuclear interaction in these processes, the energy of nuclear transformations in biological systems in vivo is released through the emission of neutrino–antineutrino pairs that are harmless to living organisms.     

Radiation processing techniques in remediation of pollutants,and the role of the IAEA in supporting capacity building in developing countries

Radiation treatment, or a combination of radiation with conventional biological–chemical–physical processes, can help in the remediation of contaminated surfaces and in combating industrial chemical effluents and air pollution. The use of ionizing radiation as a powerful tool for inactivation of microbes is a valuable option to address likely threats from biohazard contamination that could be introduced either deliberately or inadvertently into areas where the public are exposed to, as well as for treatment of volatile organic compounds and similar hazardous chemical agents is an emerging development in tackling harmful pollutants. The role of the IAEA has been crucial both in supporting the development of local capabilities as well as in fostering international cooperation due to the multidisciplinary expertise required for achieving sustainable benefits. The IAEA is implementing Coordinated Research Projects, (CRP) thematic topical reviews of issues and challenges involved, and Technical Cooperation (TC) assistance in establishing and maintaining infrastructure in the MS. This paper will give an insight into the above mentioned IAEA activities, with examples of successes achieved through CRPs, as well as challenges on the road for broader dissemination of radiation processing technology for environmental remediation.     

The effects of ionizing radiations on synthetic organic ion exchangers

Effects of ionizing radiations on organic ion exchangers are recognized as a vexing problem in the processing of special nuclear materials and high specific activity radioactive waste forms. An extensive literature survey, started in 1976 and updated periodically, indicates that radiation decomposition of ion exchange materials has the potential for a variety of undesirable consequences. It is also apparent from this survey that systematic efforts to identify and resolve these problems and to develop radiation resistant ion exchangers are extremely limited. There is, however, widely scattered information in the literature that is useful in designing and operating ion-exchange-based process systems with reasonable assurance of safety. The compilation of experimental data presented in this paper can contribute to better design and safer operations of synthetic organic ion exchange systems at nuclear material processing facilities.     

Practical applications of radiation chemistry

The physical, chemical, and biological effects of ionizing radiation on matter are the basis of many practical applications. The number of such applications is growing, and sources of gamma radiation and X-rays are now being operated in harsh, demanding environments. They play an important role in the economic development of many countries. The text was submitted by the author in English.     

Radiation synthesis of seroalbumin nanoparticles

Synthesis of small polymeric particles can be achieved by ionizing radiation technology via intramolecular crosslinking by gamma rays onto soluble polymer molecules in random coil conformation. Differently soluble globular proteins are naturally densely packed structures. Fragmentation and aggregation processes have been reported for irradiated globular proteins solutions with ionizing radiations.In this work we describe protein-based nanoparticles prepared by gamma irradiation of a soluble and globular protein, such as seroalbumin, as the basic building blocks keeping its original conformational shape. Protein nanoparticles in the range 20–40 nm were detected after gamma irradiation of the aqueous protein solution in the presence of polar organic solvents. Nanoparticles were characterized by DLS, fluorescence, and UV and CD spectroscopy, showing that the protein molecules keep their general three-dimensional structure into the created nanoparticle.     

A novel method for the study of the biophysical interface in soils using nano-scale secondary ion mass spectrometry

The spatial location of microorganisms and their activity within the soil matrix have major impacts on biological processes such as nutrient cycling. However, characterizing the biophysical interface in soils is hampered by a lack of techniques at relevant scales. A novel method for studying the distribution of microorganisms that have incorporated isotopically labelled substrate ('active' microorganisms) in relation to the soil microbial habitat is provided by nano-scale secondary ion mass spectrometry (NanoSIMS). Pseudomonas fluorescens are ubiquitous in soil and were therefore used as a model for 'active' microorganisms in soil. Batch cultures (NCTC 10038) were grown in a minimal salt medium containing 15N-ammonium sulphate (15/14N ratio of 1.174), added to quartz-based white sand or soil (coarse textured sand), embedded in Araldite 502 resin and sectioned for NanoSIMS analysis. The 15N-enriched P. fluorescens could be identified within the soil structure, demonstrating that the NanoSIMS technique enables the study of spatial location of microbial activity in relation to the heterogeneous soil matrix. This technique is complementary to the existing techniques of digital imaging analysis of soil thin sections and scanning electron microscopy. Together with advanced computer-aided tomography of soils and mathematical modelling of soil heterogeneity, NanoSIMS may be a powerful tool for studying physical and biological interactions, thereby furthering our understanding of the biophysical interface in soils.     

SOME FURTHER CONSIDERATIONS ON THE USE OF REPAIR-DEFECTIVE ORGANISMS AS BIOLOGICAL DOSIMETERS FOR BROAD-BAND ULTRAVIOLET RADIATION SOURCES

Abstract— The extreme variation in biological effectiveness of the various components of solar ultraviolet radiation (solar UV) which reaches the earth's surface, especially photons of wavelengths between 295 and 330 nm, makes the dosimetry of solar UV a complex and, as yet, unresolved problem. A proper weighting of the various components of solar UV would permit expression of expsoure as a single parameter (dose). Weighting could compensate for the variations in composition of solar UV which might occur during exposure or the differences in sources of UV radiations; weighting would permit comparison of exposures at various locations on the earth and extrapolation of laboratory observations to field situations where wavelength composition might be rather different. Various radiation-sensitive microorganisms have been proposed as biological dosimeters. Biological dosimeters automatically weight the subcomponents of solar UV differently than a purely physical irradiance meter. We have examined the available evidence regarding the weighting which repair-defective mutants provide in comparison with response of a number of wild-type organisms and would caution investigators that, for broad-band UV sources, especially those with significant biological actions through the range of 300–330 nm, repair-sensitive mutants may improperly weight the components, leading to errors of dosimetry and thus to possible errors of interpretation of results of solar UV exposure of wild-type organisms     

ACTIVATION OF NF-KB IN HUMAN SKIN FIBROBLASTS BY THE OXIDATIVE STRESS GENERATED BY UVA RADIATION

We have examined the role of the nucleus and the membrane in the activation of nuclear factor (NF)-KB by oxidant stress generated via the UVA (320–380nm) component of solar radiation. Nuclear extracts from human skin fibroblasts that had been irradiated with UVA at doses that caused little DNA damage contained activated NF-KB that bound to its recognition sequence in DNA. The UVA radiation-dependent activation of NF-KB in enucleated cells confirmed that the nucleus was not involved. On the other hand, UVA radiation-dependent activation of NF-KB appeared to be correlated with membrane damage, and activation could be prevented by a-tocopherol and butylated hydroxytol-uene, agents that inhibited UVA radiation-dependent peroxidation of cell membrane lipids. The activation of NF-KB by the DNA damaging agents UVC (200–290nm) and UVB (290–320nm) radiation also only occurred at doses where significant membrane damage was induced, and, overall, activation was not correlated with the relative levels of DNA damage induced by UVC/UVB and UVA radiations. We conclude that the oxidative modification of membrane components may be an important factor to consider in the UV radiation-dependent activation of NF-KB over all wavelength ranges examined.     

VUV absorption and its relation to the effects of ionizing corpuscular radiation

Elements of the physics of photoabsorption as well as of energy transfer from fast charged particles are discussed. Among the key notions there are oscillator-strength spectra, quantum yields, and action spectra. Throughout the discussion, emphasis is put on the important role of soft X-rays and VUV light as obtained from a synchrotron radiation source in the understanding of actions of ionizing radiations in general.     

LETHAL ACTION OF ULTRAVIOLET AND VISIBLE (BLUE-VIOLET) RADIATIONS AT DEFINED WAVELENGTHS ON HUMAN LYMPHOBLASTOID CELLS: ACTION SPECTRA AND INTERACTION SITES

Abstract— The repair proficient human lymphoblastoid line (TK6) has been employed to construcr an action spectrum for the lethal action of ultraviolet (UV) radiation in the range254–434 nm and to examine possible interactions between longer (334, 365 and 405 nm) and shorter wavelength (254 and 313 nm) radiations. The action spectrum follows a DNA absorption spectrum fairly closely out to 360 nm. As in previously determined lethal action spectra for procaryotic and eucaryotic cell populations, there is a broad shoulder in the334–405 nm region which could reflect the existence of either (a) a non-DNA chromophore or (b) a unique photochemical reaction in the DNA over this region. Pre-treatment with radiation at 334 or 365 nm causes either a slight sensitivity to (low fluences) or protection from (higher fluences) subsequent exposure to radiation at a shorter wavelength (254 or 313 nm). Pre-irradiation at a visible wavelength (405 nm) at all fluence levels employed sensitizes the populations to treatment with 254 or 313 nm radiations. These interactions will influence the lethal outcome of cellular exposure to broad-band radiation sources.     

Could Polyphenols Really Be a Good Radioprotective Strategy?

Currently, radiotherapy is one of the most effective strategies to treat cancer. However, deleterious toxicity against normal cells indicate for the need to selectively protect them. Reactive oxygen and nitrogen species reinforce ionizing radiation cytotoxicity, and compounds able to scavenge these species or enhance antioxidant enzymes (e.g., superoxide dismutase, catalase, and glutathione peroxidase) should be properly investigated. Antioxidant plant-derived compounds, such as phenols and polyphenols, could represent a valuable alternative to synthetic compounds to be used as radio-protective agents. In fact, their dose-dependent antioxidant/pro-oxidant efficacy could provide a high degree of protection to normal tissues, with little or no protection to tumor cells. The present review provides an update of the current scientific knowledge of polyphenols in pure forms or in plant extracts with good evidence concerning their possible radiomodulating action. Indeed, with few exceptions, to date, the fragmentary data available mostly derive from in vitro studies, which do not find comfort in preclinical and/or clinical studies. On the contrary, when preclinical studies are reported, especially regarding the bioactivity of a plant extract, its chemical composition is not taken into account, avoiding any standardization and compromising data reproducibility.     

PRIMARY PHOTOCHEMICAL PROCESSES OF CATIONIC ACRIDINE ORANGE IN AQUEOUS SOLUTION STUDIED BY FLASH PHOTOLYSIS

Abstract— A transformation system in Escherichia coli was employed to verify the extent of the lesions caused by ultraviolet (UV) and ionizing radiations. DNA inactivated at 280 nm could be reactivated to some extent by exposing the transforming DNA solutions at 240 nm. This reactivation has been tested using more than one strain of E. coli as recipient. Transforming DNA inactivated by ionizing radiations (⁹⁰Sr beta rays and ⁶⁰Co gamma rays) was not reactivable. Low doses of beta rays, however, reactivated the DNA inactivated by 280 nm UV to a slight but significant extent.     

Monitoring of large scale contamination of the environment: The learning of Chernobyl

The Chernobyl fallout offered the possibility to test new monitoring methods and better understand the behaviour of radionuclides in natural and semi-natural environments. The research started after the Chernobyl accident confirmed previous knowledge, yet producing new information on the radioecology of forested ecosystems. Biological indicators were used with success to establish a relationship between ground deposition and radioactive transfer to wildlife and to evaluate the biological effects of ionizing radiations at low doses.     

ESR study of ascorbic acid irradiated with gamma-rays

The interest in application of high-energy ionizing radiation for stenlization of pharmaceutical products and foodstuffs has led a number of workers to investigate the radiation sensitivity of vitamins. Aside from its use as a vitamin, ascorbic acid (AA) or some derivatives are employed as antioxidants in foodstuffs. The effects of ionizing radiation on AA in simple solutions and in mixture of naturally occurring compounds have been extensively reported in the literature. However, the effects of ionizing radiation on solid AA were reported in few works which described rather dosimetric features of AA No reports, except one, are available describing the characteristic features of the radiolytic intermediates produced after irradiation of polycrystalline AA. Irradiation studies performed on single crystal of AA has led us to reinvestigate our previous work on the radiolytic intermediates produced in irradiated polycrystalline AA. Three radical species, rather than two, having different characteristics were decided contributing to the formation of experimental electron spin resonance (ESR) spectrum of γ-irradiated polycrystalline AA. Spectral parameters of these species were calculated after exhaustive spectrum simulation calculations based on data derived from experimental microwave saturation and dose-response studies.