DNA Nucleobase under Ionizing Radiation: Unexpected Proton Transfer by Thymine Cation in Water Nanodroplets.

The effect of ionizing radiation on DNA constituents is a widely studied fundamental process using experimental and computational techniques. In particular, radiation effects on nucleobases are usually tackled by mass spectrometry in which the nucleobase is embedded in a water nanodroplet. Here, we present a multiscale theoretical study revealing the effects and the dynamics of water droplets towards neutral and ionized thymine. In particular, by using both hybrid quantum mechanics/molecular mechanics and full ab initio molecular dynamics, we reveal an unexpected proton transfer from thymine cation to a nearby water molecule. This leads to the formation of a neutral radical thymine and a Zundel structure, while the hydrated proton localizes at the interface between the deprotonated thymine and the water droplet. This observation opens entirely novel perspectives concerning the reactivity and further fragmentation of ionized nucleobases.

Physical assessments of termites (Termitidae) under 2.45 GHz microwave irradiation.

Demands for chemical-free treatments for controlling insect pests are increasing worldwide. One such treatment is microwave heating; however, two critical issues arise when using microwaves as a heat source: intensive labor and excessive energy-consumption. Optimization is thus required to reduce energy consumption while effectively killing insects. Currently, the lethal effect of microwaves on insects is considered to be due to the temperature of the irradiated materials. This study examines how the conditions of irradiation, such as resonance or traveling mode, changed the conversion of electromagnetic energy into heat when 2.45 GHz microwaves penetrated the body of the termite, C. formosanus. Our results indicated that it is possible to heat and kill termites with microwaves under resonance condition. Termites were however found to be very tolerant to microwave irradiation as the permittivity of the insect was low compared with other reported insects and plants. Electron spin resonance revealed that termites contained several paramagnetic substances in their bodies, such as Fe3+, Cu2+, Mn2+, and organic radicals. Interestingly, irradiation with traveling microwaves hardly produced heat, but increased the organic radicals in termite bodies indicating non-thermal effects of microwaves.

Electrophysiological evidence for light-activated cation transport in calcifying corals.

Light has been demonstrated to enhance calcification rates in hermatypic coral species. To date, it remains unresolved whether calcifying epithelia change their ion transport activity during illumination, and whether such a process is mediated by the endosymbiotic algae or can be controlled by the coral host itself. Using a modified Ussing chamber in combination with H+ sensitive microelectrode measurements, the present work demonstrates that light triggers the generation of a skeleton positive potential of up to 0.9 mV in the hermatypic coral Stylophora pistillata. This potential is generated by a net flux of cations towards the skeleton and reaches its maximum at blue (450 nm) light. The effects of pharmacological inhibitors targeting photosynthesis 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) and anion transport 4,4'-diisothiocyano-2,2'-stilbenedisulfonic acid (DIDS) were investigated by pH microelectrode measurements in coral tissues demonstrating a rapid decrease in tissue pH under illumination. However, these inhibitors showed no effect on the electrophysiological light response of the coral host. By contrast, metabolic inhibition by cyanide and deoxyglucose reversibly inhibited the light-induced cation flux towards the skeleton. These results suggest that ion transport across coral epithelia is directly triggered by blue light, independent of photosynthetic activity of algal endosymbionts. Measurements of this very specific and quantifiable physiological response can provide parameters to identify photoreception mechanisms and will help to broaden our understanding of the mechanistic link between light stimulation and epithelial ion transport, potentially relevant for calcification in hermatypic corals.

Cationic Photopolymerized Polydiacetylenic (PDA) Micelles for siRNA Delivery.

Polymerized micelles obtained by photopolymerization of diacetylenic surfactants and which are forming polydiacetylenic systems (PDAs) have recently gained interest as stabilized monodisperse systems showing potential for the delivery of hydrophobic drugs as well as of larger biomolecules such as nucleic acids. Introduction of pH-sensitive histidine groups at the surface of the micellar PDA systems allows for efficient delivery of siRNA resulting in specific gene silencing through RNA interference. Here, we describe the detailed experimental procedure for the reproducible preparation of these photopolymerized PDA micelles. We provide physicochemical characterization of these nanomaterials by dynamic light scattering, transmission electron microscopy, and diffusion ordered spectroscopy. Moreover, we describe standardized biological tests to evaluate the silencing efficiency by the use of a cell line constitutively expressing the luciferase reporter gene.

Photoactivity of New Octacationic Magnesium(II) and Zinc(II) Porphyrazines in a Water Solution and G-Quadruplex Binding Ability of Differently Sized Zinc(II) Porphyrazines.

The new octacations [(2-Mepy)8PzM]8+ [M = MgII(H2O), ZnII], isolated as iodide salts, were obtained from the corresponding neutral complexes [Py8PzM] (Py = 2-pyridyl; Pz = porphyrazinato dianion) upon quaternization with CH3I of the N atoms of the 2-pyridyl rings under mild experimental conditions. The absorption spectra registered in organic solvents as well as in water (H2O) confirm the presence of the complexes in their monomeric form in all cases. The two octacations behave as photosensitizers in a H2O/sodium dodecyl sulfate solution for the production of singlet oxygen, 1O2, and exhibit quantum yield values (ΦΔ) 2.2-2.5 higher than those measured for the standard PcAlSmix, a promising feature of interest for photodynamic therapy. The interaction of the ZnII octacation [(2-Mepy)8PzZn]8+ with different types of DNA has been studied by means of optical spectroscopic techniques, clearly suggesting that binding of the charged macrocycle to the DNA effectively takes place. In order to assess the effect of the aromatic ring size, the same binding study was performed for the octapyridinated zinc(II) tetraquinoxalinoporphyrazine complex having a much more expanded macrocyclic framework and compared with the behavior of the parent octapyridinated zinc(II) tetrapyrazinoporphyrazine complex having an intermediate macrocycle. The achieved information confirms the relationship between the binding of the charged macrocycle to the DNA and the dimension of the porphyrazine macrocycle.

A bivalent cationic dye enabling selective photo-inactivation against Gram-negative bacteria.

A piperazine-modified Crystal Violet was found to be able to selectively inactivate Gram-negative bacteria upon visible light irradiation but left Gram-positive bacteria less damaged, which can serve as a blueprint for the development of novel narrow-spectrum agents to replenish the current arsenal of photodynamic antimicrobial chemotherapy (PACT).

Radiation stability of cations in ionic liquids. 5. Task-specific ionic liquids consisting of biocompatible cations and the puzzle of radiation hypersensitivity.

In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the α-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5 × 10(4) per 100 eV (which is 4 orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.

Reactions of 5-methylcytosine cation radicals in DNA and model systems: thermal deprotonation from the 5-methyl group vs. excited state deprotonation from sugar.

PURPOSE: To study the formation and subsequent reactions of the 5-methyl-2'-deoxycytidine cation radical (5-Me-2'-dC•(+)) in nucleosides and DNA-oligomers and compare to one-electron oxidized thymidine. MATERIALS AND METHODS: Employing electron spin resonance (ESR), cation radical formation and its reactions were investigated in 5-Me-2'-dC, thymidine (Thd) and their derivatives, in fully double-stranded (ds) d[GC*GC*GC*GC*](2) and in the 5-Me-C/A mismatched, d[GGAC*AAGC:CCTAATCG], where C* = 5-Me-C. RESULTS: We report 5-Me-2'-dC•(+) production by one-electron oxidation of 5-Me-2'-dC by Cl(2)•- via annealing in the dark at 155 K. Progressive annealing of 5-Me-2'-dC•(+) at 155 K produces the allylic radical (C-CH(2)•). However, photoexcitation of 5-Me-2'-dC•(+) by 405 nm laser or by photoflood lamp leads to only C3'• formation. Photoexcitation of N3-deprotonated thyminyl radical in Thd and its 5'-nucleotides leads to C3'• formation but not in 3'-TMP which resulted in the allylic radical (U-CH(2)•) and C5'• production. For excited 5-Me-2',3'-ddC•(+), absence of the 3'-OH group does not prevent C3'• formation. For d[GC*GC*GC*GC*](2) and d[GGAC*AAGC:CCTAATCG], intra-base paired proton transferred form of G cation radical (G(N1-H)•: C(+ H(+))) is found with no observable 5-Me-2'-dC•(+) formation. Photoexcitation of (G(N1-H)•:C(+ H(+))) in d[GC*GC*GC*GC*](2) produced only C1'• and not the expected photoproducts from 5-Me-2'-dC•(+). However, photoexcitation of (G(N1-H)•:C(+ H(+))) in d[GGAC*AAGC:CCTAATCG] led to C5'• and C1'• formation. CONCLUSIONS: C-CH(2)• formation from 5-Me-2'-dC•(+) occurs via ground state deprotonation from C5-methyl group on the base. In the excited 5-Me-2'-dC•(+) and 5-Me-2',3'-ddC•(+), spin and charge localization at C3' followed by deprotonation leads to C3'• formation. Thus, deprotonation from C3' in the excited cation radical is kinetically controlled and sugar C-H bond energies are not the only controlling factors in these deprotonations.

Effect of ultrasound on the kinetics of cation exchange in NaX zeolite.

In this study, we focused on the effect of ultrasound on ion exchange kinetics to obtain the Li-, Ca- and Ce-rich NaX zeolite. The results were compared to those obtained from the traditional batch exchange method under similar conditions. Contact time and initial cation concentration (fold equivalent excess) were studied. Ultrasound enhanced the replacement of Na(+) ion with Li(+), Ca(2+) and Ce(3+) ions in the extra-framework of zeolite up to 76%, 72% and 66%, respectively. The intraparticle diffusion is the rate limiting step in the ion exchange for both exchange methods. As compared to the traditional exchange method, the ultrasonic method applied in this study was found to be very effective on the exchange amount at equilibrium.

Effect of alcaline cations in zeolites on their dielectric properties.

The effect on dielectric properties of alkaline cations Li+, Na+ and K+ incorporated in a zeolite Faujasite structure X or Y, has been investigated. Two major phenomena have been proved to occur: ionic conductivity and rotational polarization of the water molecules adsorbed. The polarizability of the cation which is directly linked to its radius, affects ionic conductivity as well as rotational polarization. Li cations are more strongly Linked to the framework than K+ and Na+ and induce a lower ionic conductivity. K+ is weakly fixed and induces a ionic conductivity even at low solvation level. At low water content, the cation nature and number mainly control the free rotation of the water molecules and affect the relaxation frequency. Close to saturation, the water molecules are mainly linked together by H bonds: the cation nature and number do not really affect the global dielectric properties anymore.

Multivariate analysis of anionic, cationic and nonionic textile surfactant degradation with the H(2)O(2)/UV-C process by using the capabilities of response surface methodology.

Anionic, cationic and nonionic surfactants being frequently employed in the textile preparation process were subjected to H(2)O(2)/UV-C treatment. As a consequence of the considerable number of parameters affecting the H(2)O(2)/UV-C process, an experimental design methodology was used to mathematically describe and optimize the single and combined influences of the critical process variables treatment time, initial H(2)O(2)concentration and chemical oxygen demand (COD) on parent pollutant (surfactant) as well as organic carbon (COD and total organic carbon (TOC)) removal efficiencies. Multivariate analysis was based on two different photochemical treatment targets; (i) full oxidation/complete treatment of the surfactants or, alternatively, (ii) partial oxidation/pretreatment of the surfactants to comply with the legislative discharge requirements. According to the established polynomial regression models, the process independent variables "treatment time" (exerting a positive effect) and "initial COD content" (exerting a negative effect) played more significant roles in surfactant photodegradation than the process variable "initial H(2)O(2) concentration" under the studied experimental conditions.

Proton-coupled electron transfer from a luminescent excited state.

A luminescent cationic iridium complex with a 2,2'-biimidazole ligand forms hydrogen-bonded 1 : 1 adducts with benzoate anions; photoexcitation of the metal complex in presence of 3,5-dinitrobenzoate triggers a proton-coupled electron transfer.

The facile generation of a tetramethyleneethane type radical cation and biradical utilizing a 3,4-di(alpha-styryl)furan and a photoinduced ET and back ET sequence.

Product analyses and nanosecond time-resolved spectroscopy on laser flash photolysis were studied for the photoinduced electron-transfer reaction of 3,4-di(alpha-styryl)furan (6a). A combination of these results, kinetic, density functional theoretical (DFT), and time-dependent DFT analyses enabled assignment of the absorption to the tetramethyleneethane (TME)-type radical cation (7a*+, lambda(max) = 392 nm) and the corresponding singlet biradical ((1)7a**, lambda(max) = 661 nm). These two intermediates were mechanistically linked to each other with a facile back electron-transfer reaction. The present studies provide a new method for the generation of aryl-substituted TME-type intermediates.

Solvent migration from the C- to the N-terminus of amino acid in photoionization of phenylglycine-water complex.

Photo-oxidation of amino acids is known to generate reactive protein radicals that lead to lethal disorders. We investigated photoionization of hydrated phenylglycine complexes in the gas phase and found that the excess internal energy from photoionization drives decarboxylation in competition with dehydration. We also found that, in decarboxylation, the solvent migrates a large distance from the C terminus of the neutral amino acid to the N terminus of the newly formed radical cation upon ionization, prior to the departure of the carboxyl group. It is noted that a solvent does not just act as a passive medium bound to the solute molecule but actively pursues its own course of action upon external perturbation that changes its chemical environment.

Comparison of the efficiency and the specificity of DNA-bound and free cationic porphyrin in photodynamic virus inactivation.

The risk of transmitting infections by blood transfusion has been substantially reduced. However, alternative methods for inactivation of pathogens in blood and its components are needed. Application of photoactivated cationic porphyrins can offer an approach to remove non-enveloped viruses from aqueous media. Here we tested the virus inactivation capability of meso-Tetrakis(4-N-methylpyridyl)porphyrin (TMPyP) and meso-Tri-(4-N-methylpyridyl)monophenylporphyrin (TMPyMPP) in the dark and upon irradiation. T7 bacteriophage, as a surrogate on non-enveloped viruses was selected as a test system. TMPyP and TMPyMPP reduce the viability of T7 phage already in the dark, which can be explained by their selective binding to nucleic acid. Both compounds proved to be efficient photosensitizers of virus inactivation. The binding of porphyrin to phage DNA was not a prerequisite of phage photosensitization, moreover, photoinactivation was more efficiently induced by free than by DNA bound porphyrin. As optical melting studies and agarose gel electrophoresis of T7 nucleoprotein revealed, photoreactions of TMPyP and TMPyMPP affect the structural integrity of DNA and also of viral proteins, despite their selective DNA binding.

Decarboxylative reduction of free aliphatic carboxylic acids by photogenerated cation radical.

The decarboxylation of free carboxylic acids was effected by a photogenerated cation radical of phenanthrene to yield the reduction product in the presence of a thiol, which provides an alternative method to the Barton decarboxylation procedure for aliphatic acids such as N-Boc amino acids.

Photoabsorption and photofragmentation of isolated cationic silver cluster-tryptophan hybrid systems.

We present a theoretical study of the size and structure selective absorption properties of cationic silver cluster-tryptophan Trp-Ag(n)(+) (n = 2-5,9) hybrid systems supported by photofragmentation experiments. Our time-dependent density functional theory calculations provide insight into the nature of excitations in interacting nanoparticle-biomolecule subunits and allow to determine characteristic spectral features as fingerprints of two different classes of structures: charge solvated and zwitterionic. Moreover, different types of charge transfer transitions have been identified. Charge transfer from pi system of tryptophan to silver cluster occurs for charge solvated structures while charge transfer from silver to the NH(3) (+) group takes place for zwitterionic structures. This has been confirmed by experimentally measured photofragmentation channels and molecular dynamics simulations. Our findings provide fundamental insight into the structure- and size-dependent mechanism responsible for the enhanced absorption and emission in nanoparticle-biomolecular hybrid systems.

Effect of light on self-assembly of aqueous mixtures of sodium dodecyl sulfate and a cationic, bolaform surfactant containing azobenzene.

We report light and small-angle neutron scattering measurements that characterize microstructures formed in aqueous surfactant solutions (up to 1.0 wt % surfactant) containing mixtures of sodium dodecyl sulfate (SDS) and the light-sensitive bolaform surfactant, bis(trimethylammoniumhexyloxy)azobenzene dibromide (BTHA) as a function of composition, equilibration time, and photostationary state (i.e., solutions rich in cis-BTHA or trans-BTHA). We observed formation of vesicles in both SDS-rich and trans-BTHA-rich regions of the microstructure diagram, with vesicles present over a particularly broad range of compositions for trans-BTHA-rich solutions. Illumination of mixtures of BTHA and SDS with a broadband UV light source leads to formation of photostationary states where the fraction of BTHA present as cis isomer (75-80% cis-BTHA) is largely independent of the mixing ratio of SDS and BTHA. For a relatively limited set of mixing ratios of SDS and BTHA, we observed UV illumination of SDS-rich vesicles to result in the reversible transformation of the vesicles to micellar aggregates and UV illumination of BTHA-rich vesicles to result in irreversible precipitation. Surprisingly, however, for many mixtures of trans-BTHA and SDS that formed solutions containing vesicles, illumination with UV light (which was confirmed to lead to photoisomerization of BTHA) resulted in only a small decrease in the number of vesicles in solution, relatively little change in the sizes of the remaining vesicles, and coexistance of the vesicles with micelles. These observations are consistent with a physical model in which the trans and cis isomers of BTHA present at the photostationary state tend to segregate between the different microstructures coexisting in solution (e.g., vesicles rich in trans-BTHA and SDS coexist with micelles rich in cis-BTHA and SDS). The results presented in this paper provide guidance for the design of light-tunable surfactants systems.

Pyridyne radical cations produced by photodissociation of Mg*+ (multifluoro-pyridine) complexes: a combined experimental and theoretical study.

Gas phase complexes Mg*+ (2,6-difluoropyridine) (1) and Mg*+ (pentafluoropyridine) (2) have been subjected to photodissociation in the spectral range of approximately 230-440 nm. Except for the evaporative photofragment Mg*+ , the primary photoproduct for is C(5)H(3)N*(+), which is associated with the rupture of two C-F bonds by the photoexcited Mg*+ , forming very stable MgF(2). In contrast, the direct loss of MgF(+) is more favorable for due to fluorine substitution. Given enough energy, C(5)H(3)N*(+) can undergo decomposition to form C(4)H(2)*(+) and HCN. These results are very different from those for Mg*+ (2-fluoropyridine), highlighting the significance of the additional F at C6 of and . Density functional theory (DFT) calculations have been employed to examine the geometries and energetics of the complexes as well as relevant reaction mechanisms. All of the complexes feature the direct attachment of Mg*+ to the N atom. The key intermediate is found to be FMg(+) (C(5)H(x)F(4-x)N) (x = 3 or 0), which can lead to the formation of MgF(+) directly or MgF(2) through activation of another C-F bond adjacent to N, producing the pyridyne radical cations. However, hydrogen-transfer prior to the rupture of the second C-F bond followed by ring-opening of C(5)H(3)N*(+) may result in the formation of chain forms of C(5)H(3)N*(+). The influence of the fluorine substitution on the competition of the two routes have been demonstrated.

EPR studies of amine radical cations. Part 2. Thermal and photo-induced rearrangements of propargylamine and allylamine radical cations in low-temperature freon matrices.

Matrix EPR studies and quantum chemical calculations have been used to characterize the consecutive H-atom shifts undergone by the nitrogen-centered parent radical cations of propargylamine (1b*+) and allylamine (5*+) on thermal or photoinduced activation. The radical cation rearrangements of these unsaturated parent amines occur initially by a 1,2 H-atom shift from C1 to C2 with pi-bond formation at the positively charged nitrogen; this is followed by a consecutive reaction involving a second H-atom shift from C2 to C3. Thus, exposure to red light (lambda > 650 nm) converts 1b*+ to the vinyl-type distonic radical cation 2*+ which in turn is transformed on further photolysis with blue-green light (lambda approximately 400-600 nm) to the allene-type heteroallylic radical cation 3*+. Calculations show that the energy ordering is 1b*+ > 2*+ > 3*+, so that the consecutive H-atom shifts are driven by the formation of more stable isomers. Similarly, the parent radical cation of allylamine 5*+ undergoes a spontaneous 1,2-hydrogen atom shift from C1 to C2 at 77 K with a t1/2 of approximately 1 h to yield the distonic alkyl-type iminopropyl radical cation 6*+; this thermal reaction is attributed largely to quantum tunneling, and the rate is enhanced on concomitant photobleaching with visible light. Subsequent exposure to UV light (lambda approximately 350-400 nm) converts 6*+ by a 2,3 H-shift to the 1-aminopropene radical cation 7*+, which is confirmed to be the lowest-energy isomer derived from the ionization of either allylamine or cyclopropylamine. Although the parent radical cations of N, N-dimethylallylamine (9*+) and N-methylallylamine (11*+) are both stabilized by the electron-donating character of the methyl group(s), the photobleaching of 9*+ leads to the remarkable formation of the cyclic 1-methylpyrrolidine radical cation 10*+. The first step of this transformation now involves the migration of a hydrogen atom to C2 of the allyl group from one of the methyl groups (rather than from C1); the reaction is then completed by the cyclization of the generated MeN + (=CH2) CH2CH2CH2* distonic radical cation, possibly in a concerted overall process. In contrast to the ubiquitous H-atom transfer from carbon to nitrogen that occurs in the parent radical cations of saturated amines, the alternate rearrangements of either 1b*+ or 5*+ to an ammonium-type radical cation by a hypothetical H-atom shift from C1 to the ionized NH2 group are not observed. This is in line with calculations showing that the thermal barrier for this transformation is much higher (approximately 120 kJ mol-1) than those for the conversion of 1b*+ --> 2*+ and 5*+--> 6*+ (approximately 40-60 kJ mol-1).