Sugar Radicals Research Articles

Influence of Lead (Pb) Stress on the Physiological Growth of Dishlia

This experiment mainly focuses on the influence of lead stress on the growth of dishlia. The result shows that under lead stress,the content of soluble sugar falls then rises as time goes by,while the content of saccharose rises then fall; the content change of starch and superoxide radical in experiment groups is similar to that in the control group but with lower content. Experiment results show that dishlia is tolerant of lead stress and increases such tolerance via soluble sugar,starch,saccharose and superoxide radical

Synthesis of C3′ Modified Nucleosides for Selective Generation of the C3′-Deoxy-3′-thymidinyl Radical: A Proposed Intermediate in LEE Induced DNA Damage

DNA damage pathways induced by low-energy electrons (LEEs) are believed to involve the formation of 2-deoxyribose radicals. These radicals, formed at the C3' and C5' positions of nucleotides, are the result of cleavage of the C-O phosphodiester bond through transfer of LEEs to the phosphate group of DNA oligomers from the nucleobases. A considerable amount of information has been obtained to illuminate the identity of the unmodified oligonucleotide products formed through this process. There exists, however, a paucity of information as to the nature of the modified lesions formed from degradation of these sugar radicals. To determine the identity of the damage products formed via the 2',3'-dideoxy-C3'-thymidinyl radical (C3'(dephos) sugar radical), phenyl selenide and acyl modified sugar and nucleoside derivatives have been synthesized, and their suitability as photochemical precursors of the radical of interest has been evaluated. Upon photochemical activation of C3'-derivatized nucleosides in the presence of the hydrogen atom donor tributyltin hydride, 2',3'-dideoxythymidine is formed indicating the selective generation of the C3'(dephos) sugar radical. These precursors will make the identification and quantification of products of DNA damage derived from radicals generated by LEEs possible.

Electron Spin Resonance Analyses of Grinding- and Radiation-Induced Signals in Raw and Refined Sugars

Irradiated food containing crystalline sugar may be identified using the electron spin resonance spectroscopy (ESR) in accordance with the European standard EN 13708 2001. The method is based upon the detection of sugar radicals induced by irradiation giving a typical dose-dependent spectrum. Grinding, a common industrial process, can also produce ESR signals. In this study, the grinding-induced ESR signals were investigated for their dependence on sugar purity, grinding time, particle size, and grinding method. The results were compared with radiation-induced ESR signals. The mechanical grinding, depending mainly on grinding time, provided clear signals comparable to radiation-induced signals. The specific ESR signal corresponding to sugar radical appeared at 1 min of mechanical grinding which became clearer with the increase in grinding time and sample purity. All sugar samples upon 6 min of mechanical grinding showed comparable results to ≥10 Gy-irradiated samples. Similar results with negligible differences were found using samples of different origins. The results elaborated the detection limits of sugar containing irradiated food based on ESR analysis.

Structural behavior of sugar radicals formed by proton transfer reaction of deoxycytidine cation radical: detailed view from NBO analysis

The cation radicals of DNA constituents generated by the ionizing radiation initiate the alteration of the bases, which is one main type of cytotoxic DNA lesions. These cation radical spices are known for their role in producing nucleic acid strand break, and it is important to identify the cation radical formation at particular atomic site in these molecules so that the major pathway for the nucleic acid damage may be trapped. In the present study, we explored theoretically energetic, structural, and electronic properties of the possible radicals formed via proton atom abstraction at various sites of sugar part of deoxycytidine cation radical by employing density functional theory at B3LYP/6-311++G (d,p) level. The computation revealed 0.0–22.6 kcal/mol energy disparity in these radicals. Radical-centered carbon increases the extent of bonding with its adjacent atoms. This tendency should be important in predicting the reactivity of sugar-based radicals. Based on DFT calculations, sugar radicals of deoxycytidine have following stability order: raH1′ > raH2′ > raH4′ > raH3′ > raH5′ > raO5′H > raO3′H. Furthermore, influence of cation radical formation on acidities of multiple sites in deoxycytidine nucleosides was investigated. For instance upon cation radical formation, ΔHacidity of O3′H and O5′H sites of deoxycytidine varies from 348.6 and 351.5 to 228.8 and 227.5 kcal/mol, respectively.

Structures, stabilities & conformational behaviors of hydrogen-atom abstractions of cytosine nucleosides: AIM & NBO analysis

Abstraction of hydrogen atom from DNA and RNA subunits leads to formation of a neutral radical. The formation of these radicals can lead to harmful structural alternations and formation of multiple lesions in helixes of DNA and RNA. In the present work, we explore theoretically energetic and structural properties of the possible radicals formed via hydrogen atom abstraction at various sites of sugar part of cytosine nucleosides by employing B3LYP exchange–correlation functional with 6-311++G (d,p) orbital basis sets. Two types of free radicals may be found by hydrogen abstraction of sugar part of cytosine nucleosides: carbon centered radicals and the oxygen centered radicals. The computation revealed 0–22.6 kcal/mol energy disparity in these radical. Radical-centered carbon increases the extent of bonding with its adjacent atoms. This tendency should be important in predicting the reactivity of sugar-based radicals. The hydrogen abstracted sugar radicals of cytosine nucleosides have following stability sequence: raC2 ′ > raC1 ′ > raC3 ′ > raC4 ′ > raC5 ′ > raO5 ′ > raO2 ′ > raO3 ′ for cytidine and radC1 ′ > radC2 ′ > radC4 ′ > radC3 ′ > radC5 ′ > radO5 ′ > radO3 ′ for deoxycytidine. Furthermore, to take into account the effect of solvent environment on the stability order of radicals integral equation formalism of the polarized continuum model (IEF-PCM) was employed to model aqueous solution. The role of CH⋯O and HO⋯H intramolecular hydrogen bonds in stability of radicals investigated based on results of topological properties of AIM theory. Moreover, variations of significant structural parameters such as puckering amplitudes and phase angles of sugar parts of cytosine nucleosides after radical formation are also found. These finding have several biological implications and may explain the possible degrees of damage to the DNA double strand.

Highly oxidizing excited states of one-electron-oxidized guanine in DNA: wavelength and pH dependence.

Excited states of one-electron-oxidized guanine in DNA are known to induce hole transfer to the sugar moiety and on deprotonation result in neutral sugar radicals that are precursors of DNA strand breaks. This work carried out in a homogeneous aqueous glass (7.5 M LiCl) at low temperatures (77-175 K) shows the extent of photoconversion of one-electron-oxidized guanine and the associated yields of individual sugar radicals are crucially controlled by the photon energy, protonation state, and strandedness of the oligomer. In addition to sugar radical formation, highly oxidizing excited states of one-electron-oxidized guanine are produced with 405 nm light at pH 5 and below that are able to oxidize chloride ion in the surrounding solution to form Cl(2)(•-) via an excited-state hole transfer process. Among the various DNA model systems studied in this work, the maximum amount of Cl(2)(•-) is produced with ds (double-stranded) DNA, where the one-electron-oxidized guanine exists in its cation radical form (G(•+):C). Thus, via excited-state hole transfer, the dsDNA is apparently able to protect itself from cation radical excited states by transfer of damage to the surrounding environment.

EPR study on non- and gamma-irradiated herbal pills

The results of EPR studies on herbal pills of marigold, hawthorn, yarrow, common balm, tutsan, nettle and thyme before and after gamma-irradiation are reported. Before irradiation all samples exhibit one weak singlet EPR line with a g-factor of 2.0048±0.0005. After irradiation herbal pills could be separated in two groups according to their EPR spectra. Radiation-induced free radicals in pills of marigold, yarrow, nettle, tutsan and thyme could be attributed mainly to saccharide excipients. Tablets of hawthorn and common balm show “cellulose-like” EPR spectrum, superimposed on partly resolved carbohydrate spectrum, due to the active part (herb) and inulin, which is present in the pills as an excipient. Fading study of the radiation-induced EPR signals confirms that sugar radicals are more stable than cellulose species. The reported results show that the presence of characteristic EPR spectra of herbal pills due to excipients or active part can be used as unambiguous proof of radiation processing within 35 or more days after irradiation.

Factors Affecting the Yields of C1′ and C5′ Oxidation Products in Radiation-Damaged DNA: The Indirect Effect

This study reports the effects of denaturation and deoxygenation on radiation-induced formation of 2-deoxyribonolactone (2-dL) and 5'-aldehyde (5'-Ald) lesions in highly polymerized DNA. The radiation-chemical yields of 2-dL were determined through quantification of its dephosphorylation product 5-methylenefuranone (5MF). The formation of 5'-Ald was monitored qualitatively through the release of furfural (Fur) under the same conditions. The yields of 2-dL were found to be 7.3 ± 0.3 nmol J(-1), or about 18% of the yield of free base release measured in the same samples. Denaturation increased the efficiency of 2-dL formation approximately twofold while deoxygenation resulted in a fourfold decrease. The release of Fur is about twofold lower than that of 5MF in aerated native DNA samples and is further reduced by denaturation of the DNA. Unlike 5MF, the formation of Fur requires the presence of molecular oxygen, which is consistent with peroxyl radical-mediated oxidation of C5' radicals into 5'-Ald. In contrast, the existence of an oxygen-independent pathway of 2-dL formation suggests that C1' sugar radicals can also be oxidized by radiation-produced oxidizing intermediates such as electron-loss centers on guanines.

Formation of Aminyl Radicals on Electron Attachment to AZT: Abstraction from the Sugar Phosphate Backbone versus One-Electron Oxidation of Guanine

Employing electron spin resonance (ESR) spectroscopy, we have characterized the radicals formed in 3'-azido-3'-deoxythymidine (3'-AZT) and in its 5'-analog 5'-azido-5'-deoxythymidine (5'-AZT) after electron attachment in gamma-irradiated aqueous (H(2)O or D(2)O) glassy (7.5 M LiCl) systems. ESR spectral studies and theoretical calculations show that the predominant site of electron capture in 3'-AZT and in 5'-AZT is at the azide group and not at the thymine moiety. The azide group in AZT is therefore more electron affinic than the most electron affinic DNA base, thymine. Electron attachment to 3'-AZT and 5'-AZT results in an unstable azide anion radical intermediate (RN(3)*(-)) that is too short-lived to be observed in our work even at 77 K. At 77 K, we observe the neutral aminyl radical (RNH*) after loss of N(2) from RN(3)*(-) followed by protonation of nitrene anion radical (RN*(-)) to give RNH*. The expected RN*(-) intermediate is not observed as protonation from water is complete at 77 K even under highly basic conditions. Formation of RND* in D(2)O solutions confirms water as the source of the NH proton in the RNH*. Our assignments to these radicals are aided by DFT calculations for hyperfine coupling constants that closely match the experimental values. On annealing to higher temperatures (ca. 160-170 K), RNH* undergoes bimolecular hydrogen abstraction reactions from the thymine methyl group and the sugar moiety resulting in the formation of the thymine allyl radical (UCH(2)*) and two sugar radicals, C3'* and C5'*. RNH* also results in one-electron oxidation of the guanine base in 3'-AZG. This work provides a potential mechanism for the reported radiosensitization effects of AZT.

On the dissociation of DNA enhanced by radical cations

This concerns the heat of reaction, Δ H react ∘ = Δ H f ∘ ( K · ) + Δ H f ∘ ( L · ) - Δ H f ∘ ( KL ) , accompanying the cleavage of deoxyribonucleosides (KL) to give sugar radicals (K·) and (adenine or guanine) base radicals ( L · ) under the influence of radical cations R + = H + , CH 3 + and C 2 H 5 + . (The cited Δ H f ∘ ’s are the appropriate standard enthalpies of formation at 298.15 K.) Addition of R + onto one or another nitrogen of the bases does indeed perturb the zero-point + heat-content energies Z, namely, Z ( KL ) → Z ( KL ′ ) ,Z ( L · ) → Z ( L · ′ ) , as well as the “reorganizational energies” Re, i.e., Re ( L · ) → Re ( L · ′ ) . (Re describes how a free radical differs from its hypothetical electroneutral counterpart found in a symmetrical molecule L–L.) Finally, the “Charge Neutralization Energy” CNE describes the energetics accompanying charge transfers between the fragments K and L in the original molecule, linked to one another by the bond with energy ε kl ( k ∈ K, l ∈ L ) . It turns out that CNE and Z have little (or no) saying in the decomposition KL → K · + L · . The driving force is clearly in the weakening of ε kl under the influence of added R + cations. The gas-phase Re energies, whose evaluation is reported in detail, would magnify this effect but are unlikely to be of any relevance in in vivo depurinations of DNA molecules.

Supramolecular Photochemistry in β-Cyclodextrin Hosts: A TREPR, NMR, and CIDNP Investigation

A systematic investigation of the photochemistry and ensuing radical chemistry of three guest ketones encapsulated in randomly methylated beta-cyclodextrin (beta-CD) hosts is reported. Dibenzyl ketone (DBK), deoxybenzoin (DOB), and benzophenone (BP) triplet states are rapidly formed after photolysis at 308 nm. Time-resolved electron paramagnetic resonance (TREPR) spectroscopy, steady-state NMR spectroscopy, and time-resolved chemically induced nuclear polarization (TR-CIDNP) experiments were performed on the ketone/CD complexes and on the ketones in free solution for comparison. The major reactivity pathways available from these excited states are either Norrish I alpha-cleavage or H-atom abstraction from the interior of the CD capsule or the solvent. The DOB triplet state undergoes both reactions, whereas the DBK triplet shows exclusively alpha-cleavage and the BP triplet shows exclusively H-atom abstraction. Radical pairs are observed in beta-CDs by TREPR, consisting of either DOB or BP ketyl radicals with sugar radicals from the CD interior. The TREPR spectra acquired in CDs are substantially broadened due to strong spin exchange. The electron spin polarization mechanism is mostly due to S-T(0) radical pair mechanism (RPM) in solution but changes to S-T(-) RPM in the CDs due to the large exchange interaction. The TR-CIDNP results confirm the reactivity patterns of all three ketones, and DOB shows strong nuclear spin polarization from a novel rearrangement product resulting from the alpha-cleavage reaction.

Prototropic equilibria in DNA containing one-electron oxidized GC: intra-duplex vs. duplex to solvent deprotonation.

By use of ESR and UV-vis spectral studies, this work identifies the protonation states of one-electron oxidized G:C (viz. G˙+:C, G(N1–H)˙:C(+H+), G(N1–H)˙:C, and G(N2-H)˙:C) in a DNA oligomer d[TGCGCGCA]2. Benchmark ESR and UV-vis spectra from one electron oxidized 1-Me-dGuo are employed to analyze the spectral data obtained in one-electron oxidized d[TGCGCGCA]2 at various pHs. At pH ≥7, the initial site of deprotonation of one-electron oxidized d[TGCGCGCA]2 to the surrounding solvent is found to be at N1 forming G(N1–H)˙:C at 155 K. However, upon annealing to 175 K, the site of deprotonation to the solvent shifts to an equilibrium mixture of G(N1–H)˙:C and G(N2–H)˙:C. For the first time, the presence of G(N2–H)˙:C in a ds DNA-oligomer is shown to be easily distinguished from the other prototropic forms, owing to its readily observable nitrogen hyperfine coupling (Azz(N2) = 16 G). In addition, for the oligomer in H2O, an additional 8 G N2–H proton HFCC is found. This ESR identification is supported by a UV-vis absorption at 630 nm which is characteristic for G(N2–H)˙ in model compounds and oligomers. We find that the extent of photo-conversion to the C1′ sugar radical (C1′˙) in the one-electron oxidized d[TGCGCGCA]2 allows for a clear distinction among the various G:C protonation states which can not be easily distinguished by ESR or UV-vis spectroscopies with this order for the extent of photo-conversion: G˙+:C > G(N1–H)˙:C(+H+) ≫ G(N1–H)˙:C. We propose that it is the G˙+:C form that undergoes deprotonation at the sugar and this requires reprotonation of G within the lifetime of exited state

Sugar radical formation by a proton coupled hole transfer in 2'-deoxyguanosine radical cation (2'-dG*+): a theoretical treatment.

Previous experimental and theoretical work has established that electronic excitation of a guanine cation radical in nucleosides or in DNA itself leads to sugar radical formation by deprotonation from the dexoxyribose sugar. In this work, we investigate a ground electronic state pathway for such sugar radical formation in a hydrated one electron oxidized 2'-deoxyguanosine (dG(*+) + 7H(2)O), using density functional theory (DFT) with the B3LYP functional and the 6-31G* basis set. We follow the stretching of the C(5')-H bond in dG(*+) to gain an understanding of the energy requirements to transfer the hole from the base to sugar ring and then to deprotonate to proton acceptor sites in solution and on the guanine ring. The geometries of reactant (dG(*+) + 7H(2)O), transition state (TS) for deprotonation of the C(5') site, and product (dG((*)C(5'), N(7)-H(+)) + 7H(2)O) were fully optimized. The zero point energy (ZPE) corrected activation energy (TS) for the proton transfer (PT) from C(5') is calculated to be 9.0 kcal/mol and is achieved by stretching the C(5')-H bond by 0.13 A from its equilibrium bond distance (1.099 A). Remarkably, this small bond stretch is sufficient to transfer the "hole" (positive charge and spin) from guanine to the C(5') site on the deoxyribose group. Beyond the TS, the proton (H(+)) spontaneously adds to water to form a hydronium ion (H(3)O(+)) as an intermediate. The proton subsequently transfers to the N(7) site of the guanine (product). The 9 kcal/mol barrier suggests slow thermal conversion of the cation radical to the sugar radical but also suggests that localized vibrational excitations would be sufficient to induce rapid sugar radical formation in DNA base cation radicals.

Ionization potential and structure relaxation of adenine, thymine, guanine and cytosine bases and their base pairs: A quantification of reactive sites

We present density functional theory (DFT) calculations using B3LYP/6-31++G∗∗ method to show relaxation in geometry of base pairs on cation radical formation. The changes in hydrogen bond length and angles show that in the cationic radical form the structure of the base pairs relaxes due to the distribution of charge. According to a recent study, it has been found that, upon excitation hole transfer from base to sugar occurs which results in sugar radical formation and leads to strand breakage [45] [A. Kumar, M.D. Sevilla, J. Phys. Chem. B 110 (2006) 24181]. One hydrogen bond increases, while the other decreases in Adenine–Thymine (AT) base pair and in case of Guanine–Cytosine (GC) base pair, one bond increases and other two decrease. Same is the case with bond angles for both the base pairs. Analysis of the electron density map of Singly Occupied Molecular Orbital (SOMO) reveals that electron is transferred mainly from adenine and guanine bases in the cationic radical formation of AT and GC base pair, respectively. The reactive sites of bases have been analyzed using condensed Fukui functions in a relaxed and frozen core approximation. The effects of relaxation on the reactivity indices are also analyzed.

Redox Dependence of the Reaction of α-Alkoxyalkyl Radicals with a Series of Oxidants

Oxygen and oxidants enhance the sensitivity of cells to radiation. To understand this effect at the mechanistic level, the redox dependences for the reactivity of weakly reducing alpha-monoalkoxyalkyl radicals of 1,4-dioxane and tetrahydrofuran with a series of oxidants, for example, quinones, viologens, and nitro-arenes, with one-electron reduction potentials E71 values ranging from -80 to -640 mV, have been determined using the technique of pulse radiolysis. The second-order rate constants for these reactions with the alpha-monoalkoxyalkyl radicals of 1,4-dioxane and tetrahydrofuran are in the range (0.03-1.5) x 109 and (1.0-6.6) x 109 dm3 mol(-1) s(-1), respectively. The reactions of the alpha-alkoxyalkyl radicals of 1,4-dioxane with quinones and viologens involve an outer-sphere electron transfer, in contrast to a reaction with the nitro-arenes to give adducts. The resulting long-lived nitroaromatic adduct radicals were found to react with the reductant, TMPD, probably leading to the formation of hydroxylamine-type products. In cells, adducts formed on reaction of deoxyribose sugar radical with oxidants and subsequent reactions with reductants may contribute to the mechanisms involved in radiosensitization by oxygen and those oxidants that interact through adduct formation.

Diastereoselective addition of sugar radicals to camphorsultam glyoxilic oxime ether: a route toward C-glycosylthreonine and allothreonine

C-glucosyl, mannosyl and galactosyl 2-iodopropane, readily obtained from the corresponding C-glycosyl ketones, were coupled with (+)- or (-)-camphorsultam glyoxylic oxime ether with diastereoselectivity ranging from 70:30 to 80:20. C-glucosyl allothreonine was obtained by cleavage of the camphorsultam moiety.

Photoexcitation of Adenine Cation Radical [A•+] in the near UV−vis Region Produces Sugar Radicals in Adenosine and in Its Nucleotides

In this study, we report the formation of ribose sugar radicals in high yields (85-100%) via photoexcitation of adenine cation radical (A*+) in Ado and its ribonucleotides. Photoexcitation of A*+ at low temperatures in homogeneous aqueous glassy samples of Ado, 2'-AMP, 3'-AMP, and 5'-AMP forms sugar radicals predominantly at C5'- and also at C3'-sites. The C5'* and C3'* sugar radicals were identified employing Ado deuterated at specific carbon sites: C1', C2', and C5'. Phosphate substitution is found to deactivate sugar radical formation at the site of substitution. Thus, in 5'-AMP, C3'* is observed to be the main radical formed via photoexcitation at ca. 143 K, whereas, in 3'-AMP, C5'* is the only species found. These results were supported by results obtained employing 5'-AMP with specific deuteration at the C5'-site (i.e., 5',5'-D,D-5'-AMP). Moreover, contrary to the C5'* observed in 3'-dAMP, we find that C5'* in 3'-AMP shows a clear pH-dependent conformational change as evidenced by a large increase in the C4' beta-hyperfine coupling on increasing the pH from 6 to 9. Calculations performed employing DFT (B3LYP/6-31G*) for C5'* in 3'-AMP show that the two conformations of C5'* result from strong hydrogen bond formation between the O5'-H and the 3'-phosphate dianion at higher pHs. Employing time-dependent density functional theory [TD-DFT, B3LYP/6-31G(d)], we show that, in the excited state, the hole transfers to the sugar moiety and has significant hole localization at the C5'-site in a number of allowed transitions. This hole localization is proposed to lead to the formation of the neutral C5'-radical (C5'*) via deprotonation.

Radiation-Induced Radicals in Glucose-1-phosphate. II. DFT Analysis of Structures and Possible Formation Mechanisms

Four radiation-induced carbon-centered radicals in dipotassium glucose-1-phosphate dihydrate single crystals are examined with DFT methods, consistently relying on a periodic computational scheme. Starting from a set of plausible radical models, EPR hyperfine coupling tensors are calculated for optimized structures and compared with data obtained from EPR/ENDOR measurements, which are described in part I of this work. In this way, an independent structural identification is made of all the radicals that were observed in the experiments (R1-R4) and tentative reaction schemes are proposed. Also, the first strong evidence for conformational freedom in sugar radicals is established: two species are found to have the same chemical composition but different conformations and consequently different hyperfine coupling tensors. Analysis of the calculated energies for all model compounds suggests that the radiation chemistry of sugars, in general, is kinetically and not necessarily thermodynamically controlled.

Radiation-Induced Radicals in Glucose-1-phosphate. I. Electron Paramagnetic Resonance and Electron Nuclear Double Resonance Analysis of in situ X-Irradiated Single Crystals at 77 K

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.

Formation of Sugar Radicals in RNA Model Systems and Oligomers via Excitation of Guanine Cation Radical

In previous work, we have shown that photoexcitation of guanine cation radical (G*+) in frozen aqueous solutions of DNA and its model compounds at 143 K results in the formation of neutral sugar radicals with substantial yield. In this report, we present electron spin resonance (ESR) and theoretical (DFT) evidence regarding the formation of sugar radicals after photoexcitation of guanine cation radical (G*+) in frozen aqueous solutions of one-electron-oxidized RNA model compounds (nucleosides, nucleotides and oligomers) at 143 K. Specific sugar radicals C5'*, C3'* and C1'* were identified employing derivatives of Guo deuterated at specific sites in the sugar moiety, namely, C1'-, C2'-, C3'- and C5'-. These results suggest C2'* is not formed upon photoexcitation of G*+ in one-electron-oxidized Guo and deuterated Guo derivatives. Phosphate substitution at C5'- (i.e., in 5-GMP) hinders formation of C5'* via photoexcitation at 143 K but not at 77 K. For the RNA-oligomers studied, we observe on photoexcitation of oligomer-G*+ the formation of mainly C1'* and an unidentified radical with a ca. 28 G doublet. The hyperfine coupling constants of each of the possible sugar radicals were calculated employing the DFT B3LYP/6-31G* approach for comparison to experiment. This work shows that formation of specific neutral sugar radicals occurs via photoexcitation of guanine cation radical (G*+) in RNA systems but not by photoexcitation of its N1 deprotonated species (G(-H)*). Thus, our mechanism regarding neutral sugar formation via photoexcitation of base cation radicals in DNA appears to be valid for RNA systems as well.