Free radical induced degradation and computational studies of hydroxychloroquine in aqueous solution.

Hydroxychloroquine (HCQ) is a potential drug molecule for treating malaria. Recently it has also been tried as adjustment in Covid 19 therapy. Interaction of HCQ with free radicals is very important, which controls its stability in the environment where free radicals are generated unintentionally. In this report, we present detailed investigation on the reactions of hydrated electrons (eaq -) and hydroxyl radical (•OH) with HCQ in aqueous solution through electron pulse radiolysis technique and computational studies. The degradation of HCQ was found to be faster in the case of reaction with •OH radicals. However, the degradation could be substantially slowed down in the presence of antioxidants like ascorbic acid and gallic acid. This revealed that the stability of HCQ could be enhanced in an oxidative environment in the presence of these two compounds, which are easily available through food supplements. Various global and local reactivity parameters are also determined to understand the reactivity trend using Hard-Soft Acid-Base (HSAB) principle in the realm of the DFT methods. Computational studies were performed to elucidate the site-specific reactivity trend towards the electrophilic and nucleophilic attack by calculating the condensed Fukui index for various species of HCQ.

Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion.

A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented herein. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf2) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N2O. In the DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X- + h+ → X•), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA)2•- and its reduction potential ( E(DCA)2•-/(2DCA-)) have been determined.

Size Selective Green Synthesis of Silver and Gold Nanoparticles: Enhanced Antibacterial Efficacy of Resveratrol Capped Silver Sol.

In view of potential biomedical application of the noble metal nanoparticles, we report a size controlled yet simple and green synthesis of resveratrol stabilized silver and gold nanoparticles having low polydispersity of size. Here, resveratrol plays two simultaneous roles, reducing the metal ions and providing efficient capping of the small nanoparticles. This gives rise to specific size of silver and gold nanoparticles at specific ratios of metal to resveratrol. The particles have been characterized by XRD and transmission electron microscopy. The nanoparticle sols are stable for months. The UV Visible absorption spectra of the silver sol show the plasmon peak of spherical nanoparticles, presence of which is further reflected in the TEM images. Size of the silver particles obtained is in between 11 to 21 nm depending on the ratio of resveratrol to metal ion used. Resveratrol capped silver nanoparticles exhibit high antibacterial activity against Gram negative wild type E coli BW (25113). The minimum inhibitory concentration (MIC) of nano-silver against the bacterium has been estimated to be 6.48 µg/ml, which is significantly lower than that reported in some earlier as well as recent publications. Reaction of gold ions with resveratrol, on the other hand, produces gold nanoparticles of sizes varying from 7 to 29 nm at different ratios of resveratrol to the metal ions. Particles with higher size and aspect ratio are formed at lower concentration of the capping agent whereas particles with very small size and pseudo-spherical morphology are formed at higher capping concentration. Difference in the formation kinetics of silver and gold nanoparticles has been attributed to the different growth mechanisms in the two cases. Possible modes of anchorage of resveratrol to silver nanoparticles have been investigated using surface enhanced resonance Raman spectroscopy (SERS) which shows that the silver nanoparticles are capped by resveratrol molecule primarily through O-Ag linkages of the p-OH aromatic ring. This, in turn, demonstrates the feasibility of using these nanoparticles as SERS templates.

Optical properties of irradiated imidazolium based room temperature ionic liquids: new microscopic insights into the radiation induced mutations.

Considering the future perspectives of room temperature ionic liquids (RTILs) in areas involving high radiation fields (such as the nuclear fuel cycle and space applications), it is essential to probe and have a microscopic understanding of the radiation induced perturbations in the molecular structures and the intrinsic bonding interactions existing in the ILs. Herein, a focused investigation concerning the photophysical behavior of post-irradiated FAP (fluoroalkyl phosphate) imidazolium ILs revealed considerable rearrangements and bonding realignments of the ionic moieties in the ILs on irradiation, however, their physicochemical properties do not change significantly even at high absorbed doses. Most interestingly, the well-established excitation wavelength dependent fluorescence (FL) behavior of the ILs was considerably perturbed on irradiation and this is attributed to the radiation induced decoupling of pre-existing different associated structures of ions, and the subsequent formation of oligomers and other species containing multiple bond order groups. This was further substantiated by vibrational studies, where peaks appearing in the range 1600-1800 cm(-1) indicated the formation of double bonded products. Furthermore, for the hydroxyl functionalized (in the alkyl side chain of the imidazolium cation) IL, a blue shift in the O-H stretching frequency was observed for the -OH group H-bonded to the FAP anion (νOH···[FAP](-)), while a red shift was observed for the H-bonded -OH groups in the cationic clusters. The FL lifetime values were found to increase with irradiation, which clearly indicates the enhancement in the rigidity level in the vicinity of the ions, thereby hindering the non-radiative decay processes. Such studies could contribute to the fundamental understanding of the radiation driven perturbations in the structure-property relationships, which eventually affect the radiolytic degradation pathways and the product distribution in RTILs.

Rapid and One-Pot Synthesis of Self-Assembled CdSe Quantum Dots Functionalized with ß-Cyclodextrin: Reduced Cytotoxicity and Band Gap Engineering.

We report a simple, rapid and one step method for the synthesis and in situ functionalization of CdSe quantum dots (QDs) with ß-cyclodextrin (ß-CD) in aqueous solution via electron beam (EB) irradiation technique. A probable mechanism has been elucidated for the formation of the QDs using pulse radiolysis technique. The average size of the QDs was found to be in the range of 2-3 nm with a size distribution of -14%. XPS measurements indicate that the -OH groups of the ß-CD molecules binds predominantly with the Cd atoms present on the surface of the QDs. These QDs displayed broad photoluminescence (PL) with two emission peaks at 525 nm and 600 nm, which could be tuned by varying the experimental parameters. The broad PL spectrum has been attributed to the polydispersity in the density and the distribution of trap/defects states. Time resolved PL decay measurements further substantiated the domination of surface state originated carrier relaxation processes in the overall PL decay dynamics of QDs synthesized at higher doses and dose rates. The present study reveals that ß-CD passivate the QDs by a non-inclusion complex, induces the self-assembling process into a networking architecture and simultaneously reduces their cytotoxicity as compared to the bare nanoparticles. The methodology described in this article may provide unique and interesting aspects to regulate and fine tune the formation of superstructures of nanomaterials vis-à-vis their optoelectronic properties.

Highly stable spherical shaped and blue photoluminescent cyclodextrin-coated tellurium nanocomposites prepared by in situ generated solvated electrons: a rapid green method and mechanistic and anticancer studies.

Highly stable blue photoluminescent tellurium nanocomposites (Te NCs) coated with a molecular assembly of α-cyclodextrin (α-CD) have been prepared by using in situ generated solvated electrons (esol-) in the reaction media. The methodology used is rapid and green as the preparation of colloids was over in a matter of a few seconds and no hazardous agents (reducing or stabilizing) were used. Furthermore, fine control over the size of Te NCs has been demonstrated by simply varying the absorbed irradiation dose. As a matter of fact, the anisotropic property exhibited by tellurium makes it difficult to control the phase and morphology of its nanomaterials. However, unlike the majority of the previous reports, Te NCs formed by the current approach were amorphous and spherical shaped. Another interesting aspect of this work is the cyan-blue photoluminescence (PL) exhibited by the NCs. Systematic photophysical investigations indicated bandgap radiative decay as the origin of photoluminescence. A compositional analysis indicated the presence of Te(0) along with tellurium oxides (TeOx). TGA studies revealed the formation of a dense coating (∼55%) of α-CD molecules on the NCs. Pulse radiolysis-based studies evidenced the formation of Te-based transients by the solvated electron-induced reaction. Importantly, no interference of α-CD was observed in the kinetics of the transient species. Remarkable concentration-dependent killing was observed only in the case of cancerous cells, while no such trend was seen in normal healthy cells. This is a significant observation that can be utilized to achieve differential toxicity of Te nanomaterials in tumor versus normal cells.

Direct Observation of Solvated Electrons in Deep Eutectic Solvents: Efficient Capture of Presolvated Electrons by DNA Base.

The solvated electron being the simplest form of an extremely reactive intermediate is of great fundamental interest in chemistry, physics, and biology since its discovery. Recently, deep eutectic solvents (DESs) have been in focus as biodegradable and cost-effective alternative to ionic liquids (ILs) for different applications. These include areas where electron transport and transfer processes are involved. Herein, we present the first report on the existence, yield, and properties of solvated electrons in three deep eutectic solvents, reline, ethaline, and glyceline, composed of choline chloride as a hydrogen bond acceptor and urea, ethylene glycol, and glycerol (Gly) as hydrogen bond donors, respectively, at a molar ratio of 1:2. The varied transient absorption spectra of solvated electrons in these DESs have been explained on the basis of polarity, hydrogen-bonding effect, and the moieties responsible for creating the environment for solvation. The yield and average lifetime follow the trends in viscosity as well as the reactivity of electrons with the components. The C37 value, a measure of the efficiency of scavenging presolvated electrons, is the highest in ethaline in the case of nitrate ions, which indicates the slowest solvation process in this DES. The presolvated electron capture by a DNA base, an aspect considered to be important in cancer radiotherapy, could be monitored conveniently in these liquids at a much longer time scale compared to that reported in aqueous solutions. Bimolecular rate constants for the reaction of solvated electrons with nitrate and the DNA base have been calculated and compared in the three DESs. Unlike in ILs, these experimentally obtained values are comparable to the diffusion-controlled rate constants in DESs.

Controlling the phase and morphology of amorphous Se nanoparticles: their prolonged stabilization and anticancer efficacy.

Applications of amorphous Se nanoparticles (NPs) are limited due to their meticulous synthetic procedures and rapid phase transformation leading to low stability. A highly facile one-pot green method is being reported, wherein apart from tuning the morphology and the phase of the Se NPs, their stabilization could be prolonged to months as compared to a few minutes-to-days, known hitherto.

DNA protective properties of vanillin against gamma-radiation under different conditions: possible mechanisms.

Ionizing radiation is an important genotoxic agent. Protecting against this form of toxicant, especially by a dietary component, has several potential applications. In the present study, we have examined the ability of vanillin (4-hydroxy-3-methoxybenzaldehyde), a naturally occurring food flavouring agent, to inhibit radiation-induced DNA damage measured as strand breaks under in vitro, ex vivo and in vivo conditions besides the possible mechanisms behind the observed protection. Our study showed that there was a concentration-dependent inhibition of the disappearance of super-coiled (ccc) form of plasmid pBR322 (in vitro) upon exposure to 50 Gy of gamma-radiation. Presence of 0.5 mM vanillin has a dose-modifying factor (DMF) of 6.75 for 50% inactivation of ccc form. Exposure of human peripheral blood leucocytes (ex vivo) to gamma-radiation causes strand breaks in the cellular DNA, as assessed by comet assay. When leucocytes were exposed to 2 Gy of gamma-radiation there was an increase in parameters of comet assay such as %DNA in tail, tail length, 'tail moment' and 'Olive tail moment'. The presence of 0.5 mM vanillin during irradiation significantly reduced these parameters. Damage to DNA in mouse peripheral blood leucocytes after whole-body exposure of mice (in vivo) to gamma-radiation was studied at 1 and 2 h post-irradiation. There was recovery of DNA damage in terms of the above-mentioned parameters at 2 h post-irradiation. This was more than that observed at 1 h. The recovery was more in vanillin treated mice. Hence our studies showed that vanillin offers protection to DNA against radiation-induced damage possibly imparting a role other than modulation of DNA repair. To examine the possible mechanisms of radioprotection, in terms of radiation-derived radicals, we carried out the reaction of vanillin with ABTS*(+) radical spectrophotometrically besides with DNA peroxyl and carbonyl radicals by using pulse radiolysis. Our present investigations show that vanillin has ability to protect against DNA damage in plasmid pBR322, human and mouse peripheral blood leucocytes and splenic lymphocytes besides enhancing survival in splenic lymphocytes against gamma-radiation, and that the possible mechanism may involve scavenging of radicals generated during radiation, apart from modulation of DNA repair observed earlier.

Physico-chemical studies on the evaluation of the antioxidant activity of herbal extracts and active principles of some Indian medicinal plants.

Understanding of the efficacy and mechanism for the reaction of the biologically important radicals with natural and/or synthetic antioxidants is the first step towards the development of future therapeutic agents. The kinetic parameters e.g., formation and decay rate constants predict the efficacy of an antioxidant and its fate after reaction. These parameters also dictate the ease with which competing reactions would occur in a bio-environment. The spectroscopic parameters provide the clue to the site of free radical attack to these antioxidants. Here, in this article an attempt has been made to show the use of physico-chemical methods in the evaluation of antioxidant activity of some important medicinal plants commonly used in India and the subcontinent. The systems chosen here for discussions are herbal extracts as such, curcumin from turmeric, methoxy phenols from Indian spices, dehydrogingerdione from ginger and bakuchiol from Psoralea corylifolia. All the examples shown in this article illustrate the potential of the pulse radiolysis coupled with kinetic spectroscopy and other physicochemical techniques for the study of antioxidants either in the form of mixture as in herbal extract or as an isolated compound.

Folic acid as a Fenton-modulator: possible physiological implication.

Acting as a redox switch, folic acid (1) might be a promising iron modulator to protect cellular machinery against oxidative stress and iron overload. The vitamin 1 can directly control the iron concentration by oxidizing it even if present in chelated forms. In addition, during its role as a reducing agent for the biologically relevant reactive oxygen species (ROS), it furnishes 6-formyl pterin. This folate-derived intermediate possesses a stronger Fe2+-oxidizing capacity than 1. Thus, compound 1 can reduce the iron toxicity in two ways. Although, the Fe2+-oxidizing capacity is nullified in the presence of a strong biological reductant like ascorbic acid, this property may play a predominant role during pathogenesis when the cellular ascorbic acid levels deplete significantly. The iron-modulatory property of 1 was also confirmed with the L929 mouse fibroblast cell line.

Role of surfactant derived intermediates in the efficacy and mechanism for radiation chemical degradation of a hydrophobic azo dye, 1-phenylazo-2-naphthol.

A combined methodology involving gamma and pulse radiolysis, product analysis and toxicity studies has been adopted to comprehend the degradation process of a model hydrophobic azo dye, 1-phenylazo-2-naphthol, emphasizing the role of the surfactant, which is an integral part of textile waste. Two new and important findings are underlined in this article. The first is the direct attestation of the hydrazyl radical-parent adduct, formed in the reaction of the dye with e(-)aq followed by protonation and subsequent addition to the unreacted dye molecule. This has been confirmed from concentration dependent studies. Secondly, we have clearly shown that in the reaction of hydroxyl radical with the dye in Triton X-100 media, the initially produced TX radicals cause reductive degradation of the dye. Identification and detailed analysis of HPLC and GCMS data reveals that similar products are formed in both the reactions of e(-)aq and OH radicals. Moreover, the cytotoxicity of 10(-4)moldm(-3) dye was found to be reduced significantly after irradiation. Thus, the present study not only depicts new pathways for the degradation of hydrophobic azo dye, but also demonstrates the role of a surfactant in the entire process.

Antioxidant properties of Plumbago zeylanica, an Indian medicinal plant and its active ingredient, plumbagin.

Plumbago zeylanica (known as "Chitrak") is a useful Indian medicinal plant. The root of the plant and its constituents are credited with potential therapeutic properties including anti-atherogenic, cardiotonic, hepatoprotective and neuroprotective properties. To examine possible mechanisms of action of P. zeylanica (Chitrak), in relation to its reported beneficial properties, antioxidant effects of the aqueous/alcoholic extracts of root, corresponding to medicinal preparations, and the active ingredient, plumbagin, were studied. Methods used included: ferric reducing/antioxidant power (FRAP), radical scavenging of 1,1-diphenyl-2-picryl hydrazyl (DPPH) and 2,2'-azobis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS), lipid peroxidation in rat liver mitochondria induced by different agents, and estimating phenolic and flavonoid content. In FRAP/DPPH assays, boiled ethanolic extracts were the most effective, while in the ABTS assay boiled aqueous extracts were the most efficient. These extracts also significantly inhibited lipid peroxidation induced by cumene hydroperoxide, ascorbate-Fe(2+) and peroxynitrite and contained high amounts of polyphenols and flavonoids. To examine the mechanisms of action in detail, antioxidant and pulse radiolysis studies with plumbagin were conducted. The hydroxyl (.OH), alkyl peroxyl (CCl(3)OO.), linoleic acid peroxyl (LOO.), and glutathiyl (GS.) radicals generate a phenoxyl radical upon reaction with plumbagin. The bimolecular rate constants were: .OH, 2.03 x 10(9) dm(3)mol(-1)s(-1); CCl(3)OO., 1.1 x 10(9) dm(3)mol(-1)s(-1); LOO., 6.7 x 10(7) dm(3)mol(-1)s(-1); and GS., 8.8 x 10(8) dm(3)mol(-1)s(-1). In conclusion, our studies reveal that extracts of P. zeylanica and its active ingredient plumbagin have significant antioxidant abilities that may possibly explain some of the reported therapeutic effects.

Radiation induced physicochemical changes in FAP (fluoro alkyl phosphate) based imidazolium ionic liquids and their mechanistic pathways: influence of hydroxyl group functionalization of the cation.

Future applications of ionic liquids (ILs) in a variety of areas, especially those having high radiation fields such as the nuclear fuel cycle and in space technology, are under serious consideration nowadays. For such applications to be possible, however, radiation stability of the ILs is an important issue that needs to be addressed. We envisaged that the ultra-hydrophobic, bulky and hydrolytically stable FAP (tris(perfluoroalkyl)trifluorophosphate) anion might shield the radiolytically vulnerable imidazolium cations from degradation and our result shows that these anions indeed enhance their radiolytic stability. However, introduction of a hydroxyl group into the alkyl side chain of the imidazolium moiety resulted in significant changes in the physical properties of the IL with respect to onset temperatures, conductivity and the electrochemical window. Furthermore, a nonlinear trend in absorbance with an increase in radiation dose accompanied by NMR (nuclear magnetic resonance) and mass spectrometry studies clearly demonstrated that the presence of the hydroxyl group promotes various degradation channels. Interestingly, a perturbation of the hydrogen bond between the hydroxyl group (present in the side chain of the cation) and the fluorine atom of the anion (OHF) was evident in the case of irradiated hydroxyl functionalized FAP ILs. Besides, the hydrogen gas yields of the ILs were determined and found to be comparable to those of a radiolytically stable aromatic compound, benzene. Finally, through transient spectroscopic studies we could delineate the mechanism of the radiation induced changes in the physicochemical properties of the non-hydroxyl and hydroxyl containing FAP ILs. We have clearly demonstrated that a simple functionalization of the molecular structure of the FAP based imidazolium ILs might cause marked differences in the reactivity, reaction center and the nature of the radiolytic products, which eventually lead to significant changes in their physicochemical properties.

The role of structural and fluidic aspects of room temperature ionic liquids in influencing the morphology of CdSe nano/microstructures grown in situ.

RTILs as media to synthesize a variety of nanomaterials are gaining momentum owing to their unique physicochemical properties. However, the fundamental questions regarding the role of the inherent structure of the IL in directing the morphology and the growth mechanism of the nanoparticles are still unexplored. Therefore, an attempt was made in this respect wherein CdSe nanoparticles were synthesized in a neat room temperature ionic liquid (RTIL), 1-ethyl-3-methyl imidazolium ethylsulfate ([EMIM][EtSO4]), under ambient conditions. The IL was found to play three roles, as a solvent, as a stabilizing agent and as a shape directing template. The primary nanoparticles were of the sizes in the range of 2-5 nm, as determined by HR-TEM. These primary nanoparticles grow into nanoflake-like units which further self-assemble and transform into a mixture of anisotropic nanostructures (predominantly 2D sheets and flower-like 3D patterns) as revealed by the SEM studies. The co-existence as well as the stability of these nanomorphologies point towards the intrinsic microheterogeneity prevailing in the IL. Furthermore, the vibrational spectroscopic studies comprising of FT-IR and Raman spectroscopy clearly indicate a sort of accord involving the π-π stacked aromatic geometry and the hydrogen bonding network (between the cation and the anion) of the IL with the CdSe nanoparticles. Therefore, a suitable mechanism has been provided for the resulting anisotropic nanostructures on the basis of the structural and the fluidic aspects of the IL in conjunction with the surface properties of the transient morphologies involved in the process. To further supplement this, control experiments were facilitated by diluting the IL with different amounts of water and the morphology of the CdSe nanostructures was examined at respective mole fractions of water as well as at different time intervals.

Bilirubin clearance and antioxidant activities of ethanol extract of Phyllanthus amarus root in phenylhydrazine-induced neonatal jaundice in mice.

The ability of ethanol extract of Phyllanthus amarus root (EEPA) to decrease bilirubin level and oxidative stress in phenylhydrazine-induced neonatal jaundice in mice was investigated. Administration of phenylhydrazine (75 mg/kg b.w.) significantly elevated total and unconjugated serum bilirubin level compared to control mice. EEPA (5, 10, and 20 mg/kg b.w., oral) dose-dependently reduced the bilirubin level. EEPA treatment also upregulated hepatic CAR and CYP3A1, accounting for its ability to facilitate bilirubin clearance. A single dose of EEPA (20 mg/kg b.w.) induced higher level of bilirubin clearance than phototherapy, widely used for treating neonatal jaundice. Furthermore, phenylhydrazine administration significantly increased MDA, protein carbonyl, and total thiol content and lowered the GSH level along with superoxide dismutase and catalase activity in erythrocyte compared to the control group. Single administration of EEPA (20 mg/kg b.w.) significantly reversed the trend. Presence of gallic acid, gentisic acid, and ortho-coumaric acid in EEPA was identified by HPLC analysis. Amongst these, the major phenolic constituent, gallic acid, exhibited significant bilirubin-lowering effect. These results suggested that P. amarus may be beneficial in reducing bilirubin level as well as oxidative stress in neonatal jaundice.

Evaluation of antioxidant activity and characterization of phenolic constituents of Phyllanthus amarus root.

The antioxidant property of the 70% aqueous ethanol extract of Phyllanthus amarus roots and its ether-soluble, ethyl acetate-soluble, and aqueous fractions were investigated by various in vitro assays. The root extracts showed higher DPPH, hydroxyl, superoxide, and nitric oxide radical scavenging and reducing power activity. Among all the samples, the ethyl acetate-soluble fraction demonstrated highest radical scavenging activity and total phenolics content. Twenty-eight different phenolic compounds were identified by LCMS/MS analysis of the ethyl acetate-soluble fraction. The majority of the compounds were found to exist as their glycosides, and many of these were gallic acid derivatives. Free epicatechin and gallic acid were also identified in the ethyl acetate-soluble fraction. The present investigation suggested that P. amarus root is a potent antioxidant and can be used for the prevention of diseases related to oxidative stress.

Islands of CdSe nanoparticles within Se nanofibers: a room temperature ionic liquid templated synthesis.

Herein, we present the formation of cadmium selenide (CdSe) islands embedded in a porous structure of entangled selenium (Se) nanofibers in the host matrix of a room temperature ionic liquid (RTIL). Electron beam irradiation has been employed to initiate the formation of the nanostructure while RTIL simultaneously played the role of a solvent, stabilizer and a shape guiding template for such morphology. UV-Vis absorption spectra of the irradiated samples exhibited an excitonic absorption feature in the visible region. The as-obtained nanostructure was characterized by TEM, SEM, XRD and EDX studies. Raman spectroscopic analysis of as-grown nanomaterials provided significant information about the formation of CdSe as well as distinct features of different forms of Se which further substantiated the results obtained from the above mentioned studies. Interestingly, an equivalent dose of γ-radiation led to the formation of predominantly nanosheet like structures in conjunction with a relatively homogeneous distribution of CdSe nanoparticles in the same matrix. The possible mechanism behind the obtained structures in these two methods has been proposed, and was rationalized in terms of dose rate difference and the existence of inherent heterogeneity in the structure of the IL. Finally, the implications of such a structure in various fields such as catalysis, sensing and photovoltaics have been discussed.

Generation of counter ion radical (Br2(•-)) and its reactions in water-in-oil (CTAB or CPB)/n-butanol/cyclohexane/water) microemulsion.

Herein we report the generation of counterion radicals and their reactions in quaternary water-in-oil microemulsion. Hydrated electrons in the microemulsion CTAB/H(2)O/n-butanol/cyclohexane have a remarkably short half-life (∼1 µs) and lower yield as compared to that in the pure water system. Electrons are solvated in two regions: one is the water core and other the interface; however, the electrons in the water core have a shorter half-life than those in the interface. The decay of the solvated electrons in the interface is found to be water content dependent and it has been interpreted in terms of increased interfacial fluidity with the increase in water content of the microemulsion. Interestingly another species, dibromide radical anion (Br(2)(•-)) in CTAB and CPB microemulsions have been observed after the electron beam irradiation. Assuming that the extinction coefficient of the radicals is the same as that in the aqueous solution, the yields of the radicals per 100 eV are 0.29 and 0.48 for the Br(2)(•-) radical in CTAB and CPB containing microemulsions (W(0) = 40), respectively, under N(2)O saturated conditions. Further, we intended to study electron transfer reactions, which occur at and through the interface. The reaction of the Br(2)(•-) radical anion with ABTS [2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)] has been studied to generate the ABTS radical in the water core, and further, its reaction has been investigated with the water-insoluble molecule vitamin E (tocopherol) and water-soluble vitamin C (ascorbic acid). In the present study, we were able to show that, even for molecules which are completely insoluble in water, ABTS scavenging assay is possible by pulse radiolysis technique. Furthermore, these results show that it is possible to follow the reaction of the hydrated inorganic radical with solutes dissolved in the organic phase in a microemulsion without use of a phase transfer catalyst.

Possible role of hydroxyl radicals in the oxidative degradation of folic acid.

Hydroxyl radicals have been found to cause oxidative N-dealkylation of amines including folic acid via a hydrogen atom transfer mechanism.