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.

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.

Electron injection into the surface states of ZrO2 nanoparticles from photoexcited quinizarin and its derivatives: effect of surface modification.

The effect of surface modification on interfacial electron transfer (IET) dynamics into the surface states of ZrO(2) nanoparticles sensitized by quinizarin (Qz) and its derivatives has been carried out using time-resolved emission spectroscopy. The surface of ZrO(2) nanoparticles has been modified by sodium dodecyl benzyl sulfonate . We have observed that Qz's can form a strong charge-transfer (CT) complex with both unmodified and surface-modified (SM) ZrO(2) nanoparticles. We have confirmed electron injection into the surface states of ZrO(2) nanoparticles from the photoexcited Qz molecule in our earlier work (J. Phys. Chem. B 2004, 108, 4775; Langmuir 2004, 20, 7342). In the present investigation, we have observed electron injection from photoexcited Qz derivatives into the surface states of both unmodified and SM ZrO(2) nanoparticles and also detected CT emission. Monitoring CT emission, we have determined back electron transfer (BET) dynamics of the dye-nanoparticle systems. We have found that the BET rate for the QZs/ZrO(2) systems decreases as the relative driving force increases following Marcus inverted region kinetic behavior for an IET process. BET dynamics was found to be faster on SM ZrO(2) nanoparticles as compared to that of the unmodified (bare) one. Our time-resolved emission data indicates that upon surface modification the majority of the deeper trap states of ZrO(2) nanoparticles can be removed with the formation of some new shallower trap states in the band gap region.

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.

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.

Evaluation of interparticle interaction between colloidal Ag nanoparticles coated with trisodium citrate and safranine by using FRET: spectroscopic and mechanistic approach.

Current study employs fluorescence spectroscopy, UV-Vis absorbance spectroscopy, dynamic light scattering (DLS) and cyclic voltammetry (CV) to investigate the interaction of safranine dye with spherical shaped silver nanoparticles (AgNPs) coated with trisodium citrate. In fluorescence spectroscopic study we used the AgNPs and safranine dye as component molecules for the construction of FRET, whereas AgNPs serve as donor fluorophore and safranine as acceptor. The fluorescence quenching of AgNPs followed by sensitization of safranine occurs almost simultaneously by addition of safranine dye with different concentrations, indicating fluorescence energy transfer observed between them. Interaction between safranine and AgNPs is also confirmed by using UV-Vis absorption spectroscopy. Addition of safranine results in the significant decrease in the absorbance of AgNPs at 423 nm and simultaneous increase in the absorbance of safranine at 518, 276 and 248 nm which is indication of rapid binding of safranine molecules with AgNPs. However CV measurements reveals that the safranine molecule does not alter the redox properties of the AgNPs but the safranine molecule lose their redox properties upon getting bonded with AgNPs. This clearly confirms that the safranine molecules get attached on the surface of AgNPs which was also supported by the DLS as well as zeta potential measurement.