Solvated electron-induced synthesis of cyclodextrin-coated Pd nanoparticles: mechanistic, catalytic, and anticancer studies.

Herein, using in situ generated solvated electrons in the reaction media, a highly time-efficient, one-pot green approach has been employed to synthesize palladium (Pd) nanoparticles (NPs) coated with a molecular assembly of α-cyclodextrin (α-CD). The appearance of a shoulder peak at 280 nm in the UV-Vis absorption spectra indicated the formation of Pd NPs, which was further confirmed from their cubic phase XRD pattern. The nanomorphology varied considerably as a function of the dose rate, wherein sphere-shaped NPs (average size ∼ 7.6 nm) were formed in the case of high dose rate electron-beam assisted synthesis, while nanoflakes self-assembled to form nanoflower-shaped morphologies in a γ-ray mediated approach involving a low dose rate. The formation kinetics of NPs was investigated by pulse radiolysis which revealed the formation of Pd-based transients by the solvated electron-induced reaction. Importantly, no interference of α-CD was observed in the kinetics of the transient species, rather it played the role of a morphology directing agent in addition to a biocompatible stabilizing agent. The catalytic studies revealed that the morphology of the NPs has a significant effect on the reduction efficiency of 4-nitrophenol to 4-aminophenol. Another important highlight of this work is the demonstration of the morphology-dependent anticancer efficacy of Pd NPs against lung and brain cancer cells. Notably, flower-shaped Pd NPs exhibited significantly higher cancer cell killing as compared to spherical NPs, while being less toxic towards normal lung fibroblasts. Nonetheless, these findings show the promising potential of Pd NPs in anticancer treatment.

Effect of electron beam irradiation on chemically synthesized nanoflake-like CdS electrodes for photoelectrochemical applications.

In this paper, we chemically synthesized interconnected nanoflake-like CdS thin films for photoelectrochemical solar cell applications and subsequently irradiated them with electron beam irradiation at various doses of irradiation. The as-synthesized and irradiated samples were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and electrochemical measurements. XRD and XPS results confirmed the formation of CdS with a hexagonal crystal structure. FE-SEM and HR-TEM studies confirmed the photoelectrochemical performance, which was dependent on the surface morphology. The calculated values for efficiency demonstrated an outstanding photoelectrochemical performance with a fill factor of 0.38 and efficiency of 3.06% at 30 kGy. The high photoelectrochemical performance may be due to the interconnected nanoflake-like nanostructure and higher active surface area of the CdS samples. These results show that the electron beam irradiation is capable as an electrode for photoelectrochemical solar cells.

L-Cysteine Capped CdSe Quantum Dots Synthesized by Photochemical Route.

L-cysteine capped CdSe quantum dots were synthesized via photochemical route in aqueous solution under UV photo-irradiation. The as grown CdSe quantum dots exhibit broad fluorescence at room temperature. The CdSe quantum dots were found to be formed only through the reactions of the precursors, i.e., Cd(NH3)2+4 and SeSO2-3 with the photochemically generated 1-hydroxy-2-propyl radicals, (CH3)2COH radicals, which are formed through the process of H atom abstraction by the photoexcited acetone from 2-propanol. L-Cysteine was found to act as a suitable capping agent for the CdSe quantum dots and increases their biocompatability. Cytotoxicty effects of these quantum dots were evaluated in Chinese Hamster Ovary (CHO) epithelial cells, indicated a significant lower level for the L-cysteine capped CdSe quantum dots as compare to the bare ones.

Morphological enhancement to CuO nanostructures by electron beam irradiation for biocompatibility and electrochemical performance.

This paper reports the effect of electron beam irradiation on CuO thin films synthesized by the successive ionic layer adsorption and reaction (SILAR) method on copper foil for supercapacitor and biocompatibility application. Pristine and irradiated samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, and electrochemical study. Pristine and irradiated CuO films were pure monoclinic phase, with uniform nanostructures over the whole copper foil. After irradiation, CuO samples had formed innovative nanostructures. Biocompatibility of pristine and irradiated CuO samples suggest that CuO sample is non-toxic and ecofriendly. The specific capacitance of pristine and irradiated CuO strongly depends on surface morphology, and CuO electrodes after irradiation showed superior performance than pristine CuO. The highest specific capacitance of the 20kGy irradiated CuO nanoflowers exceeded 511Fg-1 at 10mVs-1 in 1M KOH electrolyte. Irradiated CuO samples also showed lower ESR, and were superior to other report electrical energy storage materials.

High laser efficiency and photostability of pyrromethene dyes mediated by nonpolar solvent.

Many pyrromethene (PM) dyes have been shown to outperform established rhodamine dyes in terms of laser efficiency in the green-yellow spectral region, but their rapid photochemical degradation in commonly used ethanol or methanol solvents continues to limit its use in high average power liquid dye lasers. A comparative study on narrowband laser efficiency and photostability of commercially available PM567 and PM597 dyes, using nonpolar n-heptane and 1,4-dioxane and polar ethanol solvents, was carried out by a constructed pulsed dye laser, pumped by the second harmonic (532 nm) radiation of a Q-switched Nd:YAG laser. Interestingly, both nonpolar solvents showed a significantly higher laser photostability (∼100 times) as well as peak efficiency (∼5%) of these PM dyes in comparison to ethanol. The different photostability of the PM dyes was rationalized by determining their triplet-state spectra and capability to generate reactive singlet oxygen (O21) by energy transfer to dissolved oxygen in these solvents using pulse radiolysis. Heptane is identified as a promising solvent for these PM dyes for use in high average power dye lasers, pumped by copper vapor lasers or diode-pumped solid-state green lasers.

Photoelectrochemical cell studies of Fe(2+) doped ZnSe nanorods using the potentiostatic mode of electrodeposition.

The Fe(2+) doped ZnSe nanorods are synthesized using simple potentiostatic mode of electrodeposition on the ITO substrate. In order to study the doping effect of Fe(2+) in ZnSe, varied the doing percent such as 0.5%, 1%, 1.5%. These films are characterized for structural, compositional, morphological, optical and electrochemical properties using the X-ray diffraction study (XRD), X-ray photoelectron spectroscopy, field emission scanning electron microscopy, UV-vis spectroscopy and electrochemical spectroscopy. Along with these Raman spectroscopy and photoluminescence spectroscopy have been studied for understanding the characteristics vibrations of ZnSe and luminescence of ZnSe nanorods. FE-SEM shows the nanorods like morphology. Photoelectrochemical cell performance studied using the J-V measurement and it shows the maximum efficiency at 1% Fe(2+) doped ZnSe nanorods. The observed maximum efficiency of Fe(2+) doped ZnSe nanorods is 0.32%.

Facile and green synthesis of CdSe quantum dots in protein matrix: tuning of morphology and optical properties.

Herein, we have demonstrated a facile and green approach for the synthesis of Cadmium selenide (CdSe) quantum dots (QDs). The process was mediated by bovine serum albumin (BSA) and it was found that BSA plays the dual role of reducing agent as well as a stabilizing agent. The QDs exhibited sharp excitonic absorption features at ~500 nm and subsequently showed reasonably good photoluminescence (PL) at room temperature. The PL is seen to be strongly dependent on the concentration of the precursors and hence, the luminescence of these QDs could be conveniently tuned across the visible spectrum simply by varying molar ratio of the precursors. It can be envisaged from the fact that a red-shift of about 100 nm in the PL peak position was observed when the molar ratio of the precursors ([Cd2+]:[Se2-], in mM) was varied from 10:5 to 10:40. Subsequently, the charge carrier relaxation dynamics associated with the different molar ratio of precursors has been investigated and very interesting information regarding the energy level structures of these QDs were revealed. Most importantly, in conjunction with the optical tuning, the nanomorphology of these nanoparticles was found to vary with the change in molar ratios of Se and Cd precursors. This aspect can provide a new direction of controlling the shape of CdSe nanoparticles. The possible mechanism of the formation as well as for the shape variation of these nanoparticles with the molar ratios of precursors has been proposed, taking into account the role of amino acid residues (present in BSA). Moreover, the QDs were water soluble and possessed fairly good colloidal stability therefore, can have potential applications in catalysis and bio-labeling. On the whole, the present methodology of protein assisted synthesis is relatively new especially for semiconducting nanomaterials and may provide some unique and interesting aspects to control and fine tune the morphology vis-à-vis, their optical properties.

Sea urchin like shaped cdse nanoparticles grown in aqueous solutions via electron beam irradiation.

Cadmium selenide (CdSe) nanoparticles have been grown from an aqueous solutions containing equimolar ammoniated cadmium sulphate and sodium selenosulphate as precursors in presence of citric acid as a capping agent, via electron beam irradiation. The radiolytic processes occurring in the medium result in the formation of CdSe nanoparticles through the reactions mediated by hydrated electrons (e(aq)-). The dynamics of the formation of these nanoparticles was investigated by pulse radiolysis studies. The size of the primary nanoparticles as estimated from the absorption spectra recorded immediately was less than 3 nm. These nanoparticles exhibited strong excitonic absorption pattern and broad photoluminescence at room temperature, which has been attributed to the presence of surface states/defects. This has been confirmed by Raman spectral studies, where CdSe nanoparticles exhibited characteristic surface phonon modes at around 250 cm(-1). The photoluminescence lifetime decay measurements further supported the existence of surface defects on the as-grown CdSe nanoparticles. These nanoparticles were found to exist in the agglomerated form of sea urchin like shapes of uniform size of about 500 nm as revealed from TEM and SEM images. These sea urchin like shaped CdSe nanoparticles grown in this route were found to be very stable under the ambient conditions. We infer that citric acid influences the growth as well as stability of these nanoparticles. It is expected that these nanomaterials could find potential applications in the field of sensors, catalysis and photovoltaics.

Radiolytic synthesis and spectroscopic investigations of cadmium selenide quantum dots grown in cationic surfactant based quaternary water-in-oil microemulsions.

Cadmium selenide (CdSe) quantum dots (QDs) were grown in cationic surfactant cetyltrimethylammonium bromide (CTAB) based water-in-oil microemulsions using high-energy electron beam irradiation. The sizes of the primary QDs were determined from the absorption spectra as well as from high-resolution transmission electron microscope images and were found to be within 3 nm. Effects of experimental parameters, such as w0 (molar ratio of water to surfactant in a microemulsion) values and precursor concentrations on the optical properties of these QDs were investigated in detail. The QDs exhibited broad photoluminescence (PL) in the wavelength region extending from 450 to 750 nm at room temperature. The time-resolved PL showed multiexponential decay and the average lifetime was estimated to be 4.1 ns and the PL decay curve analysis indicated the presence of predominating trap state emission from the as obtained CdSe QDs. The quantum yield exhibited by as-grown QDs was determined to be 2.4%, without involving any postprocessing techniques. However, these QDs possessing ultra small size (≤5 nm) were found to exhibit CIE (Commission Internationale d'Eclairage) chromaticity x, y co-ordinates close to (0.36,0.36), which confirms their potential as white light emitters. Besides, their light emitting color tunability can be conveniently achieved just by varying the experimental parameters. Therefore, the present method employing electron beam irradiation, accompanied by various advantages of CTAB based water-in-oil microemulsion as the host matrix, offers a simple and one step method to obtain CdSe QDs possessing potential applications in white light emitting devices.

Investigation of dynamics of radiolytic formation of CdSe nanoparticles in aqueous solutions.

The formation of cadmium selenide, CdSe, nanoparticles in aqueous solutions containing equimolar ammoniated cadmium sulfate, [Cd(NH(3))](4)SO(4) and sodium selenosulfate, Na(2)SeSO(3) as the starting materials, has been investigated by electron pulse radiolysis coupled with kinetic spectrometry. The formation of CdSe nanoparticles was found to proceed through the generation of short-lived transient intermediate species having an absorption peak at 520 nm, which is formed only upon the reaction of hydrated electrons, e(aq) with the precursor ions under deaerated conditions. The transient intermediate species decays with a weighted average rate constant, 1.2 × 10(7) s(-1). The transient intermediate species formed in the case of individual precursors did not match with the transients formed when both the precursors are taken together in the solutions under the present experimental conditions. The reaction rate constants between the precursor ions, [Cd(NH(3))(4)](2+) and the transient intermediate species formed from [SeSO(3)](2-) was 1.9 × 10(10) M(-1) s(-1). Similarly, the reaction rate constants between the precursor ions, [SeSO(3)](2-) and the transient intermediate species formed from [Cd(NH(3))(4)](2+) was 5.5 × 10(10) M(-1) s(-1). This clearly indicates that the formation of CdSe nanoparticles occurs through both reaction channels. However, the major reaction channel is through the reaction of e(aq) with the [Cd(NH(3))(4)](2+) ions (k = 3.1 × 10 (10) M(-1) s(-1)), as its rate constant is one order higher than that of the reaction of e(aq) with the [SeSO(3)](2-) ions (k = 2.3 × 10(9) M(-1) s(-1)).

Electron transfer interaction of dihydroxyquinones with amine quenchers: dependence of the quenching kinetics on the aliphatic and aromatic nature of the amine donors.

Studies on the electron transfer (ET) interaction of 1,4-dihydroxy-9,10-anthraquinone and 6,11-dihydroxy-5,12-naphthacenequinone with aliphatic and aromatic amine (AlA and ArA, respectively) donors have been investigated in acetonitrile solutions. Steady-state (SS) measurements show quenching of the quinone fluorescence by amines, without indicating any change in the shape of the fluorescence spectra. No significant change in the absorption spectra of the quinones is also observed in the presence of the amines. For all the quinone-amine pairs, the bimolecular quenching constants (kq) estimated from SS and time-resolved measurements are found to be similar. Variation in the kq values with the oxidation potentials of the amines indicates the involvement of the ET mechanism for the quenching process. A reasonably good correlation between the kq values and the free energy changes (deltaG0) for the ET reactions following Marcus' outer-sphere ET theory also supports this mechanism. It is seen that for both the quinone-ArA and quinone-AlA systems, the kq values initially increase and then get saturated at some diffusion-controlled limiting values (kqDC) as deltaG0 values gradually become more negative. Interestingly, however, it is seen that the kqDC value for the quinone-AlA systems is substantially lower than that for quinone-ArA systems. Such a large difference in the kqDC values between quinone-AlA and quinone-ArA systems is quite unusual. Present results have been rationalized based on the assumption that an orientational restriction is imposed for the encounter complexes in quinone-AlA systems to undergo ET reactions, which arises because of the localized (at amino nitrogen) shapes of the highest-occupied molecular orbitals (HOMO) of AlA in comparison to the pi-like HOMO of the ArA.

Photophysics of melatonin in different environments.

Melatonin (N-acetyl-5-methoxytryptamine) is a naturally occurring hormone with a structural resemblance to tryptophan. Its fluorescence is solvent dependent and strongly quenched in the presence of oxygen. Fluorescence quenching in aqueous and organic solutions have been studied in the presence of different quenchers. A 1: 1 inclusion complex formation between melatonin and different cyclodextrins in aqueous solution has been observed. The effects of microheterogeneous media provided by cyclodextrins, micelles and reverse micelles on the fluorescence characteristics of melatonin have been investigated. The water-soluble inorganic quenchers like KBr and KI were unable to quench the fluorescence of melatonin dissolved in a microemulsion consisting of surfactant + cyclohexane + 1-propanol + water, whereas the organic quenchers like CCl4 and CHCl3 were able to quench the fluorescence with a rate constant (on the order of 10(8) dm3 mol-1 s-1) quite similar to that in neat organic solvents.

Reactions of OH and eaq- adducts of cytosine and its nucleosides or nucleotides with Cu(II) ions in dilute aqueous solutions: a steady-state and pulse radiolysis study.

The reactions of OH and eaq- adducts of cytosine, cytidine and deoxycytidine in the presence of Cu(II) ions have been studied by product analysis and pulse radiolysis. The product analysis studies show that the degradation of the base is enhanced in N2O-saturated conditions in the presence of Cu(II) ions and the major radiolytic products are Cu(I), cytosine glycols and 5(6)-hydroxycytosine. It is also interesting to note that the yields of Cu(I) are equivalent to cytosine degradation yields, which suggests that the interaction of the OH adducts with Cu(II) ions restricts the radical recombination reactions (known to be the major physicochemical repair process) which partly regenerate the parent cytosine. The rate constants of the reactions of cytosine OH adducts with Cu(II) ions determined by pulse radiolysis lie between 10(7) and 10(8) dm3 mol-1 s-1. The growth in the transient absorption spectra of cytosine OH adducts in the range 330-400 nm, observed in the presence of copper(II) ions in free and complexed state, suggests formation of copper radical adduct which decays by water insertion at the copper-carbon bond to give glycol as the major product. Such copper radical adduct formation was also observed in the case of cytidine and deoxycytidine. The protonated electron adducts (at the hetero atoms) of cytosine, cytidine and deoxycytidine transfer electrons to the Cu(II) ions with rate constants of 10(8) and 10(9) dm3 mol-1 s-1. Here no adduct formation is observed. The steady-state results show that such electron transfer reactions regenerate the parent molecules themselves. Hence such electron transfer reactions do not contribute to enhanced base degradation in the presence of copper ions.