Dual catalytic activity of a cucurbit[7]uril-functionalized metal alloy nanocomposite for sustained hydrogen generation: hydrolysis of ammonia borane and electrocatalysts for the hydrogen evolution reaction.

H2 is one of the most attractive fuel alternatives to the existing fossil fuels that cause detrimental environmental issues. Thus, there has been an upsurge in the research on the production of green hydrogen. In this view, cucurbit[7]uril (CB7)-functionalized Co:Ni alloy nanocomposites with different compositions, reported here for the first time, were synthesized to synergise the catalytic activities of a nanoalloy and CB7 and screened for hydrogen generation via hydrolysis of ammonia borane (AB). The (Co85:Ni15)50:(CB7)50 nanocomposite exhibited enhanced catalytic performance for AB hydrolysis even at room temperature as compared to the nanoalloy without CB7. Efficient release of ammonia-free green H2 is ensured by the retention of NH3 by the surface functionalized CB7 macrocycles. For sustained release, a novel and cost-effective procedure was used to regenerate AB from the by-product, and the H2 release activity was verified to be on par with commercial AB. The used nanocomposite magnetically separated from the by-product solution was shown to be an efficient electrochemical catalyst for the hydrogen evolution reaction (HER). The cucurbit[7]uril-functionalized Co:Ni nanocomposite demonstrates remarkable dual catalytic performance to generate clean hydrogen from both the hydrolysis of AB at room temperature and the electrochemical HER, thus opening new avenues in supramolecular chemistry for developing noble metal-free catalysts with high activity and long-term stability.

Mesoporous Silica-Coated Upconversion Nanoparticles Assisted Photodynamic Therapy Using 5-Aminolevulinic Acid: Mechanistic and In Vivo Studies.

Exclusively red-emitting upconversion nanoparticles (UCNPs) with the composition NaErF4:0.5%Tm as a core and NaYF4 as a shell were synthesized for performing photodynamic therapy (PDT). A possible mechanism was proposed for core-shell UCNPs formation. For loading a maximum amount of 5-aminolevulinic acid (5-ALA), mesoporous silica coating was performed on UCNPs. Studies under dark conditions confirmed the biocompatibility of 5-ALA-loaded UCNPs formulation (UCNPs-5-ALA) with MCF-7 cells. Meanwhile, studies under light-exposed conditions exhibited effective cytotoxicity against MCF-7 cells. Studies employing D2O-based cell cultured media and addition of DABCO in cell culture established that the cell death was due to oxidation of cellular components by reactive oxygen species (ROS) triggering the apoptosis. The formation of ROS was confirmed by DCF(H)DA-based ROS analysis via fluorescence microscopy to demonstrate the ROS production, which mediates the programmed cell death. Additionally, we have validated the apoptosis in MCF-7 cells with flow cytometry analyses. This was further confirmed by an electrophoretic mobility shift assay on nuclear extract and measurement of mitochondrial membrane potential. In the case of animal model studies, the formulation UCNPs-5-ALA without irradiation (980 nm) did not possess any in vivo cytotoxicity on tumor-induced SCID mice and there was a minimum migration of UCNPs-5-ALA to the vital organs but maximum retention at the tumor site only. Meanwhile, only the mice treated with UCNPs-5-ALA and irradiated on the tumor region with 980 nm laser (500 mW) for 20 min possessed a tumor with a size reduced to about 75% as compared with the corresponding control groups. To the best of our knowledge, this type of study was conducted for the first time employing exclusively red-emitting phosphors for effective PDT.

Metal-Free Supramolecular Catalytic Hydrolysis of Ammonia Borane through Cucurbituril Nanocavitands.

Ammonia borane (AB) is considered a potential "on-board" hydrogen storage material. However, its implementation as a hydrogen reservoir in fuel cells is lacking due to the extremely slow release of hydrogen at room-temperature hydrolysis. In this study, a metal-free supramolecular strategy is demonstrated at room temperature to increase the hydrolysis rate and yield of hydrogen along with significant reduction in ammonia release by using cucurbit[5/8]uril (CB5/CB8) nanocavitands as catalysts. The complex of AB with CB stabilizes the ammonium ion at the host portals, which reduces ammonia release and enhances hydrogen yield. The complexation brings down the activation energy of hydrolysis from 103.8 to ∼27.5 kJ mol-1 (for CB5), a value close to the Pt/Pd nanoparticle-based catalysts reported so far. The high catalytic performance and reusability of CB catalysts at very low concentration make AB a promising supramolecular alternative for a sustainable "on-board" energy source.

Highly selective and sensitive recognition of cobalt(II) ions directly in aqueous solution using carboxyl-functionalized CdS quantum dots as a naked eye colorimetric probe: applications to environmental analysis.

Quantum dots (QDs) are usually used as fluorescent probe, and they are difficult to use in colorimetric detection. However, in this report carboxyl-functionalized CdS (COF-CdS) QDs were synthesized in aqueous solution for colorimetric detection following a classic method. On the basis of inducing the aggregation of COF-CdS QDs, a simple naked eye colorimetric method with high sensitivity and selectivity was developed for the sensing of Co(2+) ions in aqueous solutions. The Co(2+) ions induced COF-CdS QDs results in a marked enhancement of the UV-vis absorption spectra at 360 nm, and the process was accompanied by a visible color change from colorless to yellowish brown within 5 min, which proves a sensitive detection of Co(2+) ions. The sensing of Co(2+) ions can therefore be easily achieved by a UV-vis spectrophotometer or even by the naked eye. Under the optimized circumstances, this method yields excellent sensitivity (LOD = 0.23 µg mL(-1)) and selectivity toward Co(2+) ions. The calibration plot of (A - A(0)) at 360 nm against concentration of Co(2+) ions was linear over the range from 0.5 to 14 µg mL(-1) with a correlation coefficient of 0.9996. The accuracy and reliability of the method were further ascertained by recovery studies via standard addition method with percent recoveries in the range of 99.63-102.46%. The plausible mechanism for the color change reaction has also been discussed. Our attempt may provide a cost-effective, rapid, and simple solution for the inspection of Co(2+) ions in the presence of a complex matrix from environmental aqueous samples.

BiPO4: a better host for doping lanthanide ions.

In the present manuscript it is demonstrated that BiPO(4) is a better alternative to lanthanide phosphate host for making lanthanide ion-based luminescent materials. Hexagonal and monoclinic forms of BiPO(4) phase were prepared based on the reaction of Bi(3+) and PO(4)(3-) ions in ethylene glycol medium at 100 and 185 °C, respectively. From the differential thermal analysis (DTA) studies it is confirmed that the difference in the nucleation mechanism rather than the phase transition is responsible for the monoclinic phase formation at low temperatures (125 °C). Monoclinic BiPO(4) is quite stable and forms random solid solutions with lanthanide phosphates having both monoclinic (monazite) and tetragonal (xenotime) structures, as confirmed by XRD, FTIR and (31)P solid state nuclear magnetic resonance studies. On excitation corresponding to the (1)S(0)→(3)P(1) transition of Bi(3+) in BiPO(4):Ln samples, energy transfer from host to lanthanide ions takes place. The studies are quite relevant as there is a growing interest all over the world in replacing lanthanide based host used for different applications with easily available, easily purifiable and cheap main group elements (like Sb, Bi etc.) based hosts.

Investigations of Ce3+ co-doped SbPO4:Tb3+ nano-ribbons and nanoparticles by vibrational and photoluminescence spectroscopy.

Nano-ribbons and very small nanoparticles (size 2-5 nm) of SbPO4 doped with lanthanide ions (Ce3+ and Tb3+) are prepared at a relatively low temperature of 120 degrees C based on a solution method. Detailed vibrational and luminescence studies on these samples establish that these lanthanide ions are incorporated at Sb3+ site of the SbPO4 lattice. The excitation spectrum corresponding to the Tb3+ emission and the excited state lifetime of the 5D4 level of Tb3+ ions in the sample confirm the energy transfer from Ce3+ to Tb3+ ions in the SbPO4 host. The extent of energy transfer from Ce3+ to Tb3+ in these samples is found to be around 60%. Dispersion of these nanomaterials in silica matrix effectively shields the lanthanide ions at the surface of the nano-ribbons/nanoparticles from the stabilizing ligands resulting in the reduction in the vibronic quenching of the excited state. Our results show significant reduction in the surface contribution in the decay curve corresponding to the 5D4 level of the Tb3+ ions after incorporating the nano-ribbons/nanoparticles in silica. These nanomaterials incorporated in silica matrix can have potential applications in bio-assays and bio-imaging.

Defect stabilization in ZnO nanorods by Mg2+ doping.

Luminescent ZnO and Zn0.95Mg0.05O nanorods with length around 0.5 to 3 microm and diameter 100-150 nm were prepared by a facile solvothermal method. On hydriding at room temperature, a change of morphology from nanorods with aspect ratio 5-10 to particles of sizes 100 nm has been observed in both ZnO and Zn0.95Mg0.05O. While hydrided Zn0.95Mg0.05O showed an enhanced defect related green emission, the same got suppressed in hydrided ZnO. Even though it is observed that zinc vacancies are present in both as prepared ZnO and Zn0.95Mg0.05O, luminescence studies indicate that zinc vacancies get stabilized in Zn0.95Mg0.05O on hydrogenation.

Lanthanide-ion-assisted structural collapse of layered GaOOH lattice.

GaOOH nanorods were prepared by hydrolysis of Ga(NO(3))(3)·xH(2)O by urea at ~100 °C in the presence of different amounts of lanthanide ions like Eu(3+), Tb(3+), and Dy(3+). On the basis of X-ray diffraction and vibrational studies, it is confirmed that layered structure of GaOOH collapses even when very small amounts of lanthanide ions (1 atom % and more) are present in the reaction medium during the synthesis of GaOOH nanorods. The incorporation of lanthanide ions at the interlayer spacing of the GaOOH lattice, followed by its reaction with OH groups that connect the layers containing edge-shared GaO(6) in GaOOH, is the reason for the collapse of the layered structure and associated amorphization. This leads to the formation of finely mixed hydroxides of lanthanide and gallium ions. These results are further confirmed by steady-state luminescence and excited-state lifetime measurements carried out on the samples. The morphology of the nanorods is maintained upon heat treatment at high temperatures like 500 and 900 °C, and during this process, the finely mixed lanthanide and gallium hydroxides facilitate diffusion of lanthanide ions into the Ga(2)O(3) lattice, as revealed by the existence of strong energy transfer with an efficiency of more than 90% between the host and lanthanide ions.

Nucleation sequence on the cation exchange process between Y0.95Eu0.05PO4 and CePO4 nanorods.

Nanorods of Y0.95Eu0.05PO4@CePO4 (Y0.95Eu0.05PO4 phase was nucleated first and then a CePO4 phase was nucleated) and CePO4@Y0.95Eu0.05PO4 (CePO4 phase was nucleated first and then Y0.95Eu0.05PO4 phase was nucleated) were prepared at a relatively low temperature of 140 °C in ethylene glycol medium. Based on XRD, TEM and Raman studies it has been inferred that Y0.95Eu0.05PO4@CePO4 sample consists of a mixture of bigger (length around 800-1000 nm and width around of 80-100 nm) and smaller (length around 70-100 nm and width around 10-20 nm) nanorods, having monoclinic CePO4 and tetragonal YPO4 structure, whereas CePO4@Y0.95Eu0.05PO4 sample consists of mainly small nanorods having a single phase CePO4 structure. From the detailed luminescence studies it has been established that there exists significant incorporation of Y3+/Eu3+ ions in the CePO4 phase in CePO4@Y0.95Eu0.5PO4 sample. This has been attributed to the cation exchange taking place between Ce3+ ions in CePO4 host and Eu3+ and Y3+ ions in solution during the synthesis stage. Unlike this, such an exchange is not possible for Y0.95Eu0.05PO4@CePO4 sample synthesized under identical conditions due to the higher solubility product (Ksp) value of YPO4 compared to CePO4. Incorporation of Eu3+ in the CePO4 lattice of CePO4@Y0.95Eu0.5PO4 sample is confirmed by the significant reduction in the lifetime of 5D0 level of Eu3+ and the luminescence intensity from Eu3+, arising due to the electron transfer between the Ce3+/Ce4+ and Eu3+/Eu2+ species. These results are further supported by the non-radiative decay rates and quantum yields calculated from the emission spectrum.

Luminescence studies on SbPO4:Ln3+ (Ln = Eu, Ce, Tb) nanoparticles and nanoribbons.

Nanoparticles and nanoribbons of SbPO4 and lanthanide ions (Eu3+, Ce3+ and Tb3+) doped SbPO4 were prepared at a low temperature of 120 degrees C by co-precipitation method in solvents like ethylene glycol and glycerol. By varying the relative ratios of the two solvents, average crystallite size of SbPO4 has been varied over a range of 12 to 46 nm. Based on steady state luminescence studies, existence of energy transfer between host SbPO4 and lanthanide ions has been confirmed. Co-doping SbPO4:Tb3+ nanoparticles/nanoribbons with Ce3+, resulted in improved luminescence due to energy transfer from Ce3+ to Tb3+ ions. Further, these nanomaterials can be incorporated in sol-gel derived silica glass without any deterioration of their luminescence properties. Present study offers a viable method for preparing composite luminescent materials based on nanoparticles/ nanoribbons and glasses.

Eu3+ and Dy3+ doped YPO4 nanoparticles: low temperature synthesis and luminescence studies.

Eu3+ and Dy3+ doped YPO4 nanoparticles dispersible in methanol/water were prepared by the reaction of Y3+ and Eu3+/Dy3+ ions with ammonium dihydrogen phosphate in ethylene glycol medium at 160 degrees C. Nature and extent of strain associated with lattice has been found to change with incorporation of Eu3+/Dy3+ ion in the nanoparticles as well as the heat treatment temperature. Based on the TEM studies, it has been established that particles are highly crystalline with an average particle size of around 5 nm. Co-doping YPO4:Eu nanoparticles with Dy3+ ions followed by annealing them at high temperature (900 degrees C) lead to reduction in both Eu3+ and Dy3+ luminescence intensities from the sample and this has been attributed to the clustering effect of the lanthanide ions.

Mg 2+-doped GaN nanoparticles as blue-light emitters: a method to avoid sintering at high temperatures.

Bright blue-light emission at 410 nm is observed from Mg(2+)-doped GaN nanoparticles prepared by the nitridation of Ga(2)MgO(4) nanoparticles at 950 degrees C. The sintering of these nanoparticles during high-temperature nitridation was prevented by mixing the Ga(2)MgO(4) precursor nanoparticles with La(2)O(3) as an inert matrix before the nitridation process. The Mg(2+)-doped GaN nanoparticles were isolated from the matrix by etching with 10 % nitric acid. The Mg(2+)-doped GaN nanoparticles were characterized by photoluminescence, atomic force microscopy, X-ray diffraction, and IR analyses.

Multinuclear solid-state NMR spectroscopy of doped lanthanum fluoride nanoparticles.

Multinuclear solid-state NMR spectroscopy and powder X-ray diffraction (XRD) experiments are applied to comprehensively characterize a series of pure and lanthanide-doped LaF3 nanoparticles (NPs) that are capped with di-n-octadectyldithiophosphate ligands (Ln3+ = diamagnetic Y3+ and Sc3+ and paramagnetic Yb3+ ions), as well as correlated bulk microcrystalline materials (LaF3, YF3, and ScF3). Solid-state 139La and 19F NMR spectroscopy of bulk LaF3 and the LaF3 NPs reveal that the inorganic core of the NP retains the LaF3 structure at the molecular level; however, inhomogeneous broadening of the NMR powder patterns arises from distributions of 139La and 19F NMR interactions, confirming a gradual change in the La and F site environments from the NP core to the surface. 139La and 19F NMR experiments also indicate that low levels (5 and 10 mol %) of Ln3+ doping do not significantly change the LaF3 structure in the NP core. Similar doping levels of paramagnetic Yb3+ ions severely broaden 19F resonances, but only marginally effect 139La powder patterns, suggesting that the dopant ions are uniformly distributed throughout the NP core and occupy vacant La sites. Measurements of 139La T1 and T2 relaxation constants are seen to vary between the bulk material and NPs and between samples with diamagnetic and paramagnetic dopants. 45Sc NMR experiments confirm that the dopants are integrated into the La sites of the LaF3 core. Solid-state 1H and 31P magic-angle spinning (MAS) NMR spectra aid in probing the nature of the capping ligands and their interactions at the NP surface. 31P cross-polarization (CP)/MAS NMR experiments identify not only the dithiophosphate head groups but also thiophosphate and phosphate species which may form during NP synthesis. Finally, 19F-31P CP/MAS and 1H MAS experiments confirm that ligands are coordinated to the NP surface.