Carbon
dots (C-Dots) are promising new materials for the development
of biocompatible photosensitizers for solar-driven catalysis and hydrogen
production in aqueous solution. Compared to common semiconducting
quantum dots, C-Dots have good physicochemical, as well as photochemical
stability, optical brightness, stability and nontoxicity, while their
carbon based source results in tunable surface chemistry, chemical
versatility, low cost, and biocompatibility. Herein we show that doping
the C-Dots with phosphate or boron significantly influences their
excited-state dynamics, which is observed by the formation of a unique
long-lived photoproduct as a function of the different dopants. To
probe the photosensitizing capabilities of the C-Dots, we followed
the photoreduction of methyl viologen (MV2+), which acts
as a molecular redox mediator (electron acceptor) to the C-Dots (the
photosensitizer, i.e., electron donor) in aqueous solution, using
steady-state and time-resolved fluorescence and absorption spectroscopic
techniques as well as electrochemical measurements. We show that ultrafast
electron transfer to MV2+ and slow charge recombination
results in a high quantum yield of MV2+ photoreduction,
while the doping drastically influences this quantum yield of MV2+ radical. Our findings contribute to the photophysical understanding
of this intriguing and relatively new carbon-based nanoparticle and
can improve the design and development of efficient photosensitizers
over commonly used heterogeneous catalysts in photocatalytic systems
by increasing the efficiency of radical generation.
Post formation modification of protein-based materials can attenuate the proton conduction efficiency resulting from change in conduction mechanism, charge carrier mobility, carrier concentrations and inner hydration layer.
Gold nanoclusters are promising candidates as biological markers without having toxic effects like fluorescent quantum dots. Herein, bovine serum albumin (BSA) protein stabilized gold nanoclusters of two different sizes emitting at 410 and 645 nm have been synthesized. These nanoclusters have been shown to interact with molecular oxygen differentially. Spectroscopic and chemical evidences show that dioxygen molecule gets adsorbed at two different orientations on the nanoclusters. The orientation motifs have been hypothesized to be superoxo and peroxo types on the smaller and the larger gold nanoclusters, respectively. Due to the difference in attachments, the oxygen molecule shows opposite changes in fluorescence intensity for the nanoclusters. The fluorescence intensity of the blue emitting nanocluster shows a profuse enhancement whereas the red emitting species shows quenching of emission. Superoxo type adsorption of the oxygen molecule on the blue emitting gold nanoclusters induce formation of singlet oxygen that in turn enhances the fluorescence intensity of the species. This could be verified by oxidation of diaminobenzidine (DAB) by singlet oxygen. Enhancement in fluorescence intensity of the blue emitting gold nanoclusters with an increase in concentration of molecular oxygen may enable them to be good candidates in bioimaging and detection.
Coumarin 6 precipitates in water as microcrystals resulting in a considerable loss in fluorescence yield. Differential interaction of the microcrystals with cyclodextrins of different cavity size enhances the fluorescence yield of the dye by 160 fold in some cases. Highly fluorescent ultrathin lamellar entities form through hydrogen bonding. † Electronic supplementary information (ESI) available: Structure of C6, AFM and SEM images of C6 aer incubation in water (with 1% methanol) for 30 minutes at room temperature, uorescence spectra of C6 in a-, band g-CDs in aqueous environment and time resolved uorescence decay prole for C6 in presence of band g-CDs. See
Dynamic
self-assembly of nanoparticles (NPs) for the formation
of aggregates takes place out of thermodynamic equilibrium and is
sustained by external energy supply. Herein, we present light energy
driven dynamic self-assembly process of AuNPs, decorated with pH sensitive
ligands. The process is being controlled by the use of photoacids
and photobases that undergo excited state proton or hydroxide transfer,
respectively, due to their large pK
a change
between their ground and excited electronic states. The unique design
is underlined by record subsecond conversion rates between the assembled
and disassembled AuNPs states, and the ability to control the process
using only light of different wavelengths. Measurements in both aqueous
and nonaqueous solutions resulted in different self-assembly mechanisms,
hence showing the wide versatility of photoacids and photobases for
dynamic processes.
Dopamine functionalized carbon nanoparticles (CNPs) that can act as efficient photoinduced electron donor-acceptor systems depending on the pH of the medium have been synthesized. In acidic media, dopamine on CNPs exists as hydroquinone and serves as an electron donor while under alkaline conditions the corresponding quinone form of dopamine serves as a strong electron acceptor. Application of external NADH to the system can invert the donor-acceptor roles under alkaline conditions.
Metal halide-based perovskites have emerged as a potential candidate for optoelectronic applications because of their impressive performance achieved by tuning the optical/electrical properties through tailoring the perovskite nanostructures. Herein, we report the synthesis of composite nanostructures by incorporation of ZnO (∼6 nm) into the CsPbBr 3 (CPB) perovskite framework, which shows significant enhancement of photocurrent because of efficient interfacial charge separation and reduced dielectric loss. Detailed steady-state and time-resolved photoluminescence studies have been carried out to understand charge transfer dynamics in the CsPbBr 3 /ZnO nanostructure composite system. Femtosecond transient absorption and broadband dielectric spectroscopy studies were carried out to determine the charge carrier relaxation and transfer mechanism. The redox energy-level diagram suggests that the photoexcited electron from the conduction band (CB) of CPB can be transferred to the CB of ZnO NP because of thermodynamic viability. Ultrafast studies reveal that the electron transfer takes place from the perovskite nanostructures to ZnO NP within ∼500 fs and limits the recombination process by efficient charge separation and charge accumulation at the interfaces. Dielectric studies also reveal reduced charge leakage in composite nanostructures with efficient charge separation by facilitating the charge accumulation at the interfaces. Overall, the efficient charge transfer and slow carrier recombination with reduced dielectric losses significantly improved the photocurrent behavior in the CsPbBr 3 /ZnO nanostructure composite system as desired for optoelectronic devices.
In recent past assembly of α-cyclodextrin (α-CD) functionalized carbon dots (α-CD-CDots) has been used in molecular recognition. These assemblies are effectively used for optical sensing by the help of electron transfer mechanism. Photoinduced electron transfer (PET) between CDots and surface-encapsulated derivatives of methyl viologen (MV 2+ ) is used in the present work to follow the effect of the aggregated nanostructures. Formation of the nanoaggregates was confirmed by fluorescence anisotropy, atomic force microscopy (AFM), and scanning electron microscopy (SEM). These aggregated nanostructures are found to reinforce the electron transfer dynamics between CDots and MV 2+ . PET was confirmed from steady-state and time-resolved fluorescence along with ultrafast transient absorption measurements. The present work elaborates kinetic details of PET in the formed nanotubular aggregates. The reported concepts may be prospective toward development of light energy conversion devices.
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