Fluorescent metal nanoclusters: prospects for photoinduced electron transfer and energy harvesting.

Research on noble metal nanoclusters (MNCs) (elements with filled electron d-bands) is progressing forward because of the extensive and extraordinary chemical, optical, and physical properties of these materials. Because of the ultrasmall size of the MNCs (typically within 1-3 nm), they can be applied in areas of nearly all possible scientific domains. The greatest advantage of MNCs is the tunability that can be imposed, not only on their structures, but also on their chemical, physical, and biological properties. Nowadays, MNCs are very effectively used as energy donors and acceptors under suitable conditions and hence act as energy harvesters in solar cells, semiconductors, and biomarkers. In addition, ultrafast photoinduced electron transfer (PET) can be practised using MNCs under various circumstances. Herein, we have focused on the energy harvesting phenomena of Au-, Ag-, and Cu-based MNCs and elaborated on different ways to apply them.

Hydrophobic Chain-Induced Conversion of Three-Dimensional Perovskite Nanocrystals to Gold Nanocluster-Grafted Two-Dimensional Platelets for Photoinduced Electron Transfer Substrate Formulation.

Considering the augmentation of new generation energy harvesting devices and applications of electron-hole separation therein, conversion of 3D cubic CsPbBr3 perovskite nanocrystals into 2D-platelets through ligand-ligand hydrophobic interactions has been conceived here. Cationic surfactants with various chain length coated the gold nanoclusters (AuNCs) that interact with oleic acid (OA) and oleylamine (OAm) coated 3D CsPbBr3 nanocrystals to disintegrate the crystallinity of the perovskites and reformation of AuNC-grafted 2D-platelets of unusually large size. The planar perovskite-derivatives act as an exciton donor to the embedded AuNCs through photoinduced electron transfer (PET). This process is controlled by the optimum surfactant chain length. Transient absorption spectroscopy shows that the fastest radical growth time (4 ps) was with the 14-carbon containing tail of the surfactant, followed by the 16-carbon (45 ps) and the 12-carbon (290 ps) ones. PET is administered by the energy gaps of the participating candidates that control the transition dynamics. Our findings can be a potential tool to develop metal nanocluster-based hybrid 2D perovskite-derived platelets for optoelectronic applications.

Ultrafast insights into full-colour light-emitting C-Dots.

Designing carbon dots (C-Dots) in a controlled way requires a profound understanding of their photophysical properties, such as the origin of their fluorescence and excitation wavelength-dependent emission properties, which has been a perennial problem in the last few decades. Herein, we synthesized three different C-Dots (blue, green, and red-emitting C-Dots) from the same starting materials via a hydrothermal method and separated them by silica column chromatography. All the purified C-Dots exhibited three different emission maxima after a certain range of different excitations, showing a high optical uniformity in their emission properties. It was also observed that the average distributions of the particle size in all the C-Dots were the same with a typical size of 4 nm and the same interplanar d spacing of ∼0.21 nm. Here, we tried to establish a well-defined conclusive answer to the puzzling optical properties of C-Dots via successfully investigating the carrier dynamics of their core and surface state with a myriad use of steady-state, time-resolved photoluminescence, and ultrafast transient absorbance spectroscopy techniques. The ultrafast charge-carrier dynamics of the core and surface state clearly indicated that the graphitic nitrogen in the core state and the oxygen-containing functional group in the surface state predominately contribute to controlling their wide range of emission properties. We believe that these findings will give the C-Dots their own designation in the fluorophore world and create a new avenue for designing and developing C-Dot-based new architectures.

Long-range light-modulated charge transport across the molecular heterostructure doped protein biopolymers.

Biological electron transfer (ET) across proteins is ubiquitous, such as the notable photosynthesis example, where light-induced charge separation takes place within the reaction center, followed by sequential ET via intramolecular cofactors within the protein. Far from biology, carbon dots (C-Dots) with their unique optoelectronic properties can be considered as game-changers for next-generation advanced technologies. Here, we use C-Dots for making heterostructure (HS) configurations by conjugating them to a natural ET mediator, the hemin molecule, thus making an electron donor-acceptor system. We show by transient absorption and emission spectroscopy that the rapid intramolecular charge separation happens following light excitation, which can be ascribed to an ultrafast electron and hole transfer (HT) from the C-Dot donor to the hemin acceptor. Upon integrating the HS into a protein matrix, we show that this HT within the HS configuration is 3.3 times faster compared to the same process in solution, indicating the active role of the protein in supporting the rapid light-induced long-range intermolecular charge separation. We further use impedance, electrochemical, and transient photocurrent measurements to show that the light-induced transient charge separation results in an enhanced ET and HT efficiency across the protein biopolymer. The charge conduction across our protein biopolymers, reaching nearly 0.01 S cm-1, along with the simplicity and low-cost of their formation promotes their use in a variety of optoelectronic devices, such as artificial photosynthesis, photo-responsive protonic-electronic transistors, and photodetectors.

Photosensitization Dynamics of Stable Copper Nanoclusters inside the Aqueous Core of Reverse Micelles with Different Pool Sizes.

The perennial problem of instability of fluorescent copper nanoclusters (Cu NCs), stemming principally from aerial oxidation, has prevented their vivid usage in energy harvesting compared to the other metal NCs. However, replacement of the much expensive metal NCs with the cheaper Cu NCs is desirable if the functions are met with. Although thiolate protection of Cu NCs could bring some stability to them, appreciably decentlystable Cu NCs were produced inside the aqueous core of reverse micelles (RMs). However, this recent development has not been further explored on the photosensitization of the Cu NCs inside the RMs and their controlled modulation as energy antenna. Here we have synthesized stable Cu NCs inside the aqueous core of RMs with three different pool sizes and established photoinduced electron transfer (PET) to an electron acceptor. Considering the bulk quencher concentration, it appears that the extent of PET increases with decrease in the size of the aqueous core of RMs. However, calculating the effective concentration of the electron acceptor inside the RMs and considering the polarity of the microheterogeneous systems, it becomes clear that the extent of PET actually decreases with decrease in the size of the aqueous pool (w0, i.e., [H2O]/[AOT]) = 5-20) in the RMs. This proof of concept and the results are promising toward applications in PET-driven phenomena such as solar cells or batteries.

Silver nanoclusters are probably better and cheaper protecting agents for protein from UVC radiation compared to gold nanoclusters.

It has been shown experimentally that the albumin proteins can be significantly protected by silver nanoclusters (AgNCs) from the adverse effects of UVC radiation. The parameters have been compared with the effects of gold nanoclusters (AuNCs) under similar circumstances. The protection depends on the absorptive power of the metal cluster. Since serum albumin is found in blood and lysozyme in tears, saliva, sweat, and other body fluids, hence these are often vulnerable to attack by the exposure to UV radiation. It is also shown that, the AgNCs provide greater benefits over the application of AuNCs by being more biocompatible and cheap. Au being an expensive material, a cheaper protective option is always viable as the protective mechanism depends on the radiation absorption capability of the metal core. Moreover, it has also been shown that glucose helps in protecting the proteins attached to the AgNCs.

Correction to "Application of Photoinduced Electron Transfer with Copper Nanoclusters toward Finding Characteristics of Protein Pockets".

[This corrects the article DOI: 10.1021/acsomega.8b03213.].

Application of Photoinduced Electron Transfer with Copper Nanoclusters toward Finding Characteristics of Protein Pockets.

Proteins possess various domains and subdomain pockets with varying hydrophobicity/hydrophilicity. The local polarities of these domains play a major role in oxidation-reduction-based biological processes. Herein, we have synthesized ultrasmall fluorescent copper nanoclusters (Cu NCs) that are directed to bind to the different domain-specific pockets of the model protein bovine serum albumins (BSA). Potential electron acceptors, methyl viologen (MV) derivatives, were chosen such that they specifically reach the various domains following their hydrophobicity/hydrophilicity. Here, we have used MV2+, HMV+, and DHMV2+, possessing hydrophilic, intermediate, and hydrophobic specificities. Being electron acceptors, these derivatives draw electrons from the Cu NCs through photoinduced electron transfer (PET). The rate of PET varies at the different domains of BSA based on the local environment which has been analyzed. Here, PET is confirmed by steady state as well as time-resolved fluorescence spectroscopy. This study would provide a measurable way to identify the location of the different domains of a protein which is scalable by changing the superficial conditions without unfolding the protein.

Gold Nanocluster-Grafted Cyclodextrin Suprastructures: Formation of Nanospheres to Nanocubes with Intriguing Photophysics.

Glutathione (GSH)-coated gold nanoclusters (Au NCs) were synthesized in aqueous acidic medium. On deprotonation of the carboxyl groups of the GSH molecules under alkaline condition, the anionic ends react with the added cationic surfactant molecules to convert the Au NCs hydrophobic, resulting in loss of fluorescence due to apparent insolubility in water. The fluorescence is revived by adding cyclodextrins (CDs) that encapsulate the protruding hydrophobic tails of the surfactant molecules surrounding the GSH-coated Au NCs. While addition of ß-CD showed maximum revival of the Au NC fluorescence, that by adding α-CD was lesser. Interestingly, on adding γ-CD, there was no increase in fluorescence of Au NCs at all. The size of CDs varies as γ- > ß- > α-. It appears that the cavity size of the CD-hosts controls the fluorescence from the Au NCs abruptly, and the reason behind that was found to be formation of suprastructures, the shapes of which varied from spherical to cubic. The work shows the production of Au NC-grafted CD suprastructures that develop fluorescence on-off composites on the basis of their overall shapes.