Delineating the core and surface state heterogeneity of carbon dots during electron transfer.

Exploring the heterogeneity of carbon dots (C-Dots) is challenging because of the existence of complex structural diversity, and it is a demanding task for the development and designing of efficient C-Dots for various applications. Herein, we studied the role of the core state and surface state of C-Dots in heterogeneity via the successful investigation of the electron transfer (ET) process between different (blue, green, and red) emitting C-Dots and an electron acceptor methyl viologen (MV2+) using steady-state and time-resolved fluorescence and ultrafast transient absorption (TA) spectroscopic techniques. Selective excitation in the steady-state and time-resolved mode shows that the ET ability of the core state is higher than that of the surface state. Moreover, the kinetics of MV+˙ generation was probed using TA spectroscopy after the excitation of the core and surface state, where we observed that the surface state becomes less efficient due to the presence of an oxygen-containing functional group in the surface state, which acts as an electron scavenger. Moreover, the heterogeneity of the core and surface state was explored through the detection of the MV+˙ generation yield after the irradiation of UV and visible light (exciting the core and surface state). The result indicates that the graphitic nitrogen content in the core state and the oxygen-containing functional group in the surface state play an important role in the heterogeneity in the structure and the ET process. Our findings on the fundamental understanding of the heterogeneity of different emissive C-Dots will provide a new way of designing and developing a metal-free light-harvesting system.

Efficient Charge Transfer in the Perovskite Quantum Dot-Hemin Biocomposite: Is This Effective for Optoelectronic Applications?

Inorganic perovskite quantum dots (PQDs) have great potential for optoelectronic applications as a result of their tunable optical properties, significant absorption coefficient, and high mobility. Combining PQDs with molecular adsorbates offers exciting possibilities for future applications, making it important to study interfacial electron transfer in PQD-molecular composites. Here, we present a study of PQD and hemin composites (PQD-hemin) to understand how their interfacial electron transfer dynamics are affected by adsorbate and PQD properties. Our femtosecond ultrafast transient absorption and time-resolved photoluminescence (TRPL) studies reveal that hot carrier relaxation, charge separation, and charge recombination processes are significantly impacted in the PQD-hemin composite system under different excitations, both higher and lower energy. Additionally, our alternating current (AC)- and direct current (DC)-bias-driven electrical studies show that, despite efficient charge separation in the PQD-hemin composite system, the light-induced transient photocurrent drops. The findings on the PQD-molecular composite will give useful outlooks for designing a variety of optoelectronic devices.

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.

Light-Modulated Cationic and Anionic Transport across Protein Biopolymers*.

Light is a convenient source of energy and the heart of light-harvesting natural systems and devices. Here, we show light-modulation of both the chemical nature and ionic charge carrier concentration within a protein-based biopolymer that was covalently functionalized with photoacids or photobases. We explore the capability of the biopolymer-tethered photoacids and photobases to undergo excited-state proton transfer and capture, respectively. Electrical measurements show that both the photoacid- and photobase-functionalized biopolymers exhibit an impressive light-modulated increase in ionic conductivity. Whereas cationic protons are the charge carriers for the photoacid-functionalized biopolymer, water-derived anionic hydroxides are the suggested charge carriers for the photobase-functionalized biopolymer. Our work introduces a versatile toolbox to photomodulate both protons and hydroxides as charge carriers in polymers, which can be of interest for a variety of applications.

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.

Treatment of a Pharmaceutical Industrial Effluent by a Hybrid Process of Advanced Oxidation and Adsorption.

In the present study, a combined approach of ozone-based advanced oxidation and adsorption by activated char was employed for the treatment of a pharmaceutical industrial effluent. Ozone is a selective oxidant, but the addition of H2O2 generated in situ hydroxyl radicals, which is a non-selective stronger oxidant than ozone. The effluent obtained from the pharmaceutical industry mainly contained anti-cancer drugs, anti-psychotic drugs, and some pain killers. The peroxone process had 75-88.5% chemical oxygen demand (COD) reduction efficiency at pH 5-11 in 3 h. Adsorption by activated char further reduced the COD to 85.4-92.7% for pH 5-11 in 2.5 h. All other water quality parameters were significantly decreased (>73% removal) during ozonation. The primary operational parameters (system pH and H2O2 concentration) were also varied, and their effects were analyzed. The pseudo-first-order rate constants for ozonation were calculated, and they were found to be in the range of 1.42 × 10-4 to 3.35 × 10-4 s-1 for pH 5-11. The kinetic parameters for adsorption were calculated for the pseudo-first-order, pseudo-second-order, and Elovich models. The fit of the pseudo-first-order kinetic model to the experimental data was the best.

Enhanced Proton Conductivity across Protein Biopolymers Mediated by Doped Carbon Nanoparticles.

Carbon nanoparticles, known as carbon-dots (C-Dots), are famous for their optoelectronic properties. Here it is shown that C-Dots can also mediate protons, where protein biopolymers are used as the protonic transport matrix. Energy transfer measurements indicate that different doped C-Dots bind to the protein biopolymer in different efficiencies. Electrical impedance measurements reveal enhanced conductance across the protein biopolymer upon C-Dots integration, dependent on the doping type. The enhanced conductivity is attributed to protonic conduction due to the large observed kinetic isotope effect, resulting in one of the highest measured proton conductivity across protein biopolymers. Transistor measurements show that the various doped C-Dots-protein biopolymer exhibit different increase in charge carrier density and in carrier mobility, suggesting different modes of proton transport. The ability of C-Dots to support protonic conduction opens a field of carbon-based protonic nanoparticles and due to the formation simplicity of C-Dots they can be integrated in a variety of protonic devices.

Correction: Exploring long-range proton conduction, the conduction mechanism and inner hydration state of protein biopolymers.

[This corrects the article DOI: 10.1039/C9SC04392F.].

Exploring long-range proton conduction, the conduction mechanism and inner hydration state of protein biopolymers.

Proteins are the main proton mediators in various biological proton circuits. Using proteins for the formation of long-range proton conductors is offering a bioinspired approach for proton conductive polymers. One of the main challenges in the field of proton conductors is to explore the local environment within the polymers, along with deciphering the conduction mechanism. Here, we show that the protonic conductivity across a protein-based biopolymer can be hindered using straightforward chemical modifications, targeting carboxylate- or amine-terminated residues of the protein, as well as exploring the effect of surface hydrophobicity on proton conduction. We further use the natural tryptophan residue as a local fluorescent probe for the inner local hydration state of the protein surface and its tendency to form hydrogen bonds with nearby water molecules, along with the dynamicity of the process. Our electrical and spectroscopic measurements of the different chemically-modified protein materials as well as the material at different water-aprotic solvent mixtures result in our fundamental understanding of the proton mediators within the material and gaining important insights on the proton conduction mechanism. Our biopolymer can be used as an attractive platform for the study of bio-related protonic circuits as well as a proton conducting biopolymer for various applications, such as protonic transistors, ionic transducers and fuel cells.

Efficient Photosensitizing Capabilities and Ultrafast Carrier Dynamics of Doped Carbon Dots.

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.

Use of Photoacids and Photobases To Control Dynamic Self-Assembly of Gold Nanoparticles in Aqueous and Nonaqueous Solutions.

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 p Ka 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.

Modulation of energy/electron transfer in gold nanoclusters by single walled carbon nanotubes and further consequences.

Semiconductor or metallic character in single-walled carbon nanotubes (SWCNTs) is developed because of their chirality and diameter. Depending upon the extent of these characters in a particular sample of SWCNT, various electronic and mechanical applications are formulated. In this work we used protein protected red emitting gold nanoclusters (AuNCs) to enhance the metallic character in SWCNTs through electron transfer induced by photonic excitation. The AuNCs have been synthesized following a known protocol that generates Au(+) protected Au(0) clusters. Normal and carboxylic acid functionalized SWCNTs were obtained commercially for usage in the experiments. The non-functionalized SWCNTs facilitate intersystem electron transfer while the functionalized ones defer the phenomenon, which, in turn, affects the metallic character in the nanotubes. Steady state and time resolved fluorescence spectroscopy prove the dynamics and electrochemistry supports the intersystem electron transfer process.

Promoting the "water-wire" mechanism of double proton transfer in [2,2'-bipyridyl]-3,3'-diol by porous gold nanoparticles.

The effect of nanopores in porous gold nanoparticles (Au NPs) on excited-state double proton transfer (DPT) in [2,2'-bipyridyl]-3,3'-diol (BP(OH)2) in an aqueous environment is the main focus of the present work. DPT in BP(OH)2 is known to take place through two mechanisms. In a bulk environment, an open solvated molecule facilitates the process and emits at 460 nm whereas, in a confined situation, formation of a "water wire" between the prototropic centers leads to the transfer of protons. It has been shown spectroscopically in the present study that in the nanovessels provided by nanoporous Au NPs, the unconventional mechanism of DPT through the formation of a "water wire" is promoted due to the presence of a limited number of water molecules around the probe. Experiments in the presence of solid pure Au, Ag and Au/Ag NPs were performed to support our proposition. Time-resolved fluorescence spectral changes confirm our findings.

pH triggered reversible photoinduced electron transfer to and from carbon nanoparticles.

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.

FRET-based characterisation of surfactant bilayer protected core-shell carbon nanoparticles: advancement toward carbon nanotechnology.

Surfactant bilayer protected core-shell carbon nanoparticles (CNPs) have been synthesised. Förster resonance energy transfer (FRET) between the core-shell CNPs and two strategically chosen organic dyes has been exploited to characterise the protective surfactant bilayer.

Protein-templated gold nanoclusters: size dependent inversion of fluorescence emission in the presence of molecular oxygen.

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.