The carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter.

Challenging the basis of our chemical intuition, recent experimental evidence reveals the presence of a new type of intrinsic fluorescence in biomolecules that exists even in the absence of aromatic or electronically conjugated chemical compounds. The origin of this phenomenon has remained elusive so far. In the present study, we identify a mechanism underlying this new type of fluorescence in different biological aggregates. By employing non-adiabatic ab initio molecular dynamics simulations combined with a data-driven approach, we characterize the typical ultrafast non-radiative relaxation pathways active in non-fluorescent peptides. We show that the key vibrational mode for the non-radiative decay towards the ground state is the carbonyl elongation. Non-aromatic fluorescence appears to emerge from blocking this mode with strong local interactions such as hydrogen bonds. While we cannot rule out the existence of alternative non-aromatic fluorescence mechanisms in other systems, we demonstrate that this carbonyl-lock mechanism for trapping the excited state leads to the fluorescence yield increase observed experimentally, and set the stage for design principles to realize novel non-invasive biocompatible probes with applications in bioimaging, sensing, and biophotonics.

Biofunctionalized CdS Quantum Dots: A Case Study on Nanomaterial Toxicity in the Photocatalytic Wastewater Treatment Process.

The toxic nature of inorganic nanostructured materials as photocatalysts is often not accounted for in traditional wastewater treatment reactions. Particularly, some inorganic nanomaterials employed as photocatalysts may release secondary pollutants in the form of ionic species that leach out due to photocorrosion. In this context, this work is a proof-of-concept study for exploring the environmental toxicity effect of extremely small-sized nanoparticles (<10 nm) like quantum dots (QDs) that are employed as photocatalysts, and in this study, cadmium sulfide (CdS) QDs are chosen. Typically, CdS is an excellent semiconductor with suitable bandgap and band-edge positions that is attractive for applications in solar cells, photocatalysis, and bioimaging. However, the leaching of toxic cadmium (Cd2+) metal ions due to the poor photocorrosion stability of CdS is a matter of serious concern. Therefore, in this report, a cost-effective strategy is devised for biofunctionalizing the active surface of CdS QDs by employing tea leaf extract, which is expected to hinder photocorrosion and prevent the leaching of toxic Cd2+ ions. The coating of tea leaf moieties (chlorophyll and polyphenol) over the CdS QDs (referred to hereafter as G-CdS QDs) was confirmed through structural, morphological, and chemical analysis. Moreover, the enhanced visible-light absorption and emission intensity of G-CdS QDs in comparison to that of C-CdS QDs synthesized through a conventional chemical synthesis approach confirmed the presence of chlorophyll/polyphenol coating. Interestingly, the polyphenol/chlorophyll molecules formed a heterojunction with CdS QDs and enabled the G-CdS QDs to exhibit enhanced photocatalytic activity in the degradation of methylene blue dye molecules over C-CdS QDs while effectively preventing photocorrosion as confirmed from cyclic photodegradation studies. Furthermore, detailed toxicity studies were conducted by exposing zebrafish embryos to the as-synthesized CdS QDs for 72 h. Surprisingly, the survival rate of the zebrafish embryos exposed to G-CdS QDs was equal to that of the control, indicating a significant reduction in the leaching of Cd2+ ions from G-CdS QDs in comparison to C-CdS QDs. The chemical environment of C-CdS and G-CdS before and after the photocatalysis reaction was examined by X-ray photoelectron spectroscopy. These experimental findings prove that biocompatibility and toxicity could be controlled by simply adding tea leaf extract during the synthesis of nanostructured materials, and revisiting green synthesis techniques can be beneficial. Furthermore, repurposing the discarded tea leaves may not only facilitate the control of toxicity of inorganic nanostructured materials but can also help in enhancing global environmental sustainability.

Enhancing the stability and efficiency of MAPbI3 perovskite solar cells by theophylline-BF4 - alkaloid derivatives, a theoretical-experimental approach.

Perovskite solar cells (PSCs) are an evolving photovoltaic field with the potential to disrupt the established silicon solar cell market. However, the presence of many transport barriers and defect trap states at the interfaces and grain boundaries has negative effects on PSCs; it decreases their efficiency and stability. The purpose of this work was to investigate the effects on efficiency and stability achieved by quaternary theophylline additives in MAPbI3 PSCs with the structure FTO/TiO2/perovskite/spiro-OMeTAD/Ag. The X-ray photoelectron spectroscopy (XPS) and theoretical calculation strategies were applied to study the additive's interaction in the layer. The tetrafluoroborinated additive results in an increase in device current density (J SC) (23.99 mA cm-1), fill factor (FF) (65.7%), and open-circuit voltage (V OC) (0.95 V), leading to significant improvement of the power conversion efficiency (PCE) to 15.04% compared to control devices (13.6%). Notably, films exposed to controlled humidity of 30% using the tetrafluoroborinated additive maintained their stability for more than 600 hours (h), while the control films were stable for less than 240 hours (h).

Polygonal gold nanocrystal induced efficient phase transition in 2D-MoS2for enhancing photo-electrocatalytic hydrogen generation.

Plasmonic nanocrystals (NCs) assisted phase transition of two-dimensional molybdenum disulfide (2D-MoS2) unlashes numerous opportunities in the fields of energy harvesting via electrocatalysis and photoelectrocatalysis by enhancing electronic conductivity, increasing catalytic active sites, lowering Gibbs free energy for hydrogen adsorption and desorption, etc. Here, we report the synthesis of faceted gold pentagonal bi-pyramidal (Au-PBP) nanocrystals (NC) for efficient plasmon-induced phase transition (from 2 H to 1 T phase) in chemical vapor deposited 2D-MoS2. The as-developed Au-PBP NC with the increased number of corners and edges showed an enhanced multi-modal plasmonic effect under light irradiations. The overpotential of hydrogen evolution reaction (HER) was reduced by 61 mV, whereas the Tafel slope decreased by 23.7 mV/dec on photoexcitation of the Au-PBP@MoS2hybrid catalyst. The enhanced performance can be attributed to the light-induced 2H to 1 T phase transition of 2D-MoS2, increased active sites, reduced Gibbs free energy, efficient charge separation, change in surface potential, and improved electrical conductivity of 2D-MoS2film. From density functional theory (DFT) calculations, we obtain a significant change in the electronic properties of 2D-MoS2(i.e. work function, surface chemical potential, and the density of states), which was primarily due to the plasmonic interactions and exchange-interactions between the Au-PBP nanocrystals and monolayer 2D-MoS2, thereby enhancing the phase transition and improving the surface properties. This work would lay out finding assorted routes to explore more complex nanocrystals-based multipolar plasmonic NC to escalate the HER activity of 2D-MoS2and other 2D transition metal dichalcogenides.

Prominence of fusion temperature and engineering heteroatoms on multifarious emissive shifts in carbon dots.

We present a simple but robust strategy to engineering heteroatoms (N, S) on carbon dots (CDs) surface that results in a collection of enhanced photoluminescence (PL) emissions. The use of citric acid (CA) and 2-Imidazolidinethione (2-IZT) as precursors was envisioned to study the impact of thermolysis process on the PL properties. The proposed strategy, implemented at two different temperatures (180 °C and 200 °C), is suitable to produce CDs with tunable PL and quantum yield (QY) up to ∼32%. Similar to earlier reports of CA-based CDs, the self-assembling of fluorophores integrated into the CDs edge is hypothesized, however, in our CDs a double intriguing effect of blue- and red-shifting can be observed for PL as the wavelength of excitation is increased in the range 280-480 nm. Through a comprehensive characterization and evaluation of these CDs in water suspensions, the mechanisms that lead to PL multifarious emissions are proposed.