Ultrafast Dynamics of Self-Trapped Excitons in Cs2AgInCl6:Al3+ Double Perovskite Nanocrystals.

It is a huge challenge to increase the photoluminescence (PL) of lead-free halide perovskites, and understanding the mechanism behind exciton dynamics can provide a valuable solution. Herein, we achieved enhanced broad-band emission at ambient conditions in Cs2AgInCl6 by tuning self-trapped excitons (STEs) through Al3+ doping. Cryogenic measurements showed an inhomogeneous nature of STE emission due to the presence of defect states and is subject to thermal quenching. An increased Huang-Rhys factor (S-factor) resulted in better electron-phonon coupling and high-density STE states post Al3+ doping. Femtosecond transient absorption (fs-TA) results provided insights into the distribution dynamics of excitons, which occurs through gradient energy levels from free excitons (FE) to STEs, where each STE state potentially possesses higher quantized energy states. Overall, this study aims to comprehend the origins of self-trapping and decay of STEs in Cs2AgInCl6:Al3+ and emphasizes the potential of compositional engineering to mitigate self-trapping in this material.

Nano-Formulation of Antioxidants as Effective Inhibitors of γD-Crystallin Aggregation.

The aggregation of crystallin proteins is related to cataracts and age-related macular degeneration. Apart from surgical replacement of the cataract lens, no other alternative treatment is available till date for this ailment. In the current work, we carried out an in-depth investigation of the effect of polyphenol-loaded nano-formulations on the aggregation of γD-crystallin. At first, the protein was allowed to form amorphous aggregates under denaturing conditions. Several polyphenols were then tried to inhibit the aggregation of the protein. Among the polyphenols tested, resveratrol and quercetin were found to be the most effective. Since polyphenols are prone to degradation, they were encapsulated in chitosan nanoparticles in order to provide ambient conditions for them to function effectively. The loading efficiency and polyphenol release kinetics were subsequently tested. Finally, the efficacy of resveratrol/quercetin-loaded chitosan nano-particles as inhibitors of γD-crystallin aggregation was confirmed in a series of experiments demonstrating the potency of the system in the prospective therapeutic intervention of eye ailments concerning self-assembly of γD-crystallin proteins.

Doping Mn2+in hybrid Ruddlesden-Popper phase of layered double perovskite (BA)4AgBiBr8.

The layered hybrid double perovskites emerged as excellent semiconductor materials owing to their environment compatibility and stability. However, these materials are weakly luminescent, and their photoluminescence (PL) properties can be modulated via doping. While Mn2+doping in perovskites is well known, but to the best of our knowledge the doping of Mn2+in layered double perovskites (LDPs) is yet to be explored. Herein, for the first time, we demonstrate the doping of Mn2+in hybrid inorganic-organic two-dimensional (2D) LDPs, (BA)4AgBiBr8(BA = n-butyl amine) via a simple solid-state mechanochemical route. The powder x-ray diffraction pattern, and electron paramagnetic resonance analysis confirm the successful incorporation of Mn2+ions inside (BA)4AgBiBr8lattice. The Mn2+doped 2D LDP shows energy transfer from host excitons to d-electrons of Mn2+ions, which results in red-shifted broad Mn2+emission band centered at 625 nm, attributed to thespin-forbidden4T1to6A1internal transition. This work opens up new possibilities to dope metal ions in 2D LDPs to tune the optical as well as magnetic properties.

Insight into morphology dependent charge carrier dynamics in ZnSe-CdS nanoheterostructures.

Semiconductor nanoheterostructures (NHSs) are being increasingly used for the photocatalytic conversion of solar energy in which photo-induced charge separation is an essential step and hence it is necessary to understand the effect of various factors such as size, shape, and composition on the charge transfer dynamics. Ultrafast transient absorption spectroscopy is used to investigate the nature and dynamics of photo-induced charge transfer processes in ZnSe-CdS NHSs of different morphologies such as nanospheres (NSs), nanorods (NRs), and nanoplates (NPs). It demonstrates the fast separation of charge carriers and localization of both charges in adjacent semiconductors, resulting in the formation of a charge-separated (CS) state. The lifetime of the charge-separated state follows the order of NSs < NPs < NRs, emphasizing the effect of morphology on the enhancement of photo-induced charge separation and suppression of backward recombination. The separated charge carriers have been utilized in visible light driven hydrogen production and the hydrogen generation activity follows the same order as that for the lifetime of the CS state, underlining the role of charge separation efficiency. Therefore, the variation of the morphology of NHSs plays a significant role in their charge carrier dynamics and hence the photocatalytic hydrogen production activity.

Fluorescence resonance energy transfer in multifunctional nanofibers designed via block copolymer self-assembly.

In the present study, we demonstrate the fabrication of multifunctional nanofibers, loaded with CdSe quantum dots (QDs) and sulforhodamine 101 (S101) dye, via the self-assembly process of a polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP). The CdSe QDs and S101 dye were simultaneously incorporated in the cylindrical domains, constituted of P4VP blocks, of the self-assembled BCP structure. The cylindrical domains subsequently were isolated as individual nanofibers via the selective-swelling approach. The confinement imposed due to the nano-dimension geometry of the cylindrical domains enabled the QDs and S101 dye to localize within their Förster radius enabling an efficient fluorescence resonance energy transfer (FRET) between them. The mean lifetime of donor emission varied from 4.56 to 3.38 ns with the change in the ratio of S101 dye and CdSe QDs within the nanofibers. Furthermore, using efficiency measurements and the corresponding Förster distances, donor-acceptor distances were determined. Moreover, the kinetics of energy transfer from CdSe QDs to S101 was studied by the Poisson binding model, to understand the interactions between CdSe QDs and S101 dye molecules. The numbers of dye molecules per CdSe QD were determined, by assuming random distribution of S101 dye molecules around the CdSe QDs in the nanofibers. The results showed that the number of dye molecules per QD increased with increasing concentration of dye molecules in the nanofibers. The resulting multifunctional nanofibers could have potential applications in optoelectronics, photonics and sensors which utilize the FRET process.

Nickel Selenide Nanoparticles as a Cheap Alternative for Pt-Counter Electrode in Dye-Sensitized Solar Cells.

Colloidal nickel selenide nanocrystals (NCs) of two different compositions i.e., Ni3Se2 and Ni3Se4, where one is Ni-rich while another is Se-rich are synthesized using the hot injection method by merely changing the injection and growth temperature while keeping the rest of the reaction conditions like solvent, ligands, amount of precursors and reaction time identical. These nanocrystals exhibit electrocatalytic activity in the reduction of triiodide (I-3) to iodide (3I-), therefore employed as counter electrodes (CE) in dye-sensitized solar cells (DSCs). The DSC based on nickel selenides displays an efficiency of 6.4%, comparable to the Pt-based cells prepared by us.

Nanocrystal-Dye Interactions: Studying the Feasibility of Co-Sensitization of Dyes with Semiconductor Nanocrystals.

One of the recent developments in enhancing the performance of quantum dot sensitized solar cells (QDSSCs) is to combine QDs with dyes in order to overcome the drawbacks of QDSSCs. However, implementation of this requires a detailed investigation of the interaction between QDs and dye. Here, we have studied the effect of size and surface ligands in the interaction of CdSe nanocrystals (NCs) with Ru N-719 dye. The interaction mechanism is investigated by steady-state and time-resolved photoluminescence spectroscopy, indicating the involvement of apparent static as well as dynamic quenching. Further analysis of dynamic quenching reveals the contribution of Förster resonance energy transfer and electron transfer from NCs to the dye. The Marcus model of electron transfer rationalizes the random trends of experimental electron transfer rates, which depend on the energetic offsets between the two species and the reorganizational energy. For understanding the kinetics of energy/charge transfer from CdSe NCs to Ru N-719 dye, a Poisson binding model has been proposed that assumes a Poisson distribution of dye molecules around CdSe NCs. The variation of quenching rate constants and PL quenching rate both follow the same trend, supporting the main contribution of kinetics in the interaction of CdSe NCs with the dye.

Thickness-Dependent Charge Carrier Dynamics in CdSe/ZnSe/CdS Core/Barrier/Shell Nanoheterostructures.

We report the synthesis of CdSe/ZnSe/CdS heterostructures composed of type I and type II band alignments, where ZnSe acts as a barrier for charge carriers between the CdSe core and the CdS shell as well as being an active component of the type I (CdSe/ZnSe) and type II (ZnSe/CdS) structure simultaneously. We investigated the effect of the thickness of the barrier and the shell on the charge carrier dynamics by using UV/Vis absorbance, photoluminescence (PL), and time-resolved fluorescence techniques. The experimental data are supported by simple theoretical calculations based on effective mass approximation (EMA). PL results indicate the emission from both type I and type II structures. Time-resolved fluorescence studies show that the lifetime of the core emission decreases with increasing barrier width, owing to a greater confinement of the exciton to the core, whereas it increases with shell width because of the tunneling of charge carriers, primarily electrons, delaying the recombination of the exciton. The lifetime of the shell emission decreases with shell width as well as barrier width and height, with a larger effect being observed for the barrier width and negligible for the associated changes in the barrier height.

Cancer Cell Targeting Using Folic Acid/Anti-HER2 Antibody Conjugated Fluorescent CdSe/CdS/ZnS-Mercaptopropionic Acid and CdTe-Mercaptosuccinic Acid Quantum Dots.

CdSe/CdS/ZnS and CdTe quantum dots (QDs) were synthesized by successive ion layer adsorption and reaction (SILAR) technique and direct aqueous synthesis respectively using thiol stabilizers. Synthesized CdSe/CdS/ZnS and CdTe QDs stabilized with 3-mercaptopropionic acid (MPA) and mercaptosuccinic acid (MSA) were used as fluorescent labels after conjugation with folic acid (FA) and anti-HER2 antibodies. Photoluminescence quantum yield of folated CdSe/CdS/ZnS-MPA and CdTe-MSA QDs was 59% and 77% than that of non-folated hydrophilic QDs. The folate receptor-mediated delivery of folic acid-conjugated CdTe-MSA and CdSe/CdS/ZnS-MPA QDs showed higher cellular internalization as observed by confocal laser scanning microscopic studies. Folated and non-folated CdTe-MSA QDs were highly toxic and exhibited only 10% cell viability as compared to > 80% cell viability with CdSe/CdS/ZnS-MPA QDs over the concentration ranging from 3.38 to 50 pmoles. Immunohistochemistry (IHC) results of human breast cancer tissue samples showed positive results with anti-HER2 antibody conjugated CdSe/CdS/ZnS-MPA QDs with better sensitivity and specificity as compared to conventional IHC analysis using diaminobenzedene staining.

Localization and dynamics of long-lived excitations in colloidal semiconductor nanocrystals with dual quantum confinement.

Semiconductor nanocrystals consisting of a quantum dot (QD) core and a quantum well (QW) shell, where the QD and QW are separated by a tunneling barrier, offer a unique opportunity to engineer the photophysical properties of individual nanostructures. Using the thicknesses of the corresponding layers, the excitons of the first and second excited states can be separated spatially, localizing one state to the QD and the other to the QW. Thus the wave function overlap of the two states can be minimized, suppressing non-radiative thermalization between the two wells, which in turn leads to radiative relaxation from both states. The molecular analogy to such dual emission would be the inhibition of internal conversion, a special case that violates Kasha's rule. Using nanosecond time-resolved spectroscopy of QDQW CdSe/ZnS onion-like nanocrystals, an intermediate regime of exciton separation and suppressed thermalization is identified where the non-radiative relaxation of the higher-energy state is slowed, but not completely inhibited. In this intermediate thermalization regime, the temporal evolution of the delayed emission spectra resulting from trapped carriers mimic the dynamics of such states in nanocrystals that consist of only a QD core. In stark contrast, when a higher-energy metastable state exists in the QW shell due to strongly suppressed interwell thermalization, the spectral dynamics of the long-lived excitations in the QD and QW, which are spectrally distinct, are amplified and differ from each other as well as from those in the core-only nanocrystals. This difference in spectral dynamics demonstrates the utility of exploiting well-defined exciton localization to study the nature and spatial dependence of the intriguing photophysics of colloidal semiconductor nanocrystals, and illustrates the power of nanosecond gated luminescence spectroscopy in illuminating complex relaxation dynamics which are entirely masked in steady-state or ultrafast spectroscopy.

Cancer Cell Targeting Using Folic Acid/Anti-HER2 Antibody Conjugated Fluorescent CdSe/CdS/ZnS-MPA and CdTe-MSA Quantum Dots.

CdSe/CdS/ZnS and CdTe quantum dots (QDs) were synthesized by successive ion layer adsorption and reaction (SILAR) technique and direct aqueous synthesis respectively using thiol stabilizers. Synthesized CdSe/CdS/ZnS and CdTe QDs stabilized with 3-mercaptopropionic acid (MPA) and mercaptosuccinic acid (MSA) were used as fluorescent labels after conjugation with folic acid (FA) and anti-HER2 antibodies. Photoluminescence quantum yield of folated CdSe/CdS/ZnS-MPA and CdTe-MSA QDs was 59% and 77% than that of non-folated hydrophilic QDs. The folate receptor-mediated delivery of folic acid-conjugated CdTe-MSA and CdSe/CdS/ZnS-MPA QDs showed higher cellular internalization as observed by confocal laser scanning microscopic studies. Folated and non-folated CdTe-MSA QDs were highly toxic and exhibited only 10% cell viability as compared to > 80% cell viability with CdSe/CdS/ZnS-MPA QDs over the concentration ranging from 3.38 to 50 pmoles. Immunohistochemistry (IHC) results of human breast cancer tissue samples showed positive results with anti-HER2 antibody conjugated CdSe/CdS/ZnS-MPA QDs with better sensitivity and specificity as compared to conventional IHC analysis using diaminobenzedene staining.

Prevention of ion migration in lead halide perovskites upon plugging the anion vacancies with PbSe islands.

To circumvent the issue of halide ion exchange in perovskites, we have decorated CsPbBr3 and CsPbI3 nanocrystals with different sized PbSe nanoparticles and demonstrated that it effectively prevents anion exchange reaction in CsPbBr3/CsPbI3 nanoheterostructures (NHSs) as a consequence of halide vacancy passivation by the more covalent selenide anion.

On the unique temperature-dependent interplay of a B-exciton and its trion in monolayer MoSe2.

Plasmonics in metal nanoparticles can enhance their near field optical interaction with matter, promoting emission into selected optical modes. Here, using Ga nanoparticles with carefully tuned plasmonic resonance in proximity to MoSe2 monolayers, we show selective photoluminescence enhancement from the B-exciton and its trion with no observable A-exciton emission. The nanoengineered substrate allows for the first direct experimental observation of the B-trion binding energy in semiconducting monolayers. Using temperature-dependent photoluminescence measurements, we show the following features of the MoSe2 B-exciton family: (i) the trion binding energy has an observable temperature dependence with a decreasing trend towards low temperatures and (ii) the exciton-trion emission ratio varies non-monotonically with temperature with a steep increase in the trion emission at lower temperatures. Using detailed models, we identify the particle size required for selective excitation and describe the underlying physical processes. This opens newer avenues for selectively promoting excitonic species and tuning the effective particle lifetimes in monolayer semiconductors. These results demonstrate the excellent plasmonic properties of Ga nanoparticles, which along with facile processing techniques makes it an attractive alternative to the prevalent noble metal plasmonics having applications in flexible/stretchable materials and textiles.

Quantum dots self assembly based interface for blood cancer detection.

Results of the studies related to fabrication of sensitive electrochemical biosensor using an interface based on quantum dots (QDs) self-assembly is reported. The QDs assembly is sought to provide improved fundamental characteristics to the electrode interface in terms of electroactive surface area, diffusion coefficient, and electron transfer kinetics. This QDs modified electrode has been utilized to serve as a transducer surface for covalent immobilization of chronic myelogenous leukemia (CML) specific probe oligonucleotide, designed from the BCR-ABL fusion gene. The electrochemical characteristics of this biosensor toward various designed synthetic oligonucleotides reveal a significant enhancement in its mismatch discrimination capability compared to the biosensing assay without QDs under similar experimental conditions. The sensing characteristics of this biosensor offer a potential for detection of target oligonucleotide at a concentration as low as 1.0 pM. Furthermore, the PCR-amplified CML-positive patient samples with various BCR-ABL transcript ratios can be electrochemically distinguished from healthy samples, indicating promising application of the QDs based biosensor for clinical investigations.

Electron transfer from CdSe-ZnS core-shell quantum dots to cobalt(III) complexes.

Fluorescence quenching of CdSe-ZnS quantum dots (core-shell QDs) is shown to be affected in the presence of cobalt(III) complexes with pyridyl anchors. Steady-state and time-resolved fluorescence spectra indicate that the quenching has primarily a static component. The decrease in photoluminescence intensity can be best explained by charge transfer from the QDs to the Co(III) complexes whereas the energy transfer pathways have been methodically ruled out. The fact that quenching is a result of electron transfer is also supported by electrochemical data showing the positions of the energy levels.

Hesperidin: A Potential Therapeutic Agent against COVID-19.

COVID-19, aka Coronavirus Disease 2019, triggered by new severe acute respiratory syndrome coronavirus-2 or SARS-CoV-2, is now a public health emergency due to its rapid spread, high transmission efficiency, and severe viral pandemic that is significantly increasing the number of patients and associated deaths. Currently, no specific treatment is available for this highly contagious virus. The unavailability of effective and specific treatments and the severity of this epidemic situation potentiate medicinal chemists' in supporting new prophylactic or therapeutic interventions against COVID-19. This study discusses the therapeutic potential of hesperidin, a traditionally used herbal medicine with an exceptional safety profile. Recent studies on hesperidin advocate its promising potential in the prevention and management of COVID-19. This paper also discusses the recent clinical studies based on the previously documented antiviral activity of hesperidin. Herein, we propose the detailed preclinical and clinical manifestations of hesperidin based on its multifaceted bioactivities to develop a novel anti-COVID-19 lead.

Nanopatterned cadmium selenide Langmuir-Blodgett platform for leukemia detection.

We present results of the studies relating to preparation of Langmuir-Blodgett (LB) monolayers of tri-n-octylphosphine oxide-capped cadmium selenide quantum dots (QCdSe) onto indium-tin oxide (ITO) coated glass substrate. The monolayer behavior has been studied at the air-water interface under various subphase conditions. This nanopatterned platform has been explored to fabricate an electrochemical DNA biosensor for detection of chronic myelogenous leukemia (CML) by covalently immobilizing the thiol-terminated oligonucleotide probe sequence via a displacement reaction. The results of electrochemical response studies reveal that this biosensor can detect target DNA in the range of 10(-6) to 10(-14) M within 120 s, has a shelf life of 2 months, and can be used about 8 times. Further, this nucleic acid sensor has been found to distinguish the CML-positive and the control negative clinical patient samples.

Impact of Bifunctional Ligands on Charge Transfer Kinetics in CsPbBr3-CdSe/CdS/ZnS Nanohybrids.

Mixed dimensional nanohybrids (MDNHs) between zero-dimensional (0D) perovskites and two-dimensional (2D) II-VI semiconductors hold great potential for photonic device applications. An in-depth study to understand the shuttling of charge carriers is carried out utilizing bifunctional ligands such as 4-aminothiophenol (4-ATP), p-aminobenzoic acid, and 6-amino-2-naphthoic acid in the synthesis of MDNHs of CsPbBr3 nanocrystals (NCs) and CdSe/CdS/ZnS core/shell/shell (CSS) nanoplatelets (NPLs). These MDNHs form donor-bridge-acceptor systems, where the electronic interaction is greatly influenced by the nature of ligands. The smaller size and stronger binding affinity of 4-ATP to CSS NPLs lead to a faster rate of charge transfer as compared to other linkers. Electronic structure calculations under the framework of density functional theory (DFT) confirms that in 4-ATP capped CSS NPLs, stronger electronic overlap occurs between CSS NPLs and 4-ATP at the valence band maxima (VBM). Furthermore, Poisson distribution modeling proposes that in 4-ATP linked MDNHs, the number of CSS NPLs around CsPbBr3 NCs is highest.

Development of magnetic nanoparticle assisted aptamer-quantum dot based biosensor for the detection of Escherichia coli in water samples.

The contamination of food and potable water with microorganisms may cause food-borne and water-borne diseases. The common contaminants include Escherichia coli (E. coli), Salmonella sp. etc. The conventional methods for monitoring the water quality for the presence of bacterial contaminants are time-consuming, expensive, and not suitable for rapid on-spot detection in field conditions. In the current study, super paramagnetic iron oxide nanoparticles (SPIONs) were synthesized and conjugated with E. coli specific Aptamer I to detect E. coli cells qualitatively as well as quantitatively. The sludge consisting of E. coli- SPION complex was separated via magnetic separation. The presence of E. coli cells was confirmed with the help of standard techniques and confocal laser scanning microscopy (CLSM) employing Aptamer II conjugated CdTe-MPA quantum dots (QDs). Finally, an ATmega 328P prototype biosensor based on Aptamer II conjugated CdTe MPA QDs exhibited quantitative and qualitative abilities to detect E.coli. This prototype biosensor can even detect low bacterial counts (up to 1 × 102 cfu) with the help of a photodiode and plano-convex lens. Further, the prototype biosensor made up of ultraviolet light-emitting diode (UV LED), liquid crystal display (LCD) and ATmega328Pmicrocontroller offers on-spot detection of E.coli in water samples with high resolution and sensitivity. Similarly, this in-house developed prototype biosensor can also be utilized to detect bacterial contamination in food samples.

A rational approach for the design and synthesis of 1-acetyl-3,5-diaryl-4,5-dihydro(1H)pyrazoles as a new class of potential non-purine xanthine oxidase inhibitors.

Xanthine oxidase is a complex molybdoflavoprotein that catalyses the hydroxylation of xanthine to uric acid. Fifty three analogues of 1-acetyl-3,5-diaryl-4,5-dihydro(1H)pyrazoles were rationally designed and synthesized and evaluated for in vitro xanthine oxidase inhibitory activity for the first time. Some notions about structure activity relationships are presented. Six compounds 41, 42, 44, 46, 55 and 59 were found to be most active against XO with IC(50) ranging from 5.3 µM to 15.2 µM. The compound 59 emerged as the most potent XO inhibitor (IC(50)=5.3 µM). Some of the important interactions of 59 with the amino acid residues of active site of XO have been figured out by molecular modeling.