Unraveling the cation dependent carrier cooling and transient mobility in lead-free A3Sb2I9 perovskites.

Lead halide perovskites (LHPs) have gained prominence for their exceptional photophysical properties, holding promise for applications in high-end optoelectronic devices. However, the presence of lead is one of the major obstacles to the commercialization of LHPs in the field of photovoltaics. To address this, researchers have explored environment friendly lead-free perovskite solar cells by investigating non-toxic perovskite materials. This study explores the enhancement of photophysical properties through chemical engineering, specifically cation exchange, focusing on the crucial photophysical process of hot carrier cooling. Employing femtosecond transient absorption spectroscopy and optical pump terahertz probe spectroscopy, we have probed the carrier relaxation dynamics in A3Sb2I9 with cesium and rubidium cations. This study unravels that the carrier relaxation is found to be slower in Rb3Sb2I9; along with this, the transient mobility decay is found to be retarded. Overall, this study suggests that an antimony-based Rb3Sb2I9 perovskite could be a substantial lead-free perovskite in photovoltaics. These findings provide valuable insights into cation engineering strategies, aiming to improve the overall performance of lead-free-based photovoltaic devices.

Cell selective BCL-2 inhibition enabled by lipid nanoparticles alleviates lung fibrosis.

Idiopathic pulmonary fibrosis (IPF) is a devastating lung disease with a high mortality rate due to limited treatment options. Current therapies cannot effectively reverse the damage caused by IPF. Research suggests that promoting programmed cell death (apoptosis) in myofibroblasts, the key cells driving fibrosis, could be a promising strategy. However, inducing apoptosis in healthy cells like epithelial and endothelial cells can cause unwanted side effects. This project addresses this challenge by developing a targeted approach to induce apoptosis specifically in myofibroblasts. We designed liposomes (LPS) decorated with peptides that recognize VCAM-1, a protein highly expressed on myofibroblasts in fibrotic lungs. These VCAM1-targeted LPS encapsulate Venetoclax (VNT), a small molecule drug that inhibits BCL-2, an anti-apoptotic protein. By delivering VNT directly to myofibroblasts, we hypothesize that VCAM1-VNT-LPS can selectively induce apoptosis in these cells, leading to reduced fibrosis and improved lung function. We successfully characterized VCAM1-VNT-LPS for size, surface charge, and drug loading efficiency. Additionally, we evaluated their stability over three months at different temperatures. In vitro and in vivo studies using a bleomycin-induced mouse model of lung fibrosis demonstrated the therapeutic potential of VCAM1-VNT-LPS. These studies showed a reduction in fibrosis-associated proteins (collagen, α-SMA, VCAM1) and BCL-2, while simultaneously increasing apoptosis in myofibroblasts. These findings suggest that VCAM1-targeted delivery of BCL-2 inhibitors using liposomes presents a promising and potentially selective therapeutic approach for IPF.

Glycol Chitosan-Poly(lactic acid) Conjugate Nanoparticles Encapsulating Ciprofloxacin: A Mucoadhesive, Antiquorum-Sensing, and Biofilm-Disrupting Treatment Modality for Bacterial Keratitis.

Bacterial keratitis (BK) causes visual morbidity/blindness if not treated effectively. Here, ciprofloxacin (CIP)-loaded nanoparticles (NPs) using glycol chitosan (GC) and poly(lactic acid) (PLA) conjugate at three different ratios (CIP@GC(PLA) NPs (1:1,5,15)) were fabricated. CIP@GC(PLA) NPs (1:1) were more effective than other tested ratios, indicating the importance of optimal hydrophobic/hydrophilic balance for corneal penetration and preventing bacterial invasion. The CIP@GC(PLA) (NPs) (1:1) realized the highest association with human corneal epithelial cells, which were nonirritant to the hen's egg-chorioallantoic membrane test (HET-CAM test) and demonstrated significant antibacterial response in the in vitro minimum inhibitory, bactericidal, live-dead cells, zone of inhibition, and biofilm inhibition assays against the keratitis-inducing pathogen Pseudomonas aeruginosa. The antiquorum sensing activity of GC has been explored for the first time. The NPs disrupted the bacterial quorum sensing by inhibiting the production of virulence factors, including acyl homoserine lactones, pyocyanin, and motility, and caused significant downregulation of quorum sensing associated genes. In the in vivo studies, CIP@GC(PLA) NPs (1:1) displayed ocular retention in vivo (∼6 h) and decreased the opacity and the bacterial load effectively. Overall, the CIP@GC(PLA) NP (1:1) is a biofilm-disrupting antiquorum sensing treatment regimen with clinical translation potential in BK.

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.

Cadherin-11 targeted cell-specific liposomes enabled skin fibrosis treatment by inducing apoptosis.

Continuous and aberrant activation of myofibroblasts is the hallmark of pathological fibrosis (e.g., abnormal wound healing). The deposition of excessive extracellular matrix (ECM) components alters or increases the stiffness of tissue and primarily accounts for multiple organ dysfunctions. Among various proteins, Cadherin-11 (CDH11) has been reported to be overexpressed on myofibroblasts in fibrotic tissues. Anti-apoptotic proteins such as (B cell lymphoma-2) (BCL-2) are also upregulated on myofibroblasts. Therefore, we hypothesize that CDH11 could be a targeted domain for cell-specific drug delivery and targeted inhibition of BCL-2 to ameliorate the development of fibrosis in the skin. To prove our hypothesis, we have developed liposomes (LPS) conjugated with CDH11 neutralizing antibody (antiCDH11) to target cell surface CDH11 and loaded these LPS with a BCL-2 inhibitor, Navitoclax (NAVI), to induce apoptosis of CDH11 expressing fibroblasts. The developed LPS were evaluated for physicochemical characterization, stability, in vitro therapeutic efficacy using dermal fibroblasts, and in vivo therapeutic efficacy in bleomycin-induced skin fibrosis model in mice. The findings from in vitro and in vivo studies confirmed that selectivity of LPS was improved towards CDH11 expressing myofibroblasts, thereby improving therapeutic efficacy with no indication of adverse effects. Hence, this novel research work represents a versatile LPS strategy that exhibits promising potential for treating skin fibrosis.

Liver fibrosis pathologies and potentials of RNA based therapeutics modalities.

Liver fibrosis (LF) occurs when the liver tissue responds to injury or inflammation by producing excessive amounts of scar tissue, known as the extracellular matrix. This buildup stiffens the liver tissue, hinders blood flow, and ultimately impairs liver function. Various factors can trigger this process, including bloodborne pathogens, genetic predisposition, alcohol abuse, non-steroidal anti-inflammatory drugs, non-alcoholic steatohepatitis, and non-alcoholic fatty liver disease. While some existing small-molecule therapies offer limited benefits, there is a pressing need for more effective treatments that can truly cure LF. RNA therapeutics have emerged as a promising approach, as they can potentially downregulate cytokine levels in cells responsible for liver fibrosis. Researchers are actively exploring various RNA-based therapeutics, such as mRNA, siRNA, miRNA, lncRNA, and oligonucleotides, to assess their efficacy in animal models. Furthermore, targeted drug delivery systems hold immense potential in this field. By utilizing lipid nanoparticles, exosomes, nanocomplexes, micelles, and polymeric nanoparticles, researchers aim to deliver therapeutic agents directly to specific biomarkers or cytokines within the fibrotic liver, increasing their effectiveness and reducing side effects. In conclusion, this review highlights the complex nature of liver fibrosis, its underlying causes, and the promising potential of RNA-based therapeutics and targeted delivery systems. Continued research in these areas could lead to the development of more effective and personalized treatment options for LF patients.

Thermo-Chemical Cues-Mediated Strategy to Control Peptide Self-Assembly and Charge Transfer Complexation.

Peptide amphiphiles (PAs) are known for their remarkable ability to undergo molecular self-assembly, a process that is highly responsive to the local microenvironment. Herein, we design a pyrene tethered peptide amphiphile Py-VFFAKK, 1 that exhibits pathway-driven self-assembly from metastable nanoparticles to kinetically controlled nanofibers and thermodynamically stable twisted bundles upon modulations in pH, temperature, and chemical cues. The presence of the pyrene moiety ensures donation of the electron to an electron acceptor, namely, 7,7,8,8-tetracyanoquinodimethane (TCNQ), to form a supramolecular charge transfer complex in aqueous solution that was studied in detail with microscopic and spectroscopic techniques. Excitation of the donor species in its excimer state facilitates electron donation to the acceptor moiety, paving away a long-lived charge-separated state that persists for over a nanosecond, as ascertained through transient absorption spectroscopy. Finally, the self-assembled charge transfer complex is explored toward antimicrobial properties with Escherichia coli while maintaining biocompatibility toward L929 mice fibroblast cells.

Emerging delivery approaches for targeted pulmonary fibrosis treatment.

Pulmonary fibrosis (PF) is a progressive, and life-threatening interstitial lung disease which causes scarring in the lung parenchyma and thereby affects architecture and functioning of lung. It is an irreversible damage to lung functioning which is related to epithelial cell injury, immense accumulation of immune cells and inflammatory cytokines, and irregular recruitment of extracellular matrix. The inflammatory cytokines trigger the differentiation of fibroblasts into activated fibroblasts, also known as myofibroblasts, which further increase the production and deposition of collagen at the injury sites in the lung. Despite the significant morbidity and mortality associated with PF, there is no available treatment that efficiently and effectively treats the disease by reversing their underlying pathologies. In recent years, many therapeutic regimens, for instance, rho kinase inhibitors, Smad signaling pathway inhibitors, p38, BCL-xL/ BCL-2 and JNK pathway inhibitors, have been found to be potent and effective in treating PF, in preclinical stages. However, due to non-selectivity and non-specificity, the therapeutic molecules also result in toxicity mediated severe side effects. Hence, this review demonstrates recent advances on PF pathology, mechanism and targets related to PF, development of various drug delivery systems based on small molecules, RNAs, oligonucleotides, peptides, antibodies, exosomes, and stem cells for the treatment of PF and the progress of various therapeutic treatments in clinical trials to advance PF treatment.

Mucoadhesive Carrier-Mediated Oral Co-delivery of Bcl2 Inhibitors Improves Gastric Cancer Treatment.

Gastric cancer treatment is challenging due to the lack of early-stage diagnostic technology and targeted delivery systems. Currently, the available treatments for gastric cancer are surgery, chemotherapy, immunotherapy, and radiation. These strategies are either invasive or require systemic delivery, exerting toxicities within healthy tissues. By creation of a targeted delivery system to the stomach, gastric cancer can be treated in the early stages. Such an approach reduces the negative effects on the rest of the body by minimizing systemic absorbance and random localization. With this in mind, we developed a mucoadhesive vehicle composed of ß-Glucan And Docosahexaenoic Acid (GADA) for controlled drug/gene delivery. In the current study, we investigated the therapeutic effect of codelivery Bcl2 inhibitors navitoclax (NAVI) and siRNA (Bcl2) via oral using GADA. The therapeutic efficacy of the GADA-mediated oral NAVI/siRNA was investigated in a gastric cancer mouse model. Higher Bcl2 inhibition efficacy was observed in Western blotting and TUNEL assay in mice treated with GADA/NAVI/siRNA compared to free NAVI, siRNA, and NAVI/siRNA. Histology (H&E) and immunohistochemistry (Ki67, TUNEL, and BCl2) analyses confirmed a significant reduction of the tumor region. Interaction between GADA and mucus resulted in retention for over 6 h and thereby sustained local payload release. The developed oral carrier GADA is an emerging vehicle that has promising potential in oral delivery of both small and large molecules, and their mucoadhesive property results in improved therapeutic efficacy with minimal side effects compared to conventional treatment. This study opens a new window for the effective delivery of oral medicine for the treatment of gastric cancer and other gastrointestinal diseases.

Temperature dependent charge carrier dynamics in 2D ternary Cu2MoS4 nanoflakes: An effect of electron-phonon coupling.

Two-dimensional transition metal chalcogenides (2D TMCs) like MoS2, WS2 etc., have established significant dominance in the field of nanoscience and nanotechnology, owing to their unique properties like strong light-matter interaction, high carrier mobility, large photo-responsivity etc. Despite the widespread utilization of these binary TMCs, their potential in the advancement of the optoelectronic research is limited due to the constraints in band tuning and charge carrier lifetime. To overcome these limitations, ternary transition metal chalcogenides have emerged as promising alternatives. Although, the optical properties of these materials have never been explored properly. Herein, we have investigated one such promising member of this group, Cu2MoS4 (CMS) using both steady state and time-resolved spectroscopic techniques. The material exhibits a broad range of visible light absorption, peaking at 576 nm. Photoluminescence spectroscopy confirmed the presence of both band gap emission and trap state-mediated emissions. Transient absorption spectroscopy unraveled the excited state charge carrier dynamics of CMS in sub-ps timescale, upon irradiation of visible light. We found significant influence of the trap mediated recombination, while Auger process being dominant at high charge density. We extended our study in a wide temperature range (5-300 K), which reveals the impact of electron-phonon coupling strength on the band gap and charge carrier dynamics of this material. This detailed study would draw more attention toward the unexplored optical properties of ternary 2D chalcogenides and will open new avenues for the construction of 2D material-based optical devices.

Ultrafast glimpses of the excitation energy-dependent exciton dynamics and charge carrier mobility in Cs2SnI6 nanocrystals.

Advancements in photovoltaic research suggest that tin-based perovskites are potential alternatives to traditional lead-based structures. Cs2SnI6, specifically, stands out as a notable candidate, exhibiting impressive performance. However, its complete potential remains untapped primarily owing to the limited understanding of its photophysics. In light of this, this study aims to bridge this knowledge gap. To commence our study, we first executed theoretical investigations to locate the energetically diverse excitons within the Brillouin zone. Building on this knowledge, we then utilized transient absorption spectroscopy to investigate their temporal evolution. Herein, we observed the formation of high-energy excitons even when the incident photon energy was below the necessary threshold, which is quite distinctive and intriguing. Of particular interest is the generation of ultraviolet (UV) domain exciton using visible photons, which implies that Cs2SnI6 has the potential for efficient solar light harvesting. Tracking the kinetics revealed that this unique finding arises due to the intertwined formation and decay pathways undertaken by the different excitons, aided by intervalley scattering and phonon absorption processes. In addition, we found that the decay of the UV exciton was unusually slow. Transient mobility investigations were undertaken to probe the carrier transport behavior that further established hot carriers (HCs) in Cs2SnI6 to be highly mobile and susceptible to polaron formation. Overall, our findings demonstrate that Cs2SnI6 is a strong candidate for HC-based photovoltaics because it possesses all the prerequisites desired for such applications.

A photothermal driven chemotherapy for the treatment of metastatic melanoma.

Solid tumors are abnormal mass of tissue, which affects the organs based on its malignancy and leads to the dysfunction of the affected organs. The major problem associated with treatment of solid tumors is delivering anticancer therapeutics to the deepest layers/core of the solid tumor. Deposition of excessive extracellular matrix (ECM) hinders the therapeutics to travel towards the core of the tumor. Therefore, conventional anticancer therapeutics can only reduce the tumor size and that also for a limited duration, and tumor recurrence occurs once the therapy is discontinued. Additionally, by the time the cancer is diagnosed, the cancer cells already started affecting the major organs of the body such as lung, liver, spleen, kidney, and brain, due to their ability to metastasize and lung is the primary site for them to be infiltrated. To facilitate the anticancer therapeutics to penetrate the deeper layers of tumor, and to provide concurrent treatment of both the solid tumor and metastasis, we have designed and developed a Bimodal Light Assisted Skin Tumor and Metastasis Treatment (BLAST), which is a combination of photothermal and chemotherapeutic moieties. The BLAST is composed of 2D boron nitride (BN) nanosheet with adsorbed molecules of BCL-2 inhibitor, Navitoclax (NAVI) on its surface, that can breakdown excessive ECM network and thereby facilitate dissociation of the solid tumor. The developed BLAST was evaluated for its ability to penetrate solid tumors using 3D spheroids for the uptake, cytotoxicity, growth inhibition, reactive oxygen species (ROS) detection, penetration, and downregulation of proteins upon laser irradiation. The in vivo therapeutic studies on a skin cancer mice model revealed that the BLAST with and without laser were able to penetrate the solid tumor, reduce tumor volume in mice, dissociate the protein network, and prevent lung metastasis as confirmed by immunohistochemistry and western blot analysis. Post analysis of serum and blood components revealed the safety and efficacy of BLAST in mice. Hence, the developed BLAST holds strong promise in solid tumor treatment and metastasis prevention simultaneously.

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.

ß-Glucan and Fatty Acid Based Mucoadhesive Carrier for Gastrointestinal Tract Specific Local and Sustained Drug Delivery.

The oral route is considered the most convenient route of drug administration for both systemic and local delivery. Besides stability and transportation, another unmet but important issue regarding oral medication is retention duration within the specific region of the gastrointestinal (GI) tract. We hypothesize that an oral vehicle that can adhere and maintain retention within the stomach for a longer duration can be more effective to treat stomach-related diseases. Therefore, in this project, we developed a carrier that is highly specific to the stomach and maintains its retention for a longer duration. We developed a vehicle composed of ß-Glucan And Docosahexaenoic Acid (GADA) to observe its affinity and specificity to the stomach. GADA forms a spherical-shaped particle with negative zeta potential values that vary based on the feed ratio of docosahexaenoic acid. Docosahexaenoic acid is an omega-3 fatty acid that has transporters and receptors throughout the GI tract, such as CD36, plasma membrane-associated fatty acid-binding protein (FABP (pm)), and a family of fatty acid transport proteins (FATP1-6). The in vitro studies and characterization data showed that GADA has the capability to carry a payload of hydrophobic molecules and specifically deliver the payload to the GI tract, exert its therapeutic effects, and help to maintain stability for more than 12 h in the gastric and intestinal fluid. The particle size and surface plasmon resonance (SPR) data showed that GADA has a strong binding affinity with mucin in the presence of simulated gastric fluids. We observed a comparatively higher drug release of lidocaine in gastric juice than that in intestinal fluids, demonstrating the influence of the pH values of the media on drug-release kinetics. In vivo and ex vivo imaging of mice demonstrated that GADA maintains its retention within the stomach for at least 4 hr. This stomach-specific oral vehicle holds strong promise to translate various injectable therapeutic drugs to oral form upon further optimizations.

Potential and Progress of 2D Materials in Photomedicine for Cancer Treatment.

Over the last decades, photomedicine has made a significant impact and progress in treating superficial cancer. With tremendous efforts many of the technologies have entered clinical trials. Photothermal agents (PTAs) have been considered as emerging candidates for accelerating the outcome from photomedicine based cancer treatment. Besides various inorganic and organic candidates, 2D materials such as graphene, boron nitride, and molybdenum disulfide have shown significant potential for photothermal therapy (PTT). The properties such as high surface area to volume, biocompatibility, stability in physiological media, ease of synthesis and functionalization, and high photothermal conversion efficiency have made 2D nanomaterials wonderful candidates for PTT to treat cancer. The targeting or localized activation could be achieved when PTT is combined with chemotherapies, immunotherapies, or photodynamic therapy (PDT) to provide better outcomes with fewer side effects. Though significant development has been made in the field of phototherapeutic drugs, several challenges have restricted the use of PTT in clinical use and hence they have not yet been tested in large clinical trials. In this review, we attempted to discuss the progress, properties, applications, and challenges of 2D materials in the field of PTT and their application in photomedicine.

Temperature driven charge transfer process in quantum confined two-dimensional Mn-doped CsPbBr3 perovskite nanoplatelets.

A temperature dependent transient absorption study has been demonstrated for Mn2+ doped CsPbBr3 nanoplatelets. At 5 K, charge transfer is suppressed due to the trapping of charge carriers in defect states. By contrast, at 300 K, an efficient charge/energy transfer process is observed as the thermally active carriers become de-trapped from the defect states upon strong exciton-phonon coupling.

Efficient Hot Electron Transfer and Extended Separation of Charge Carriers at the 1P Hot State in Sb2Se3/CdSe p-n Heterojunction.

Utilization of hot carriers is very crucial in improving the efficiency of solar energy devices. In this work, we have fabricated an Sb2Se3/CdSe p-n heterojunction via a cation exchange method and investigated the possibility of hot electron transfer and relaxation pathways through ultrafast spectroscopy. The enhanced intensity of the CdSe hot excitonic (1P) bleach in the heterostructure system confirmed the hot electron transfer from Sb2Se3 to CdSe. Both the 1S and 1P signals are dynamically very slow in the heterosystem, validating this charge migration phenomenon. Interestingly, recovery of the 1P signal is much slower than that of 1S. This is very unusual as 1S is the lowest-energy state. This observation indicates the strength of hot electron transfer in this unique heterojunction, which helps in increasing the carrier lifetime in the hot state. Extended separation of charge carriers and enhanced hot carrier lifetime would be extremely helpful in extracting carriers and boost the performance of optoelectronic devices.

Myofibroblast specific targeting approaches to improve fibrosis treatment.

Fibrosis has been shown to develop in individuals with underlying health conditions, especially chronic inflammatory diseases. Fibrosis is often diagnosed in various organs, including the liver, lungs, kidneys, heart, and skin, and has been described as excessive accumulation of extracellular matrix that can affect specific organs in the body or systemically throughout the body. Fibrosis as a chronic condition can result in organ failure and result in death of the individual. Understanding and identification of specific biomarkers associated with fibrosis has emerging potential in the development of diagnosis and targeting treatment modalities. Therefore, in this review, we will discuss multiple signaling pathways such as TGF-ß, collagen, angiotensin, and cadherin and outline the chemical nature of the different signaling pathways involved in fibrogenesis as well as the mechanisms. Although it has been well established that TGF-ß is the main catalyst initiating and driving multiple pathways for fibrosis, targeting TGF-ß can be challenging as this molecule regulates essential functions throughout the body that help to keep the body in homeostasis. We also discuss collagen, angiotensin, and cadherins and their role in fibrosis. We comprehensively discuss the various delivery systems used to target collagen, angiotensin, and cadherins to manage fibrosis. Nevertheless, understanding the steps by which this molecule drives fibrosis development can aid in the development of specific targets of its cascading mechanism. Throughout the review, we will demonstrate the mechanism of fibrosis targeting to improve targeting delivery and therapy.

Atomically thin 2D photocatalysts for boosted H2 production from the perspective of transient absorption spectroscopy.

Excited state photophysical processes play the most important role in deciding the efficiency of any photonic applications like solar light driven H2 evolution, which is considered to be the next big thing in the global search of renewable energy sources. Two-dimensional (2D) materials are getting enormous attention in the field of photocatalysis owing to their exquisite optical and catalytic properties, like high absorption coefficient, appropriate band positions, large specific surface area, high charge carrier mobility, etc. Considering the huge potential of these, many different approaches are being adapted to fabricate suitable photocatalytic systems for the efficient production of H2. Transient absorption spectroscopy (TAS) could be a great help in this regard, considering its efficacy in understanding any optical application. This perspective primarily deals with a few recent reports on 2D photocatalyst fabrication techniques using mechanistic insights from TAS. We have discussed the effect of doping, exfoliation and heterojunction fabrication on the photocatalytic activity of different 2D materials and explored the inherent photophysical phenomena influencing the optical behavior of these materials. A tentative future direction and possible challenges are also highlighted in this report. Overall, this unique perspective throws light on all the possible aspects of a 2D material, which are crucial and need to be addressed prior to fabrication of a photocatalyst and would be extremely helpful for the growth of the 2D photocatalytic field.

Probing the charge transfer mechanisms in type-II Cs2AgBiBr6-CdSe composite system: ultrafast insights.

Lead-free halide-based double perovskites (DPs) have established themselves as the emerging nontoxic alternatives for photovoltaic (PV) applications thus substituting the long-standing lead halide perovskites. Among the prospective lead-free DPs, Cs2AgBiBr6has gained immense popularity owing to the fascinating properties demonstrated by them including low carrier effective mass and microsecond lifetime for electron-hole recombination. Nevertheless, the large, indirect bandgap remains the prime hurdle that restrains commercialization of the Cs2AgBiBr6DPs based PV devices. A rational solution could be designing its heterostructure with another suitable material that could mitigate the inadequacies of Cs2AgBiBr6DPs. With this line of thought, herein we synthesized a composite of Cs2AgBiBr6DPs with CdSe NCs and then performed transient absorption (TA) spectroscopic measurements to introspect its photophysical aspects. Executing excitation energy-dependent studies clearly reveal the carrier transfer efficiency to be strongly pump-dependent. Upon exciting with 350 nm pump, in compliance with the energy band alignment and tendency of both the constituents to be photoexcited across their bandgap, there is a bidirectional transfer of hot electrons anticipated in the composite system. Nevertheless, the TA outcomes indicate the transfer of hot electrons from CdSe to Cs2AgBiBr6to be more favorable out of the bidirectional pathways. Employing further lower pump energies (480 nm) when only CdSe NCs are capable of being excited, the transfer efficiency of the electrons from CdSe to Cs2AgBiBr6is noticed to be fairly low. Besides this, when the pump wavelength is tuned to 530 nm i.e. quite close to the CdSe band edge, no electron transfer is noticeable despite the anticipation from thermodynamic feasibility. Thus, as reflected by the TA kinetics, electron transfer is discerned to be more efficient from the hot states rather than the band edges. Most advantageously, charge separation is successfully achieved in this never explored composite architecture which eases the carrier extraction and minimizes the otherwise prevalent fast recombination processes.