Search Results (107)

The precise determination of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels is critical for understanding the photophysical and photochemical properties of carbon dots (C-dots), which directly govern their performance in optoelectronic, catalytic, and sensing applications. However, the lack of distinct redox peaks in cyclic voltammetry (CV) curves of C-dots poses a major challenge to conventional energy level calculation methods. Herein, we propose a novel strategy to calculate the HOMO–LUMO energy levels of C-dots by combining electron transfer (ET) kinetics with Marcus theory. A series of quinones (electron acceptors, EAs) and ferrocene derivatives (electron donors, EDs) were employed to quench the fluorescence of C-dots, and the ET rate constants (K) were derived from fluorescence lifetime measurements. The CV curves of EAs and EDs provided their respective oxidation and reduction potentials, which were used as reference energy levels. The UV–Vis absorption spectra confirmed that the fluorescence quenching mechanism was dominated by ET rather than energy transfer. Based on Marcus theory, the free energy change (ΔG) of ET reactions was correlated with K, and the HOMO and LUMO energy levels of C-dots were calculated to be −1.84 V (vs. SCE) and +1.60 V (vs. SCE), respectively. This study not only provides a reliable method for determining the energy levels of C-dots without distinct redox peaks but also deepens the understanding of ET mechanisms between C-dots and small molecules. The proposed strategy is expected to be extended to other fluorescent nanomaterials with similar CV limitations. Full article

Background: Extracellular vesicles (EVs) are increasingly explored as nanocarriers in drug delivery; however, selecting an appropriate loading strategy for a given small-molecule cargo still relies largely on empirical, resource-intensive parallel screening within EV formulation workflows. Despite the widespread application of passive incubation, electroporation, saponin-mediated permeabilization, freeze–thaw cycling, and sonication, there is currently no mechanistically grounded, descriptor-informed framework that enables rational prioritization of loading methods during the early design stage of EV-based dosage forms, leading to inefficient trial-and-error experimentation. Methods: We assembled a chemically diverse dataset of 21 compounds with experimentally determined loading efficiencies across five EV loading methods and calculated seven mechanistically motivated physicochemical descriptors (LogP, molecular weight, aqueous solubility, hydrogen bond donors/acceptors, polar surface area, and formal charge) for each drug. Separate Elastic Net regression models were trained for each loading strategy. Model performance was evaluated using leave-one-out cross-validation, a predefined external validation set (n = 4), and 50 repeated random train–test splits. The analysis emphasized decision-level ranking of loading methods rather than the precise prediction of absolute efficiencies. The applicability domain was assessed via leverage analysis to define the supported chemical space for prospective implementation in EV-based formulation development. Results: As anticipated for biologically heterogeneous EV systems, continuous regression performance remained modest (LOOCV R² = 0.06–0.41). In contrast, decision-level accuracy for identifying the experimentally optimal loading method was consistently high across validation schemes (internal: 76.5%; predefined external: 75%; repeated random validation: 80.5 ± 16.8%). Mechanical disruption methods (freeze–thaw and sonication) demonstrated comparatively greater predictive stability, while misclassification patterns suggested potential nonlinear behavior for highly polar, ionizable cargos. All compounds resided within the leverage-defined applicability domain, confirming adequate descriptor-space representation. Conclusions: This study establishes a mechanistically interpretable, descriptor-based decision-support framework capable of reliably prioritizing EV loading strategies for small-molecule cargos beyond empirical chance without altering standard protocols. By reframing the modeling objective from high-precision efficiency prediction to robust ranking of candidate methods, the approach offers a practical tool to triage between commonly used techniques, thereby reducing experimental burden in early-stage EV formulation development. The framework provides a quantitative basis for integrating molecular-descriptor-guided method selection into rational EV-based drug delivery design and can be expanded with membrane-specific descriptors and larger datasets. Full article

Constructing a donor–acceptor (D–A) architecture in luminescent radicals is an effective strategy for enhancing luminescent properties. However, further structural modification of the radical core through the simple substitutions in the framework of D–A radicals remains relatively underexplored. Herein, we synthesized two radical derivatives TTM-Mes-Cz-Mz and TTM-Mes-Dpa-Mz through modification of the TTM unit of TTM-Cz and TTM-Dpa with imidazole and mesitylene groups. These radical derivatives exhibited high photoluminescence quantum efficiency (PLQE) (80% for TTM-Mes-Cz-Mz and 39% for TTM-Mes-Dpa-Mz) and photostability. The radical units were further covalently grafted onto the polymer chains to synthesize ionic radical polymers LT-Cz and LT-Dpa. LT-Cz and LT-Dpa showed PLQE of 39% and 29% in a solid state, respectively. Furthermore, the polymers exhibited solvent-responsive luminescence with dichloromethane and tetrahydrofuran. A significant redshift in emission wavelength and decrease in emission intensity were observed. The polymers could return to their initial state with solvent evaporation. This work advances the exploration of the role of simple substituent modifications in D–A radical systems, thereby enabling highly efficient luminescence in both small-molecule radicals and radical polymers. Full article

We report a notable enhancement in the performance of small-molecule-based organic photovoltaics (OPVs) through the use of a ternary blend comprising a small-molecule donor (DTS(FBTTh₂)₂), a polymer donor (PBDTTT-EFT), and a fullerene acceptor (PC₇₁BM). By optimizing the composition of this ternary active layer, we achieved a significant increase in power conversion efficiency from 7.99% to 9.08%. This improvement is attributed to the broader light absorption spectrum and enhanced charge transport pathways provided by the polymeric donor. PBDTTT-EFT optimizes the nanomorphology and ordering of the bulk heterojunction films and forms a cascade energy level that enhances charge carrier mobility. Our results demonstrate that semiconducting polymer donors can effectively control light absorption, charge transport, and exciton dissociation by optimizing morphology and crystallinity. This approach offers new possibilities for advancing the performance of various optoelectronic devices through strategic use of different semiconducting polymer donors. Full article

Developing organic photothermal agents that are highly stable and have tunable electronic properties is important for advancing low-invasive cancer therapy. In this study, we present the synthesis and evaluation of three conjugated photothermal agents inspired by non-fullerene Y-series acceptors: the small molecule BTPT-OD, as well as two of its polymer derivatives with regular (r-BTPT) and irregular (ir-BTPT) structures. All of the compounds absorb light effectively in the red and near-infrared spectral ranges, with absorption maxima from 734 to 746 nm, and form stable nanoparticles (NPs) via nanoprecipitation, ranging in size from 13 to 39 nm. NPs exhibited negative surface charges, with ζ-potentials of −12.9, −15.5, and −17.9 mV for BTPT-OD, r-BTPT, and ir-BTPT NPs, respectively. Irradiation at a wavelength of 730 nm revealed that r-BTPT and ir-BTPT polymer NPs exhibited a 22- to 40-fold greater phototoxicity against A-549, Sk-Br-3, and MCF-7 human carcinoma cells than the non-polymeric analogue BTPT-OD. The measured photothermal conversion efficiencies ranged from 24 to 27 ± 5%. At the same time, the intracellular ROS generation quantified by the 2′,7′-dichlorodihydrofluorescein diacetate (DCFH-DA) assay was low, allowing us to propose heat-mediated photothermal therapy as a more significant cell death predictor than ROS-mediated photodynamic therapy. This work is one of the first to compare small and polymeric non-fullerene acceptor materials for phototherapy purposes, demonstrating the advantages of using polymers. Full article

A new π-conjugated acceptor–donor–acceptor small molecule, designed for applications in organic solar cells, containing a terthiophene core and indandione- and benzonitrile-based electron-withdrawing units, was synthesized via a multi-step process involving Suzuki–Miyaura cross-coupling and Knoevenagel condensation reactions. The structure was confirmed by NMR spectroscopy, HRMS, and its optoelectronic properties were evaluated by UV–vis spectroscopy and cyclic voltammetry. Full article

Organic nonvolatile transistor memories (ONVMs) using a hybrid spiro [fluorene-9,7′-dibenzo [c, h] acridine]-5′-one (SFDBAO)/polystyrene (PS) film as bulk-heterojunction-like tunneling and trapping elements were fabricated. From the characterization of the 10% SFDBAO/PS based on ONVM, a sterically hindered small-molecule SFDBAO with rigid orthogonal configuration and a donor–acceptor (D-A) structure as a molecular-scale charge storage element demonstrated significantly higher charge trapping ability than other small-molecule materials such as C₆₀ and Alq₃. The ONVM based on 10% SFDBAO/PS presents ambipolar memory behaviors with a wide memory window (146 V), a fast-switching speed (20 ms), an excellent retention time (over 5 × 10⁴ s), and stable reversibility (36 cycles without any noticeable decay). By applying different gate voltages, the above ONVM shows reliable four-level data storage characteristics. The investigation demonstrates that the strategical bulk-heterojunction-like tunneling and trapping elements composed of small-molecule materials and polymers exhibit promising potential for high-performance ambipolar ONVMs. Full article

Extracellular electron transport (EET) supports the survival of specific microorganisms on the Earth’s surface by facilitating microbial respiration with diverse electron acceptors. A key aspect of EET is the organization of electron relays, i.e., multi-heme c-type cytochromes (MHCs), within the periplasmic space of microbial cells. In this study, we investigated the mobility of periplasmic electron relays in Shewanella oneidensis MR-1, a model strain capable of EET, using in vivo protein crosslinking to the MHCs. First, we established that crosslinking efficiency correlates with the spatial proximity and diffusion coefficient of protein molecules through in vitro tests. Based on these findings, we identified distinct molecular behaviors of periplasmic MHCs, showing that the tetraheme flavocytochrome FccA, which also serves as a periplasmic fumarate reductase, forms protein complexes with limited motility, while the small tetraheme c-type cytochrome CctA remains discrete and mobile. Both MHCs contribute to EET for bioelectrochemical nitrate and nitrite reduction. These findings reveal dual mechanisms for organizing periplasmic electron relays in EET, advancing our understanding of microbial extracellular respiration. Full article

Organic solar cells (OSCs) have witnessed significant advancements in recent years, largely propelled by innovations in material design and device engineering. Among the emerging materials, dimerized small-molecule acceptors (DSMAs) have garnered considerable attention due to their unique advantages. For instance, DSMAs can directly inherit the excellent optoelectronic properties of corresponding small-molecule monomers. Moreover, their relatively larger molecular weight can effectively suppress molecular diffusion in the active layer, thereby enhancing the stability of OSCs. Compared to polymer acceptors, DSMAs have a well-defined structure, which is free from batch-to-batch variability, greatly enhancing the reproducibility of devices. This review comprehensively summarizes recent progress in DSMAs for OSCs, with a focus on their two primary linkage configurations: conjugative and non-conjugative connections. Additionally, the impact of various connection positions (including core-unit, end-group, and side-chain connection sites) on molecular packing, optoelectronic properties, and device performance is systematically reviewed. The review highlights the critical role of DSMAs in addressing key challenges in OSCs, such as photodegradation and morphological instability, while balancing power conversion efficiency and long-term stability. By consolidating recent breakthroughs and identifying future research directions, this work aims to provide valuable insights into the rational design of DSMAs, paving the way for the development of high-performance and commercially viable OSCs. Full article

Azulene has been attracting much attention as a charge transfer material in organic electronics due to its inherent large dipole moment and small band gap, but its application in perovskite solar cells (PSCs) is very limited. Herein, azulene was applied as the core acceptor for hole transport materials (HTMs), and two molecules named Azu-Py-DF and Azu-Py-OMeTPA were designed and synthesized, in which 4-pyridyl was introduced on the 6-position of the 1,3-substituted azulene core to adjust energy levels. The different spatial orientations of pyridine and the azulene core improve the solubility and reduce the crystallinity of the material, which is conducive to creating a thin film morphology. Azu-Py-OMeTPA exhibited good hole and electron mobility compared with standard Spiro-OMeTAD. Applied as an HTM in PSCs, the Azu-Py-OMeTPA-based device achieved a power conversion efficiency (PCE) of 18.10%, which is higher than that of the 6-position unsubstituted counterpart. Nevertheless, the anticipated passivation effect of the 4-pyridyl group was diminished due to the electron-deficient nature of azulene’s seven-membered ring. These results demonstrate that optimizing the structure of azulene-based HTMs can significantly alter molecular spatial structure, film formation properties, electron delocalization characteristics and charge transport, and can lead to improved device performance, providing insights for the future design of novel HTMs. Full article

Efficient and stable hole-transport material (HTM) is essential for enhancing the efficiency and stability of high-efficiency perovskite solar cells (PSCs). The commonly used HTMs such as spiro-OMeTAD need dopants to produce high efficiency, but those dopants degrade the perovskite film and cause instability. Therefore, the development of dopant-free N,N′-bicarbazole-based HTM is receiving huge attention for preparing stable, cost-effective, and efficient PSCs. Herein, we designed and proposed seven distinct small-molecule-based HTMs (B1–B7), which are synthesized and do not require dopants to fabricate efficient PSCs. To design this new series, we performed synergistic side-chain engineering on the synthetic reference molecule (B) by replacing two methylthio (–SCH3) terminal groups with a thiophene bridge and electron-withdrawing acceptor. The enhanced phase inversion geometry of the proposed molecules resulted in reduced energy gaps and better electrical, optical, and optoelectronic properties. Density functional theory (DFT) and time-dependent DFT simulations have been used to study the precise photo-physical and optoelectronic properties. We also looked into the effects of holes and electrons and the materials’ structural and photovoltaic properties, including light harvesting energy, frontier molecular orbital, transition density matrix, density of states, electron density matrix, and natural population analysis. Electron density difference maps identify the interfacial charge transfer from the donor to the acceptor through the bridge, and natural population analysis measures the amount of charge on each portion of the donor, bridge, and acceptor, which most effectively represents the role of the end-capped moieties in facilitating charge transfer. Among these designed molecules, the B6 molecule has the greatest absorbance (λ_max of 444.93 nm in dichloromethane solvent) and a substantially shorter optical band gap of 3.93 eV. Furthermore, the charge transfer analysis reveals superior charge transfer with improved intrinsic characteristics. Furthermore, according to the photovoltaic analysis, the designed (B1–B7) HTMs have the potential to provide better fill factor and open-circuit voltages, which will ultimately increase the power conversion efficiency (PCE) of PSCs. Therefore, we recommend these molecules for the next-generation PSCs. Full article

Due to their low cost, good biocompatibility, and ease of structural modification, organic long-persistent luminescence (LPL) materials have garnered significant attention in organic light-emitting diodes, biological imaging, information encryption, and chemical sensing. Efficient charge separation and carrier migration by the host–guest structure or using polymers and crystal to build rigid environments are effective ways of preparing high-performance materials with long-lasting afterglow. In this study, four types of crystalline materials (MODPA: DDF-O, MODPA: DDF-CHO, MODPA: DDF-Br, and MODPA: DDF-TRC) were prepared by a convenient host–guest doping method at room temperature under ambient conditions, i.e., in the presence of oxygen. The first three types exhibited long-lived charge-separated (CS) states and achieved visible LPL emissions with durations over 7, 4, and 2 s, respectively. More surprisingly, for the DDF-O material prepared with PMMA as the polymer substrate, the afterglow time of DDF-O: PMMA was longer than 10 s. The persistent room-temperature phosphorescence effect caused by different CS state generation efficiencies and rigid environment were the main reason for the difference in LPL duration. The fourth crystalline material was without charge separation and exhibited no LPL because it was not a D-A system. The research results indicate that the CS state generation efficiency and a rigid environment are the key factors affecting the LPL properties. This work provides new understandings in designing organic LPL materials. Full article

A major challenge in improving the overall efficiency of dye-sensitized solar cells is improving the optoelectronic properties of small molecule acceptors. This work primarily investigated the effects of conjugation in nitriles incorporated as acceptor moieties into a newly designed series of D-A-A dyes. Density functional theory was employed to specifically study how single–double and single–triple conjugation in nitriles alters the optical and electronic properties of these dyes. The Cy-4c dye with a highly conjugated nitrile unit attained the smallest band gap (1.80 eV), even smaller than that of the strong cyanacrylic anchor group (2.07 eV). The dyes lacking conjugation in nitrile groups did not contribute to the LUMO, while LUMOs extended from donors to conjugated nitrile components, facilitating intramolecular charge transfer and causing a strong bind to the film surface. Density of state analysis revealed a considerable impact of conjugated nitrile on the electronic properties of dyes through an effective contribution in the LUMO, exceeding the role of the well-known strong 2,1,3-benzothiadiazole acceptor unit. The excited state properties and the absorption spectra were investigated using time-dependent density functional theory (TD-DFT). Conjugation in the nitrile unit caused the absorption band to broaden, strengthen, and shift toward the near-infrared region. The proposed dyes also showed optimum photovoltaic properties; all dyes possess high light-harvesting efficiency ($LHE$) values, specifically 96% for the dyes Cy-3b and Cy-4c, which had the most conjugated nitrile moieties. The dyes with higher degrees of conjugation had longer excitation lifetime values, which promote charge transfer by causing steady charge recombination at the interface. These findings may provide new insights into the structure of conjugated nitriles and their function as acceptor moieties in DSSCS, which may lead to the development of extremely effective photosensitizers for solar cells. Full article

The resolution of Si complementary metal–oxide–semiconductor field-effect transistor (C-MOSFET) image sensors (CISs) has been intensively enhanced to follow the technological revolution of smartphones, AI devices, autonomous cars, robots, and drones, approaching the physical and material limits of a resolution increase in conventional Si CISs because of the low quantum efficiency (i.e., ~40%) and aperture ratio (i.e., ~60%). As a novel solution, a hybrid organic–Si image sensor was developed by implementing B, G, and R organic photodiodes on four n-MOSFETs for photocurrent sensing. Photosensitive organic donor and acceptor materials were designed with cost-effective small molecules, i.e., the B, G, and R donor and acceptor small molecules were Coumarin6 and C_60, DMQA and MePTC, and ZnPc and TiOPc, respectively. The output voltage sensing margins (i.e., photocurrent signal difference) of the hybrid organic–Si B, G, and R image sensor pixels presented results 17, 11, and 37% higher than those of conventional Si CISs. In addition, the hybrid organic–Si B, G, and R image sensor pixels could achieve an ideal aperture ratio (i.e., ~100%) compared with a Si CIS pixel using the backside illumination process (i.e., ~60%). Moreover, they may display a lower fabrication cost than image sensors because of the simple image sensor structure (i.e., hybrid organic–Si photodiode with four n-MOSFETs). Full article

The diketopyrrolopyrrole (DPP) unit represents one of the building blocks more widely employed in the field of organic electronics; in most of the reported DPP-based small molecules, this unit represents the electron acceptor core symmetrically coupled to donor moieties, and the solubility is guaranteed by functionalizing lactamic nitrogens with long and branched alkyl tails. In this paper, we explored the possibility of modulating the solubility by realizing asymmetric DPP derivatives, where the molecular structure is extended in just one direction. Four novel derivatives have been prepared, characterized by a common dithyenil-DPP fragment and functionalized on one side by a thiophene unit linked to different auxiliary electron acceptor groups. As compared to previously reported symmetric analogs, the novel dyes showed an increased solubility in chloroform and proved to be soluble in THF as well. The novel dyes underwent a thorough optical and electrochemical characterization. Electronic properties were studied at the DFT levels. All the dyes were used as active layers in organic field effect transistors, showing balanced charge transport properties. Full article