The incorporation of biorecognition elements with electronic components into point-of-care testing (POCT) devices expands their capabilities and enables intricate quantitative assays. The combination of near field communication (NFC) technology and biosensors offers endless possibilities in this context, which has the potential to provide simple and intelligent sensing solutions for both electrical and nonelectrical parameter measurements. In an effort to tap into this potential, we present the first example of a screen-printed electrode (SPE)-based sensing platform for ethanol in serum samples. NFC-assisted electrochemical biosensors were created using SPE and altered by drop-casting two different diketopyrrolopyrrole (DPP)-based conjugated polymer nanoparticles ( poly -DPP-Se; poly -DPP-SeSe) and platinum nanoparticles (PtNPs) to construct an alcohol oxidase (AOx)-based electrochemical biosensor. The fabricated biosensors, SPE/PtNPs/ poly -DPP-Se NPs/AOx and SPE/PtNPs/ poly -DPP-SeSe NPs/AOx, respond linearly to ethanol in the ranges of 1.7-12.8 mM and 0.85-12.8 mM with 1.22 mM and 0.39 mM detection limits, respectively. K Mapp, I max, and sensitivity values were calculated for SPE/PtNPs/ poly -DPP-Se NPs/AOx as 2.52 mM, 3.20 mu A, and 2.27 mu A mM-1 cm-2 and for SPE/PtNPs/ poly -DPP-SeSe NPs/AOx as 0.4 mM, 2.51 mu A, and 2.15 mu A mM-1 cm-2, respectively. Excellent stability and electrocatalytic activity to electrooxidation of ethanol were achieved with the SPE/PtNPs/ poly -DPP-SeSe NPs/AOx configuration. Furthermore, artificial serum samples were used to assess the sensor's reliability. The experimental findings reveal that the proposed biosensors could provide ease of use, fast analysis times, portability, and reliability for food and healthcare research and applications.
Trialkyl oxonium salts are among the most powerful electrophiles known. They are immediately quenched by nucleophiles like alcohols and halide ions, and are therefore used in unreactive solvents and have non-nucleophilic counterions. Any proposal to incorporate a nucleophilic hydroxy substituent into a trialkyl oxonium species would thus be ill-considered, and pairing an R3O+ cation with an alkoxide counterion would be an abstract notion, at best. Here, we describe how these combinations are made possible within the context of the robust environment of the heterotriquinane ring system. A stable, C3 symmetric oxatriquinanetriol can be simply accessed by reaction of the tris-epoxide of 1,4,7-cyclononatriene with aqueous acid. The three OH groups of this hemispherical cation point into the endo space of the bowl and participate in strong intramolecular hydrogen bonding. A close balance in the dynamics of proton exchange between these hydroxy functions and amine bases is predicted by modeling. In practice, treatment of oxatriquinanetriol with the non-nucleophilic base 2-tert-butyl-1,1,3,3-tetramethylguanidine (Barton's base) leads to a zwitterionic oxonium alkoxide.
The increasing demand for high-performance and cost-effective solar cells is a driving factor in the development of new nanomaterials or compounds compatible with low-cost, low-temperature fabrication routes. Titanium oxide (TiOx), an inexpensive earth-abundant material, is among the most extensively investigated candidates for electron-selective layer implementation in silicon solar cells. In this context, we investigate the effect of hydrogen peroxide (H2O2) modification of a solution-processed TiOx precursor on the resulting film and device properties. Through various characterization studies, the formation of titanium-peroxo (Ti-OO) complexes upon H2O2 modification is consolidated, and the subsequent structural, optical, and electrochemical properties are examined. Owing to H2O2 modification, an outstanding implied open-circuit voltage (iVoc) of 713 mV and a low contact resistivity (rho c) of 1.96 m Omega cm2 are simultaneously achieved. At the device level, a maximum power conversion efficiency (PCE) of 21.9% is measured for cells incorporating a modified-TiOx/LiFx/Al rear contact, representing a gain of 1.8% compared to control cells with a LiFx/Al rear contact. Notably, this performance is attained using dopant-free standalone TiOx produced at room temperature, without any annealing steps throughout the fabrication process. Stability assessments of unencapsulated devices reveal the superior thermal stability of the modified devices under practical conditions. Moreover, the devices' behavior under illumination is simulated using Solar Cell Capacitance Simulator (SCAPS) software to elucidate the role of modified-TiOx properties in the enhanced photovoltaic (PV) performance metrics. The accomplishments outlined in this study open new avenues for advancing high-efficiency crystalline silicon (c-Si) solar cells through a simplified fabrication process.
Photodynamic therapy (PDT) is a minimally invasive and tumor-selective treatment modality; however, despite notable progress in several cancer types, effective treatment options for brain tumors remain limited. Although explored only in a limited number of studies, the intrinsic selectivity of photosensitizers bearing activatable groups makes PDT an attractive strategy for brain cancers. Here, we report, for the first time, the photodynamic efficacy of a leucine aminopeptidase (LAP)-activatable iodinated resorufin derivative (LAP-RI) in neuroblastoma cells (SH-SY5Y). By incorporating a LAP-responsive handle group, the photosensitizer remains silent until enzymatic activation, exploiting the elevated LAP expression in SH-SY5Y observed in this work. This activatable design enabled a measurable, yet modest (∼2-fold) enhancement in phototoxicity toward neuroblastoma cells relative to healthy fibroblasts, reflecting enzyme-dependent activation rather than strong intrinsic tumor selectivity. Rather than constituting strong intrinsic cell-line selectivity, this difference reflects enzyme-dependent activation, consistent with elevated LAP activity in SH-SY5Y cells. These findings highlight the potential of resorufin-based, enzyme-activatable photosensitizers as a mechanistically selective platform for PDT of extracranial tumors and underscore the broader promise of activatable PDT agents.
Non-Newtonian microfluidics play a crucial role in modern industrial and technological advancements, and in biological phenomena. We report how local variations in the alignment at the boundary of nematic liquid crystals (LCs) govern their flow characteristics under pressure-driven microfluidic conditions. Specifically, we micropatterned the LC anchoring conditions using a photocleavable self-assembled monolayers and investigated the resulting flow characteristics through measurement of flow resistances, and spatial variations in LC director fields as a function of the microfluidic flow. Combined experimental measurements and computational simulations showed that patterned anchoring induces pronounced coupling between flow and molecular alignment, leading to spatially heterogeneous flow regimes revealing backflow mechanisms, hysteresis, pattern-dependent, and rich topological structures. These findings establish a framework for controlling soft anisotropic fluids through interfacial patterning, offering new opportunities for adaptive and reconfigurable microfluidic systems. Nematic liquid crystals offer a way to explore anisotropic fluid dynamics, but are typically confined to uniform boundaries. Combining experiments and simulations, the authors show that patterning anchoring conditions with photocleavable monolayers induces strong flow-alignment coupling, revealing heterogeneous flow regimes.
Background: Photodynamic therapy (PDT) offers a promising complementary strategy for treating glioblastoma multiforme (GBM); however, limited control over photosensitizer activation and reduced efficacy under hypoxic conditions remain significant limitations. Methods: In this study, we present the synthesis and functional evaluation of Gal-SiX, an enzymatically activatable Si-xanthene-based activatable PDT agent designed to address these challenges. Prepared via an improved 10-step synthetic route, Gal-SiX exhibits clear turn-on fluorescence and absorbance responses upon β-galactosidase activation and efficiently generates reactive oxygen species in aqueous media. Results: Mechanistic studies revealed that Gal-SiX enables both Type I and Type II PDT pathways, a favorable feature for GBM environments characterized by restricted oxygen availability. In vitro assays conducted on U87MG glioblastoma cells and L929 healthy fibroblasts demonstrated light-dependent cytotoxicity, with IC50 values of 3.30 μM and 7.19 μM, respectively. Gal-SiX also showed minimal dark toxicity (>80 μM) and potent light-induced cytotoxicity, yielding a phototoxicity index of 24.8 in glioblastoma cells. Confocal imaging and MTT assays consistently confirmed enzymatic activation and effective PDT response at the cellular level. Conclusions: Overall, this work introduces the first activatable Si-xanthene-based PDT agent for glioblastoma and provides the first evidence that the Si-xanthene scaffold can support dual Type I/II phototoxicity. These results underscore Gal-SiX’s potential as a PDT platform for addressing the unique constraints of GBM biology.
Photodynamic therapy (PDT) offers a promising complementary strategy for the treatment of glioblastoma multiforme (GBM); however, achieving selective activation in tumor tissue and maintaining efficacy under hypoxic conditions remain significant limitations. In this study, we present the synthesis and functional evaluation of Gal-SiX, an enzymatically activatable Si-xanthene photosensitizer designed to address these challenges. Prepared through an improved 10-step synthetic route, Gal-SiX displays a clear turn-on fluorescence and absorbance response upon β-galactosidase activation and generates reactive oxygen species efficiently in aqueous media. Mechanistic studies revealed that Gal-SiX enables both Type I and Type II PDT pathways, an advantageous feature for GBM, where oxygen availability is restricted. In vitro assays conducted on U87MG glioblastoma cells and L929 healthy fibroblasts demonstrated meaningful selectivity, with IC50 values of 3.30 μM and 7.19 μM, respectively. Gal-SiX also showed minimal dark toxicity (>80 μM) and potent light-induced cytotoxicity, yielding a phototoxicity index of 24.8 in glioblastoma cells. Confocal imaging and MTT assays consistently demonstrated its activation and PDT efficacy. Overall, this work introduces the first activatable Si-xanthene–based PDT agent for glioblastoma and provides the first evidence that the Si-xanthene scaffold can support dual Type I/II phototoxicity. These results underscore Gal-SiX’s potential as a selective PDT platform for addressing the unique constraints of GBM biology.
One of the leading approaches to enhancing the performance and stability of perovskite solar cells (PSCs) involves passivating the perovskite surface and grain boundaries with large ammonium salts. Here, we report the synthesis of furan-, thiophene-, and selenophene-functionalized phenyl methanaminium iodide salts (FPMAI, TPMAI, and SPMAI) and their application as passivating agents on 3D [(Cs0.04FA0.85MA0.11)Pb(I0.96Br0.01Cl0.03)3] perovskite. The TPMAI-passivated PSCs performed the best and achieved a power conversion efficiency (PCE) of 23.15% compared to the reference (without a passivating agent) at 20.91%. Efficiencies reduced to 98 and 54% of the initial value after 1250 h of continuous illumination for TPMAI-treated PSCs and the reference, respectively. DFT calculations revealed that TPMAI offers superior passivation, disfavoring iodine vacancy formation. Our findings highlight the potential of functionalized PMAI salts as passivation agents for improved efficiency and stability in PSCs.
Perovskite solar cells (PSCs) have exhibited significant advancements over the last decade, positioning them as the most promising candidate for the next-generation photovoltaic technology. Recently, significant efforts have been focused on the scale-up of PSCs towards enabling their commercialization. In this study, we performed electrical simulations to elucidate the balance between electrical and geometric losses in PSMs and verified our model by fabricating opaque (PSMs) and semi-transparent wide-bandgap perovskite solar modules (ST-PSMs). We showed that a P2 width of 20-50 mu m provides an optimized P2 contact resistance, resulting in high geometric fill factor (GFF) and fill factor (FF), simultaneously. PSMs with an aperture area of 4.2 cm(2), reaching a GFF of 98.4%, an FF of 81.5%, and a PCE of 17.78% were fabricated. To demonstrate the scalability of this approach, 16 cm(2) PSMs, reaching a GFF of 97.0%, an FF of 80.1%, and a PCE of 17.58% were fabricated. ST-PSMs (4 cm(2)) with >92.5% GFF, 81.4% FF, and 15.68% PCE were fabricated. We believe that the proposed optoelectronic model, along with its validation through the fabrication, exhibiting exceptionally high GFFs and FFs, elucidates the optical-electrical trade-off in PSMs and thus offers valuable insights for the design of highly efficient PSMs.
Minimizing surface recombination is crucial for enhancing silicon solar cell passivation. Conventional dielectric materials require vacuum deposition and high-temperature annealing, increasing complexity and cost. This study explores Nonafluorobutane sulfonic acid (C4HF9O3S), a superacid, as a passivation layer for silicon solar cells. Unlike traditional dielectrics, it eliminates the need for vacuum processing or high-temperature annealing while offering excellent passivation. Results show that the superacid forms a self-assembled monolayer on silicon, improving passivation and enabling efficient charge extraction. N-type silicon coated with the superacid achieves an effective lifetime exceeding 8.5 ms, and when combined with Al, it forms an interface with a contact resistivity as low as 5.75 m Omega.cm2. Characterization and density functional theory (DFT) calculations confirm both chemical and field-effect passivation mechanisms, validating the monolayer's superior performance. When integrated into a full solar cell, the Nona layer enhances device performance, yielding a 3.05% absolute efficiency gain compared to the reference cell without Nona. This study introduces a cost-effective alternative to conventional dielectrics, simplifying processing while reducing production costs and CO2 emissions, paving the way for sustainable, high-efficiency silicon solar cells.
Solution‐processed kesterite (copper zinc tin sulfide [CZTS]) solar cells attract significant attention owing to their low cost, ease of large‐scale production, and earth‐abundant elemental composition, which make these devices promising to fulfill the ever‐increasing demand of the photovoltaic (PV) industry. Compared to the performances of expensive vacuum‐based techniques, colloidal nanocrystal kesterite solar cells garner substantial interest due to their economical and rapid processing. Led by the hot‐injection method, organic solvent‐based techniques are widely adopted to realize CZTS nanocrystal inks. With organic solvents, ligand‐stabilized nanoparticles are formed leading to dispersive and homogenous kesterite inks. However, the presence of carbon‐rich ligands around the nanocrystal surface often leads to the formation of a fine‐grain layer that is rich in carbon content. The organic ligands decompose into amorphous carbon residues during a high‐temperature annealing process and hinder the grain growth process. The carbon‐rich fine‐grain (CRFG) layer generally poses a negative influence on the PV performance of the kesterite solar cell; however, few reports maintain their disposition about CRFG as innocuous. In this review study, a detailed discussion on CRFG is presented, aiming to understand the insights about its formation and impact on the device's performance.
The lack of long-term stability and reproducibility of perovskite solar cells (PSCs) is the main roadblock preventing their successful commercialization. 3D/2D PSCs are one of the most prominent ways to address these issues. Various salts that are mostly based on phenyl ethyl ammonium iodide (PEAI) have been utilized to grow a 2D perovskite layer on 3D perovskites. Herein, we report the effect of substituting the methoxy (-OMe) group at the ortho (o), meta (m), and para (p) positions on PEAI salts. Photoluminescence and time-resolved photoluminescence show that o-OMe-PEAI-treated surfaces achieve reduced defect densities and nonradiative recombination rates compared with the other analogs. Devices with PCEs over 23% are achieved for o-OMe-PEAI-based 3D/2D PSCs, and the enhanced performance is attributed to the favorable formation energy and desired vertical orientation according to the density functional theory (DFT) analyses. Finally, the unique orientation of the o-OMe-PEAI-based 2D perovskite results in significantly enhanced long-term, moisture, and thermal stability.
Surface passivation with 2D perovskites is a powerful strategy to achieve improved stability and performance in perovskite solar cells (PSCs). Various large organic cations have been successfully implemented, led by phenylethylammonium ( PEA + ) and its derivatives. However, systematic studies on large sets of cations to understand the effect of substituent position on 2D perovskite passivation and device performance are lacking. Herein, a collection of halogenated PEA + iodide salts ( x ‐XPEAI where x : ortho ( o ), meta ( m ) , para ( p ), X : F, Cl, Br) are synthesized by a facile method and deposited on top of 3D perovskite. The 2D perovskite layer formation is confirmed by X‐ray diffraction (XRD) and grazing‐incidence wide‐angle X‐ray scattering analyses for all cations, regardless of the nature and position of the halogen. Density functional theory analysis reveals that lower formation energies and higher interfacial dipoles achieved by m ‐substituted cations are responsible for enhanced performance compared to their o ‐ and p ‐ counterparts. While the m ‐BrPEAI ‐treated device shows a champion efficiency of 23.42%, ( V OC =1.13 V, FF=81.2%), considering average efficiencies, stability, and reproducibility, the treatment with m ‐ClPEAI salt yields the best overall performance. This comprehensive study provides guidelines for understanding the influence of large cation modification on performance and stability of 3D/2D PSCs.
Wide‐bandgap perovskite solar cells (WBG‐PSCs), when partnered with Si bottom cells in tandem configuration, can provide efficiencies up to 44%; yet, the development of stable, efficient, and scalable WBG‐PSCs is required. Here, the utility of the hybrid evaporation‐solution method (HESM) is investigated to meet these demanding requirements via its unique advantages including ease of control and reproducibility. A PbI 2 /CsBr layer is co‐evaporated followed by coating of organic‐halide solutions in a green solvent. Bandgaps between 1.55–1.67 eV are systematically screened by varying CsBr and MABr content. Champion efficiencies of 21.06% and 20.35% in cells and 19.83% and 18.73% in mini‐modules (16 cm 2 ) for perovskites with 1.64 and 1.67 eV bandgaps are achieved, respectively. Additionally, 18.51%‐efficient semi‐transparent WBG‐PSCs are implemented in 4T perovskite/bifacial silicon configuration, reaching a projected power output of 30.61 mW cm −2 based on PD IEC TS 60904‐1‐2 (BiFi200) protocol. Despite similar bandgaps achieved by incorporating Br via MABr solution and/or CsBr evaporation, PSCs having a perovskite layer without MABr addition show significantly higher thermal and moisture stability. This study proves scalable, high‐performance, and stable WBG‐PSCs are enabled by HESM, hence their use in tandems and in emerging applications such as indoor photovoltaics are now within reach.
3D/2D Perovskite Solar Cells In article number 2302038, Xiao-Xin Gao, Paul J. Dyson, Selcuk Yerci, Mohammad Khaja Nazeeruddin, Gorkem Gunbas and co-workers systematically screen a series of halogenated phenylethylammonium iodide salts to elucidate the impact of substituent position on 2D perovskite passivation and device efficiency. Notably, meta-substituted salts outperform their counterparts (PCE >%23) owing to their lower formation energies and higher interfacial dipoles.
Activity-based photosensitizers (aPSs) are highly attractive as they offer improved selectivity and better therapeutic outcome in the scope of photodynamic therapy (PDT). Here, a hydrogen sulfide (H2S) responsive iodinated resorufin-based PS (RHS) was developed to treat neuroblastoma cancer cells selectively. RHS was shown to be a phototheranostic agent as it turned on its fluorescence signal and singlet oxygen (O-1(2)) generation capability after reacting with H2S. RHS exhibited remarkable sensitivity towards H2S and proved to be highly cytotoxic in H2S rich SH-SY5Y human neuroblastoma cells upon light irradiation. In contrast, no photocytotoxicity was observed in H2S deficient nonmalignant fibroblast L929 cells. RHS marks the first example of a resorufin-based H2S activatable photo-theranostic agent, which paves the way for effective treatment of neuroblastoma through PDT modality.
Cancer is still among the leading health issues today, considering the cost, effectiveness, complexity of detection/treatment modalities and survival rates. One of the most important criteria for higher survival rates is the early and sensitive diagnosis of the disease that can direct the treatment modalities effectively. Fluorescence imaging agents emerged as an important alternative to the current state of the art due to their spatial and temporal resolution, high sensitivity and selectivity, ease of modification towards generating activatable agents, ease of operation, and low cost. In addition to imaging, light-based treatment modality, photodynamic therapy (PDT), attained remarkable attention, as it is minimally invasive and has fewer side effects compared to the current standard of care treatments. Even though fluorescence imaging and PDT have these significant advantages, light that needs to excite the agent has limited penetration in tissues, hindering widespread utilization. Hybrid xanthene dyes, particularly ones bearing silicon or phosphine oxide as the bridging unit of xanthene moiety, gained significant interest not only due to their excellent photochemical properties in aqueous media, high fluorescence quantum yield, photostability but also their proper absorption and emission maxima that allow for deep tissue imaging and therapy. Here, the design and synthesis strategies, key photophysical properties, their application in fluorescence imaging applications, and surprisingly limited utilization as PDT agents of hybrid xanthene dyes that emerged in the last decade have been reviewed in detail.
The molecular engineering of conjugated systems has proven to be an effective method for understanding structure-property relationships toward the advancement of optoelectronic properties and biosensing characteristics. Herein, a series of three thieno[3,4-c]pyrrole-4,6-dione (TPD)-based conjugated monomers, modified with electron-rich selenophene, 3,4-ethylenedioxythiophene (EDOT), or both building blocks (Se-TPD, EDOT-TPD, and EDOT-Se-TPD), were synthesized using Stille cross-coupling and electrochemically polymerized, and their electrochromic properties and applications in a glucose biosensing platform were explored. The influence of structural modification on electrochemical, electronic, optical, and biosensing properties was systematically investigated. The results showed that the cyclic voltammograms of EDOT-containing materials displayed a high charge capacity over a wide range of scan rates representing a quick charge propagation, making them appropriate materials for high-performance supercapacitor devices. UV-Vis studies revealed that EDOT-based materials presented wide-range absorptions, and thus low optical band gaps. These two EDOT-modified materials also exhibited superior optical contrasts and fast switching times, and further displayed multi-color properties in their neutral and fully oxidized states, enabling them to be promising materials for constructing advanced electrochromic devices. In the context of biosensing applications, a selenophene-containing polymer showed markedly lower performance, specifically in signal intensity and stability, which was attributed to the improper localization of biomolecules on the polymer surface. Overall, we demonstrated that relatively small changes in the structure had a significant impact on both optoelectronic and biosensing properties for TPD-based donor-acceptor polymers.
Activity-based theranostic photosensitizers are highly attractive in photodynamic therapy as they offer enhanced therapeutic outcome on cancer cells with an imaging opportunity at the same time. However, photosensitizers (PS) cores that can be easily converted to activity-based photosensitizers (aPSs) are still quite limited in the literature. In this study, we modified the dicyanomethylene-4H-chromene (DCM) core with a heavy iodine atom to get two different PSs (DCMO-I, I-DCMO-Cl) that can be further converted to aPS after simple modifications. The effect of iodine positioning on singlet oxygen generation capacity was also evaluated through computational studies. DCMO-I showed better performance in solution experiments and further proved to be a promising phototheranostic scaffold via cell culture studies. Later, a cysteine (Cys) activatable PS based on the DCMO-I core (DCMO-I-Cys) was developed, which induced selective photocytotoxicity along with a fluorescence turn-on response in Cys rich cancer cells.