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Effect of Π-Π Conjugation in Benzylammonium Cations on Crystal Structure, Morphology, Optical Properties, and Optoelectronic Performance of Bi-Based Perovskite
Bi-based organic halides have attracted widespread attention as potential substitutes for lead-based organic halide perovskites and have been explored and applied in many optoelectronic devices. The rational design of organic Bi-based halides is a popular research topic. In this work, we used benzylammonium (BA) cations to synthesize BA 3 Bi 2 I 9 (BBI) perovskite material and FA 3 Bi 2 I 9 (FBI, FA [formamidinium]) as control. We observe that the benzene rings in BA cations overlap with each other due to the benzene rings Π-Π conjugation in the crystal structure of BBI, which exhibits large interplanar spacing due to large BA ions. BBI has preferential orientation along the (020) crystal plane. Due to conjugation, scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS) mapping images indicate that the surface of the BBI thin film is smoother and more uniform than that of the FBI thin film. We fabricated the device by growing thin films of BBI and FBI on ITO interdigital electrodes. The photodetector based on BBI SC exhibits stability and regularity with turning on/off of the light at different intensities (10, 20, 30, and 40 W m −2 ) and wavelengths (386, 397, 405, and 433 nm). The ultraviolet–visible (UV–vis) absorption and reflection spectrum analysis shows that BBI has a slightly wider bandgap than FBI. This study can provide some ideas for the design Π-Π conjugation in organic metal halides.
Vertically ordered mesoporous silica film-assisted electrochemical cytosensor for the sensitive detection of HeLa cells
Designing fast and simple quantitative methods on cheap and disposable electrodes for the early detection of HeLa cells is highly desirable for clinical diagnostics and public health. In this work, we developed a label-free and sensitive electrochemical cytosensor for HeLa cell detection based on the gated molecular transport across vertically ordered mesoporous silica films (VMSFs) on the disposable indium tin oxide (ITO) electrode. As high affinity for a folate receptor existed on the membrane of HeLa cancer cells, folic acid (FA) functionalized VMSF could regulate the transport of electrochemical probe (Fe(CN) 6 3− ) by the specific recognition and adhesion of HeLa cells toward the VMSF surface. In addition, VMSF, served as a solid skeleton, is able to effectively prevent the direct contact of cells with the underlying electrode, remaining the underlying electrode activity and favoring the diffusion of Fe(CN) 6 3− . Once specific adhesion of HeLa cells to the VMSF surface happens, Fe(CN) 6 3− redox probe exhibits impeded transport in the silica nanochannels, ultimately resulting in the decreased electrochemical responses and realizing the quantitative determination of HeLa cells with a broad linear range (10 1 –10 5 cells/mL) and a low limit of detection (4 cells/mL). The proposed electrochemical cytosensor shows a great potential application for the early diagnosis of cervical cancer.
Cu Nanoparticles/CoO/Carbon Nanofibers as an Enhanced Peroxidase Mimic for Total Antioxidant Capacity Assessment in Drinks
With the improvement of the quality of life, the assessment of total antioxidant capacity (TAC) has attracted much attention in the field of a healthy diet, food analysis, or health guidelines. In this work, Cu nanoparticles (NPs)/CoO/carbon nanofibers (CNFs) as a promising nanozyme for peroxidase (POD) mimicking was synthesized by electrospinning and carbonation. Subsequently, a colorimetric sensing platform is constructed for TAC assessment by using 3,3′,5,5′-tetramethylbenzidine (TMB) as a chromogenic substrate based on Cu NPs/CoO/CNFs under presence of H2O2. The enhanced POD catalytic efficiency of Cu NPs/CoO/CNFs for TMB oxidation (ox-TMB) was about 3.2-fold higher than that of bare Cu NPs/CNFs or CoO/NFs, which was ascribed to the synergistic catalytic effect and the generation of heterogeneous interfaces between Cu NPs and CoO in CNFs. When some antioxidants such as AA, FA, TA, and GA were introduced in the chromogenic system, ox-TMB was reduced to colorless TMB, allowing the subsequent assessment of TAC. The results show that the limits of detection toward AA, FA, TA, and GA were 8.7, 8.3, 2.7, and 2.4 μM, respectively. Moreover, this proposed method was used for the TAC assay in real samples including fresh juices and commercial beverages, which showed good promise in practical applications such as food nutrition assessment, food analysis, personalized nutrition intervention, or staple food research.
Targeting Macrophages via Ultrasonic Contrast Microspheres for Monitoring and Treatment of Knee Synovitis
The malignant cycle of synovitis considerably impacts the progression of osteoarthritis (OA). Therefore, the precise localization of synovitis, targeted disruption of the inflammatory cycle, and real-time monitoring of its dynamics are crucial for the effective diagnosis and management of OA. Here, porous HAMA/GelMA microspheres are synthesized using microfluidic technology. Interleukin-10 (IL-10) nanobubbles, prepared via double emulsification, are grafted with folic acid (FA) via an amide reaction and subsequently impregnated and adsorbed onto the microspheres, thereby constructing an ultrasonic contrast microsphere system. This system facilitates not only ultrasonic imaging for accurate localization of synovitis but also the targeted and controlled delivery of IL-10 under ultrasound conditions. In vitro, under ultrasound intensities of 0, 0.5, and 1.5 W, the system effectively releases IL-10 at the rates of 19.95%, 30.95%, and 40.67%, respectively. In vivo, the biodegradability of the system facilitates real-time tracking and monitoring of synovitis for at least 14 days. In summary, ultrasonic contrast microspheres enable precise localization and real-time monitoring of synovitis. Under ultrasound conditions, these microspheres enable targeted and controlled drug delivery, effectively disrupting vicious inflammatory cycles. This strategy pioneers new pathways for the management and precise treatment of OA.
Luminescent Inorganic–Organic Hybrid Nondoped Double Perovskite Nanocrystals for Optoelectronics
One of the key issues of lead-free halide double perovskite nanocrystals (DPNCs) is their low photoluminescence quantum yields (PLQYs), and the PLQYs of nondoped pristine DPNCs are currently below 2%, though they can be enhanced via strategies such as ion doping or surface passivation. Herein, we report an organic–inorganic hybrid approach to significantly increase the PLQYs of nondoped pristine DPNCs. With Cs2NaBiCl6 NCs as the model, we selected methylammonium (MA+) and formamidine (FA+) as organic A-site ions and for the first time successfully synthesized the organic–inorganic hybrid in-direct bandgap DPNCs, e.g., MA2NaBiCl6 and FA2NaBiCl6. The PLQYs of the prepared Cs2NaBiCl6, MA2NaBiCl6, and FA2NaBiCl6 are 1.9%, 6.2%, and 15.4%, respectively. The enhancement of PLQYs can be due to the lattice distortion on using the unsymmetric rod-like MA+ and V-like FA+ to replace the symmetric Cs+, which yields faster charge transfer, enhanced excitation, and reduced nonradiative recombination, which are combined to make the self-trapped excited state brighter with significantly enhanced PLQYs. Overall, our results clearly demonstrate that the organic–inorganic hybrid strategy is an effective way to tune the lattice distortion and significantly enhance the emission of nondoped DPNCs, which will open doors for designing functional optoelectronic materials.
Dual-mode probe based on mesoporous silica coated gold nanorods for targeting cancer cells
A dual-mode imaging probe for targeting cancer cells has been fabricated based on mesoporous silica coated gold nanorods (MS-GNRs) for the first time. In this probe, fluorescence and surface enhanced Raman scattering (SERS) signals can be generated independently by using different excitation wavelengths. To investigate the targeting performance of the probe, folic acid (FA) is conjugated on the outer surfaces of MS-GNRs as a targeting ligand and HeLa cells were used as model cancer cells because they overexpress folate receptors (FRs). The endocytosis mechanism was verified by competing experiments with free FA through both fluorescence images and SERS mappings. Moreover, the cytotoxicity of the probe was remarkably reduced in comparison with the GNRs without the silica shell as proved by the results of MTT assay . Compared with traditional imaging probes, this new type of nanoprobe has great potential for multiplexed imaging in living cells, which can be easily realized by using fluorescence and SERS signals.
Mitochondria-Targeted Nanoscale MOFs for Improved Photodynamic Therapy
Graphical A metal-organic framework (MOF)-based nanoplatform with dual-targeting functions toward cancer cells and their mitochondria is established, via a proposed phosphorylation modification strategy. With the complete coverage of targeting molecules (i. e., TPP molecules for mitochondrial targeting and FA molecules for tumoral targeting), the efficacy of photodynamic therapy is greatly improved. Due to the existence of hypoxic microenvironment, the efficacy of photodynamic therapy (PDT) is frequently weakened. As a result, targeted treatment toward oxygen-rich mitochondria is considered as a promising cancer therapy. Herein, both triphenylphosphine (TPP) and folic acid (FA) are simultaneously grafted onto nanoscale metal-organic frameworks (NMOFs) to realize dual-targeting delivery of the nanoplatforms into cancer cells and their mitochondria via the proposed phosphorylation modification strategy. A large amount of highly efficient photosensitizer of porphyrinic molecules is integrated into the NMOFs with a uniform particle size of about 65 nm. Thanks to the strong Zr−O−P bonding, a dense coverage of phosphonate-conjugating targeting molecules on NMOFs is obtained and each surficial unsaturated Zr−O cluster is adequately occupied. The resultant dual-targeting NMOFs feature high biostability and biocompatibility, as well as improved cellular uptake and mitochondrial accumulation. The PDT efficacy of these dual-targeting NMOFs is significantly improved with a low IC 50 of 0.74 μM upon 10 min light radiation, which is at least four times higher than that of non-targeting counterparts. This phosphorylation strategy would be hopeful for immobilizing a variety of biogenic groups on NMOFs to make them targetable to various specific organelles and to improve the therapy efficacy on related diseases.
Thermal tolerance of perovskite quantum dots dependent on A-site cation and surface ligand
A detailed picture of temperature dependent behavior of Cs x FA 1-x PbI 3 perovskite quantum dots across the composition range is constructed by performing in situ optical spectroscopic and structural measurements, supported by theoretical calculations that focus on the relation between A-site chemical composition and surface ligand binding. The thermal degradation mechanism depends not only on the exact chemical composition, but also on the ligand binding energy. The thermal degradation of Cs-rich perovskite quantum dots is induced by a phase transition from black γ-phase to yellow δ-phase, while FA-rich perovskite quantum dots with higher ligand binding energy directly decompose into PbI 2 . Quantum dot growth to form large bulk size grain is observed for all Cs x FA 1-x PbI 3 perovskite quantum dots at elevated temperatures. In addition, FA-rich quantum dots possess stronger electron−longitudinal optical phonon coupling, suggesting that photogenerated excitons in FA-rich quantum dots have higher probability to be dissociated by phonon scattering compared to Cs-rich quantum dots.
Facile synthesis of Au NCs@POMA-Fe-FA nanoregulators with precise-targeted/NIR-laser-triggered/tumor microenvironment-responsive abilities for enhanced photothermal /photodynamic/chemodynamic therapy with photothermal imaging guidence
For overcoming the insurmountable obstacles of the multimodal combined therapy (MCT) in anti-cancer, tumor microenvironment regulation is considered an effective method. Hence, a TME adjustable, precise-targeted and near-infrared (NIR)-laser-responsive Au nanoclusters (NCs)@poly-o-mercaptoaniline (POMA)-Fe nanoregulators (NRGs) grafting with folic acid (FA) was designed and successfully fabricated by a simple redox with coordination method. The obtained Au NCs@POMA-Fe-FA NRGs could achieve the excellent TME regulation ability via the following avenues: the Fe 3+ ions are released by the acidic TME from the POMA-Fe-FA shell to transform the hydrogen peroxide (H 2 O 2 ) into O 2 for overcoming the hypoxia of TME. Further, the massive Fe 3+ ions are reduced by the excessive glutathione (GSH) in TME into Fe 2+ ions, which further react with H 2 O 2 to produce the hydroxyl radical (·OH) by Fenton reaction, realizing the chemodynamic therapy (CDT) to tumor. Moreover, the Au NC cores and the POMA-Fe-FA shell endow the nanoregulators with outstanding photodynamic and photothermal abilities triggered by NIR laser respectively. In addition, the consumption of GSH enhances the photodynamic therapy (PDT) and CDT synergistically. More importantly, the FA-induced targeting and NIR guided photothermal imaging grant the obtained nanoregulators outstanding selectivity for the precise tumor treatment and minimized side effect. The in vivo experimental results displayed that the tumor inhibition of the prepared Au NCs@POMA-Fe-FA NRGs could reach as high as about 84%. Obviously, the synthesized Au NCs@POMA-Fe-FA NRGs pave a new path for the design and preparation of novel multi-mode therapy for cancer with regulatory effects to TME.
Integrated volatolomics and lipidomics analysis reveal the characteristic flavor formation mechanism in steamed large yellow croaker (Pseudosciaena crocea)
The internal relationship between lipid composition and characteristic flavor in the steamed large yellow croaker (LYC) was investigated using volatolomics, lipidomics, and electronic sensory systems. Compared to fresh LYC, the concentrations of five key volatile flavor compounds detected after steaming exceeded human sensory thresholds. Notably, nonanal, hexanal, and 1-octen-3-ol significantly influenced the flavor of the cooked meat. Steaming at 70 °C enhanced the LYC flavor profile, with the strongest flavor observed at 80 °C. The content of three key volatile flavor compounds peaked, especially hexanal, which reached 54.55 μg/kg. Phosphatidylcholines, triacylglycerols, and fatty acids were closely associated with the volatile flavor profile of steamed LYC. The oxidation of FA 22:6 was identified as a crucial source of flavor in LYC. This study aimed to improve consumer experience by exploring the nutritional quality and flavor formation mechanisms in the thermal processing of LYC.
Receptor-mediated photothermal/photodynamic synergistic anticancer nanodrugs with SERS tracing function
Phototherapy, especially the photothermal therapy (PTT) and the photodynamic therapy (PDT), have become very promising in cancer treatment due to its low invasiveness and high efficacy. Both PTT and PDT involve the utilization of light energy, and their synergistic treatment should be a good solution for cancer treatment by ingenious design. The therapeutic effect of phototherapy is closely associated with the amount and location of anticancer-nanodrugs accumulated in tumor cells, and the receptor-mediated endocytosis should be an excellent candidate for enhancing anticancer-nanodrugs internalization. Surface enhanced Raman spectroscopy (SERS) imaging is suitable for tracing nanodrugs due to its high selectivity, sensitivity and reliability. In this paper, we hope to construct a receptor-mediated PTT/PDT synergistic anticancer nanodrugs and evaluate the corresponding efficacy through SERS tracing function. Here, the receptor-mediated PTT/PDT synergistic anticancer nanodrugs are prepared by the chemical modification of gold nanorods (GNRs), involving protoporphyrin IX (PpIX), 4-mecaptobenzoic acid (MBA), and folic acid (FA). The achieved results show that the receptor-mediated endocytosis can greatly facilitate the internalized amount and intracellular distribution of the nanodrugs, thus lead to the anti-cancer efficacy improvement. Importantly, this receptor-mediated PTT/PDT synergistic treatment with SERS tracing function will provide a simple and effective strategy for the design and application of anticancer phototherapy nanodrugs.
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