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A Lesson from Nature: Biomimetic Self-assembling Phthalocyanines for High-efficient Photothermal Therapy within the Biological Transparent Window
摘要： Development of facile but high-efficient small organic molecule based photothermal therapy (PTT) in the in vivo transparent window (800-900 nm) has been regarded as a minimally invasive and most promising strategy for potential clinical cancer treatment. Phthalocyanine (Pc) molecules with remarkable photophysical and photochemical properties as well as high extinction coefficients in the near-infrared region are highly desirable for PTT, but as far satisfying single-component Pc-based PTT within the in vivo transparent window (800-900 nm) has very rarely been reported. Herein, inspired by the self-assembly algorithm of natural bacteriochlorophylls (BChl's) c, d, and e, biomimetic self-assembling tetrahexanoyl Pc Bio-ZnPc with outstanding light-harvesting capacity was demonstrated to exhibit excellent PTT efficacy evidenced by both in vitro and in vivo results, within the biological transparent window.
关键词： photothermal therapy,phthalocyanine,biological transparent window,self-assembly,biomimetics
更新于2025-09-23 15:23:52
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Voltage Stimulated Anion Binding of Metallo-Porphyrin Induced Crystalline 2D Nanoflakes
摘要： Voltage stimulated redox active materials received significant attention in the field of organic electronics and sensor technology. Consequently, such stimuli responsive materials triggered the formation of crystalline nanostructures facilitates the design of efficient smart devices hitherto unknown. Thus, we reported free base and metallo- tetratolylporphyrin linked ferrocene derivatives (H2TTP-Fc and ZnTTP-Fc) undergo distinct proton/anion binding mechanism in CHCl3 during bulk electrolysis at applied voltage of 1.4 V followed by nanospheres and crystalline 2D nanoflakes formation via MVD approach. Cyclic voltammetry and UV-Vis absorption studies of H2TTP-Fc and ZnTTP-Fc revealed the cation (H+)/anion (Cl-) binding affinity towards free ‘N’ atoms and Zn leads [H4TTP-Fc]+Cl- and H+[(Cl)ZnTTP-Fc]- thereby improvement in current and charge generation compared to initial state. SEM and TEM images revealed the nanospheres and 2D nanoflakes with average diameter of 50 – 200 nm and 0.2 - 1 μm. x-ray diffraction analysis suggest that protonated H2TTP-Fc aggregates exhibit amorphous nature, while H+[(Cl)ZnTTP-Fc]- revealed crystalline nature from layer-by-layer arrangement of nanoflakes assisted by π-π stacking and ion-dipole interactions. Hence, voltage responsive anion binding of metallo-porphyrins unique observation offer remarkable design of smart organic materials for sensors and biological applications.
关键词： anion binding,crystalline nanoflakes,metallo-porphyrin,self-assembly,bulk electrolysis
更新于2025-09-23 15:23:52
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An infrared IgG immunoassay based on the use of a nanocomposite consisting of silica coated Fe3O4 superparticles
摘要： A reliable, rapid and ultrasensitive immunoassay is described for determination of immunoglobulin G (IgG). It is making use of biofunctional magnetite (Fe3O4) superparticles coated with SiO2 and serving as an infrared (IR) probe. The unique IR fingerprint signals originating from the transverse and longitudinal phonon modes, respectively, of the asymmetric stretching of the Si–O–Si bridges display a satisfactory resistance to optical interference from the environment. The adoption of Fe3O4 superparticles instead of Fe3O4 nanoparticles as the magnetic core warrants a controllable structure and a strong magnetic response. This facilitates the efficient purification of the probes and the alleviation of the interfacial resistance between the liquid-solid interfaces by using a magnet. The gold-coated substrate was used to immobilize goat-anti-human IgG. The analyte (human IgG) was incubated with the IR probes, and then captured by the substrate immobilized antibody with the assistance of an external magnetic field. The integral area of the IR absorption band between 1250 cm?1 – 900 cm?1 was chosen for quantitative assay. The limit of detection is 95 fM, which is two orders of magnitude better than that without the magnetic field. The assay time was shortened from 2 h to 1 min. High selectivity, specificity, and long-term stability of the immunoassay were achieved. The performance of the assay when analyzing blood samples confirmed the practicability of the method.
关键词： Molecular vibration,IR spectroscopy,Core-shell,Sandwich immunoassay,Self-assembly,Protein,Blood,Superparamagnetism,Magnetic beads
更新于2025-09-23 15:23:52
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Luminescent Lanthanide–Collagen Peptide Framework for pH-Controlled Drug Delivery
摘要： Collagen mimetic scaffolds play a pivotal role in regenerative medicine and tissue engineering due to their extraordinary structural and biological features. We have herein for the first time reported the construction of luminescent lanthanide-collagen peptide hybrid three-dimensional nanofibrous scaffolds, which well mimic the characteristic architectural structure of native collagen. Three collagen mimetic peptides composed of repetitive central (GPO)7 sequences and altered terminal amino acids, have been shown to consistently self-assemble to form biocompatible nanofibers under the trigger of a variety of lanthanide ions, which also functionalize the assembled materials with easily tunable photoluminescence. Furthermore, the collagen peptide-lanthanide hybrid scaffolds possess programmable pH-responsive features. The lanthanide ion-mediated assembly of all the three collagen peptides are conveniently and reversibly regulated by pH, while their pH-dependent patterns are finely tuned by the identity of terminal amino acids. Using camptothecin and cefoperazone sodium as two model drugs, the drug-loading and releasing efficiency of the collagen peptide-lanthanide scaffolds are nicely modulated by pH, demonstrating the efficacy of these nanofibrous scaffolds as pH-responsive drug carriers. These novel luminescent collagen peptide-lanthanide scaffolds provide a facile system for pH-controlled drug delivery, suggesting promising applications in the development of therapies for many diseases.
关键词： self-assembly,scaffold,pH-responsive,Collagen mimetic peptides,drug delivery
更新于2025-09-23 15:23:52
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2D reentrant micro-honeycomb structure of graphene-CNT in polyurethane: High stretchability, superior electrical/thermal conductivity, and improved shape memory properties
摘要： The recent rapid development of soft electronics and wearable technology has demanded materials with the function of combining mechanical deformation and electronics. Particularly, materials simultaneously having memory shape characteristics in which mechanical deformation repeatedly occurs in response to stimulus, high stretchability and excellent electric/heat transfer characteristics are interesting actuator materials in future applications. As a stretchable and conductive platform, we fabricated a reentrant micro-honeycomb structure from graphene-CNT, which had structural stretchability due to the accordion-like reentrant structure and continuous conductive paths in the vertical and horizontal directions. To impart shape memory properties, we fabricated composites by simply infiltrating shape memory polyurethane (SMPU) into a stable graphene/CNT framework. Our resulting reentrant micro-honeycomb graphene-CNT/SMPU composites simultaneously exhibited a relatively low resistivity of 5 Ω cm, a change in resistance of less than 10% in the 50% stretching/releasing states, long term stability, and superior tensile shape memory properties, including 95.6% shape fixity and a 90.6% recovery ratio. Regularly distributed graphene-CNT structures offer heterogeneous nucleation sites and undisturbed crystal growth in neat SMPU pillars, resulting in superior shape memory properties. We also constructed a circuit with portable batteries to demonstrate that our reentrant graphene-CNT/SMPU composite offers potential applications as an emergency circuit breaker.
关键词： Shape memory,Polyurethane,Reentrant graphene-CNT,Composite,Ice-templated self-assembly
更新于2025-09-23 15:23:52
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Effect of solvents on the self-assembly of long chain alkylphosphonic acids on indium tin oxide surface - In situ studies on the adsorption kinetics and electron transfer process
摘要： The spontaneous self-assembly process of phosphonic acids (PAs) onto indium tin oxide (ITO) surface has been studied in this work. We have carried out in situ adsorption kinetics studies of phosphonic acids in ethanol as a solvent using electrochemical impedance spectroscopy (EIS). Further, the effect of different solvents like ethanol, water, toluene and hexane on the structural integrity of the alkylphosphonic acid (CH3 (CH2)n PO3H2, n = 15,17) thin films on ITO surface has been investigated by using [Fe(CN)6]3-/4- as a redox probe. From the study of formation kinetics, it is concluded that molecular self-assembly process follows two adsorption steps, a fast first step followed by a slower second step. The results of cyclic voltammetric (CV) and impedance measurements show that phosphonic acids form a highly impermeable surface film on ITO when polar solvents like ethanol and water are used.
关键词： self assembly,Adsorption Kinetics,microelectrode array,Contact Angle,Capacitance,ITO,Phosphonic acid
更新于2025-09-23 15:23:52
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H-complexes in the “4-n-alkoxybenzoic acid: 4-pyridyl 4′-n-alkoxybenzoate” system. IR spectroscopy and quantum chemical calculations
摘要： IR spectra of individual 4-n-dodecyloxybenzoic acid (A) and 4-pyridyl 4'-n-dodecyloxybenzoate (B) compounds as well as IR spectra of 2A:1B and 1A:1B systems were recorded. For the assignment of the experimental vibrational spectra a series of quantum chemical calculations of DFT(B97-D)/6-311++G** level was carried out. Hydrogen-bonded complexes of types A···A, A···B, as well as various trimers that can be formed at different component ratios in system A-B were simulated. The geometric structure of these complexes was optimized and the vibrational frequencies were calculated. The conclusions on the molecular organization of system A-B for different ratios of the components A and B were based on the interpretation of IR spectra and the analysis of calculated thermodynamic characteristics of self-assembly processes. Thus, it is determined that the system A consists of cyclic A···Acycl dimers; in 1A:1B system the H-complexes of A···B type are formed. In the 2A:1B system in the process of self-assembly, instead of the complexes A···A···B and A···B···A of stoichiometric composition, the complexes A···B and A···Acycl are formed in the ratio 2:1. These results are confirmed by the dilatometric method data.
关键词： thermodynamic characteristics,4-pyridyl 4'-n-alkoxybenzoate,DFT,IR spectra,self-assembly,4-n-alkoxybenzoic acid,hydrogen bonded complexes
更新于2025-09-23 15:23:52
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Capillarity-Driven Self-Assembly of Silver Nanowires-Coated Fibers for Flexible and Stretchable Conductor
摘要： The rapid development of smart textiles requires the large-scale fabrication of conductive fibers. In this study, we develop a simple, scalable and low-cost capillary-driven self-assembly method to prepare conductive fibers with uniform morphology, high conductivity and good mechanical strength. Fiber-shaped flexible and stretchable conductors are obtained by coating highly conductive and flexible silver nanowires (Ag NWs) on the surfaces of yarn and PDMS fibers through evaporation-induced flow and capillary-driven self-assembly, which is proven by the in situ optical microscopic observation. The density of Ag NWs and linear resistance of the conductive fibers could be regulated by tuning the assembly cycles. A linear resistance of 1.4 Ω/cm could be achieved for the Ag NWs-coated nylon, which increases only 8% after 200 bending cycle, demonstrating high flexibility and mechanical stability. The flexible and stretchable conductive fibers have great potential for the application in wearable devices.
关键词： flexible,self-assembly,Fiber conductor,stretchable,silver nanowires.
更新于2025-09-23 15:23:52
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One-drop Self-assembly and Size Control of Organic Nonlinear Optical Crystal DSNS Nanowires
摘要： In this study, we demonstrate a one-drop self-assembly method for fabricating nanowires (NWs) of organic second-order nonlinear optical (NLO) material, 4-N, N-dimethylamino-4'-N'-methyl- stilbazolium 2-naphthalenesulfonate (DSNS). By controlling the parameters of the self-assembly process, we successfully controlled the length of DSNS from a few micrometers to millimeters. The obtained NWs have very high surface quality with surface roughness <150 pm, which is highly beneficial for fabricating integrated optical devices. DSNS NW has the same triclinic crystal structure as that of bulk crystal and exhibits excellent second-order NLO and fluorescent properties, which could provide wide opportunities for on-chip optoelectronic devices and integrated photonic systems. Furthermore, the one-drop self-assembly method only requires reagents in microgram quantities, and thus this method is extremely environment-friendly.
关键词： one-drop self-assembly,organic nanowire,size control,nonlinear optical material
更新于2025-09-23 15:23:52
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Heterobimetallic (Fe <sup>II</sup> /Pt <sup>II</sup> )-Based Supramolecular Coordination Complexes Using 1,1′-Ferrocene Dicarboxylate: Self-Assembly and Interaction with Carbon Dots
摘要： The synthesis and characterization of a new pyrazine-based ditopic organoplatinum(II) complex having a bite angle of 180° is reported. The facile and efficient syntheses are described of three discrete neutral Fe(II)/Pt(II) heterobimetallic SCCs with Pt(II) acceptor clips of different binding angles, 0, 120, and 180°. These new SCCs were characterized by multinuclear NMR and mass spectrometry. Electrochemical response of these ferrocene containing self-assembled ensembles was studied using cyclic voltammetry. The diplatinum acceptor organometallic clips significantly quench the fluorescence of highly emitting carbon quantum dots (CD), while the self-assembled macrocycles tend to nullify the quenching effect of the organometallic clips. Interestingly, the inefficient quenching of CD fluorescence by these SCCs was found to be directly related to the angular disposition of the binding sites in the Pt(II) based organometallic clips.
关键词： carbon dots,heterobimetallic,electrochemical response,self-assembly,supramolecular coordination complexes,fluorescence quenching,ferrocene
更新于2025-09-23 15:23:52