The novel concept of modifying and enhancing the properties of existing functional micelles through self-complementary interactions has significant potential. In this study, a practical approach to living polymerization of functionalized thermoresponsive monomers enabled the incorporation of self constituted multiple hydrogen bonded groups into micelles that have potential as supramolecular drug-delivery systems. Phase transitions and morphological studies in aqueous solution showed that the microstructure can be controlled to achieve well-defined vesicle-like micelles with respect to the strength of the hydrogen bond segment. Thus, the resulting micelles have a very low critical micellization concentration and very high loading capacity (16.1%), making the loading process extremely stable and efficient. Incorporation of the anticancer drug doxorubicin (DOX) affected the micellization process in aqueous solution and enabled fine-tuning of drug loading and precise control of drug release rate with excellent sensitivity. Release studies in vitro showed that DOX-loaded micelles exerted dose dependent cytotoxicity against human liver carcinoma (HepG2) cells at the physiological temperature of 37 degrees C. In addition, DOX-loaded micelles were efficiently endocytosed by the cancer cells, which may enable the micelles to serve as suitable vehicles for effective delivery of anticancer drugs to primary tumors and metastatic disease. This newly developed material may provide a potential route towards next-generation drug delivery vehicles.Statement of SignificanceA breakthrough innovation in water-based thermo-responsive polymers has enabled significant progress in developing smart stimuli-responsive nanocarriers by generating novel "supramolecular polymeric micelles" via self-complementary hydrogen-bonding interactions. These newly developed micelles exhibit extremely high micellar stability and drug loading capacity (up to 16%), excellent thermo-responsive behavior and precise control of drug release rate due to hydrogen-bond-induced physical cross-linking. In addition, doxorubicin-loaded micelles were efficiently endocytosed by the cancer cells, which allows them to serve as suitable vehicles for effective delivery of anticancer drugs to primary tumors and metastatic disease. Thus, this work provides a potential route for the development of next generation multifunctional nanocarriers that have improved safety and to increase the therapeutic efficacy of anticancer therapy. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Self-healing supramolecular polymers can be rapidly reprocessed under mild temperature conditions via dynamic reshuffling of the hydrogen bond networks.
A breakthrough innovation in water-based polymeric nanoparticles has enabled significant progress in mimicking the folding of natural proteins by generating novel "single-chain polymeric nanoparticles" (SCPNs) via supramolecular interactions. In this study, a practical approach to the living polymerization of functionalized oligo(ethylene glycol) methacrylate monomers allows the incorporation of self-constituted multiple hydrogen-bonded groups into physically cross-linked polymer networks, which enables the formation of highly functionalized SCPNs in an aqueous environment. The newly developed materials are particularly attractive from a practical point of view since they have a very low critical micellization concentration and uniform particle diameters of ca. 25 nm, making them extremely stable under dilute conditions. Concentration-dependent experiments showed that SCPNs formed at polymer concentrations up to 40 mg/mL with no significant change in morphology observed. Moreover, the formed SCPNs had a very high stability in an aqueous solution containing surfactant, suggesting potential for a wide variety of applications as a promising candidate nanocarrier for bioimaging, controlled release, and drug delivery systems.
A new thermally cross-linkable triphenylamine derivative containing a benzoxazine functional group for application in organic light-emitting diodes (OLEDs.)
A new concept to supramolecular assembly of existed functional polymers, capable of forming network-like organizational clusters through multiple hydrogen-bonding interactions has been exploited. In this paper, a new adenine-based poly(triphenylamine-carbazole) (PTC-A) has been prepared which exhibits a high self-complementary ability in solution and solid states owing to the formation of adenine–adenine (A–A) pairs by induced hierarchical self-assembly. Comparing with uracil-substituted PTC sample (PTC-U), PTC-A presents a much higher thermal stability, electrochemical stability and solvent-resistance ability due to the formation of the more stable physically cross-linking structure. When the PTC-A is utilized as a hole injection/transport layer in a trilayer OLED device, a remarkable improvement in performance relative to the control PTC and PTC-U under similar experimental conditions has been achieved. Further comparison with a control device using a conventional PEDOT:PSS, the efficiency of the solution-processed phosphorescent PLED device with PTC-A is significantly higher than those of PTC-U and PEDOT:PSS-based devices. Thus, PTC-A represents the next-generation hole injection/transport material for high efficiency LED device and low-cost fabrication process.
Core–shell supramolecular micelles exhibit excellent memory performances, providing a potential route towards next-generation energy storage/memory materials.
A series of polylactic acid-polyethylene glycol-polylactic acid diacrylate macromers (PEGLM) were synthesized, and a novel chitosan-PEGLM double network (DN) hydrogel was further successfully fabricated by the sequential interpenetrating technology with highly cross-linked chitosan as the rigid component and PEGLM as the flexible component. Their structures and components were characterized by 1H NMR, FTIR, and XRD. Their fracture morphology was investigated by SEM. It was interesting to found that the compressive strength of hydrogel wound reach its maximum value when the chitosan content was 10%, no matter what the molecular weight of PEGLM component was. What’s more, we found that the compressive strength of 6KL7 could reach 1.07 MPa at gel state, whose PEG segment molecular weight was 6,000, and polymerization degree of PLA was 7. The effects of glutaraldehyde ratio, polymerization degree of PLA, and molecular weight of PEG segment on the mechanical strength of DN hydrogels were also discussed in this article. To further strengthen DN hydrogels, the double network-linear (DNL) hydrogels were fabricated by introducing linear poly(vinyl alcohol) (PVA) into the DN hydrogels. The DN-L hydrogels exhibited better mechanical properties, with the compressive strength up to 1.45 MPa. These hydrogels may have prospective applications in the fields of wound dressing, artificial cartilage and tissue engineering scaffold materials which require high mechanical properties.
A new process for modifying a polymeric material for use as a hole injection transport layer in organic light-emitting diodes has been studied, which is through 2π + 2π photodimerization of a DNA-mimetic π-conjugated poly(triphenylamine-carbazole) presenting pendent uracil groups (PTC-U) under 1 h of UV irradiation. Multilayer florescence OLED (Organic light-emitting diodes) device with the PTC-U-1hr as a hole injection/transport layer (ITO (Indium tin oxide)/HITL (hole-injection/transport layer) (15 nm)/N,N'-di(1-naphthyl)- N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine (NPB) (15 nm)/Tris-(8-hydroxyquinoline) aluminum (Alq3) (60 nm)/LiF (1 nm)/Al (100 nm)) is fabricated, a remarkable improvement in performance (Qmax (external quantum efficiency) = 2.65%, Bmax (maximum brightness) = 56,704 cd/m2, and LE (luminance efficiency)max = 8.9 cd/A) relative to the control PTC-U (Qmax = 2.40%, Bmax = 40,490 cd/m2, and LEmax = 8.0 cd/A). Multilayer phosphorescence OLED device with the PTC-U-1hr as a hole injection/transport layer (ITO/HITL (15 nm)/Ir(ppy)3:PVK (40 nm)/BCP (10nm)/Alq3 (40 nm)/LiF (1 nm)/Al (100 nm)) is fabricated by successive spin-coating processes, a remarkable improvement in performance (Qmax = 9.68%, Bmax = 41,466 cd/m2, and LEmax = 36.6 cd/A) relative to the control PTC-U (Qmax = 8.35%, Bmax = 34,978 cd/m2, and LEmax = 30.8 cd/A) and the commercial product (poly(3,4-ethylenedioxythiophene):polystyrenesulfonate) PEDOT:PSS (Qmax = 4.29%, Bmax = 15,678 cd/m2, and LEmax = 16.2 cd/A) has been achieved.
A novel UrCy–PPG was developed for the synthesis of high-quality supramolecular polymers in large-scale production utilizing only commercially-available chemicals.
A novel urea-cytosine end-capped polypropylene glycol (UrCy-PPG) can self-assemble into a long-range ordered lamellar microstructure on the surface of graphene, due to the strong specific interactions between UrCy-PPG and graphene. In addition, the graphene composite produced exhibits a high conductivity (∼1093 S m(-1)) with a dramatic thermo-responsive ON/OFF resistance-switching behavior (10 consecutive cycles).
A simple methodology for overcoming interfacial mixing, based on the use of a photo-crosslinkable conjugated polymer as HITM for fluorescent and solution-processed phosphorescent OLEDs.
A nucleobase-assembled supramolecular nanofiber is capable of forming network-like polymeric clusters through complementary hydrogen-bonding interactions. It behaves as an effective chromophore that greatly enhances the light emission efficiency of fluorescent fibers, reaching up to three times higher efficiency than the control samples.
A new urea–cytosine-functionalized supramolecular polymer can be rapidly reshaped and reprocessed under mild conditions via rearrangement of the hydrogen bonding network.
In this paper we demonstrate the use of low-temperature-solution-processable bismuth iodide (BiI3) nanosheets as hole transport layers in organic photovoltaics with an active layer comprising poly(3-hexylthiophene) (P3HT) mixed with a fullerene derivative. The performance of the resulting devices was comparable with that of corresponding conventionally used systems incorporating polyethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS). UV–vis spectroscopy revealed that the transparency of a BiI3 layer in the visible (>620nm) and near-infrared range is greater than that of a PEDOT:PSS layer. X-ray photoemission spectroscopy of a BiI3 film revealed signals at 158.8, 164, 618.6, and 630eV—characteristic of Bi 4f7/2, Bi 4f5/2, I 3d5/2, and I 3d3/2, respectively—that indicated a stoichiometric BiI3 film. Wet milling of BiI3 crystals resulted in the formation of nanosheets, the presence of which we confirmed using scanning electron microscopy. The resultant power conversion efficiency of the device was approximately 3.5%, with an open-circuit voltage of 0.56V, a short-circuit current density of 10.4mAcm–2, and a fill factor of 60.1% under AM1.5G irradiation (100mWcm−2).
Poly(3-hexylthiophene)-graft-poly(ethylene oxide) (P3HT-g-PEO) rod–coil conjugated random copolymers through oxidative polymerization with FeCl3 and facile click chemistry.
This paper describes a simple and environmentally friendly approach—a facile, one-pot, quenching/chelation method—for the fabrication of a silver paste in the form of Ag/oligothiophene complex composites. These Ag/oligothiophene complex composites possess excellent conductivities of 1.8 × 104 S cm−1 in the bulk state and 6.08 × 102 S cm−1 in the form of thin films. We have used X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and scanning electron microscopy (SEM) to characterize the microstructures of these novel Ag/oligothiophene complex composites.
New polystyrene (PS)/carbon nanofiber (CNF) and PS/graphite foams with an inter-connected honeycomb-like carbon particulate network of CNF or graphite were prepared by first coating the surface of polymer pellets with either CNF or graphite and then conducting batch foaming using carbon dioxide (CO2) as a blowing agent. It was found that the inter-connected honeycomb-like carbon particulate network could significantly reduce the compression yielding of conventional PS foams. With 1 wt% of CNFs or graphite, the PS foams with inter-connected honeycomb-like carbon particulate network were 5–9 times more electrically conductive than foams made of compounded PS nanocomposite with the same carbon particle loading. In addition, the PS foams with inter-connected honeycomb-like carbon particulate network were more thermally conductive and revealed significantly improved thermal stability comparing to foams made of compounded polymer nanocomposites.
In this study, nanopillar arrays of silicon oxide are fabricated through a process involving very‐large‐scale integration, for use as two‐dimensional periodic relief gratings (2DPRGs) on silicon surfaces. Oligonucleotides are successively immobilized on the pillar surface, allowing the system to be used as an optical detector specific for the targeted single‐stranded DNAs (ssDNAs). The surfaces of the oligonucleotides‐modified 2DPRGs undergo insignificant structural changes, but upon hybridizing with target ssDNA, the 2DPRGs undergo dramatic changes in terms of their pillar scale. Binding of the oligonucleotides to the 2DPRG occurs in a way that allows them to retain their function and selectively bind the target ssDNA. The performance of the sensor is evaluated by capturing the target ssDNA on the 2DPRGs and measuring the effective refractive index (neff). The binding of the target ssDNA species to the 2DPRGs results in a color change from pure blue to red, observable by the naked eye along an angle of 15–20°. Moreover, effective medium theory is used to calculate the filling factors inside the 2DPRGs and, thereby, examine the values of neff during the structural changes of the 2DPRGs. Accordingly, these new films have potential applications as label‐free optical biosensors.