Phase behavior, crystallization, and hierarchical nanostructures in self-organized thermoset blends of epoxy resin and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) triblock copolymers

Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and amphiphilic poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers were successfully prepared. Two samples of PEO-PPO-PEO triblock copolymer with different ethylene oxide (EO) contents, denoted as EO30 with 30 wt % EO content and EO80 with 80 wt % EO content, were used to form the self-organized thermoset blends of varying compositions using 4,4'-methylenedianiline (MDA) as curing agent. The phase behavior, crystallization, and morphology were investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM), atomic force microscopy (AFM), and small-angle X-ray scattering (SAXS). It was found that macroscopic phase separation took place in the MDA-cured ER/EO30 blends containing 60-80 wt % EO30 triblock copolymer. The MDA-cured ER/EO30 blends with EO30 content up to 50 wt % do not show macroscopic phase separation but exhibit nanostructures on the order of 10-30 nm as revealed by both the TEM and SAXS studies. The AFM study further shows that the ER/EO30 blend at some composition displays structural inhomogeneity at two different nanoscales and is hierarchically nanostructured. The spherical PPO domains with an average size of about 10 nm are uniformly dispersed in the 80/20 ER/EO30 blend; meanwhile, a structural inhomogeneity on the order of 50-200 nm is observed. The ER/EO80 blends are not macroscopically phase-separated over the entire composition range because of the much higher PEO content of the EO80 triblock copolymer. However, the ER/EO80 blends show composition-dependent nanostructures on the order of 10-100 nm. The 80/20 ER/EO80 blend displays hierarchical structures at two different nanoscales, i.e., a bicontinuous microphase structure on the order of about 100 nm and spherical domains of 10-20 nm in diameter uniformly dispersed in both the continuous microphases. The blends with 60 wt % and higher EO80 content are completely volume-filled with spherulites. Bundles of PEO lamellae with spacing of 20-30 nm interwoven with a microphase structure on the order of about 100 nm are revealed by AFM study for the 30/70 ER/EO80 blend.

Nanostructures, semicrystalline morphology, and nanoscale confinement effect on the crystallization kinetics in self-organized block copolymer/thermoset blends

This work reports the first instance of self-organized thermoset blends containing diblock copolymers with a crystallizable thermoset-immiscible block. Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and a low-molecular-weight (Mn = 1400) amphiphilic polyethylene-block-poly(ethylene oxide) (EEO) symmetric diblock copolymer were prepared using 4,4'-methylenedianiline (MDA) as curing agent and were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). All the MDA-cured ER/EEO blends do not show macroscopic phase separation but exhibit microstructures. The ER selectively mixes with the epoxy-miscible PEO block in the EEO diblock copolymer whereas the crystallizable PE blocks that are immiscible with ER form separate microdomains at nanoscales in the blends. The PE crystals with size on nanoscales are formed and restricted within the individual spherical micelles in the nanostructured ER/EEO blends with EEO content up to 30 wt %. The spherical micelles are highly aggregated in the blends containing 40 and 50 wt % EEO. The PE dentritic crystallites exist in the blend containing 50 wt % EEO whereas the blends with even higher EEO content are completely volume-filled with PE spherulites. The semicrystalline microphase-separated lamellae in the symmetric EEO diblock copolymer are swollen in the blend with decreasing EEO content, followed by a structural transition to aggregated spherical micellar phase morphology and, eventually, spherical micellar phase morphology at the lowest EEO contents. Three morphological regimes are identified, corresponding precisely to the three regimes of crystallization kinetics of the PE blocks. The nanoscale confinement effect on the crystallization kinetics in nanostructured thermoset blends is revealed for the first time. This new phenomenon is explained on the basis of homogeneous nucleation controlled crystallization within nanoscale confined environments in the block copolymer/thermoset blends.

Reducing the photocatalytic activity of zinc oxide quantum dots by surface modification

The use of zinc oxide (ZnO) nanoparticles as ultraviolet (UV) absorbers for many organic substrates is limited because of the high photocatalytic activity of ZnO. In this study, a facile and efficient technique for the preparation of a hybrid material of silica-coated ZnO nanoparticles was used to reduce the photocatalytic activity of ZnO. Monodispersed ZnO nanopartcles were prepared by wet chemistry and the particle surface was modified by tetraethylorthosilicate to form a silica coating via the Sto¨ ber method. ZnO samples, both before and after the coating process, were investigated by transmission electron microscopy, X-ray diffraction, dynamic light scanning, infrared, and UV-Vis absorption spectroscopy. The effect of the surface modification on the photocatalytic activity of ZnO was studied by monitoring the degradation of Rhodamine B caused by photo-generated free radicals. The results implied that the photo-generation of free-radicals was strongly quenched by the presence of silica on the particle surface.

Low temperature solvothermal synthesis of ZnO quantum dots

ZnO quantum dots were synthesized via a low-temperature solvothermal process without using surfactants. Heat treatment of ZnCl2 and NaOH solutions in tetra-ethylene glycol at 140°C led to the formation of spherical ZnO nanoparticles consisting of the aggregates of uniform-sized quantum dots. The particle size and morphology were characterized using transmission electron microscopy, dynamic light scattering, X-ray diffraction, and Brunauer–Emmett–Teller gas absorption measurements. It was found that the quantum dots in the particles were single crystals of ZnO of ∼5 nm in diameter having the wurtzite structure. The quantum dots showed quantum size effects even in the agglomerated form. The growth mechanism of this new type of ZnO nanoparticles is proposed.

The application of Cd Se/ZnS quantum dots and confocal laser scanning microscopy for three-dimensional imaging of nanfibrous structures

This paper reports a fast, accurate, and non-destructive three-dimensional imaging approach based on using quantum dots and confocal laser scanning microscopy to get three-dimensional images of internal pore structure of the nanofibrous materials. A practical method of making the fiber fluorescent using quantum dots was applied before three-dimensional imaging by confocal laser scanning microscopy. Fibrous scaffolds with different porosity parameters produced by electrospinning and their three-dimensional pore structure was evaluated by this approach. Furthermore, the introduced approach can be used to measure the pore interconnectivity of the scaffold

Graphene quantum dots induce apoptosis, autophagy, and inflammatory response via p38 mitogen-activated protein kinase and nuclear factor-κB mediated signaling pathways in activated THP-1 macrophages.

The biomedical application of graphene quantum dots (GQDs) is a new emerging area. However, their safety data are still in scarcity to date. Particularly, the effect of GQDs on the immune system remains unknown. This study aimed to elucidate the interaction of GQDs with macrophages and the underlying mechanisms. Our results showed that GQDs slightly affected the cell viability and membrane integrity of macrophages, whereas GQDs significantly increased reactive oxygen species (ROS) generation and apoptotic and autophagic cell death with an increase in the expression level of Bax, Bad, caspase 3, caspase 9, beclin 1, and LC3-I/II and a decrease in that of Bcl-2. Furthermore, low concentrations of GQDs significantly increased the expression of tumor necrosis factor-α (TNF-α), interleukin-1β (IL-1β), IL-8, whereas high concentrations of GQDs elicited opposite effects on the cytokines production. SB202190, a selective inhibitor of p38 mitogen-activated protein kinase (MAPK), abolished the cytokine-inducing effect of GQDs in macrophages. Moreover, GQDs significantly increased the phosphorylation of p38 MAPK and p65, and promoted the nuclear translocation of nuclear factor-κB (NF-κB). Taken together, these results show that GQDs induce ROS generation, apoptosis, autophagy, and inflammatory response via p38MAPK and NF-κB mediated signaling pathways in THP-1 activated macrophages.

Graphene quantum dots directly generated from graphite via magnetron sputtering and the application in thin-film transistors

This work presents a novel method to prepare graphene quantum dots (GQDs) directly from graphite. A composite film of GQDs and ZnO was first prepared using the composite target of graphite and ZnO via magnetron sputtering, followed with hydrochloric acid treatment and dialysis. Morphology and optical properties of the GQDs were investigated using a number of techniques. The as-prepared GQDs are 4-12 nm in size and 1-2 nm in thickness. They also exhibited typical excitation-dependent properties as expected in carbon-based quantum dots. To demonstrate the potential applications of GQDs in electronic devices, pure ZnO and GQD-ZnO thin-film transistors (TFTs) using ZrOx dielectric were fabricated and examined. The ZnO TFT incorporating the GQDs exhibited enhanced performance: an on/off current ratio of 1.7 × 107, a field-effect mobility of 17.7 cm2/Vs, a subthreshold swing voltage of 90 mV/decade. This paper provides an efficient, reproducible and eco-friendly approach for the preparation of monodisperse GQDs directly from graphite. Our results suggest that GQDs fabricated using magnetron sputtering method may envision promising applications in electronic devices.

Graphene quantum dots and Nafion composite as an ultrasensitive electrochemical sensor for the detection of dopamine

A novel electrochemical sensor for highly sensitive and selective detection of dopamine (DA) was developed based on a graphene quantum dots (GQDs) and Nafion composite modified glassy carbon electrode (GCE). GQDs were synthesized by a hydrothermal approach for cutting graphene sheets into GQDs and characterized by TEM, UV-vis, photoluminescence, and FT-IR spectra. The GQDs had carboxyl groups with a negative charge, which not only provided good stability, but also enabled interaction with amine functional groups in DA through electrostatic interaction to enhance the specificity of DA. The interaction and electron communication between GQDs and DA can be further strengthened via π-π stacking force. Nafion was used as an anchoring agent to increase the robustness of GQDs on the electrode surface and sensor stability and reproducibility. The GQDs-Nafion composite exhibits a good linear range of 5 nM to 100 μM and a limit of detection as low as 0.45 nM in the detection of DA. The proposed electrochemical sensor also displays good selectivity and high stability and could be used for the determination of DA in real samples with satisfactory results. The present study provides a powerful avenue for the design of an ultrasensitive detection method for clinical application.

One-step synthesis of graphene quantum dots from defective CVD graphene and their application in IGZO UV thin film phototransistor

Chemical vapor deposition (CVD) has recently been considered as the most reliable method to prepare high-quality monolayer graphene films, yet the as-grown graphene usually contains wrinkles and cracks or suffers from discontinuity. These defects can easily result in the shredding of large-sized graphene into small pieces even under a gentle disturbance. Herein, this work presents a cost-effective new method to produce high-quality GQDs by vigorous sonication of defective CVD graphene. The prepared GQDs can be easily and stably dispersed in organic solvents. Morphology and optical properties of the GQDs are investigated using a number of techniques. And we observed the as-prepared GQDs are highly homogeneous, mostly consisted of single-layered graphene, roughly round shapes less than 8 nm in a diameter, and exhibited a strong blue luminescence. Impressively, it is also confirmed that the as-obtained GQDs can act as a promising light absorption material for phototransistor with a hybrid film of GQDs and indium gallium zinc oxide (IGZO) as the channel layer. The GQD/IGZO phototransistor exhibited an appreciated photocurrent, which is 10 times larger than that of the IGZO one when exposed to 270 nm light.

Engineering molecular self-assembled fibrillar networks by ultrasound

The architecture of self-organized three-dimensionally interconnected nanocrystal fibrillar networks has been achieved by ultrasound from a solution consisting of separate spherulites. The ultrasound stimulated structural transformation is correlated to the striking ultrasonic effects on turning nongelled solutions or weak gels into strong gels instantly, with enhancement of the storage modulus up to 3 magnitudes and up to 4 times more gelling capability. The basic principle involved in the ultrasound-induced structural transformation is established on the basis of the nucleation-and-growth model of a fiber network formation, and the mechanism of seeding multiplication, aggregation suppressing, and fiber distribution and growth promotion is proposed. This novel technique enables us to produce self-supporting gel functional materials possessing significantly modified macroscopic properties, from materials previously thus far considered to be “useless”, without the use of chemical stimuli. Moreover, it provides a general strategy for the engineering of self-organized fiber network architectures, and we are consequently able to achieve the supramolecular functional materials with controllable macroscopic properties.