ABSTRACT
Octahedral symmetry is one of the parameters to tune the functional properties of complex oxides. VO2, a complex oxide with a 3d1 electronic system, exhibits an insulator-metal transition (IMT) near room temperature (â¼68 °C), accompanying a change in the octahedral structure from asymmetrical to symmetrical. However, the role of octahedral symmetry in VO2 on the IMT characteristics is unclear. Crystal and electronic structure analyses combined with density-functional-theory calculations showed the bandwidth-controlled IMT characteristics of monoclinic VO2 with high octahedral symmetry. The expanded apical V-O length for a high octahedral symmetry of a VO2 film increased the bandwidth of the conduction band by depressing V 3d-O 2p hybridization. As a result, the interdimer hopping energy increased and thereby decreased the IMT temperature, although the short V-V chain enhanced electron correlation. These findings suggest that octahedral symmetry can control the IMT characteristics of VO2 by changing the orbital occupancy.
ABSTRACT
Beamline 8A (BLâ 8A) is an undulator-based soft X-ray beamline at Pohang Accelerator Laboratory. This beamline is aimed at high-resolution ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), soft X-ray absorption spectroscopy (soft-XAS) and scanning photoemission microscopy (SPEM) experiments. BLâ 8A has two branches, 8A1 SPEM and 8A2 AP-XPS, that share a plane undulator, the first mirror (M1) and the monochromator. The photon beam is switched between the two branches by changing the refocusing mirrors after the monochromator. The acceptance angle of M1 is kept glancing at 1.2°, and Pt is coated onto the mirrors to achieve high reflectance, which ensures a wide photon energy range (100-2000â eV) with high resolution at a photon flux of â¼1013â photonsâ s-1. In this article, the main properties and performance of the beamline are reported, together with selected experiments performed on the new beamline and experimental system.
ABSTRACT
The discovery of new families, beyond graphene, of two-dimensional (2D) layered materials has always attracted great attention. However, it has been challenging to artificially develop layered materials with honeycomb atomic lattice structure composed of multicomponents such as hexagonal boron nitride. Here, through the dimensional manipulation of a crystal structure from sp3-hybridized 3D-ZnSb, we create an unprecedented layered structure of Zintl phase, which is constructed by the staking of sp2-hybridized honeycomb ZnSb layers. Using structural analysis combined with theoretical calculation, it is found that the 2D-ZnSb has a stable and robust layered structure. The bidimensional polymorphism is a previously unobserved phenomenon at ambient pressure in Zintl families and can be a common feature of transition metal pnictides. This dimensional manipulation of a crystal structure thus provides a rational design strategy to search for new 2D layered materials in various compounds, enabling unlimited expansion of 2D libraries and corresponding physical properties.
ABSTRACT
Silicon nanowires (SiNWs) opened up exciting possibilities in a variety of research fields due to their unique anisotropic morphologies, facile tuning capabilities, and accessible fabrication methods. The SiNW-based photoelectrochemical (PEC) conversion has recently been known to provide an efficiency superior to that of various photo-responsive semiconductor heterostructures. However, a challenge still remains in designing optimum structures to minimize photo-oxidation and photo-corrosion of the Si surface in a liquid electrolyte. Here, we report a simple method to synthesize hierarchically branched carbon nanowires (CNWs) on SiNWs utilizing copper vapor as the catalyst in a chemical vapor deposition (CVD) process, which exhibits outstanding photocatalytic activities for hydrogen generation along with excellent chemical stability against oxidation and corrosion. Thus, we believe that the CNW-SiNW photoelectrodes would provide a new route to developing high-performing cost-effective catalysts essential for advanced energy conversion and storage technologies.
ABSTRACT
Herein, we fabricated a super-hydrophobic SERS substrate using Sn-doped indium oxide (Indium-tin-oxide: ITO) nano-branches as a template. ITO nano-branches with tens of nanometer diameter are first fabricated through the vapor-liquid-solid (VLS) growth to provide roughness of the substrate. 10 nm thickness of Ag thin film was deposited and then treated with the post-annealing process to create numerous air-pockets in the Ag film, forming a hierarchical Ag nanostructures. The resulting substrate obtained Cassie's wetting property with a water contact angle of 151°. Compared to the normal hydrophobic Ag nanoparticle substrate, increase of about 4.25-fold higher SERS signal was obtained for 7 µL of rhodamine 6G aqueous solutions.
ABSTRACT
Multifunctional carbon-based nanodots (C-dots) are synthesized using atmospheric plasma treatments involving reactive gases (oxygen and nitrogen). Surface design was achieved through one-step plasma treatment of C-dots (AC-paints) from polyethylene glycol used as a precursor. These AC-paints show high fluorescence, low cytotoxicity and excellent cellular imaging capability. They exhibit bright fluorescence with a quantum yield twice of traditional C-dots. The cytotoxicity of AC-paints was tested on BEAS2B, THLE2, A549 and hep3B cell lines. The in vivo experiments further demonstrated the biocompatibility of AC-paints using zebrafish as a model, and imaging tests demonstrated that the AC-paints can be used as bio-labels (at a concentration of <5 mg mL-1). Particularly, the oxygen plasma-treated AC-paints (AC-paints-O) show antibacterial effects due to increased levels of reactive oxygen species (ROS) in AC-paints (at a concentration of >1 mg mL-1). AC-paints can effectively inhibit the growth of Escherichia coli (E. coli) and Acinetobacter baumannii (A. baumannii). Such remarkable performance of the AC-paints has important applications in the biomedical field and environmental systems.
Subject(s)
Carbon/chemistry , Fluorescence , Plasma Gases , Quantum Dots/chemistry , Acinetobacter baumannii/drug effects , Animals , Anti-Bacterial Agents/chemistry , Cell Line, Tumor , Escherichia coli/drug effects , Humans , Materials Testing , Polyethylene Glycols , Reactive Oxygen Species/metabolism , ZebrafishABSTRACT
We have fabricated high quality bismuth vanadate (BiVO4) polycrystalline thin films as photoanodes by pulsed laser deposition (PLD) without a postannealing process. The structure of the grown films is the photocatalytically active phase of scheelite-monoclinic BiVO4 which was obtained by X-ray diffraction (XRD) analysis. The change of surface morphology for the BIVO4 thin films depending on growth temperature during synthesis has been observed by scanning electron microscopy (SEM), and its influence on water splitting performance was investigated. The current density of the BiVO4 film grown on a glass substrate covered with fluorine-doped tin oxide (FTO) at 230 °C was as high as 3.0 mA/cm2 at 1.23 V versus the potential of the reversible hydrogen electrode (VRHE) under AM 1.5G illumination, which is the highest value so far in previously reported BiVO4 films grown by physical vapor deposition (PVD) methods. We expect that doping of transition metal or decoration of oxygen evolution catalyst (OEC) in our BiVO4 film might further enhance the performance.
ABSTRACT
The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by â¼1.41% and â¼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.
ABSTRACT
We report an effect involving hydrogen (H2)-plasma-treated nanoporous TiO2(H-TiO2) photocatalysts that improve photocatalytic performance under solar-light illumination. H-TiO2 photocatalysts were prepared by application of hydrogen plasma of assynthesized TiO2(a-TiO2) without annealing process. Compared with the a-TiO2, the H-TiO2 exhibited high anatase/brookite bicrystallinity and a porous structure. Our study demonstrated that H2 plasma is a simple strategy to fabricate H-TiO2 covering a large surface area that offers many active sites for the extension of the adsorption spectra from ultraviolet (UV) to visible range. Notably, the H-TiO2 showed strong ·OH free-radical generation on the TiO2 surface under both UV- and visible-light irradiation with a large responsive surface area, which enhanced photocatalytic efficiency. Under solar-light irradiation, the optimized H-TiO2 120(H2-plasma treatment time: 120 min) photocatalysts showed unprecedentedly excellent removal capability for phenol (Ph), reactive black 5(RB 5), rhodamine B (Rho B) and methylene blue (MB) - approximately four-times higher than those of the other photocatalysts (a-TiO2 and P25) - resulting in complete purification of the water. Such well-purified water (>90%) can utilize culturing of cervical cancer cells (HeLa), breast cancer cells (MCF-7), and keratinocyte cells (HaCaT) while showing minimal cytotoxicity. Significantly, H-TiO2 photocatalysts can be mass-produced and easily processed at room temperature. We believe this novel method can find important environmental and biomedical applications.
ABSTRACT
Few-layer black phosphorus (BP) is the most promising material among the two-dimensional materials due to its layered structure and the excellent semiconductor properties. Currently, thin BP atomic layers are obtained mostly by mechanical exfoliation of bulk BP, which limits applications in thin-film based electronics due to a scaling process. Here we report highly crystalline few-layer black phosphorus thin films produced by liquid exfoliation. We demonstrate that the liquid-exfoliated BP forms a triangular crystalline structure on SiO2/Si (001) and amorphous carbon. The highly crystalline BP layers are faceted with a preferred orientation of the (010) plane on the sharp edge, which is an energetically most favorable facet according to the density functional theory calculations. Our results can be useful in understanding the triangular BP structure for large-area applications in electronic devices using two-dimensional materials. The sensitivity and selectivity of liquid-exfoliated BP to gas vapor demonstrate great potential for practical applications as sensors.
ABSTRACT
Recently, the appeal of 2D black phosphorus (BP) has been rising due to its unique optical and electronic properties with a tunable band gap (≈0.3-1.5 eV). While numerous research efforts have recently been devoted to nano- and optoelectronic applications of BP, no attention has been paid to promising medical applications. In this article, the preparation of BP-nanodots of a few nm to <20 nm with an average diameter of ≈10 nm and height of ≈8.7 nm is reported by a modified ultrasonication-assisted solution method. Stable formation of nontoxic phosphates and phosphonates from BP crystals with exposure in water or air is observed. As for the BP-nanodot crystals' stability (ionization and persistence of fluorescent intensity) in aqueous solution, after 10 d, ≈80% at 1.5 mg mL(-1) are degraded (i.e., ionized) in phosphate buffered saline. They showed no or little cytotoxic cell-viability effects in vitro involving blue- and green-fluorescence cell imaging. Thus, BP-nanodots can be considered a promising agent for drug delivery or cellular tracking systems.
Subject(s)
Biomedical Technology/methods , Nanoparticles/chemistry , Phosphorus/chemistry , Animals , Biocompatible Materials/pharmacology , Cell Line , Cell Survival/drug effects , Fluorescence , Humans , Microscopy, Atomic Force , Optical Phenomena , Spectrum Analysis, Raman , X-Ray DiffractionABSTRACT
We have investigated the cytotoxic assay of Fe-aminoclay (FeAC) nanoparticles (NPs) and simultaneous imaging in HeLa cells by photoluminescent carbon nanodots (CD) conjugation. Non-cytotoxic, photostable, and CD NPs are conjugated with cationic FeAC NPs where CD NPs play a role in bio-imaging and FeAC NPs act as a substrate for CD conjugation and help to uptake of NPs into cancer cells due to positively charged surface of FeAC NPs in physiological media. As increase of CD-FeAC NPs loading in HeLa cell in vitro, it showed slight cytotoxicity at 1000 µg/mL but no cytotoxicity for normal cells up to concentration of 1000 µg/mL confirmed by two 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and neutral red (NR) assays, with further observations by 4',6-diamidino-2-phenylindole (DAPI) stained confocal microscopy images, possessing that CD-FeAC NPs can be used as potential drug delivery platforms in cancer cells with simultaneous imaging. Graphical abstract CD conjugation with organo-building blocks of delaminated FeAC NPs.
Subject(s)
Carbon/chemistry , Imaging, Three-Dimensional/methods , Iron Compounds/chemistry , Iron/chemistry , Nanoparticles/chemistry , Silicates/chemistry , Animals , Cell Death , Cell Survival , Endocytosis , HeLa Cells , Humans , Hydrodynamics , Indoles/metabolism , Mice , Microscopy, Confocal , Nanoparticles/ultrastructure , Particle Size , Spectrometry, Fluorescence , Spectroscopy, Fourier Transform Infrared , Static Electricity , X-Ray DiffractionABSTRACT
Fluorescent carbon nanomaterials, especially zero-dimensional (0D) carbon nanodots (CDs), are widely used in broad biological and optoelectronic applications. CDs have unique characteristics such as strong fluorescence, biocompatibility, sun-light response, and capability of mass-production. Beyond the previous green CD obtained from harmful natural substances, we report a new type of fluid-based fluorescent CD paints (C-paints) derived from polyethylene glycol (PEG; via simple ultrasound irradiation at room temperatures) and produced in quantum yields of up to ~14%. Additionally, C-paints possess a strong, UV- and visible-light-responsive photoluminescent (PL) property. Most especially, C-paints, by incorporation into a photocatalytic system, show additional roles in the emission of fluorescent light for activation of TiO2 nanoparticles (NPs) and the resultant detoxification of most organic dyes, thus further enabling embarkation in advanced water purification.
Subject(s)
Carbon/chemistry , Fluorescent Dyes/chemical synthesis , Green Chemistry Technology/methods , Paint , Photochemistry/methods , Quantum Dots/chemistry , Catalysis/radiation effects , Light , Materials Testing , Quantum Dots/ultrastructureABSTRACT
Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as â¼723.7 mA h g(-1) even after 100 cycles at 0.5 C.
ABSTRACT
Over the past few decades, two-dimensional (2D) and layered materials have emerged as new fields. Due to the zero-band-gap nature of graphene and the low photocatalytic performance of MoS2, more advanced semiconducting 2D materials have been prompted. As a result, semiconductor black phosphorus (BP) is a derived cutting-edge post-graphene contender for nanoelectrical application, because of its direct-band-gap nature. For the first time, we report on robust BP@TiO2 hybrid photocatalysts offering enhanced photocatalytic performance under light irradiation in environmental and biomedical fields, with negligible affected on temperature and pH conditions, as compared with MoS2@TiO2 prepared by the identical synthesis method. Remarkably, in contrast to pure few layered BP, which, due to its intrinsic sensitivity to oxygen and humidity was readily dissolved after just several uses, the BP@TiO2 hybrid photocatalysts showed a ~92% photocatalytic activity after 15 runs. Thus, metal-oxide-stabilized BP photocatalysts can be practically applied as a promising alternative to graphene and MoS2.
ABSTRACT
It is known that water purified by conventional TiO2 photocatalysts may not be safe enough for drinking, due to the toxicity by tiny existence of TiO2 nanoparticles after water treatment. We herein demonstrate a facile design of a three-dimensional (3D) TiO2 photocatalyst structure with which both the efficiency of purification and the safety level of the final purified water can be improved and ensured, respectively. The structure, consisting of 3D sulfur-doped TiO2 microtubes in nanotubes (eco-TiO2), is suitable for both environmental and bio-medical applications. Investigation of its formation mechanism reveals that anodic aluminum oxide (AAO), owing to a spatial constraint, causes a simple, nanoparticles-to-nanotubes structural rearrangement as a template for nanotube growth. It is found that eco-TiO2 can be activated under visible-light irradiation by non-metal (sulfur; S) doping, after which it shows visible-light photocatalytic activities over a range of solar energy. Importantly, an in vitro cytotoxicity test of well-purified water by eco-TiO2 confirms that eco-TiO2 satisfies the key human safety conditions.
Subject(s)
Drinking Water , Titanium/toxicity , Water Purification , Aluminum Oxide/chemistry , Humans , Nanoparticles/chemistry , Nanotubes/chemistry , Titanium/chemistryABSTRACT
This study evaluates the utility of an antibacterial microneedle composed of green tea (GT) extract and hyaluronic acid (HA), for the efficient delivery of GT. These microneedles have the potential to be a patient-friendly method for the conventional sustained release of drugs. In this study, a fabrication method using a mold-based technique to produce GT/HA microneedles with a maximum area of ~50mm(2) with antibacterial properties was used to manufacture transdermal drug delivery systems. Fourier transform infrared (FTIR) spectrometry was carried out to observe the potential modifications in the microneedles, when incorporated with GT. The degradation rate of GT in GT/HA microneedles was controlled simply by adjusting the HA composition. The effects of different ratios of GT in the HA microneedles were determined by measuring the release properties. In HA microneedles loaded with 70% GT (GT70), a continuous higher release rate was sustained for 72h. The in vitro cytotoxicity assays demonstrated that GT/HA microneedles were not generally cytotoxic to Chinese hamster ovary cells (CHO-K1), human embryonic kidney cells (293T), and mouse muscle cells (C2C12), which were treated for 12 and 24h. Antimicrobial activity of the GT/HA microneedles was demonstrated by ~95% growth reduction of gram negative [Escherichia coli (E. coli), Pseudomonas putida (P. putida), and Salmonella typhimurium (S. typhimurium)] and gram positive bacteria [Staphylococcus aureus (S. Aureus) and Bacillus subtilis (B. subtilis)], with GT70. Furthermore, GT/HA microneedles reduced bacterial growth of infected wound sites in the skin and improved wound healing process of skin in rat model.
Subject(s)
Anti-Bacterial Agents/pharmacology , Camellia sinensis/chemistry , Microtechnology/instrumentation , Needles , Plant Extracts/pharmacology , Wound Healing/drug effects , Animals , Anti-Bacterial Agents/chemistry , Bacteria/drug effects , Bacterial Infections , CHO Cells , Cricetinae , Cricetulus , Disease Models, Animal , Drug Delivery Systems , HEK293 Cells , Humans , Hyaluronic Acid/chemistry , Male , Plant Extracts/chemistry , Rats, Sprague-Dawley , Transdermal PatchABSTRACT
Using a simple method of mass production of green carbon nanotags (G-tags) from harmful cyanobacteria, we developed an advanced and efficient imaging platform for the purpose of anticancer therapy. Approximately 100 grams of G-tags per 100 kilograms of harmful cyanobacteria were prepared using our eco-friendly approach. The G-tags possess high solubility, excellent photostability, and low cytotoxicity (<1.5 mg/mL for 24 h). Moreover, doxorubicin-conjugated G-tags (T-tags; >0.1 mg/mL) induced death in cancer cells (HepG2 and MCF-7) in-vitro at a higher rate than that of only G-tags while in-vivo mice experiment showed enhanced anticancer efficacy by T-tags at 0.01 mg/mL, indicating that the loaded doxorubicin retains its pharmaceutical activity. The cancer cell uptake and intracellular location of the G- and T-tags were observed. The results indicate that these multifunctional T-tags can deliver doxorubicin to the targeted cancer cells and sense the delivery of doxorubicin by activating the fluorescence of G-tags.
Subject(s)
Carbon/chemistry , Drug Carriers/chemistry , Nanostructures/chemistry , Animals , Antibiotics, Antineoplastic/administration & dosage , Antibiotics, Antineoplastic/chemistry , CHO Cells , COS Cells , Cell Survival/drug effects , Chlorocebus aethiops , Cricetinae , Cricetulus , Cyanobacteria/metabolism , Doxorubicin/administration & dosage , Doxorubicin/chemistry , Hep G2 Cells , Humans , MCF-7 Cells , Male , Mice , Mice, Nude , Neoplasms/drug therapy , Transplantation, HeterologousABSTRACT
High-quality N-doped graphene quantum sheets are successfully fabricated from as-grown monolayer graphene on Cu using nitrogen plasma, which can be transferred as a film-like layer or easily dispersed in an organic solvent for further optoelectronic or photoelectrochemical applications.
ABSTRACT
We have developed a simple approach for the large-scale synthesis of water-soluble green carbon nanodots (G-dots) from many kinds of large food waste-derived sources. About 120 g of G-dots per 100 kg of food waste can be synthesized using our simple and environmentally friendly synthesis approach. The G-dots exhibit a high degree of solubility in water because of the abundant oxygen-containing functional groups around their surface. The narrow band of photoluminescence emission (400-470 nm) confirms that the size of the G-dots (â¼4 nm) is small because of a similar quantum effects and emission traps on the surfaces. The G-dots have excellent photostability; their photoluminescence intensity decreases slowly (â¼8%) under continuous excitation with a Xe lamp for 10 days. We carried out cell viability assay to assess the effect of cytotoxicity by introducing G-dots in cells such as Chinese hamster ovary cells (CHO-K1), mouse muscle cells (C2C12), and African green monkey kidney cells (COS-7), up to a concentration of 2 mg mL(-1) for 24 h. Due to their high photostability and low cytotoxicity, these G-dots are excellent probes for in vitro bioimaging. Moreover, the byproducts (not including G-dots) of G-dot synthesis from large food-waste derived sources promoted the growth and development of seedlings germinated on 3DW-supplemented gauze. Because of the combined advantages of green synthesis, high aqueous stability, high photostability, and low cytotoxicity, the G-dots show considerable promise in various areas, including biomedical imaging, solution state optoelectronics, and plant seed germination and/or growth.