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1.
J Colloid Interface Sci ; 652(Pt A): 184-194, 2023 Dec 15.
Article in English | MEDLINE | ID: mdl-37595436

ABSTRACT

The development of quantum dot (QD)-based modular bioprobe that has a compact size and enable a facile conjugation of various biofunctional groups is in high demand. To address this, we surface engineered QDs with zwitterion polymer ligands to have an inherent compact size and derivatized them sequentially with the recombinant proteins SpyCatcher/SpyTag (SC/ST) to use their protein ligation system. SC/ST spontaneously form one complex through the isopeptide bond between them. SC-conjugated QDs (QD-SC) were used as base building blocks. Then, ST-biomolecules were added for modular biofunctionalization. We synthesized compact sized (∼15 nm) QD-SC-ST-affibody (antibody-mimicking small protein for tumor detection) conjugates, which showed successful cell-receptor targeting. The target cell-receptor could be easily tuned by changing the type of ST-affibody. We also demonstrated that anti-human-chorionic-gonadotropin mouse IgG1 antibodies can be labeled on the QD surface by mixing QD-SC with the ST-MG1Nb (mouse-IgG1-specific protein). The immunoassay performance of the antibody-labeled QDs was evaluated using a pregnancy test kit, displaying equivalent detection sensitivity to a commercially available kit. This study proposed an innovative strategy for QD biofunctionalization in a modular manner, which can be expanded to a diverse range of colloidal particle derivatization.


Subject(s)
Quantum Dots , Mice , Animals , Polymers , Recombinant Proteins/chemistry , Immunoglobulin G
2.
Nanoscale Adv ; 5(12): 3368-3375, 2023 Jun 13.
Article in English | MEDLINE | ID: mdl-37325533

ABSTRACT

Surface engineered iron oxide nanoparticles (IONPs) with catecholic ligands have been investigated as alternative T1 contrast agents. However, complex oxidative chemistry of catechol during IONP ligand exchange causes surface etching, heterogeneous hydrodynamic size distribution, and low colloidal stability because of Fe3+ mediated ligand oxidation. Herein, we report highly stable and compact (∼10 nm) Fe3+ rich ultrasmall IONPs functionalized with a multidentate catechol-based polyethylene glycol polymer ligand through amine-assisted catecholic nanocoating. The IONPs exhibit excellent stability over a broad range of pHs and low nonspecific binding in vitro. We also demonstrate that the resultant NPs have a long circulation time (∼80 min), enabling high resolution T1 magnetic resonance angiography in vivo. These results suggest that the amine assisted catechol-based nanocoating opens a new potential of metal oxide NPs to take a step forward in exquisite bio-application fields.

3.
Small ; 19(17): e2206668, 2023 Apr.
Article in English | MEDLINE | ID: mdl-36703517

ABSTRACT

Low-dimensional Cu(I)-based metal halide materials are gaining attention due to their low toxicity, high stability and unique luminescence mechanism, which is mediated by self-trapped excitons (STEs). Among them, Cs5 Cu3 Cl6 I2 , which emits blue light, is a promising candidate for applications as a next-generation blue-emitting material. In this article, an optimized colloidal process to synthesize uniform Cs5 Cu3 Cl6 I2 nanocrystals (NCs) with a superior quantum yield (QY) is proposed. In addition, precise control of the synthesis parameters, enabling anisotropic growth and emission wavelength shifting is demonstrated. The synthesized Cs5 Cu3 Cl6 I2 NCs have an excellent photoluminescence (PL) retention rate, even at high temperature, and exhibit high stability over multiple heating-cooling cycles under ambient conditions. Moreover, under 850-nm femtosecond laser irradiation, the NCs exhibit three-photon absorption (3PA)-induced PL, highlighting the possibility of utilizing their nonlinear optical properties. Such thermally stable and highly luminescent Cs5 Cu3 Cl6 I2 NCs with nonlinear optical properties overcome the limitations of conventional blue-emitting nanomaterials. These findings provide insights into the mechanism of the colloidal synthesis of Cs5 Cu3 Cl6 I2 NCs and a foundation for further research.

4.
Biosens Bioelectron ; 213: 114441, 2022 Oct 01.
Article in English | MEDLINE | ID: mdl-35696868

ABSTRACT

Lateral flow assays (LFA) enable development of portable and rapid diagnostic kits; however, their capacity to detect low levels of disease markers remains poor. Here, we report a highly sensitive pregnancy test kit as a proof of concept, by combining brush-type ligand-coated quantum beads (B-type QBs) and nanobody, which can control the antibody orientation and enhance sensitivity. The brush-type ligand provided excellent dispersion stability and high-binding capacity toward antibody. Fc-binding nanobody increased the antigen-binding capacity of conjugated antibodies on the B-type QBs. To facilitate convenient acquisition of the LFA results, we developed a smartphone-based reader with a 3D-printed optical imaging module, and validated the diagnostic performance of the sensing platform. The pregnancy test kit achieved a 5.1 pg mL-1 limit of detection, corresponding to the levels for early-stage detection of heart disease and malaria. Our LFA application can potentially be expanded to diagnosis other diseases by simply changing the antibody pair in the kit.


Subject(s)
Biosensing Techniques , Pregnancy Tests , Antibodies , Biosensing Techniques/methods , Female , Humans , Ligands , Pregnancy
5.
ACS Appl Mater Interfaces ; 14(12): 14410-14421, 2022 Mar 30.
Article in English | MEDLINE | ID: mdl-35312277

ABSTRACT

Organic optoelectronic devices that can be fabricated at low cost have attracted considerable attention because they can absorb light over a wide frequency range and have high conversion efficiency, as well as being lightweight and flexible. Moreover, their performance can be significantly affected by the choice of the charge-selective interlayer material. Nonstoichiometric nickel oxide (NiOx) is an excellent material for the hole-transporting layer (HTL) of organic optoelectronic devices because of the good alignment of its valence band position with the highest occupied molecular orbital level of many p-type polymers. Herein, we report a simple low-temperature process for the synthesis of NiOx nanoparticles (NPs) that can be well dispersed in solution for long-term storage and easily used to form thin NiOx NP layers. NiOx NP-based organic photodiode (OPD) devices demonstrated high specific detectivity (D*) values of 1012-1013 jones under various light intensities and negative biases. The D* value of the NiOx NP-based OPD device was 4 times higher than that of a conventional poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)-based device, an enhancement that originated mainly from the 16 times decreased leakage current. The NiOx NP-based OPD device demonstrated better reliability over a wide range of light intensities and operational biases in comparison to a device with a conventional sol-gel-processed NiOx film. More importantly, the NiOx NP-based OPD showed long-term device stability superior to those of the PEDOT:PSS and sol-gel-processed NiOx-based devices. We highlight that our low-temperature solution-processable NiOx NP-based HTL could become a crucial component in the fabrication of stable high-performance OPDs.

6.
Nanoscale ; 14(7): 2771-2779, 2022 Feb 17.
Article in English | MEDLINE | ID: mdl-35119065

ABSTRACT

Despite the importance of separating nucleation steps from growth steps for the production of monodisperse highly luminescent In(Zn)P quantum dots (QDs), the practical implementation of this strategy is hindered by the high reactivity and fast depletion of conventional P precursors. This problem can be mitigated through the use of (i) Zn oxo clusters, which effectively regulate the kinetics of QD growth and prevent the fast depletion of conventional P precursors in the nucleation step, or (ii) seed-mediated continuous growth methods, which avoid secondary nucleation in the growth step and yield red-emitting InP QDs. Herein, we combine approaches (i) and (ii) to synthesize red-emitting In(Zn)P QDs with a high photoluminescence quantum yield (>93%) and a low emission bandwidth (full width at half maximum = 38 nm), revealing that our strategy hinders the carboxylate ketonization-induced generation of byproducts and suppresses the surface oxidation of In(Zn)P QDs during growth steps. The prepared In(Zn)P QDs are used to fabricate QD light-emitting diodes with a maximum brightness of 1164 cd m-2 and an external quantum efficiency of 3.61%. Thus, our results pave the way to the replacement of toxic Cd- and Pb-based QDs with more eco-friendly Zn- and In-based analogs for a variety of applications.

7.
Adv Sci (Weinh) ; 9(5): e2104660, 2022 Feb.
Article in English | MEDLINE | ID: mdl-34957694

ABSTRACT

Although metal halide perovskites are candidate high-performance light-emitting diode (LED) materials, blue perovskite LEDs are problematic: mixed-halide materials are susceptible to phase segregation and bromide-based perovskite quantum dots (QDs) have low stability. Herein, a novel strategy for highly efficient, stable cesium lead bromide (CsPbBr3 ) QDs via in situ surface reconstruction of CsPbBr3 -Cs4 PbBr6 nanocrystals (NCs) is reported. By controlling precursor reactivity, the ratio of CsPbBr3 to Cs4 PbBr6 NCs is successfully modulated. A high photoluminescence quantum yield (PLQY) of >90% at 470 nm is obtained because octahedron CsPbBr3 QD surface defects are removed by the Cs4 PbBr6 NCs. The defect-engineered QDs exhibit high colloidal stability, retaining >90% of their initial PLQY after >120 days of ambient storage. Furthermore, thermal stability is demonstrated by a lack of heat-induced aggregation at 120 °C. Blue LEDs fabricated from CsPbBr3 QDs with reconstructed surfaces exhibit a maximum external quantum efficiency of 4.65% at 480 nm and excellent spectral stability.

8.
ACS Omega ; 6(41): 26952-26958, 2021 Oct 19.
Article in English | MEDLINE | ID: mdl-34853820

ABSTRACT

Recently, the double perovskite Cs2AgInCl6, which has high stability and low toxicity, has been proposed as a potential alternative to Pb-based perovskites. However, the calculated parity-allowed transition bandgap of Cs2AgInCl6 is 4.25 eV; this wide bandgap makes it difficult to use as an efficient solar absorber. In this study, we explored the effect of Cu doping on the optical properties of Cs2AgInCl6 double perovskite nano- and microcrystals (MCs), particularly in its changes of absorption profile from the ultraviolet (UV) to near-infrared (NIR) region. Undoped Cs2AgInCl6 showed the expected wide bandgap absorbance, but the Cu-doped sample showed a new sharp absorption peak at 419 nm and broad absorption bands near 930 nm, indicating bandgap reduction. Electron paramagnetic resonance (EPR) spectroscopy demonstrated that this bandgap reduction effect was due to the Cu doping in the double perovskite and confirmed that the Cu2+ paramagnetic centers were located on the surface of the nanocrystals (NCs) and at the center of the perovskite octahedrons (g∥ > g⊥ > ge). Finally, we synthesized Cu-doped Cs2AgInCl6 MCs and observed results similar to those of the NCs, showing that the application range could be expanded to multidimensions.

9.
Nanomaterials (Basel) ; 11(11)2021 Nov 14.
Article in English | MEDLINE | ID: mdl-34835832

ABSTRACT

The surface charge of iron oxide nanoparticles (IONPs) plays a critical role in the interactions between nanoparticles and biological components, which significantly affects their toxicity in vitro and in vivo. In this study, we synthesized three differently charged IONPs (negative, neutral, and positive) based on catechol-derived dopamine, polyethylene glycol, carboxylic acid, and amine groups, via reversible addition-fragmentation chain transfer-mediated polymerization (RAFT polymerization) and ligand exchange. The zeta potentials of the negative, neutral, and positive IONPs were -39, -0.6, and +32 mV, respectively, and all three IONPs showed long-term colloidal stability for three months in an aqueous solution without agglomeration. The cytotoxicity of the IONPs was studied by analyzing cell viability and morphological alteration in three human cell lines, A549, Huh-7, and SH-SY5Y. Neither IONP caused significant cellular damage in any of the three cell lines. Furthermore, the IONPs showed no acute toxicity in BALB/c mice, in hematological and histological analyses. These results indicate that our charged IONPs, having high colloidal stability and biocompatibility, are viable for bio-applications.

10.
Nanomaterials (Basel) ; 10(12)2020 Dec 01.
Article in English | MEDLINE | ID: mdl-33271971

ABSTRACT

Silica aerogels have attracted much attention owing to their excellent thermal insulation properties. However, the conventional synthesis of silica aerogels involves the use of expensive and toxic alkoxide precursors and surface modifiers such as trimethylchlorosilane. In this study, cost-effective water-glass silica aerogels were synthesized using an eco-friendly catechol derivative surface modifier instead of trimethylchlorosilane. Polydopamine was introduced to increase adhesion to the SiO2 surface. The addition of 4-tert-butyl catechol and hexylamine imparted hydrophobicity to the surface and suppressed the polymerization of the polydopamine. After an ambient pressure drying process, catechol-modified aerogel exhibited a specific surface area of 377 m2/g and an average pore diameter of approximately 21 nm. To investigate their thermal conductivities, glass wool sheets were impregnated with catechol-modified aerogel. The thermal conductivity was 40.4 mWm-1K-1, which is lower than that of xerogel at 48.7 mWm-1K-1. Thus, by precisely controlling the catechol coating in the mesoporous framework, an eco-friendly synthetic method for aerogel preparation is proposed.

11.
Sci Rep ; 10(1): 18055, 2020 Oct 22.
Article in English | MEDLINE | ID: mdl-33093600

ABSTRACT

Significant aggregation between ZnO nanoparticles (ZnO NPs) dispersed in polar and nonpolar solvents hinders the formation of high quality thin film for the device application and impedes their excellent electron transporting ability. Herein a bifunctional coordination complex, titanium diisopropoxide bis(acetylacetonate) (Ti(acac)2) is employed as efficient stabilizer to improve colloidal stability of ZnO NPs. Acetylacetonate functionalized ZnO exhibited long-term stability and maintained its superior optical and electrical properties for months aging under ambient atmospheric condition. The functionalized ZnO NPs were then incorporated into polymer solar cells with conventional structure as n-type buffer layer. The devices exhibited nearly identical power conversion efficiency regardless of the use of fresh and old (2 months aged) NPs. Our approach provides a simple and efficient route to boost colloidal stability of ZnO NPs in both polar and nonpolar solvents, which could enable structure-independent intense studies for efficient organic and hybrid optoelectronic devices.

12.
J Phys Chem Lett ; 11(14): 5785-5791, 2020 Jul 16.
Article in English | MEDLINE | ID: mdl-32608240

ABSTRACT

Chemical characterizations of biochemically functionalized single nanoparticles are necessary to optimize the nanoparticle surface functionality in recently advanced nanobiological applications but have not yet been fully explored because of technical difficulties. Exploiting the photoinduced force exerted on a light-illuminated nanoscale tip, nanoscale mid-infrared hyperspectral images with a 10 nm spatial resolution of a monolayer ligand-functionalized single gold nanoparticle under ambient and environmental conditions are presented. We extend our study to the diagnosis of nanoscale heterogeneous chemical contaminants which come from a particle functionalization process but are undetectable in conventional ensemble-averaged imaging technique. High sensitivity and high spatial resolution are achieved via the strongly localized tip-enhanced force at the junction between the gold-coated tip and the functionalized nanoparticle in photoinduced force microscopy, which far exceeds the capability of the conventional methods. The present study paves a new way to directly detect heterogeneous nanochemicals at the single-component level, which is necessary to evaluate nanomaterial safety in biomedical applications.


Subject(s)
Magnetite Nanoparticles/chemistry , Gold/chemistry , Ligands , Microscopy, Atomic Force/methods , Polyethylene Glycols/chemistry , Surface Properties
13.
Anal Chem ; 92(7): 5473-5481, 2020 04 07.
Article in English | MEDLINE | ID: mdl-32142265

ABSTRACT

In general immunoassays, secondary antibodies are covalently linked with enzymes and bind to the Fc region of target-bound primary antibodies to amplify signals of low-abundant target molecules. The antibodies themselves are obtained from large mammals and are further modified with enzymes. In this study, we developed novel recombinant immunoglobulin G (IgG)-binding luciferase-based signal amplifiers (rILSAs) by genetically fusing luciferase (Nluc) with antimouse IgG1 nanobody (MG1Nb) and antibody-binding domain (ABD), individually or together, in a mix-and-match manner. We obtained three different highly pure rILSAs in large quantities using a bacterial overexpression system and one-step purification. Mouse-specific rILSA, MG1Nb-Nluc, and rabbit-specific rILSA, Nluc-ABD, selectively bound to target-molecule-bound mouse IgG1 and rabbit IgG primary antibodies, whereas the bispecific rILSA, MG1Nb-Nluc-ABD, mutually bound to both mouse IgG1 and rabbit IgG primary antibodies. All rILSAs exhibited an outstanding signal-amplifying capability comparable to those of conventional horseradish-peroxidase-conjugated secondary antibodies, regardless of the target molecules, in various immunoassay formats, such as enzyme-linked immunosorbent assay, Western blot, and lateral flow assays. Each rILSA was selected for its own individual purpose and applied to various types of target analytes, in combination with a variety of target-specific primary antibodies, effectively minimizing the use of animals as well as reducing the costs and time associated with the production and chemical conjugation of signal-amplifying enzymes.


Subject(s)
Immunoassay/methods , Immunoglobulin G/immunology , Immunoglobulin G/metabolism , Luciferases/metabolism , Recombinant Proteins/immunology , Recombinant Proteins/metabolism , Animals , Antibody Specificity , Mice
14.
ACS Appl Mater Interfaces ; 11(8): 8428-8435, 2019 Feb 27.
Article in English | MEDLINE | ID: mdl-30714373

ABSTRACT

Lead halide perovskites (LHPs) are emerging as promising materials for light-emitting device applications because of the tunability of the band gap, narrow emission, solution processability, and flexibility. Typically, LHP nanocrystals (NCs) with surface ligands show high photoluminescence quantum yields because of charge-carrier confinement with higher exciton binding energy ( Eb). However, the conventionally used oleylamine (OAm) ligands result in the low electrical conductivity and stability of perovskite NCs (PNCs) because of a long carbon chain without conjugation bonds and weak interaction with the surface of NCs. Here, we report the effect of bulkiness and chain length of ligand materials on the properties and stability of CsPbBr3 PNCs by replacing OAm with other suitable ligands. The effect of the bulkiness of quaternary ammonium bromide (QAB) ligands was systemically studied. The less bulky QAB ligands surrounded the surface of NCs effectively, and brought better surface passivation and less aggregation compared to bulky QAB ligands, and finally the optical property and stability of CsPbBr3 PNCs were enhanced. Furthermore, the electrical property of CsPbBr3 PNCs was optimized by tuning the long-chain length of QAB ligands for balanced charge-carrier transport. Finally, we achieved highly efficient green emissive CsPbBr3 PNC light-emitting diodes (LEDs) by using PNCs with optimized didecyldimethyl ammonium bromide ligands with a current efficiency of 31.7 cd A-1 and external quantum efficiency of 9.7%, which were enhanced 16-fold compared to those of CsPbBr3 LEDs using PNCs with conventional OAm ligands.

15.
RSC Adv ; 9(24): 13714-13721, 2019 Apr 30.
Article in English | MEDLINE | ID: mdl-35519563

ABSTRACT

In this article, the facile synthesis of sea urchin-shaped LiFePO4 nanoparticles by thermal decomposition of metal-surfactant complexes and application of these nanoparticles as a cathode in lithium ion secondary batteries is demonstrated. The advantages of this work are a facile method to synthesize interesting LiFePO4 nanostructures and its synthetic mechanism. Accordingly, the morphology of LiFePO4 particles could be regulated by the injection of oleylamine, with other surfactants and phosphoric acid. This injection step was critical to tailor the morphology of LiFePO4 particles, converting them from nanosphere shapes to diverse types of urchin-shaped nanoparticles. Electron microscopy analysis showed that the overall dimension of the urchin-shaped LiFePO4 particles varied from 300 nm to 2 µm. A closer observation revealed that numerous thin nanorods ranging from 5 to 20 nm in diameter were attached to the nanoparticles. The hierarchical nanostructure of these urchin-shaped LiFePO4 particles mitigated the low tap density problem. In addition, the nanorods less than 20 nm attached to the edge of urchin-shaped nanoparticles significantly increased the pathways for electronic transport.

16.
Chem Commun (Camb) ; 54(82): 11586-11589, 2018 Oct 11.
Article in English | MEDLINE | ID: mdl-30264087

ABSTRACT

Self-assembly of monodisperse superparamagnetic iron oxide nanocrystals into a close-packed, three-dimensional (3D) superlattice is designed within cross-linked protein-based nanoparticles composed of human serum albumin and polyethylene glycol. The prepared nanoparticles are very stable in serum and exhibit a high T2 relaxivity as well as anti-cancer activity, indicating the practical benefits of ordering nanocrystals.


Subject(s)
Antineoplastic Agents, Phytogenic/administration & dosage , Magnetite Nanoparticles/chemistry , Paclitaxel/administration & dosage , Polyethylene Glycols/chemistry , Serum Albumin, Human/chemistry , Antineoplastic Agents, Phytogenic/chemistry , Antineoplastic Agents, Phytogenic/pharmacology , Cell Survival/drug effects , HeLa Cells , Humans , Injections , MCF-7 Cells , Magnetite Nanoparticles/ultrastructure , Models, Molecular , Nanoparticles/chemistry , Nanoparticles/ultrastructure , Neoplasms/drug therapy , Paclitaxel/chemistry , Paclitaxel/pharmacology
17.
ACS Appl Mater Interfaces ; 10(26): 22110-22118, 2018 Jul 05.
Article in English | MEDLINE | ID: mdl-29901390

ABSTRACT

Electrode materials exploiting multielectron-transfer processes are essential components for large-scale energy storage systems. Organic-based electrode materials undergoing distinct molecular redox transformations can intrinsically circumvent the structural instability issue of conventional inorganic-based host materials associated with lattice volume expansion and pulverization. Yet, the fundamental mechanistic understanding of metal-organic coordination polymers toward the reversible electrochemical processes is still lacking. Herein, we demonstrate that metal-dependent spatial proximity and binding affinity play a critical role in the reversible redox processes, as verified by combined 13C solid-state NMR, X-ray absorption spectroscopy, and transmission electron microscopy. During the electrochemical lithiation, in situ generated metallic nanoparticles dispersed in the organic matrix generate electrically conductive paths, synergistically aiding subsequent multielectron transfer to π-conjugated ligands. Comprehensive screening on 3d-metal-organic coordination polymers leads to a high-capacity electrode material, cobalt-2,5-thiophenedicarboxylate, which delivers a stable specific capacity of ∼1100 mA h g-1 after 100 cycles.

18.
ACS Omega ; 3(7): 7655-7662, 2018 Jul 31.
Article in English | MEDLINE | ID: mdl-31458916

ABSTRACT

Conversion reaction materials (transition metal oxides, sulfides, phosphides, etc.) are attractive in the field of lithium-ion batteries because of their high theoretical capacity and low cost. However, the realization of these materials in lithium-ion batteries is impeded by large voltage hysteresis, high polarization, inferior cycle stability, rate capability, irreversible capacity loss in first cycling, and dramatic volume change during redox reactions. One method to overcome these problems is the introduction of amorphous materials. This work introduces a facile method to synthesize amorphous and crystalline dinickel phosphide (Ni2P) nanoparticle clusters with identical morphology and presents a direct comparison of the two materials as anode materials for rechargeable lithium-ion batteries. To assess the effect of crystallinity and hierarchical structure of nanomaterials, it is crucial to conserve other factors including size, morphology, and ligand of nanoparticles. Although it is rarely studied about synthetic methods of well-controlled Ni2P nanomaterials to meet the above criteria, we synthesized amorphous, crystalline Ni2P, and self-assembled Ni2P nanoparticle clusters via thermal decomposition of nickel-surfactant complex. Interestingly, simple modulation of the quantity of nickel acetylacetonate produced amorphous, crystalline, and self-assembled Ni2P nanoparticles. A 0.357 M nickel-trioctylphosphine (TOP) solution leads to a reaction temperature limitation (∼315 °C) by the nickel precursor, and crystalline Ni2P (c-Ni2P) nanoparticles clusters are generated. On the contrary, a lower concentration (0.1 M) does not accompany a temperature limitation and hence high reaction temperature (330 °C) can be exploited for the self-assembly of Ni2P (s-Ni2P) nanoparticle clusters. Amorphous Ni2P (a-Ni2P) nanoparticle clusters are generated with a high concentration (0.714 M) of nickel-TOP solution and a temperature limitation (∼290 °C). The a-Ni2P nanoparticle cluster electrode exhibits higher capacities and Coulombic efficiency than the electrode based on c-Ni2P nanoparticle clusters. In addition, the amorphous structure of Ni2P can reduce irreversible capacity and voltage hysteresis upon cycling. The amorphous morphology of Ni2P also improves the rate capability, resulting in superior performance to those of c-Ni2P nanoparticle clusters in terms of electrode performance.

19.
ACS Macro Lett ; 7(8): 962-967, 2018 Aug 21.
Article in English | MEDLINE | ID: mdl-35650973

ABSTRACT

While incorporation of nanoparticles in a polymer matrix generally enhances the physical properties, effective control of the nanoparticle/polymer interface is often challenging. Here, we report a dramatic enhancement of the mechanical properties of polymer nanocomposites (PNCs) using a simple physical grafting method. The PNC consists of low molecular weight poly(ethylene glycol) (PEG) and silica nanoparticles whose surfaces are modified with dopamine-modified PEG (DOPA-mPEG) brush polymers. With DOPA-mPEG grafting, the nanoparticle surface can be readily altered, and the shear modulus of the PNC is increased by a factor of 105 at an appropriate surface grafting density. The detailed microstructure and mechanical properties are examined with small-angle X-ray scattering (SAXS) and oscillatory rheometry experiments. The attractive interactions between particles induced by DOPA-mPEG grafting dramatically improve the mechanical properties of PNCs even in an unentangled polymer matrix, which shows a much higher shear modulus than that of a highly entangled polymer matrix.

20.
J Phys Chem Lett ; 7(18): 3627-35, 2016 Sep 15.
Article in English | MEDLINE | ID: mdl-27571033

ABSTRACT

We report a strategy toward the synthesis of colloidal nanocrystals capped with inorganic molybdenum and tungsten sulfide ligands. MoS4(2-) and WS4(2-) thiometalates were utilized to replace organic ligands capping a wide range of nanocrystals such as metals, semiconductors, and well-conserved primary properties of nanocrystals in polar media. Especially, MoS4(2-)- and WS4(2-)-capped CdSe nanocryatals showed the dramatic enhancement of photoluminescence properties by the photo-oxidation treatment, which originated from the preferential formation of MoSxOy layers on the CdSe surface. The highest quantum yield reached up to 51%. Furthermore, we studied the charge-transport properties of MoS4(2-)-capped PbS nanocryatals by the fabrication of a field-effect transistor and photodetectors. Finally, MoS4(2-)- and WS4(2-)-capped nanocrystals were used for the production of two-dimensional MoS2 and WS2 thin layers on nanostructures by heat treatment. Such versatility of these thiometalate ligands offers an additional degree of control over the functionality of nanocrystals for optoelectronic and catalytic applications.

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