Extremely Monodispersed Micrometer-Scale Spherical Particle Synthesis of Ag Inside a Microdroplet Vaporizing in Plasma.

Spherical Ag particles have received considerable attention because of their unique properties as well as their applications in various fields. In the present study, the synthesis of micrometer-scale spherical Ag particles with an extremely narrow size distribution is demonstrated using a simple capacitively coupled atmospheric-pressure plasma reactor with an inkjet head. Droplets of a Ag nitrate aqueous solution are ejected from the inkjet head to synthesize Ag particles. The gaseous temperature in the reactor is adjusted such that Ag can be melted with a negligibly small vapor pressure. These particles exhibit a spherical shape with a smooth surface. The mean diameter of the particles is 0.91 ± 0.013 µm with a small coefficient of variation of 1.5%, the smallest value ever reported for Ag particles of less than 1 µm. The grain sizes of the particles are larger than 100 nm, as expected from the broadening of the X-ray diffraction peaks. The excellent monodispersity of the particles synthesized by this method may expand the applications with micrometer-scale spheres such as ball spacer, microsized ball bearing, and inks for printed electronics.

Surface-Specific Modification of Graphitic Carbon Nitride by Plasma for Enhanced Durability and Selectivity of Photocatalytic CO2 Reduction with a Supramolecular Photocatalyst.

Photocatalytic CO2 reduction is in high demand for sustainable energy management. Hybrid photocatalysts combining semiconductors with supramolecular photocatalysts represent a powerful strategy for constructing visible-light-driven CO2 reduction systems with strong oxidation power. Here, we demonstrate the novel effects of plasma surface modification of graphitic carbon nitride (C3N4), which is an organic semiconductor, to achieve better affinity and electron transfer at the interface of a hybrid photocatalyst consisting of C3N4 and a Ru(II)-Ru(II) binuclear complex (RuRu'). This plasma treatment enabled the "surface-specific" introduction of oxygen functional groups via the formation of a carbon layer, which worked as active sites for adsorbing metal-complex molecules with methyl phosphonic-acid anchoring groups onto the plasma-modified surface of C3N4. Upon photocatalytic CO2 reduction with the hybrid under visible-light irradiation, the plasma-surface-modified C3N4 with RuRu' enhanced the durability of HCOOH production by three times compared to that achieved when using a nonmodified system. The high selectivity of HCOOH production against byproduct evolution (H2 and CO) was improved, and the turnover number of HCOOH production based on the RuRu' used reached 50 000, which is the highest among the metal-complex/semiconductor hybrid systems reported thus far. The improved activity is mainly attributed to the promotion of electron transfer from C3N4 to RuRu' under light irradiation via the accumulation of electrons trapped in deep defect sites on the plasma-modified surface of C3N4.

Cross-Linking-Filler Composite Materials of Functionalized Hexagonal Boron Nitride and Polyrotaxane Elastomer.

This study demonstrates cross-linking-filler composites in which covalent bonds between the fillers and polymer chains act as the main cross-linking points for the development of flexible and thermally conductive materials. Cross-linking-filler composites are fabricated using functionalized hexagonal boron nitride (hBN) fillers and polyrotaxane, called slide-ring polymers. The hBN particles modified with a carbon layer were produced by plasma processing in hydroquinone aqueous solution and functionalized with isocyanate groups. As the functionalized hBN provides cross-linking points for polyrotaxane, the cross-linking-filler composites can reduce cross-linking agents among polyrotaxane and exhibit considerable flexibility. Young's moduli of the cross-linking-filler composites are much lower than those of previously reported polyrotaxane composites while retaining their toughness. These values are relatively close to those of unfilled polyrotaxane elastomers, despite containing hBN fillers with a content of 50 wt %. Thus, the cross-linking-filler composites exhibit a combination of flexibility and thermal conductivity, which few hBN/elastomer composites have achieved.

Carbon Layer Formation on Hexagonal Boron Nitride by Plasma Processing in Hydroquinone Aqueous Solution.

Although hexagonal boron nitride (hBN) is a thermally conductive and electrically insulating filler in composite materials, surface modification remains difficult, which limits its dispersibility and functionalization. In this study, carbon layer formation on hBN particles by plasma processing in hydroquinone aqueous solution was investigated as a surface modification technique. Carbon components with features of polymeric hydrogenated amorphous carbon were found to be uniformly distributed on the hydroquinone-aided plasma-modified hBN (HQpBN) particles. Electron spin resonance measurements revealed abundant unpaired electrons in HQpBN, indicating that defects were formed on hBN by plasma processing and that the carbon layer contained dangling bonds. The defects on hBN could help in the attachment of the carbon layer, whereas the dangling bonds could act as reactive sites for further functionalization. The carbon layer on HQpBN was successfully functionalized with isocyanate groups, thus confirming the ability of this carbon layer to facilitate surface modification. These results demonstrate that the carbon layer formed on hBN can provide a designable interface in organic/inorganic composite materials.

Electric-Field-Induced Coherent Anti-Stokes Raman Scattering of Hydrogen Molecules in Visible Region for Sensitive Field Measurement.

Nonintrusive optical measuring of electric fields in space is crucial for various sciences and technologies. In this study, a simple and highly sensitive optical electric field measurement is demonstrated in high-pressure hydrogen by performing electric-field-induced coherent anti-Stokes Raman scattering (E-CARS) in the visible region. The minimum detectable electric field is 0.5 V/mm at atmospheric pressure. This method does not require excited or atomic species and shows a considerably higher sensitivity than those demonstrated by the commonly applied E-CARS method in the infrared region and electric-field-induced second-harmonic generation. This method can be applied to various Raman-active molecules.

Soft X-ray emission spectroscopy for the electronic state of water molecules influenced by plasma-treated multi-walled carbon nanotubes.

In this study, soft X-ray emission spectroscopy of an aqueous colloidal dispersion of multi-walled carbon nanotubes modified via the plasma process in an aqueous solution was performed for investigating the electronic state of water molecules on the colloidal particles. In the aqueous dispersion, reconstruction of the hydrogen-bonded network was implied by the O 1s spectral changes in the 1b1' and 1b1'' peaks. Furthermore, the O 1s spectral intensity around the 3a1 state was enhanced to an unusually broad energy range in comparison with previous studies. This unusual spectral change might be attributed to the hybridization of the electronic states of oxygen-containing functional groups on the surface of the plasma-modified multi-walled carbon nanotubes and that of the surrounding water molecules. Our observation indicates not only reconstruction of the hydrogen-bonded network in the aqueous dispersion but also a significant interaction of the electronic states between the water molecules and the plasma-modified multi-walled carbon nanotubes.

Synthesis of a metal-organic framework by plasma in liquid to increase reduced metal ions and enhance water stability.

Synthesis of a metal-organic framework by plasma in liquid was demonstrated with HKUST-1 as an example. HKUST-1 synthesized by this method contains a higher amount of monovalent copper ions than that synthesized by other conventional methods. The enhanced water stability was also confirmed.

Dynamics of solvated electrons during femtosecond laser-induced plasma generation in water.

We studied the dynamics of solvated electrons in the early stage of plasma generation in water induced with an intense femtosecond laser pulse. According to the decay kinetics of solvated electrons, a fast recombination process of solvated electrons (geminate recombination) occurred with a more prolonged lifetime (500 ps to 1 ns) than that observed in previous pulse photolysis studies (10-100 ps). This unusually longer lifetime is attributed to additional production of solvated electrons due to abundant free electrons generated with the laser-induced plasma, implying significant influence of free electrons on the dynamics of solvated electrons.

Slide-Ring Material/Highly Dispersed Graphene Oxide Composite with Mechanical Strength and Tunable Electrical Conduction as a Stretchable-Base Substrate.

The development of stretchable elastomer composites with considerable mechanical strength and electrical conductivity is desired for future applications in communication tools, healthcare, and robotics. Herein, we have developed a novel stretchable elastomer composite by employing a slide-ring (SR) material as a matrix for restoration and graphene oxide (GO) as a precursor for a conductive filler. Highly dispersed GO in an organic solvent, prepared via a new method developed by the authors, allowed the uniform dispersion of GO into the matrix by simply mixing the solvent and SR. The resultant SR/GO composite exhibited considerably high mechanical toughness and cyclic durability. These properties were approximately maintained after pulse laser irradiation to add electrical conductivity on the composite by photoreducing of the dispersed GO, and its electrical conductivity was higher than that of the SR/graphene, carbon nanotubes, or graphite composites. The potential of the SR/GO composite as a stretchable base substrate for wearable devices was demonstrated by producing a prototype humidity sensor, a human motion monitoring sensor, and an electrical heater based on the composite with conductive circuits drawn using pulse laser patterning.

Glioma stem cell (GSC)-derived autoschizis-like products confer GSC niche properties involving M1-like tumor-associated macrophages.

Spontaneous necrosis is a defining feature of glioblastomas (GBMs), the most malignant glioma. Despite its strong correlations with poor prognosis, it remains unclear whether necrosis could be a possible cause or mere consequence of glioma progression. Here we isolated a particular fraction of necrotic products spontaneously arising from glioma cells, morphologically and biochemically defined as autoschizis-like products (ALPs). When administered to granulocyte macrophage colony-stimulating factor (GM-CSF)-primed bone marrow-derived macrophage/dendritic cells (Mφ/DCs), ALPs were found to be specifically engulfed by Mφs expressing a tumor-associated macrophage (TAM) marker CD204. ALPs from glioma stem cells (GSCs) had higher activity for the TAM development than those from non-GSCs. Of note, expression of the Il12b gene encoding a common subunit of IL-12/23 was upregulated in ALPs-educated Mφs. Furthermore, IL-12 protein evidently enhanced the sphere-forming activity of GBM patient-derived cells, although interestingly IL-12 is generally recognized as an antitumoral M1-Mφ marker. Finally, in silico analysis of The Cancer Genome Atlas (TCGA) transcriptome data of primary and recurrent GBMs revealed that higher expression of these IL-12 family genes was well correlated with more infiltration of M1-type TAMs and closely associated with poorer prognosis in recurrent GBMs. Our results highlight a role of necrosis in GSC-driven self-beneficial niche construction and glioma progression, providing important clues for developing new therapeutic strategies against gliomas.

Plasma-Ice Interface as Thermodynamically Size-Tunable Reaction Field: Development of Plasma-Assisted Freeze Templating.

Interfaces or interfacial layers, such as gas-liquid interfaces, are critical for many physical and chemical reactions and are utilized for designing a wide range of materials. In this study, we propose a plasma-assisted freeze templating (PFT) method for materials processing. It uses a new type of interfacial reaction field, i.e., plasma-ice interface. In PFT, a micro- or nanoscale liquid layer formed on the ice body of a frozen aqueous solution is used as a reaction field in which the solutes are highly enriched and the chemical reactions are initiated by reactive species from the plasma. We demonstrated the synthesis of a self-standing gold nanoparticle (AuNP) film of porous structure by PFT in which a helium cryoplasma jet was irradiated onto a frozen solution of auric ions. This PFT method accomplished a surfactant-free and area-selective synthesis of a AuNP film and was unique in comparison with the conventional chemical synthesis of nanostructured gold materials. Furthermore, simple control of the AuNP film was demonstrated by tuning the thickness of the thin liquid layer. This was done by changing the temperature or concentration of the aqueous solution. PFT was demonstrated as a thermodynamically size-tunable scheme for material design; it exploits the plasma-ice interface and is expected to become a novel technique for a wide range of micro- and nanoengineering applications.

A Synthetic Polymer Scaffold Reveals the Self-Maintenance Strategies of Rat Glioma Stem Cells by Organization of the Advantageous Niche.

Cancer stem cells (CSCs) are believed to be maintained within a microenvironmental niche. Here we used polymer microarrays for the rapid and efficient identification of glioma CSC (GSC) niche mimicries and identified a urethane-based synthetic polymer, upon which two groups of niche components, namely extracellular matrices (ECMs) and iron are revealed. In cultures, side population (SP) cells, defined as GSCs in the rat C6 glioma cell line, are more efficiently sustained in the presence of their differentiated progenies expressing higher levels of ECMs and transferrin, while in xenografts, ECMs are supplied by the vascular endothelial cells (VECs), including SP cell-derived ones with distinctively greater ability to retain xenobiotics than host VECs. Iron is stored in tumor infiltrating host macrophages (Mφs), whose protumoral activity is potently enhanced by SP cell-secreted soluble factor(s). Finally, coexpression of ECM-, iron-, and Mφ-related genes is found to be predictive of glioma patients' outcome. Our polymer-based approach reveals the intrinsic capacities of GSCs, to adapt the environment to organize a self-advantageous microenvironment niche, for their maintenance and expansion, which redefines the current concept of anti-CSC niche therapy and has the potential to accelerate cancer therapy development. Stem Cells 2016;34:1151-1162.

Micrometer-scale electrical breakdown in high-density fluids with large density fluctuations: Numerical model and experimental assessment.

Experimentally observed electrical breakdown voltages (U(B)) in high-pressure gases and supercritical fluids deviate from classical theories for low-pressure gas discharges, and the underlying breakdown mechanisms for the high-density fluids making the U(B) differ from those in the classical discharges are not yet well understood. In this study, we developed an electrical breakdown model for the high-density fluids taking into account the effects of density fluctuations and ion-enhanced field emission (IEFE). The model is based on the concept that a critical anomaly of the U(B) (local minimum near the critical point) is caused by long mean free electron path leading to a large first Townsend coefficient in locally low-density spatial domains generated by the density fluctuations. Also, a modified Paschen's curve considering the effect of the IEFE on the second Townsend coefficient was used to reproduce the U(B) curve in the high-density fluids. Calculations based on the novel model showed good agreements with the experimentally measured U(B) even near the critical point and it also suggested that the critical anomaly of the U(B) depends on the gap distance. These results indicate that both the density fluctuations and the IEFE have to be considered to comprehend the plasmas in high-density and density-fluctuating fluids.

Cryogenic plasmas for controlled processing of nanoporous materials.

Plasma processing at cryogenic temperatures tremendously suppresses the depth penetration of plasma radical species within nanoporous materials. We demonstrate that this confining effect is surprisingly unrelated to changes in the phase diffusivity of radical species gas, but is determined by the increase of the sticking coefficient and the radical recombination and reaction factors, favoring an early irreversible surface adsorption of the plasma radical species.

T cell-mediated control of Epstein-Barr virus infection in humanized mice.

Humanized NOD/Shi-scid/interleukin-2Rgamma(null) (NOG) mice with full T cell development had significantly longer life span after Epstein-Barr virus (EBV) infection, compared with those with minimal T cell development. Removing CD3(+) or CD8(+) T cells from EBV-infected humanized mice by administration of anti-CD3 or anti-CD8 antibodies reduced their life span. CD8(+) T cells obtained from EBV-infected mice suppressed the outgrowth of autologous B cells isolated from uninfected mice and inoculated with EBV in vitro. These results indicate that humanized NOG mice are capable of T cell-mediated control of EBV infection and imply their usefulness as a tool to evaluate immunotherapeutic and prophylactic strategies for EBV infection.

Follicular dendritic cells activate HIV-1 replication in monocytes/macrophages through a juxtacrine mechanism mediated by P-selectin glycoprotein ligand 1.

Follicular dendritic cells (FDCs) are located in the lymphoid follicles of secondary lymphoid tissues and play a pivotal role in the selection of memory B lymphocytes within the germinal center, a major site for HIV-1 infection. Germinal centers are composed of highly activated B cells, macrophages, CD4(+)T cells, and FDCs. However, the physiological role of FDCs in HIV-1 replication remains largely unknown. We demonstrate in our current study that FDCs can efficiently activate HIV-1 replication in latently infected monocytic cells via an intercellular communication network mediated by the P-selectin/P-selectin glycoprotein ligand 1 (PSGL-1) interaction. Upon coculture with FDCs, HIV-1 replication was significantly induced in infected monocytic cell lines, primary monocytes, or macrophages. These cocultures were found to synergistically induce the expression of P-selectin in FDCs via NF-kappaB activation and its cognate receptor PSGL-1 in HIV-1-infected cells. Consistent with this observation, we find that this response is significantly blocked by antagonistic Abs against PSGL-1 and almost completely inhibited by PSGL-1 small interfering RNA. Moreover, a selective inhibitor for Syk, which is a downstream effector of PSGL-1, blocked HIV-1 replication in our cultures. We have thus elucidated a novel regulatory mechanism in which FDCs are a potent positive bystander that facilitates HIV-1 replication in adjacent infected monocytic cells via a juxtacrine signaling mechanism.

Follicular dendritic cell sarcoma with microtubuloreticular structure and virus-like particle production in vitro.

Neoplasm of follicular dendritic cells (FDC), follicular dendritic cell sarcoma (FDCS), is a rare tumor of intermediate to high-grade malignancy in lymph nodes and visceral organs. Reported herein is a case of FDCS arising from cervical lymph nodes in a 16-year-old Japanese boy, who died of the disease 3 years after diagnosis. The tumor cells were pale eosinophilic and elongated with euchromatic nuclei and were positive for CD21, clusterin, and CNA-42 on immunohistochemistry, as well as desmosome-like junctions on electron microscopy. The presence of microtubuloreticular structures (MTRS) in the tumor cells and associated lymphocytes characterized this case, suggesting some viral infection, although qualitative polymerase chain reaction of genomic and complementary DNA obtained from the tumor failed to demonstrate any viral infection at the laboratory level. The stimulation of dispersed tumor cells and peripheral blood mononuclear cells with mAb to CD3 and interleukin-2 was attempted; and the cell line established by the authors (FDCS-Sa) was stimulated with iododeoxyuridine. Virus-like particles (VLP) were successfully induced from each cellular source. The VLP, 100 nm in diameter, showed an electron-dense thorny envelope and granular core. This is the first case of FDCS with MTRS accompanying VLP production in vitro.

A new humanized mouse model of Epstein-Barr virus infection that reproduces persistent infection, lymphoproliferative disorder, and cell-mediated and humoral immune responses.

The functional human immune system, including T, B, and natural killer lymphocytes, is reconstituted in NOD/Shi-scid/IL-2Rgamma(null) (NOG) mice that receive hematopoietic stem cell transplants. Here, we show that these humanized mice can recapitulate key aspects of Epstein-Barr virus (EBV) infection in humans. Inoculation with approximately 1 x 10(3) TD(50) (50% transforming dose) of EBV caused B cell lymphoproliferative disorder, with histopathological findings and latent EBV gene expression remarkably similar to that in immunocompromised patients. Inoculation with a low dose of virus (

Efficacy and safety of combination therapy with latanoprost after a change in therapeutic regimen from timolol to brinzolamide in Japanese adult patients with primary open-angle glaucoma and ocular hypertension: open, non-randomized 12-week study.

PURPOSE: To compare the efficacy of brinzolamide in Japanese patients with primary open-angle glaucoma (POAG) or ocular hypertension (OH) after a change from timolol in combination therapy with latanoprost. METHODS: A 12-week, prospective, open-label, comparative study was performed in 20 patients [11 males and 9 females, mean age of 64.5 +/- 11.0 (SD)y] with POAG or OH treated with both latanoprost once daily and timolol 0.5% twice daily. During the study brinzolamide was substituted for timolol. Intraocular pressure (IOP) was measured at baseline, 4, 8, and 12 weeks. Blood pressure (BP), pulse rate (PR), and adverse events were also recorded. RESULTS: IOPs at baseline, 4, 8, and 12 weeks were 18.6 +/- 2.1 mmHg, 17.8 +/- 2.6 mmHg, 17.4 +/- 2.5 mmHg, and 17.3 +/- 3.5 mmHg, respectively. IOP reduction at 4 and 8 weeks was statistically significant (p < 0.05). The PR was significantly increased at 12 weeks (p < 0.01), but BP was not significantly affected. Four ocular adverse events were noted, but all were mild and transient. CONCLUSIONS: Substituting brinzolamide 1% for timolol 0.5% in combination therapy with latanoprost 0.005% demonstrated significant IOP reduction with improvement in PR with POAG or OH. Combination therapy using latanoprost and brinzolamide may be recommended for better IOP control with fewer systemic adverse events.