Fabrication of graphene oxide/montmorillonite nanocomposite flexible thin films with improved gas-barrier properties.

Nanocomposites are potential substitutes for inorganic materials in fabricating flexible gas-barrier thin films. In this study, two nanocomposites are used to form a flexible gas-barrier film that shows improved flexibility and a decreased water vapor transmission rate (WVTR), thereby extending the diffusion path length for gas molecules. The nanoclay materials used for the flexible gas-barrier thin film are Na+-montmorillonite (MMT) and graphene oxide (GO). A flexible gas-barrier thin film was fabricated using a layer-by-layer (LBL) deposition method, exploiting electronic bonding under non-vacuum conditions. The WVTR of the film, in which each layer was laminated by LBL assembly, was analyzed by Ca-test and the oxygen transmission rate (OTR) was analyzed by MOCON. When GO and MMT are used together, they fill each other's vacancies and form a gas-barrier film with high optical transmittance and the improved WVTR of 3.1 × 10-3 g per m2 per day without a large increase in thickness compared to barrier films produced with GO or MMT alone. Thus, this film has potential applicability as a barrier film in flexible electronic devices.

Hydrolyzed hexagonal boron nitride/polymer nanocomposites for transparent gas barrier film.

A flexible thin gas barrier film formed by layer-by-layer (LBL) assembly has been studied. We propose for the first time that hexagonal boron nitride (h-BN) can be used in LBL assembly. When dispersed in water through sonication-assisted hydrolysis, h-BN develops hydroxyl groups that electrostatically couple with the cationic polymer polydiallyldimethylammonium chloride (PDDA). This process produces hydroxyl-functional h-BN/PDDA nanocomposites. The nanocomposites exhibit well exfoliated and highly ordered h-BN nanosheets, which results in an extremely high visual clarity, with an average transmittance of 99% in the visible spectrum. Moreover, well aligned nanocomposites extend gas diffusion path that reduce water vapor transmission rate to 1.3 × 10-2 g m-2 d-1. The simple and fast LBL process demonstrated here can be applied in many gas barrier applications.

Plasmonic Periodic Nanodot Arrays via Laser Interference Lithography for Organic Photovoltaic Cells with >10% Efficiency.

In this study, we demonstrate a viable and promising optical engineering technique enabling the development of high-performance plasmonic organic photovoltaic devices. Laser interference lithography was explored to fabricate metal nanodot (MND) arrays with elaborately controlled dot size as well as periodicity, allowing spectral overlap between the absorption range of the active layers and the surface plasmon band of MND arrays. MND arrays with ∼91 nm dot size and ∼202 nm periodicity embedded in a poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) hole transport layer remarkably enhanced the average power conversion efficiency (PCE) from 7.52% up to 10.11%, representing one of the highest PCE and degree of enhancement (∼34.4%) levels compared to the pristine device among plasmonic organic photovoltaics reported to date. The plasmonic enhancement mechanism was investigated by both optical and electrical analyses using finite difference time domain simulation and conductive atomic force microscopy studies.

PLZF(+) Innate T Cells Support the TGF-ß-Dependent Generation of Activated/Memory-Like Regulatory T Cells.

PLZF-expressing invariant natural killer T cells and CD4 T cells are unique subsets of innate T cells. Both are selected via thymocyte-thymocyte interaction, and they contribute to the generation of activated/memory-like CD4 and CD8 T cells in the thymus via the production of IL-4. Here, we investigated whether PLZF(+) innate T cells also affect the development and function of Foxp3(+) regulatory CD4 T cells. Flow cytometry analysis of the thymus and spleen from both CIITA transgenic C57BL/6 and wild-type BALB/c mice, which have abundant PLZF(+) CD4 T cells and invariant natural killer T cells, respectively, revealed that Foxp3(+) T cells in these mice exhibited a CD103(+) activated/memory-like phenotype. The frequency of CD103(+) regulatory T cells was considerably decreased in PLZF(+) cell-deficient CIITA(Tg)Plzf(lu/lu) and BALB/c.CD1d(-/-) mice as well as in an IL-4-deficient background, such as in CIITA(Tg)IL-4(-/-) and BALB/c.lL-4(-/-) mice, indicating that the acquisition of an activated/memory-like phenotype was dependent on PLZF(+) innate T cells and IL-4. Using fetal thymic organ culture, we further demonstrated that IL-4 in concert with TGF-ß enhanced the acquisition of the activated/memory-like phenotype of regulatory T cells. In functional aspects, the activated/memory-like phenotype of Treg cells was directly related to their suppressive function; regulatory T cells of CIITA(Tg)PIV(-/-) mice more efficiently suppressed ovalbumin-induced allergic airway inflammation compared with their counterparts from wild-type mice. All of these findings suggest that PLZF(+) innate T cells also augmented the generation of activated/memory-like regulation via IL-4 production.

Localized-surface-plasmon-enhanced multifunction silicon nanomembrane Schottky diodes based on Au nanoparticles.

Au nanoparticle (NP)-modified Si nanomembrane (Si NM) Schottky barrier diodes (SBDs) were fabricated by using a transfer-printing method to create pedestals using only one photomask on a flexible substrate. The transfer using the pedestals afforded a yield of >95% with no significant cracks. The plasmonic Au NPs can facilitate the improvement of the incident optical absorption. The Au NP-modified Si NM SBD exhibited enhanced photoresponse characteristics with an external quantum efficiency (η(EQE)) of 34%, a photosensitivity (P) of 27 at a voltage bias of -5 V, a light intensity of 1.2 W cm(-2), and a responsivity (R(ph)) of 0.21 A W(-1). Additionally, the mechanical bending characteristics of the device were observed while a compressive strain up to 0.62% was applied to the diode. The results suggest that the Au NP-modified Si NM SBD has great potential for use in multifunction devices as a strain sensor and photosensor.

IL-4 Induced Innate CD8+ T Cells Control Persistent Viral Infection.

Memory-like CD8+ T cells expressing eomesodermin are a subset of innate T cells initially identified in a number of genetically modified mice, and also exist in wild mice and human. The acquisition of memory phenotype and function by these T cells is dependent on IL-4 produced by PLZF+ innate T cells; however, their physiologic function is still not known. Here we found that these IL-4-induced innate CD8+ T cells are critical for accelerating the control of chronic virus infection. In CIITA-transgenic mice, which have a substantial population of IL-4-induced innate CD8+ T cells, this population facilitated rapid control of viremia and induction of functional anti-viral T-cell responses during infection with chronic form of lymphocytic choriomeningitis virus. Characteristically, anti-viral innate CD8+ T cells accumulated sufficiently during early phase of infection. They produced a robust amount of IFN-γ and TNF-α with enhanced expression of a degranulation marker. Furthermore, this finding was confirmed in wild-type mice. Taken together, the results from our study show that innate CD8+ T cells works as an early defense mechanism against chronic viral infection.

Involvement of PI3K/AKT and MAPK Pathways for TNF-α Production in SiHa Cervical Mucosal Epithelial Cells Infected with Trichomonas vaginalis.

Trichomonas vaginalis; induces proinflammation in cervicovaginal mucosal epithelium. To investigate the signaling pathways in TNF-α production in cervical mucosal epithelium after T. vaginalis infection, the phosphorylation of PI3K/AKT and MAPK pathways were evaluated in T. vaginalis-infected SiHa cells in the presence and absence of specific inhibitors. T. vaginalis increased TNF-α production in SiHa cells, in a parasite burden-dependent and incubation time-dependent manner. In T. vaginalis-infected SiHa cells, AKT, ERK1/2, p38 MAPK, and JNK were phosphorylated from 1 hr after infection; however, the phosphorylation patterns were different from each other. After pretreatment with inhibitors of the PI3K/AKT and MAPK pathways, TNF-α production was significantly decreased compared to the control; however, TNF-α reduction patterns were different depending on the type of PI3K/MAPK inhibitors. TNF-α production was reduced in a dose-dependent manner by treatment with wortmannin and PD98059, whereas it was increased by SP600125. These data suggested that PI3K/AKT and MAPK signaling pathways are important in regulation of TNF-α production in cervical mucosal epithelial SiHa cells. However, activation patterns of each pathway were different from the types of PI3K/MAPK pathways.

Thymic low affinity/avidity interaction selects natural Th1 cells.

Identification of intrathymic eomesodermin(+) (Eomes(+)) CD4 T cells creates a novel idea that there is more than one way for the generation of innate CD4 T cells. Promyelocytic leukemia zinc finger protein(+) T cells and natural Th17 cells are known to be generated by sensing a high and persistent TCR strength, whereas this is not the case for Eomes(+) CD4 T cells. These cells go through low-level signal during the entire maturation pathway, which subsequently leads to induction of high susceptibility to cytokine IL-4. This event seems to be a major determinant for the generation of this type of cell. These T cells are functionally equivalent to Th1 cells that are present in the periphery, and this event takes place both in transgenic and in wild-type mice. There is additional evidence that this type of Eomes(+) innate CD4 T cell is also present in human cord blood.

Analyses of the TCR repertoire of MHC class II-restricted innate CD4⁺ T cells.

Analysis of the T-cell receptor (TCR) repertoire of innate CD4(+) T cells selected by major histocompatibility complex (MHC) class II-dependent thymocyte-thymocyte (T-T) interaction (T-T CD4(+) T cells) is essential for predicting the characteristics of the antigens that bind to these T cells and for distinguishing T-T CD4(+) T cells from other types of innate T cells. Using the TCR(mini) Tg mouse model, we show that the repertoire of TCRα chains in T-T CD4(+) T cells was extremely diverse, in contrast to the repertoires previously described for other types of innate T cells. The TCRα chain sequences significantly overlapped between T-T CD4(+) T cells and conventional CD4(+) T cells in the thymus and spleen. However, the diversity of the TCRα repertoire of T-T CD4(+) T cells seemed to be restricted compared with that of conventional CD4(+) T cells. Interestingly, the frequency of the parental OT-II TCRα chains was significantly reduced in the process of T-T interaction. This diverse and shifted repertoire in T-T CD4(+) T cells has biological relevance in terms of defense against diverse pathogens and a possible regulatory role during peripheral T-T interaction.

Highly oriented gold/nanoclay-polymer nanocomposites for flexible gas barrier films.

Layer-by-layer (LBL) assembly, which uses electronic and ionic intermolecular bonding under nonvacuum conditions, is a promising technology for fabricating gas barrier films owing to its simple processing and easy formation of a multilayer structure. In this research, nanoclay-polymer multilayers of Na(+)-montmorillonite (Na-MMT) were fabricated. Particularly, the addition of AuCl3 on fabricated MMT layers caused a reaction with the surface silanol functional groups (Si-O-H) of the MMT platelets, resulting in the formation of Au2O3 on the MMT-polymer multilayers. The Au2O3 filled the vacancies between the MMT platelets and linked the MMT platelets together, thus forming a gas barrier film that reduced the water vapor transmission rate (WVTR) to 3.2 × 10(-3) g m(-2) day(-1). AuCl3-treated MMT-polymer multilayers thus have the potential to be utilized for manufacturing gas barrier films for flexible electronics on a large scale.

Design of a multi-walled carbon nanotube field emitter with micro vacuum gauge.

The variation of vacuum level inside a field emission device when electron is emitted from multi-walled carbon nanotubes (MWCNTs) by electric field was measured where MWCNT gauge packaged with a vacuum device was used to measure the degree of a vacuum until the end of the vacuum device life. It was found that the electrical properties of MWCNTs altered with the degree of a vacuum. We fabricated MWCNT gauge which were printed and pasted by the screen printer. In this paper, we report the successful detection of the ionization of gases in vacuum state.

Detection of a CO and NH3 gas mixture using carboxylic acid-functionalized single-walled carbon nanotubes.

Carbon nanotubes (CNT) are extremely sensitive to environmental gases. However, detection of mixture gas is still a challenge. Here, we report that 10 ppm of carbon monoxide (CO) and ammonia (NH3) can be electrically detected using a carboxylic acid-functionalized single-walled carbon nanotubes (C-SWCNT). CO and NH3 gases were mixed carefully with the same concentrations of 10 ppm. Our sensor showed faster response to the CO gas than the NH3 gas. The sensing properties and effect of carboxylic acid group were demonstrated, and C-SWCNT sensors with good repeatability and fast responses over a range of concentrations may be used as a simple and effective detection method of CO and NH3 mixture gas.

Effect of plasma treatment on the gas sensor with single-walled carbon nanotube paste.

The effect of plasma treatment on the gas sensing properties of screen-printed single-walled carbon nanotube (SWCNT) pastes is reported. The gas sensors, using SWCNT pastes as a sensing material, were fabricated by photolithography and screen printing. The SWCNT pastes were deposited between interdigitated electrodes on heater membrane by screen printing. In order to functionalize the pastes, they were plasma treated using several gases which produce defects caused by reactive ion etching. The Ar and O(2) plasma-treated SWCNT pastes exhibited a large response to NO(2) exposure and the fluorinated gas, such as CF(4) and SF(6), plasma-treated SWCNT pastes exhibited a large response to NH(3) exposure.

In situ induction of dendritic cell-based T cell tolerance in humanized mice and nonhuman primates.

Induction of antigen-specific T cell tolerance would aid treatment of diverse immunological disorders and help prevent allograft rejection and graft versus host disease. In this study, we establish a method of inducing antigen-specific T cell tolerance in situ in diabetic humanized mice and Rhesus monkeys receiving porcine islet xenografts. Antigen-specific T cell tolerance is induced by administration of an antibody ligating a particular epitope on ICAM-1 (intercellular adhesion molecule 1). Antibody-mediated ligation of ICAM-1 on dendritic cells (DCs) led to the arrest of DCs in a semimature stage in vitro and in vivo. Ablation of DCs from mice completely abrogated anti-ICAM-1-induced antigen-specific T cell tolerance. T cell responses to unrelated antigens remained unaffected. In situ induction of DC-mediated T cell tolerance using this method may represent a potent therapeutic tool for preventing graft rejection.

Targeting of a developmentally regulated epitope of CD43 for the treatment of acute leukemia.

Previously, we developed a JL1 mouse monoclonal antibody that specifically recognizes the leukemic cells of T, B, and myeloid lineages, but not the peripheral blood cells and pluripotent hematopoietic stem cells. Here, we identified that JL1 mAb recognized a specific epitope of human CD43 and validated its potential as an anti-leukemic targeting agent. After the comprehensive screening of JL1 Ag in the human thymocyte cDNA library, multiple fusion gene constructs encoding human CD43 were generated to identify its specific epitope to JL1 antibody. JL1 antibody interacted with a developmentally regulated and non-glycosylated epitope of the human CD43 extracellular domain (AA 73-81, EGSPLWTSI). In an in vivo leukemia model using NOD/SCID mice injected with CCRF-CEM7 cells, JL1 antibody induced effective cytotoxicity in tumor cells and prolonged survival (p < 0.05). Saporin conjugation to JL1 antibody effectively depleted tumor cells in in vitro cytotoxic assays and also prolonged survival in a leukemic mouse model (p < 0.001). These preclinical results further support the therapeutic potential of the JL1 antibody in the management of acute leukemia.

MHC class II-restricted interaction between thymocytes plays an essential role in the production of innate CD8+ T cells.

We have recently shown that MHC class II-dependent thymocyte-thymocyte (T-T) interaction successfully generates CD4(+) T cells (T-T CD4(+) T cells), and that T-T CD4(+) T cells expressing promyelocytic leukemia zinc finger protein (PLZF) show an innate property both in mice and humans. In this article, we report that the thymic T-T interaction is essential for the conversion of CD8(+) T cells into innate phenotype in the physiological condition. CD8(+) T cells developed in the presence of PLZF(+) CD4(+) T cells showed marked upregulation of eomesodermin (Eomes), activation/memory phenotype, and rapid production of IFN-γ on ex vivo stimulation. Their development was highly dependent on the PLZF expression in T-T CD4(+) T cells and the IL-4 secreted by PLZF(+) T-T CD4(+) T cells. The same events may take place in humans, as a substantial number of Eomes expressing innate CD8(+) T cells were found in human fetal thymi and spleens. It suggests that PLZF(+) T-T CD4(+) T cells in combination with Eomes(+) CD8(+) T cells might actively participate in the innate immune response against various pathogens, particularly in human perinatal period.

Generation of PLZF+ CD4+ T cells via MHC class II-dependent thymocyte-thymocyte interaction is a physiological process in humans.

Human thymocytes, unlike mouse thymocytes, express major histocompatibility complex (MHC) class II molecules on their surface, especially during the fetal and perinatal stages. Based on this observation, we previously identified a novel developmental pathway for the generation of CD4+ T cells via interactions between MHC class II-expressing thymocytes (thymocyte-thymocyte [T-T] interactions) with a transgenic mouse system. However, the developmental dissection of this T-T interaction in humans has not been possible because of the lack of known cellular molecules specific for T-T CD4+ T cells. We show that promyelocytic leukemia zinc finger protein (PLZF) is a useful marker for the identification of T-T CD4+ T cells. With this analysis, we determined that a substantial number of fetal thymocytes and splenocytes express PLZF and acquire innate characteristics during their development in humans. Although these characteristics are quite similar to invariant NKT (iNKT) cells, they clearly differ from iNKT cells in that they have a diverse T cell receptor repertoire and are restricted by MHC class II molecules. These findings define a novel human CD4+ T cell subset that develops via an MHC class II-dependent T-T interaction.