Hydrodynamic synthesis of Fe2O3@MoS2 0D/2D-nanocomposite material and its application as a catalyst in the glycolysis of polyethylene terephthalate.

We report a fast and simple synthesis of Fe2O3@MoS2 0D/2D-nanocomposite material using a Taylor-Couette flow reactor. A Taylor-Couette flow with high shear stress and mixing characteristics was used for fluid dynamic exfoliation of MoS2 and deposition of uniform Fe2O3 nanoparticles, resulting in a Fe2O3@MoS2 in the form of 0D/2D-nanocomposite material. Using Taylor-Couette flow reactor, we could synthesize Fe2O3@MoS2 0D/2D-nanocomposite material at a rate higher than 1000 mg h-1 which is much higher than previously reported production rate of 0.2-116.7 mg h-1. The synthesis of Fe2O3@MoS2 nanocomposite was achieved in an aqueous solution without thermal or organic solvent treatment. Exfoliated MoS2 nanosheets show an average thickness of 2.6 ± 2.3 nm (<6 layers) and a lateral size of 490 ± 494 nm. Fe2O3 nanoparticles have an average size of 7.4 ± 3.0 nm. Fe2O3 nanoparticles on chemically and thermally stable MoS2 nanosheets show catalytic activity in the glycolysis of polyethylene terephthalate (PET). High conversion of PET (97%) and a high yield (90%) for bis(hydroxyethyl) terephthalate (BHET) were achieved in a reaction time of 3 h at the reaction temperature of 225 °C.

Controllable P- and N-Type Conversion of MoTe2 via Oxide Interfacial Layer for Logic Circuits.

To realize basic electronic units such as complementary metal-oxide-semiconductor (CMOS) inverters and other logic circuits, the selective and controllable fabrication of p- and n-type transistors with a low Schottky barrier height is highly desirable. Herein, an efficient and nondestructive technique of electron-charge transfer doping by depositing a thin Al2 O3 layer on chemical vapor deposition (CVD)-grown 2H-MoTe2 is utilized to tune the doping from p- to n-type. Moreover, a type-controllable MoTe2 transistor with a low Schottky barrier height is prepared. The selectively converted n-type MoTe2 transistor from the p-channel exhibits a maximum on-state current of 10 µA, with a higher electron mobility of 8.9 cm2 V-1 s-1 at a drain voltage (Vds ) of 1 V with a low Schottky barrier height of 28.4 meV. To validate the aforementioned approach, a prototype homogeneous CMOS inverter is fabricated on a CVD-grown 2H-MoTe2 single crystal. The proposed inverter exhibits a high DC voltage gain of 9.2 with good dynamic behavior up to a modulation frequency of 1 kHz. The proposed approach may have potential for realizing future 2D transition metal dichalcogenide-based efficient and ultrafast electronic units with high-density circuit components under a low-dimensional regime.

All MoS2-Based Large Area, Skin-Attachable Active-Matrix Tactile Sensor.

Large-area, ultrathin flexible tactile sensors with conformal adherence are becoming crucial for advances in wearable electronics, electronic skins and biorobotics. However, normal passive tactile sensors suffer from high crosstalk, resulting in inaccurate sensing, which consequently limits their use in such advanced applications. Active-matrix-driven tactile sensors could potentially overcome such hurdles, but it demands the high performance and reliable operations of the thin-film-transistor array that could efficiently control integrated pressure gauges. Herein, we utilized the benefit of the semiconducting and mechanical excellence of MoS2 and placed it between high- k Al2O3 dielectric sandwich layers to achieve the high and reliable performance of MoS2-based back-plane circuitry and strain sensor. This strategical combination reduces the fabrication complexity and enables the demonstration of an all MoS2-based large area (8 × 8 array) active-matrix tactile sensor offering a wide sensing range (1-120 kPa), sensitivity value (Δ R/ R0: 0.011 kPa-1), and a response time (180 ms) with excellent linearity. In addition, it showed potential in sensing multitouch accurately, tracking a stylus trajectory, and detecting the shape of an external object by grasping it using the palm of the human hand.

Controlled crack propagation for atomic precision handling of wafer-scale two-dimensional materials.

Although flakes of two-dimensional (2D) heterostructures at the micrometer scale can be formed with adhesive-tape exfoliation methods, isolation of 2D flakes into monolayers is extremely time consuming because it is a trial-and-error process. Controlling the number of 2D layers through direct growth also presents difficulty because of the high nucleation barrier on 2D materials. We demonstrate a layer-resolved 2D material splitting technique that permits high-throughput production of multiple monolayers of wafer-scale (5-centimeter diameter) 2D materials by splitting single stacks of thick 2D materials grown on a single wafer. Wafer-scale uniformity of hexagonal boron nitride, tungsten disulfide, tungsten diselenide, molybdenum disulfide, and molybdenum diselenide monolayers was verified by photoluminescence response and by substantial retention of electronic conductivity. We fabricated wafer-scale van der Waals heterostructures, including field-effect transistors, with single-atom thickness resolution.

Flexible active-matrix organic light-emitting diode display enabled by MoS2 thin-film transistor.

Atomically thin molybdenum disulfide (MoS2) has been extensively investigated in semiconductor electronics but has not been applied in a backplane circuitry of organic light-emitting diode (OLED) display. Its applicability as an active drive element is hampered by the large contact resistance at the metal/MoS2 interface, which hinders the transport of carriers at the dielectric surface, which in turn considerably deteriorates the mobility. Modified switching device architecture is proposed for efficiently exploiting the high-k dielectric Al2O3 layer, which, when integrated in an active matrix, can drive the ultrathin OLED display even in dynamic folding states. The proposed architecture exhibits 28 times increase in mobility compared to a normal back-gated thin-film transistor, and its potential as a wearable display attached to a human wrist is demonstrated.

CVD-grown monolayer MoS2 in bioabsorbable electronics and biosensors.

Transient electronics represents an emerging technology whose defining feature is an ability to dissolve, disintegrate or otherwise physically disappear in a controlled manner. Envisioned applications include resorbable/degradable biomedical implants, hardware-secure memory devices, and zero-impact environmental sensors. 2D materials may have essential roles in these systems due to their unique mechanical, thermal, electrical, and optical properties. Here, we study the bioabsorption of CVD-grown monolayer MoS2, including long-term cytotoxicity and immunological biocompatibility evaluations in biofluids and tissues of live animal models. The results show that MoS2 undergoes hydrolysis slowly in aqueous solutions without adverse biological effects. We also present a class of MoS2-based bioabsorbable and multi-functional sensor for intracranial monitoring of pressure, temperature, strain, and motion in animal models. Such technology offers specific, clinically relevant roles in diagnostic/therapeutic functions during recovery from traumatic brain injury. Our findings support the broader use of 2D materials in transient electronics and qualitatively expand the design options in other areas.

Lithography-free plasma-induced patterned growth of MoS2 and its heterojunction with graphene.

Application-oriented patterned growth of transition metal dichalcogenides (TMDCs) and their heterojunctions is of critical importance for sophisticated, customized two-dimensional (2D) electronic and optoelectronic devices; however, it is still difficult to fabricate these patterns in a simple, clean, and high controllability manner without using optical lithography. Here, we report the direct synthesis of patterned MoS2 and graphene-MoS2 heterojunctions via selective plasma treatment of a SiO2/Si substrate and chemical vapor deposition of MoS2. This method has multiple merits, such as simple steps, a short operating time, easily isolated MoS2 layers with clean surfaces and controllable locations, shapes, sizes and thicknesses, which enable their integration into the device structure without using a photoresist. In addition, we demonstrate the direct growth of patterned graphene-MoS2 heterojunctions for the fabrication of transistor. This study reveals a novel method to fabricate and use patterned MoS2 and graphene-MoS2 heterojunctions, which could be generalized to the rational design of other 2D materials, heterojunctions and devices in the future.

MoS2 -Based Tactile Sensor for Electronic Skin Applications.

A conformal tactile sensor based on MoS2 and graphene is demonstrated. The MoS2 tactile sensor exhibits excellent sensitivity, high uniformity, and good repeatability in terms of various strains. In addition, the outstanding flexibility enables the MoS2 strain tactile sensor to be realized conformally on a finger tip. The MoS2 -based tactile sensor can be utilized for wearable electronics, such as electronic skin.

Graphene-Based Flexible and Stretchable Electronics.

Graphene provides outstanding properties that can be integrated into various flexible and stretchable electronic devices in a conventional, scalable fashion. The mechanical, electrical, and optical properties of graphene make it an attractive candidate for applications in electronics, energy-harvesting devices, sensors, and other systems. Recent research progress on graphene-based flexible and stretchable electronics is reviewed here. The production and fabrication methods used for target device applications are first briefly discussed. Then, the various types of flexible and stretchable electronic devices that are enabled by graphene are discussed, including logic devices, energy-harvesting devices, sensors, and bioinspired devices. The results represent important steps in the development of graphene-based electronics that could find applications in the area of flexible and stretchable electronics.

Self-Limiting Layer Synthesis of Transition Metal Dichalcogenides.

This work reports the self-limiting synthesis of an atomically thin, two dimensional transition metal dichalcogenides (2D TMDCs) in the form of MoS2. The layer controllability and large area uniformity essential for electronic and optical device applications is achieved through atomic layer deposition in what is named self-limiting layer synthesis (SLS); a process in which the number of layers is determined by temperature rather than process cycles due to the chemically inactive nature of 2D MoS2. Through spectroscopic and microscopic investigation it is demonstrated that SLS is capable of producing MoS2 with a wafer-scale (~10 cm) layer-number uniformity of more than 90%, which when used as the active layer in a top-gated field-effect transistor, produces an on/off ratio as high as 10(8). This process is also shown to be applicable to WSe2, with a PN diode fabricated from a MoS2/WSe2 heterostructure exhibiting gate-tunable rectifying characteristics.

Graphene-based conformal devices.

Despite recent progress in bendable and stretchable thin-film transistors using novel designs and materials, the development of conformal devices remains limited by the insufficient flexibility of devices. Here, we demonstrate the fabrication of graphene-based conformal and stretchable devices such as transistor and tactile sensor on a substrate with a convoluted surface by scaling down the device thickness. The 70 nm thick graphene-based conformal devices displayed a much lower bending stiffness than reported previously. The demonstrated devices provided excellent conformal coverage over an uneven animal hide surface without the need for an adhesive. In addition, the ultrathin graphene devices formed on the three-dimensionally curved animal hide exhibited stable electrical characteristics, even under repetitive bending and twisting. The advanced performance and flexibility demonstrated here show promise for the development and adoption of wearable electronics in a wide range of future applications.

Influence of moonlight on mRNA expression patterns of melatonin receptor subtypes in the pineal organ of a tropical fish.

The goldlined spinefoot, Siganus guttatus, is a lunar-synchronized spawner, which repeatedly releases gametes around the first quarter moon during the reproductive season. A previous study reported that manipulating moonlight brightness at night disrupted synchronized spawning, suggesting involvement of this natural light source in lunar synchronization. The present study examined whether the mRNA expression pattern of melatonin receptor subtypes MT1 and Mel1c in the pineal organ of the goldlined spinefoot is related to moonlight. Real-time quantitative polymerase chain reaction analysis revealed that the abundance of MT1 and Mel1c mRNA at midnight increased during the new moon phase and decreased during the full moon phase. Exposing fish to moonlight intensity during the full moon period resulted in a decrease in Mel1c mRNA abundance within 1h. Fluctuations in the melatonin receptor genes according to changes in the moon phase agreed with those of melatonin levels in the blood. These results indicate that periodic changes in cues from the moon influence melatonin receptor mRNA expression levels. The melatonin-melatonin receptor system may play a role in predicting the moon phase through changes in night brightness.

Moonlight affects mRNA abundance of arylalkylamine N-acetyltransferase in the retina of a lunar-synchronized spawner, the goldlined spinefoot.

Melatonin synthesis in the pineal gland and retina shows a rhythmic fashion with high levels at night and is controlled by a rate-limiting enzyme, arylalkylamine N-acetyltransferase (AANAT). A previous study revealed that moonlight suppresses the plasma melatonin levels of the goldlined spinefoot (Siganus guttatus), which exhibits a lunar cycle in its reproductive activity and repeats gonadal development toward and spawning around the first quarter moon. Whether the retina of this species responds to moonlight is unknown. To clarify the photoperceptive ability of this species, we aimed to clone the full-length cDNA of Aanat1 (sgAanat1) from the retina and examine its transcriptional pattern under several daylight and moonlight regimes. The full-length sgAanat1 cDNA (1,038 bp) contained a reading frame encoding a protein of 225 amino acids, which was highly homologous to AANAT1 of other teleosts. Reverse transcription-polymerase chain reaction (PCR) analysis revealed that among the tissues tested, sgAanat1 fragments were expressed exclusively in the retina. Real-time quantitative PCR analysis revealed that sgAanat1 fluctuated with high abundance at night under light-dark cycle and at subjective night under constant darkness, but not under constant light. These results suggest that sgAanat1 is regulated by both the external light signal and internal clock system. The abundance of sgAanat1 in the retina was higher at the culmination time around new moon than full moon phase. Additionally, exposing fish to brightness around the full moon period suppressed sgAanat1 mRNA abundance. Thus, moonlight is perceived by fish and has an impact on melatonin fluctuation in the retina.

Expression of type II iodothyronine deiodinase gene in the brain of a tropical spinefoot, Siganus guttatus.

Type II iodothyronine deiodinase (D2) converts 3,5,3',5'-tetraiodothyronine to 3,5,3'-triiodothyronine and is involved in regulating thyroid hormone-dependent processes in various tissues. D2 mRNA expression in the mediobasal hypothalamus is affected by photoperiod, which influences reproductive processes in temperate birds and mammals. We examined whether D2 mRNA is expressed in the hypothalamus (located in the forebrain within the diencephalon area) and whether its abundance is affected by day length, temperature, or food availability in the tropical spinefoot, Siganus guttatus, which is endemic to tropical monsoon areas. The reverse transcription-polymerase chain reaction (RT-PCR) revealed that D2 mRNA is expressed in various brain regions. The abundance of hypothalamic D2 mRNA was higher at 12.00h than at 06.00h or 24.00h. Rearing fish under constant dark conditions resulted in a decrease in D2 mRNA abundance during the subjective night. A single injection of melatonin lowered D2 mRNA abundance within 3h. Collectively, it appears that hypothalamic D2 mRNA abundance is regulated by the circadian system and/or melatonin. No differences in D2 mRNA abundance were observed, when fish were reared at 20, 25, and 30°C. However, food deprivation stimulated D2 mRNA expression during the daytime. These results suggest that photoperiodic and nutritive conditions affect hypothalamic D2 mRNA expression in S. guttatus.

Diurnal expression patterns of neurohypophysial hormone genes in the brain of the threespot wrasse Halichoeres trimaculatus.

The aim of this study was to determine the involvement of neurohypophysial hormones in the diurnal patterns of the threespot wrasse Halichoeres trimaculatus, which is common in coral reefs and exhibits daily behavioral periodicity. Prohormone cDNAs of the neurohypophysial peptides, arginine vasotocin (AVT) and isotocin (IT), were cloned by 3'- and 5'-rapid amplification of cDNA ends (RACE). The distribution and expression patterns of pro-AVT and -IT mRNAs in the brain were determined using reverse-transcription polymerase chain reaction (RT-PCR) and real-time quantitative PCR, respectively. The respective full-length cDNAs of pro-AVT and -IT were 945 and 755 bp in length, respectively. The deduced amino acid sequences for pro-AVT and pro-IT were 154 and 156 residues in length, respectively. Both pro-peptides contained a signal sequence followed by the respective hormones and neurophysin connected by a Gly-Lys-Arg bridge. Pro-AVT mRNA was detected only in the hypothalamus area, while pro-IT mRNA in the whole part of the brain. The relative abundance of pro-AVT and -IT mRNA varied according to time of day; it was significantly greater at 12:00 h than at 24:00 h. Following intraperitoneal administration of melatonin, pro-AVT mRNA abundance in the brain decreased, while pro-IT mRNA abundance remained unchanged. These results demonstrate that daily fluctuations of pro-AVT and pro-IT levels in the brain of threespot wrasse are differentially regulated.

Effect of cortisol on melatonin production by the pineal organ of tilapia, Oreochromis mossambicus.

The aim of the present study was to examine the involvement of cortisol on melatonin synthesis in the pineal organ of the Mozambique tilapia, Oreochromis mossambicus. The circulating levels of melatonin in this species exhibited daily variations with a decrease during the photophase (0600, 1200, and 1800 h) and an increase during the scotophase (0000 h), while cortisol levels peaked during the early photophase (0600 h). The pineal organ was cultured in vitro in the dark in the presence of cortisol mimicking either stressed (100 ng/mL) or resting (10 ng/mL) concentration in tilapia. High cortisol concentration significantly reduced the levels of melatonin secreted into the medium. In the fish reared under stressful conditions, the nocturnal circulating levels of cortisol increased significantly, while melatonin did not change significantly. We detected glucocorticoid receptor (GR) transcripts in the pineal organ and a quantitative real-time PCR revealed that this receptor mRNA abundance fluctuated diurnally, increasing at 0600, 1800, and 0000 h and decreasing at 1200 h. The GR mRNA abundance in the pineal organ was not altered either in vitro when the organ was cultured in the presence of 100 ng/mL cortisol or in vivo when the fish were reared under stressful conditions. On the basis of these findings, it is proposed that cortisol lowers melatonin synthesis in the pineal organ, while the role of GR signaling in this process remains to be established.

Moonlight affects nocturnal Period2 transcript levels in the pineal gland of the reef fish Siganus guttatus.

The golden rabbitfish Siganus guttatus is a reef fish with a restricted lunar-synchronized spawning cycle. It is not known how the fish recognizes cues from the moon and exerts moon-related activities. In order to evaluate the perception and utilization of moonlight by the fish, the present study aimed to clone and characterize Period2 (Per2), a light-inducible clock gene in lower vertebrates, and to examine daily variations in rabbitfish Per2 (rfPer2) expression as well as the effect of light and moonlight on its expression in the pineal gland. The partially-cloned rfPer2 cDNA (2933 bp) was highly homologous (72%) to zebrafish Per2. The rfPer2 levels increased at ZT6 and decreased at ZT18 in the whole brain and several peripheral organs. The rfPer2 expression in the pineal gland exhibited a daily variation with an increase during daytime. Exposing the fish to light during nighttime resulted in a rapid increase of its expression in the pineal gland, while the level was decreased by intercepting light during daytime. Two hours after exposing the fish to moonlight at the full moon period, the rfPer2 expression was upregulated. These results suggest that rfPer2 is a light-inducible clock gene and that its expression is affected not only by daylight but also by moonlight. Since the rfPer2 expression level during the full moon period was higher than that during the new moon period, the monthly variation in the rfPer2 expression is likely to occur with the change in amplitude between the full and new moon periods.

Tissue-specific suppression of estrogen, androgen and glucocorticoid receptor gene expression in feral vitellogenic male Mozambique tilapia.

While vitellogenesis in male fish is commonly used as a biomarker of xenoestrogen exposure, very little is known about the impacts associated with this unusual protein synthesis in feral populations. To this end, a recent study showed elevated circulating vitellogenin (VTG) levels in male Mozambique tilapia (Oreochromis mossambicus) collected from the Aja but not Tengan Rivers in Okinawa, Japan. Here we investigated whether this unusual protein synthesis in male fish from the Aja River affect transcript abundance of estrogen (ER), androgen (AR) and glucocorticoid (GR) receptors in the liver, brain and testis. The detection of plasma VTG levels ( approximately 100 microg ml(-1)) in male tilapia confirmed xenoestrogenic exposure in the Aja, but not the Tengan River. This protein induction was not associated with any changes in the reproductive capacity as assessed by sperm mobility and testis histology in the Aja fish. Plasma levels of estradiol-17beta, 11-ketotestosterone and cortisol were not significantly different between fish from the two rivers. Quantitative real-time PCR revealed a significant reduction in transcript levels of ERalpha and ERbeta, GR and ARalpha but not ARbeta, in the livers of tilapia from the Aja compared with the Tengan River. There were no significant changes in any of the steroid receptor transcript levels in either the brain or testis between the two rivers. Overall, our results imply that xenoestrogen exposure and VTG synthesis may lead to disruption of liver responsiveness to sex steroids and glucocorticoid stimulation in feral male fish.

Molecular cloning and daily variations of the Period gene in a reef fish Siganus guttatus.

As the first step in understanding the molecular oscillation of the circa rhythms in the golden rabbitfish Siganus guttatus--a reef fish with a definite lunar-related rhythmicity--we cloned and sequenced a Period gene (rfPer). The rfPer gene contained an open reading frame that encodes a protein consisting of 1,452 amino acids; this protein is highly homologous to PER proteins of vertebrates including zebrafish. Phylogenetic analyses indicated that the rfPER protein is related to the zebrafish PER1 and PER4. The expression of rfPer mRNA in the whole brain, retina, and liver under light/dark (LD) conditions increased at 06:00 h and decreased at 18:00 h, suggesting that its robust circadian rhythm occurs in neural and peripheral tissues. When daily variation in the expression in rfPer mRNA in the whole brain and cultured pineal gland were examined under LD conditions, similar expression patterns of the gene were observed with an increase around dawn. Under constant light condition, the increased expression of rfPer mRNA in the whole brain disappeared around dawn. The present results demonstrate that rfPer is related to zPer4 and possibly zPer1. The present study is the first report on the Period gene from a marine fish.

Expression of the melatonin receptor Mel(1c) in neural tissues of the reef fish Siganus guttatus.

The golden rabbitfish, Siganus guttatus, is a reef fish exhibiting a restricted lunar-related rhythm in behavior and reproduction. Here, to understand the circadian rhythm of this lunar-synchronized spawner, a melatonin receptor subtype-Mel(1c)-was cloned. The full-length Mel(1c) melatonin receptor cDNA comprised 1747 bp with a single open reading frame (1062 bp) that encodes a 353-amino acid protein, which included 7 presumed transmembrane domains. Real-time PCR revealed high Mel(1c) mRNA expression in the retina and brain but not in the peripheral tissues. When the fish were reared under light/dark (LD 12:12) conditions, Mel(1c) mRNA in the retina and brain was expressed with daily variations and increased during nighttime. Similar variations were noted under constant conditions, suggesting that Mel(1c) mRNA expression is regulated by the circadian clock system. Daily variations of Mel(1c) mRNA expression with a peak at zeitgeber time (ZT) 12 were observed in the cultured pineal gland under LD 12:12. Exposure of the cultured pineal gland to light at ZT17 resulted in a decrease in Mel(1c) mRNA expression. When light was obstructed at ZT5, the opposite effect was obtained. These results suggest that light exerts certain effects on Mel(1c) mRNA expression directly or indirectly through melatonin actions.