Enhanced Thermal Conductivity of Single-Walled Carbon Nanotube with Axial Tensile Strain Enabled by Boron Nitride Nanotube Anchoring.

Thermal conductivity measurements are conducted by optothermal Raman technique before and after the introduction of an axial tensile strain in a suspended single-walled carbon nanotube (SWCNT) through end-anchoring by boron nitride nanotubes (BNNTs). Surprisingly, the axial tensile strain (<0.4 %) in SWCNT results in a considerable enhancement of its thermal conductivity, and the larger the strain, the higher the enhancement. Furthermore, the thermal conductivity reduction with temperature is much alleviated for the strained nanotube compared to previously reported unstrained cases. The thermal conductivity of SWCNT increases with its length is also observed.

One-dimensional van der Waals heterostructures: Growth mechanism and handedness correlation revealed by nondestructive TEM.

We recently synthesized one-dimensional (1D) van der Waals heterostructures in which different atomic layers (e.g., boron nitride or molybdenum disulfide) seamlessly wrap around a single-walled carbon nanotube (SWCNT) and form a coaxial, crystalized heteronanotube. The growth process of 1D heterostructure is unconventional-different crystals need to nucleate on a highly curved surface and extend nanotubes shell by shell-so understanding the formation mechanism is of fundamental research interest. In this work, we perform a follow-up and comprehensive study on the structural details and formation mechanism of chemical vapor deposition (CVD)-synthesized 1D heterostructures. Edge structures, nucleation sites, and crystal epitaxial relationships are clearly revealed using transmission electron microscopy (TEM). This is achieved by the direct synthesis of heteronanotubes on a CVD-compatible Si/SiO2 TEM grid, which enabled a transfer-free and nondestructive access to many intrinsic structural details. In particular, we have distinguished different-shaped boron nitride nanotube (BNNT) edges, which are confirmed by electron diffraction at the same location to be strictly associated with its own chiral angle and polarity. We also demonstrate the importance of surface cleanness and isolation for the formation of perfect 1D heterostructures. Furthermore, we elucidate the handedness correlation between the SWCNT template and BNNT crystals. This work not only provides an in-depth understanding of this 1D heterostructure material group but also, in a more general perspective, serves as an interesting investigation on crystal growth on highly curved (radius of a couple of nanometers) atomic substrates.

[A longitudinal study of the association between physical activity and apathy among community-dwelling older adults].

AIM: This study clarified the association between the amount of physical activity and apathy after one year among community-dwelling older adults. METHODS: Two hundred community-dwelling older adults (mean age: 74.3±5.0 years old, female: 52.5%) who participated in the 2018 and 2019 "Kasama Longevity Health Examination" were included. Apathy was assessed using the Apathy Scale (0-42 points; the higher the score, the lower the motivation), physical activity by Physical Activity Scale for the Elderly (PASE), and Geriatric Depression Scale-15 (GDS). The 2018 PASE data were grouped into tertiles. A multiple regression analysis was performed with the 2019 Apathy Scale as the dependent variable and the 2018 PASE as the independent variable, and the sex, age, years of education, economic situation, body mass index, chronic illness, smoking history, alcohol drinking habits, physical function, cognitive function, GDS, and the 2018 Apathy Scale as adjustment variables. The PASE subcategories (leisure-time, household, and work-related activities) were examined using a similar method. RESULTS: The mean Apathy Scale in 2019 was 14.0±6.2 for the low physical activity group, 12.8±6.0 for the medium physical activity group, and 10.1±5.9 for the high physical activity group. The high physical activity group showed a significant negative association with the Apathy Scale (B=-1.56, 95% confidence interval=-2.91 to -0.21, p=0.023). No association was found for any activity of the PASE sub-items. CONCLUSIONS: A high level of physical activity may protect against apathy among community-dwelling older adults.

Chemical screening of inhibitors specific for MdDOX-Co that cause an apple columnar tree-shape.

MdDOX-Co, the ectopic expression of which is considered to cause the apple columnar tree shape, belongs to the 2-oxoglutarate-dependent dioxygenase (2ODD) family. It adds a hydroxyl group to position 12 of gibberellins (GAs). However, the 2ODD enzymes related to GA biosynthesis and catabolism are phylogenetically distinct from MdDOX-Co. Thus, it is possible that substrates other than GAs exist in MdDOX-Co. To identify the previously unidentified substrate(s) of MdDOX-Co, we searched for MdDOX-Co-specific inhibitors. Chemical screening using gas chromatography-mass spectrometry was performed to investigate the effects of 2400 compounds that inhibited the catalytic reaction of MdDOX-Co, but not the catabolic reaction of GA 2-oxidase, an enzyme involved in GA catabolism. By applying two positive compounds in Arabidopsis, a chemical 3-((2-chloro-6-fluorobenzyl)thio)-5,7-dimethyl-5H-pyrazolo[3,4-e][1,4,2]dithiazine-1,1-dioxide designated as TPDD that did not inhibit GA biosynthesis was selected. The structure-activity relationships among the TPDD analogs were also obtained.

[Relationship between performance on the Digital Trail Making Peg test and cognitive function in older adults].

AIM: To determine the relationship between performance on the Digital Trail Making Peg test (DTMP) and cognitive function in older adults. METHODS: A total of 203 community-dwelling older adults (mean age: 76.4±5.1 years old) participated in this study. The five-cog test was used to assess the cognitive function. The DTMP measured completion time, number of errors and intra-individual variability for performance variability (coefficient of variation, CV; inter-elemental variability, IEV). Spearman's rank correlation coefficient (ρ) was calculated to examine the association between each variable. In addition, a multiple regression analysis was performed with the cognitive function score as the dependent variable and the DTMP completion time, number of errors, CV, and IEV as the independent variables, with adjusting for the sex, age, years of education, body mass index, medical history, depression, and physical function. RESULTS: The rank correlation coefficients with cognitive function scores were as follows: completion time, ρ = -0.479 (P < 0.01), number of errors, ρ = -0.068 (P = 0.332), CV, ρ = 0.085 (P = 0.225), IEV, ρ = -0.316 (P < 0.01). The results of the multiple regression analysis showed that completion time (ß = -0.566), CV (ß = 0.164), IEV (ß = 2.736) were significantly associated with cognitive function scores. CONCLUSIONS: The shorter the DTMP completion time, the better the overall cognitive function. However, the intra-individual variability of CV and IEV did not show consistent results, with smaller values indicating less intra-individual variability.

Phenomenological model of thermal transport in carbon nanotube and hetero-nanotube films.

The thermal properties of individual single-walled carbon nanotubes (SWCNTs) have been well documented in the literature following decades of intensive study. However, when SWCNTs form a macroscale assembly, the thermal transport in these complex structures usually not only depends on the properties of the individual tubes, but also is affected and sometimes dominated by inner structural details, e.g. bundles and junctions. In this work, we first performed an experimental measurement of the thermal conductivities of individual SWCNT bundles of different sizes using a suspended micro-thermometer. The results, together with the data that we obtained from a previous work, give a complete experimental understanding of the effect of bundling on the thermal conductivity of SWCNTs. With these quantitative understandings, we propose a phenomenological model to describe the thermal transport in two-dimensional (2D) SWCNT films. The term 'line density' is defined to describe the effective thermal transport channels in this complex 2D network. Along with experimentally obtained geometric statistics and film transparency, the thermal conductance of SWCNTs is estimated, and the effects of bundle length, diameter, and contact conductance are systematically discussed. Finally, we extend this model to explain thermal transport in 2D networks of one-dimensional van der Waals heterostructures, which are coaxial hetero-nanotubes we recently synthesized using SWCNTs as the template. This extended model suggests that the contribution of boron nitride nanotubes (BNNTs) to the overall performance of a SWCNT-BNNT heterostructured film depends on the transparency of the original SWCNT film. The increase in the thermal conductance of a highly transparent film is estimated to be larger than that of a less transparent film, which shows a good agreement with our experimental observations and proves the validity of the proposed phenomenological model.

Effects of Morning Versus Evening Home-Based Exercise on Subjective and Objective Sleep Parameters in Older Adults: A Randomized Controlled Trial.

OBJECTIVE: This study aimed to determine whether the timing of exercise influenced the effects of home-based low-intensity stepping exercises on the sleep parameters of older adults. METHOD: For 8 weeks, 60 healthy older adults participated in a randomized controlled trial, performing low-intensity aerobic exercise (70-80 bpm) for about 30 minutes every day at home, either in the morning (from waking until 12:00) or evening (18:00 to bedtime). RESULTS: In the evening exercise group, both subjectively and objectively measured sleep latency significantly improved throughout the intervention. Further, postintervention subjective sleep satisfaction was significantly higher in the evening group (6.2 ± 1.3 points) than in the morning group (5.2 ± 1.4 points; P = .006). Additionally, sleep variables related to evening exercise had larger effect sizes (Cohen d) than those performed in the morning. CONCLUSION: Engaging in low-intensity stepping exercises during the evening is potentially a useful nonpharmacological approach to improving sleep quality among older adults.

Combined effect of daily physical activity and social relationships on sleep disorder among older adults: cross-sectional and longitudinal study based on data from the Kasama study.

BACKGROUND: This study investigated whether daily physical activity of older adults, combined with social relationships, is associated with the risk of sleep disorder. Further, it determined whether a high level of one variable with a low level of the other, leads to a significantly lower risk of sleep disorder than low levels of both. METHODS: The sample comprised 1339 community-dwelling older Japanese adults: 988 in Study 1 and 351 in Study 2. The level of daily physical activity and range of social relationships were assessed using the Physical Activity Scale for the Elderly and the Lubben Social Network Scale, respectively. The Pittsburgh Sleep Quality Index was used to assess sleep disorder. To test the combined relationships and effects in Studies 1 and 2, the medians for the respective scores of each of the following four groups that the participants were categorized into, were calculated: (1) low activity group with low social relationships, (2) low activity group with high social relationships, (3) high activity group with low social relationships, and (4) high activity group with high social relationships. After adjusting for potential confounders, a logistic regression analysis was conducted in Study 1. After adjusting for potential confounders, a Cox proportional hazards regression analysis was conducted in Study 2. RESULTS: Study 1 revealed that the high activity group with high social relationships showed a significantly lower risk of sleep disorder (ORs: 0.585, 95% CI: 0.404-0.847) than the low activity group with low social relationships. Study 2 also revealed that the high activity group with high social relationships showed a significantly lower prevalence of sleep disorder (HRs: 0.564, 95% CI: 0.327-0.974) than the low activity group with low social relationships. CONCLUSIONS: Our findings suggest that for older adults with high social relationships, being physically active is favorably associated with sleep quality. However, a high level of one variable with a low level of the other has not been confirmed in improving sleep quality among older adults.

Associations between exercising in a group and physical and cognitive functions in community-dwelling older adults: a cross-sectional study using data from the Kasama Study.

[Purpose] To examine the associations of exercise habits, particularly exercising in a group, with physical and cognitive functions in community-dwelling older adults. [Participants and Methods] A total of 615 older adults participated in this cross-sectional study. We conducted three physical performance tests (grip strength, five times sit-to-stand, and 5-meter walk tests) and the Five-Cog test (attention, memory, visuospatial, language, and reasoning). We investigated exercise habits using questionnaires and classified the participants into three groups as follows: those who did not exercise (n=86), those who exercised alone (n=168), and those who exercised in a group (n=362). To clarify the associations of exercise habits with physical and cognitive functions, we used the analysis of covariance with adjustment for potential confounders. [Results] The participants who exercised in a group had better lower limb strength than those who exercised alone and better scores for all the variables than the non-exercisers. Furthermore, those who exercised in a group scored significantly higher on the attention, memory, visuospatial, and overall cognitive function tests than those who exercised alone. [Conclusion] Our results highlight the importance of the social aspects associated with exercising, such as the presence of exercise peers, to improve the physical and cognitive health of older adults.

Growth of Single-Walled Carbon Nanotubes from Solid Carbon Nanoparticle Seeds via Cap Formation Engineering with a Two-Step Growth Process and Water Vapor Supply.

Solid carbon nanoparticles are promising growth seeds to prepare single-walled carbon nanotubes (SWCNTs) at high temperatures, at which the SWCNT crystallinity should be improved significantly but conventional metal catalyst nanoparticles are unstable and suffer from aggregation. The noncatalytic nature of solid carbon nanoparticles, however, makes SWCNT growth inefficient, resulting in a limited growth yield. In this study, we develop a two-step chemical vapor deposition process to efficiently synthesize high-crystallinity SWCNTs at high temperatures from solid carbon nanoparticles obtained from nanodiamond. Based on thermodynamic considerations, the growth conditions are separately adjusted to supply different growth driving forces which are suitable for the formation of the initial cap structures and for the stationary elongation of SWCNTs. This process, called cap formation engineering, improves the nucleation density of the cap structures. We examined the changes in crystallinity, amorphous carbon deposition, diameter, and yield of SWCNTs with respect to the synthesis conditions. By controlling the initial growth conditions, high-quality SWCNTs are grown with improved yield. With the addition of water vapor as the etchant, deposition of amorphous carbon at high temperatures was further prevented. The results provide a pathway for precise growth control of SWCNTs from unconventional solid growth seeds.

Formation of organic color centers in air-suspended carbon nanotubes using vapor-phase reaction.

Organic color centers in single-walled carbon nanotubes have demonstrated exceptional ability to generate single photons at room temperature in the telecom range. Combining the color centers with pristine air-suspended nanotubes would be desirable for improved performance, but all current synthetic methods occur in solution which makes them incompatible. Here we demonstrate the formation of color centers in air-suspended nanotubes using a vapor-phase reaction. Functionalization is directly verified by photoluminescence spectroscopy, with unambiguous statistics from more than a few thousand individual nanotubes. The color centers show strong diameter-dependent emission, which can be explained with a model for chemical reactivity considering strain along the tube curvature. We also estimate the defect density by comparing the experiments with simulations based on a one-dimensional exciton diffusion equation. Our results highlight the influence of the nanotube structure on vapor-phase reactivity and emission properties, providing guidelines for the development of high-performance near-infrared quantum light sources.

Universal Map of Gas-Dependent Kinetic Selectivity in Carbon Nanotube Growth.

Single-walled carbon nanotubes have been a candidate for outperforming silicon in ultrascaled transistors, but the realization of nanotube-based integrated circuits requires dense arrays of purely semiconducting species. In order to directly grow such nanotube arrays on wafers, control over kinetics and thermodynamics in tube-catalyst systems plays a key role, and further progress requires a comprehensive understanding of seemingly contradictory reports on the growth kinetics. Here, we propose a universal kinetic model that decomposes the growth rates of nanotubes into the adsorption and removal of carbon atoms on the catalysts, and we provide its quantitative verification by ethanol-based isotope labeling experiments. While the removal of carbon from catalysts dominates the growth kinetics under a low supply of precursors, resulting in chirality-independent growth rates, our kinetic model and experiments demonstrate that chiral angle-dependent growth rates emerge when sufficient amounts of carbon and etching agents are cosupplied. The kinetic maps, as a product of generalizing the model, include five types of kinetic selectivity that emerge depending on the absolute quantities of gases with opposing effects. Our findings not only resolve discrepancies existing in the literature but also offer rational strategies to control the chirality, length, and density of nanotube arrays for practical applications.

One-Dimensional van der Waals Heterojunction Diode.

The synthesis of one-dimensional van der Waals heterostructures was realized recently, which offers alternative possibilities for prospective applications in electronics and optoelectronics. The even reduced dimension will enable different properties and further miniaturization beyond the capabilities of their two-dimensional counterparts. The natural doping results in p-type electrical characteristics for semiconducting single-walled carbon nanotubes and n-type for molybdenum disulfide with conventional noble metal contacts. Therefore, we demonstrate here a one-dimensional heterostructure nanotube, 11 nm wide, with the coaxial assembly of a semiconducting single-walled carbon nanotube, insulating boron nitride nanotube, and semiconducting molybdenum disulfide nanotube, which induces a radial semiconductor-insulator-semiconductor heterojunction. When opposite potential polarity was applied on a semiconducting single-walled carbon nanotube and molybdenum disulfide nanotube, respectively, the rectifying effect was materialized.

Photoluminescence from Single-Walled MoS2 Nanotubes Coaxially Grown on Boron Nitride Nanotubes.

Single-walled and multiwalled molybdenum disulfide (MoS2) nanotubes have been coaxially synthesized on small-diameter boron nitride nanotubes (BNNTs) that are obtained from removing single-walled carbon nanotubes (SWCNTs) in heteronanotubes of SWCNTs coated by BNNTs. The photoluminescence (PL) from single-walled MoS2 nanotubes supported by core BNNTs is observed in this work, which evidences the direct bandgap structure of single-walled MoS2 nanotubes with a diameter around 6-7 nm. The observation is consistent with our DFT results that the single-walled MoS2 nanotube changes from an indirect-gap to a direct-gap semiconductor when the diameter of a nanotube is more than around 5.2 nm. On the other hand, when there are SWCNTs inside the heteronanotubes of BNNTs and single-walled MoS2 nanotubes, the PL signal from MoS2 nanotubes is considerably quenched. The charge transfer and energy transfer between SWCNTs and single-walled MoS2 nanotubes were examined through characterizations by PL, X-ray photoelectron spectroscopy, and Raman spectroscopy. Moreover, the PL signal from multiwalled MoS2 nanotubes is significantly quenched. Single-walled and multiwalled MoS2 nanotubes exhibit different Raman features in both resonant and nonresonant Raman spectra.

Non-catalytic heteroepitaxial growth of aligned, large-sized hexagonal boron nitride single-crystals on graphite.

Although van der Waals heterostructures composed of graphene and hexagonal boron nitride (h-BN) have attracted wide interest, it is still challenging to prepare them with high quality and controllability. Since contamination induced by transfer cannot be avoided in the case of growth on a metal catalyst, the non-catalytic growth of graphene and h-BN is highly desired. However, unlike graphene, few studies have reported the non-catalytic growth of h-BN, and the lack of controllability in terms of crystal orientation and nucleation density, and size of h-BN has hindered the practical applications of the heterostructures. In this work, we demonstrate the heteroepitaxial growth of aligned monolayer h-BN single-crystals on exfoliated graphite by chemical vapour deposition (CVD) without a metal catalyst. Triangular shaped domains were aligned with each other, which suggests the epitaxy between h-BN and the underlying graphite. Characterisation by Raman spectroscopy, Auger electron spectroscopy, and X-ray photoelectron spectroscopy also confirmed that the h-BN/graphite samples were of high quality. A growth kinetics study over different temperatures indicated an increase in the growth rate at high temperature. Control of nucleation density was realised by changing the hydrogen pressure during CVD or by the heating temperature in air before CVD. Under the optimised growth conditions, the edge length of h-BN single-crystals grew to ∼1 µm, which is the largest size to date for non-catalytic growth. These results will help to obtain structure-controlled, large-area, and impurity-free heterostructures based on h-BN and graphene.

Enhanced In-Plane Thermal Conductance of Thin Films Composed of Coaxially Combined Single-Walled Carbon Nanotubes and Boron Nitride Nanotubes.

Carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs) are one-dimensional materials with high thermal conductivity and similar crystal structures. Additionally, BNNTs feature higher thermal stability in air than CNTs. In this work, a single-walled carbon nanotube (SWCNT) film was used as a template to synthesize a BNNT coating by the chemical vapor deposition (CVD) method to form a coaxial heterostructure. Then, a contact-free steady-state infrared (IR) method was adopted to measure the in-plane sheet thermal conductance of the as-synthesized film. The heterostructured SWCNT-BNNT film demonstrates an enhanced sheet thermal conductance compared with the bare SWCNT film. The increase in sheet thermal conductance shows a reverse relationship with SWCNT film transparency. An enhancement of over 80% (from ∼3.6 to ∼6.4 µW·K-1·sq-1) is attained when the BNNT coating is applied to an SWCNT film with a transparency of 87%. This increase is achieved by BNNTs serving as an additional thermal conducting path. The relationship between the thermal conductance increase and transparency of the SWCNT film is studied by a structured modeling of the SWCNT film. We also discuss the effect of annealing on the thermal conductance of SWCNTs before BNNT growth. Along with the preservation of high electrical conductance, the enhanced thermal conductance of the heterostructured SWCNT-BNNT films makes them a promising building block for thermal and optoelectronic applications.

Multiplexed single-molecule enzyme activity analysis for counting disease-related proteins in biological samples.

We established an ultrasensitive method for identifying multiple enzymes in biological samples by using a multiplexed microdevice-based single-molecule enzymatic assay. We used a paradigm in which we "count" the number of enzyme molecules by profiling their single enzyme activity characteristics toward multiple substrates. In this proof-of-concept study of the single enzyme activity-based protein profiling (SEAP), we were able to detect the activities of various phosphoric ester-hydrolyzing enzymes such as alkaline phosphatases, tyrosine phosphatases, and ectonucleotide pyrophosphatases in blood samples at the single-molecule level and in a subtype-discriminating manner, demonstrating its potential usefulness for the diagnosis of diseases based on ultrasensitive detection of enzymes.

One-dimensional van der Waals heterostructures.

We present the experimental synthesis of one-dimensional (1D) van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked. We demonstrate the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on single-walled carbon nanotubes (SWCNTs). For the latter, larger-diameter nanotubes that overcome strain effect were more readily synthesized. We also report a 5-nanometer-diameter heterostructure consisting of an inner SWCNT, a middle three-layer BN nanotube, and an outer MoS2 nanotube. Electron diffraction verifies that all shells in the heterostructures are single crystals. This work suggests that all of the materials in the current 2D library could be rolled into their 1D counterparts and a plethora of function-designable 1D heterostructures could be realized.

Molecular Dynamics of Chirality Definable Growth of Single-Walled Carbon Nanotubes.

In order to achieve the chirality-specific growth of single-walled carbon nanotubes (SWCNTs), it is crucial to understand the growth mechanism. Even though many molecular dynamics (MD) simulations have been employed to analyze the SWCNT growth mechanism, it has been difficult to discuss the chirality determining kinetics because of the defects remaining on the SWCNTs grown in simulations. In this study, we demonstrate MD simulations of defect-free SWCNTs, that is, chirality definable SWCNTs, under the optimized carbon supply rate and temperature. The chiralities of the SWCNTs were assigned as (14,1), (15,2), and (9,0), indicating the preference of near-zigzag and pure-zigzag SWCNTs. The SWCNTs contained at least one complete row of defect-free walls consisting of only hexagons. The near-zigzag SWCNTs grew via a kink-running process, in which bond formation between a carbon atom at a kink and a neighboring carbon chain led to formation of a hexagon with a new kink at the SWCNT edge. Defects including pentagons and heptagons were sometimes formed but effectively healed into hexagons on metal surfaces. The pure-zigzag SWCNTs grew by the kink-running and the hexagon nucleation processes. In addition, chirality change events along SWCNTs with incorporation of pentagon-heptagon pair defects were observed in the MD simulations. Here, pentagons and heptagons were frequently observed as adjacent pairs, resulting in ( n, m) chirality changes by (±1,0), (0,±1), (1,-1), or (-1,1).