Controlling the Surface Morphology of Two-Dimensional Nano-Materials upon Molecule-Mediated Crystal Growth.

The surface morphology of Mg-Al-layered double hydroxide (LDH) was successfully controlled by reconstruction during systematic phase transformation from calcined LDH, which is referred to as layered double oxide (LDO). The LDH reconstructed its original phase by the hydration of LDO with expanded basal spacing when reacted with water, including carbonate or methyl orange molecules. During the reaction, the degree of crystal growth along the ab-plane and stacking along the c-axis was significantly influenced by the molecular size and the reaction conditions. The lower concentration of carbonate gave smaller particles on the surface of larger LDO (2000 nm), while the higher concentration induced a sand-rose structure. The reconstruction of smaller-sized LDH (350 nm) did not depend on the concentration of carbonate due to effective adsorption, and it gave a sand-rose structure and exfoliated the LDH layers. The higher the concentration of methyl orange and the longer the reaction time applied, the rougher the surface was obtained with a certain threshold point of the methyl orange concentration. The surface roughness generally increased with the loading mount of methyl orange. However, the degree of the surface roughness even increased after the methyl orange loading reached equilibrium. The result suggested that the surface roughening was mediated by not only the incorporation of guest molecules into the LDH but also a crystal arrangement after a sufficient amount of methyl orange was accommodated.

Biocompatible MgFeCO3 Layered Double Hydroxide (LDH) for Bone Regeneration-Low-Temperature Processing through Cold Sintering and Freeze-Casting.

Layered Double Hydroxides (LDHs) are inorganic compounds of relevance to various domains, where their surface reactivity and/or intercalation capacities can be advantageously exploited for the retention/release of ionic and molecular species. In this study, we have explored specifically the applicability in the field of bone regeneration of one LDH composition, denoted "MgFeCO3", of which components are already present in vivo, so as to convey a biocompatibility character. The propensity to be used as a bone substitute depends, however, on their ability to allow the fabrication of 3D constructs able to be implanted in bone sites. In this work, we display two appealing approaches for the processing of MgFeCO3 LDH particles to prepare (i) porous 3D scaffolds by freeze-casting, involving an alginate biopolymeric matrix, and (ii) pure MgFeCO3 LDH monoliths by Spark Plasma Sintering (SPS) at low temperature. We then explored the capacity of such LDH particles or monoliths to interact quantitatively with molecular moieties/drugs in view of their local release. The experimental data were complemented by computational chemistry calculations (Monte Carlo) to examine in more detail the mineral-organic interactions at play. Finally, preliminary in vitro tests on osteoblastic MG63 cells confirmed the high biocompatible character of this LDH composition. It was confirmed that (i) thermodynamically metastable LDH could be successfully consolidated into a monolith through SPS, (ii) the LDH particles could be incorporated into a polymer matrix through freeze casting, and (iii) the LDH in the consolidated monolith could incorporate and release drug molecules in a controlled manner. In other words, our results indicate that the MgFeCO3 LDH (pyroaurite structure) may be seen as a new promising compound for the setup of bone substitute biomaterials with tailorable drug delivery capacity, including for personalized medicine.

Fibriform Organic Electrochemical Diodes with Rectifying, Complementary Logic and Transient Voltage Suppression Functions for Wearable E-Textile Embedded Circuits.

In this study, a fibriform electrochemical diode capable of performing rectifying, complementary logic and device protection functions for future e-textile circuit systems is fabricated. The diode was fabricated using a simple twisted assembly of metal/polymer semiconductor/ion gel coaxial microfibers and conducting microfiber electrodes. The fibriform diode exhibited a prominent asymmetrical current flow with a rectification ratio of over 102, and its performance was retained after repeated bending deformations and washings. Fundamental studies on the electrochemical interactions of polymer semiconductors with ions reveal that the Faradaic current generated in polymer semiconductors by electrochemical reactions results in an abrupt current increase under a forward bias, in which the threshold voltages of the device are determined by the oxidation or reduction potential of the polymer semiconductor. Textile-embedded full-wave rectifiers and logic gate circuits were implemented by simply integrating the fibriform diodes, exhibiting AC-to-DC signal conversion and logic operation functions, respectively. It was also confirmed that the proposed fibriform diode can suppress transient voltages and thus protect a low-voltage operational wearable e-textile circuit.

Bio-Activation of HA/ß-TCP Porous Scaffolds by High-Pressure CO2 Surface Remodeling: A Novel "Coating-from" Approach.

Biphasic macroporous Hydroxyapatite/ß-Tricalcium Phosphate (HA/ß-TCP) scaffolds (BCPs) are widely used for bone repair. However, the high-temperature HA and ß-TCP phases exhibit limited bioactivity (low solubility of HA, restricted surface area, low ion release). Strategies were developed to coat such BCPs with biomimetic apatite to enhance bioactivity. However, this can be associated with poor adhesion, and metastable solutions may prove difficult to handle at the industrial scale. Alternative strategies are thus desirable to generate a highly bioactive surface on commercial BCPs. In this work, we developed an innovative "coating from" approach for BCP surface remodeling via hydrothermal treatment under supercritical CO2, used as a reversible pH modifier and with industrial scalability. Based on a set of complementary tools including FEG-SEM, solid state NMR and ion exchange tests, we demonstrate the remodeling of macroporous BCP surface with the occurrence of dissolution-reprecipitation phenomena involving biomimetic CaP phases. The newly precipitated compounds are identified as bone-like nanocrystalline apatite and octacalcium phosphate (OCP), both known for their high bioactivity character, favoring bone healing. We also explored the effects of key process parameters, and showed the possibility to dope the remodeled BCPs with antibacterial Cu2+ ions to convey additional functionality to the scaffolds, which was confirmed by in vitro tests. This new process could enhance the bioactivity of commercial BCP scaffolds via a simple and biocompatible approach.

Periodic charge matching driven immobilization of gentamicin in nanoclays for stable and long-term antibacterial coating.

Matching of charge periodicity between a guest and a host enabled effective immobilization of highly water-soluble antibiotic drug, gentamicin C, in a bentonite clay by cation exchange. X-ray diffraction, infrared spectroscopy and CHNS analysis revealed the immobilization manner of gentamicin C, which was immobilized between bentonite layers via periodic charge-charge interaction with tilted arrangement, as a trication. Both gentamicin alone and a gentamicin/bentonite hybrid were coated onto a polyurethane substrate using water-borne polyurethane binder. The antibiotic character of both films was investigated as prepared or after immersion in phosphate-buffered saline till 5 days against E. coli and B. subtilis bacteria. It was clearly shown that the gentamicin/bentonite hybrid-coated film showed sustained antibacterial efficacy even after exposure to phosphate-buffered saline, while gentamicin only-coated film gradually lost its performance under the same condition.

Development of Mesopore Structure of Mixed Metal Oxide through Albumin-Templated Coprecipitation and Reconstruction of Layered Double Hydroxide.

Mixed metal oxide (MMO) with relatively homogeneous mesopores was successfully obtained by calcination and reconstruction of albumin-templated layered double hydroxide (LDH). The aggregation degree of albumin-template was controlled by adjusting two different synthesis routes, coprecipitation and reconstruction. X-ray diffraction patterns and scanning electron microscopic images indicated that crystal growth of LDH was fairly limited during albumin-templated coprecipitation due to the aggregation. On the hand, crystal growth along the lateral direction was facilitated in albumin-templated reconstruction due to the homogeneous distribution of proteins moiety. Different state of albumin during LDH synthesis influenced the local disorder and porous structure of calcination product, MMO. The N2 adsorption-desorption isotherms demonstrated that calcination on reconstructed LDH produced MMO with large specific surface area and narrow distribution of mesopores compared with calcination of coprecipitated LDH.

Spirally Wrapped Carbon Nanotube Microelectrodes for Fiber Optoelectronic Devices beyond Geometrical Limitations toward Smart Wearable E-Textile Applications.

Fiber optoelectronics technology has recently attracted attention as enabling various form factors of wearable electronics, and the issue of how to control and optimize the configuration and physical properties of the electrode micropatterns in the microfiber devices has become important. Here, spirally wrapped carbon nanotube (CNT) microelectrodes with a controlled dimension are demonstrated for high-performance fiber optoelectronic devices. Inkjet-printed CNT microelectrodes with the desired dimension on an agarose hydrogel template are rolling-transferred onto a microfiber surface with an efficient electrical interface. A fiber organic field-effect transistor with spirally wrapped CNT microelectrodes verifies the feasibility of this strategy, where the transferred microelectrodes intimately contact the organic semiconductor active layer and the output current characteristics are simply controlled, resulting in characteristics that exceed the previous structural limitations. Furthermore, a fiber organic photodiode with spirally wrapped CNT microelectrodes, when used as a transparent electrode, exhibits a high Ilight/Idark ratio and good durability of bending. This fiber photodiode can be successfully incorporated into a textile photoplethysmography bandage for the real-time monitoring of human vital signals. This work offers a promising and efficient strategy to overcome the geometric factors limiting the performance of fiber-optic optoelectronic devices.

Contents of the Standardized Suicide Prevention Program for Gatekeeper Intervention in Korea, Version 2.0.

OBJECTIVE: Suicide is a huge nationwide problem that incurs a lot of socio-economic costs. Suicide also inflicts severe distress on the people left behind. The government of the Republic of Korea has been making many policy efforts to reduce suicide rate. The gatekeeper program, 'Suicide CARE', is one of the meaningful modalities for preventing suicide. METHODS: Multidisciplinary research team collaborated to update the 'Suicide CARE' to version 2.0. RESULTS: In the 'Introductory part', the authors have the time to think about the necessity and significance of the program before conducting full-scale gatekeeper training. In the 'Careful observation' part, trainees learn how to understand and recognize the various linguistic, behavioral, and situational signals that a person shows before committing suicide. In the 'Active listening' part, trainees learn how to ask suicide with a value-neutral attitude as well listening empathetically. In the 'Risk evaluation and Expert referral' part, trainees learn intervening strategies to identify a person's suicidal intention, plan, and past suicide attempts, and connect the person to appropriate institutes or services. CONCLUSION: Subsequent studies should be conducted to verify the efficacy of the gatekeeper program.

"Suicide CARE" (Standardized Suicide Prevention Program for Gatekeeper Intervention in Korea): An Update.

OBJECTIVE: In 2011, "Suicide CARE" (Standardized Suicide Prevention Program for Gatekeeper Intervention in Korea) was originally developed for the early detection of warning signs of suicide completion, since there is a tendency to regard emotional suppression as a virtue of Korean traditional culture. A total of 1.2 million individuals completed the training program of "Suicide CARE" in Korea. METHODS: More sophisticated suicide prevention approaches according to age, sex, and occupation have been proposed, demanding for a more detailed revision of "Suicide CARE." Thus, during the period from August 2019 to February 2020, "Suicide CARE" has been updated to version 2.0. The assessments on domestic gatekeeper training programs for suicide prevention, international gatekeeper training programs for suicide prevention, psychological autopsy interview reports between 2015 and 2018, and the evaluation of feedback from people who completed "Suicide CARE" version 1.6 training were performed. RESULTS: We describe the revision process of "Suicide CARE," revealing that "Suicide CARE" version 2.0 has been developed using an evidence-based methodology. CONCLUSION: It is expected that "Suicide CARE" version 2.0 be positioned as the basic framework for many developing gatekeeper training programs for suicide prevention in Korea in the near future.

Random array of inorganic nanoparticles on polymer surface for anti-biofouling property through cost-effective and high-performance dip-coating.

Anti-biofouling treatment is required in various fields such as biomedical application, construction, civil engineering, and so on. Currently available techniques such as lithography and replica methods have several limitations in application and accessibility. We introduced a simple, biocompatible, and cost-effective anti-biofouling dip-coating method with polyurethane-inorganic (anisotropic montmorillonite and spherical TiO2) hybrid coating agent. Layer thickness of coating was as thin as 5 µm. It was cross-confirmed with thickness gauge and cross-section scanning electron microscopy. Through atomic force microscopy, inorganic nanoparticles were observed to be randomly arrayed with particles partially embedded in the polyurethane network. The calculated surface roughness of inorganic-polyurethane hybrid coating was five times larger than the neat substrate film and three times larger than coating without inorganic nanoparticles. Surface energy of the inorganic-polyurethane film decreased with increasing surface roughness as random pattern of inorganic particle reduced van der Waals interaction. Biofouling efficacy was evaluated by mucin adsorption and consecutive alcian blue assay. Results showed that coated film decreased biofouling 81% compared to bare film.

Zingiber officinale Extract (ZOE) Incorporated with Layered Double Hydroxide Hybrid through Reconstruction to Preserve Antioxidant Activity of ZOE against Ultrasound and Microwave Irradiation.

We prepared Zingiber officinale extract (ZOE) incorporated in a layered double hydroxide (LDH) hybrid through a reconstruction method in order to preserve the antioxidant activity of ZOE from ultrasound and microwave irradiation. X-ray patterns, infrared spectroscopy, and scanning electron microscopy suggested that ZOE moieties were encapsulated in the interparticle space of reconstructed LDH, thus preserving its intact structure. Dynamic light scattering and zeta-potential measurement also supported the hypothesis that ZOE moieties were located in the interparticle pore of LDH rather than at the surface of LDH particles. Thermogravimetry analysis revealed that thermal stability of encapsulated ZOE could be enhanced by LDH encapsulation. Radical scavenging assay showed that antioxidant activity of ZOE-LDH hybrid was increased after ultrasound and microwave irradiation, while ZOE itself dramatically lost its antioxidant activity upon ultrasound and microwave treatment.

Incorporation of Glycine max Merrill Extract into Layered Double Hydroxide through Ion-Exchange and Reconstruction.

We incorporated extract of Glycine max Merrill (GM), which is generally known as soybean, into a layered double hydroxide (LDH) nanostructure through two different methods, ion-exchange and reconstruction. Through X-ray diffraction, field-emission scanning electron microscopy, and zeta-potential measurement, GM moiety seemed to be simply attached on the surface of LDH by ion-exchange process, while the extract could be incorporated in the inter-particle pore of LDHs by reconstruction reaction. The quantification exhibited that both incorporation method showed comparable extract loading capacity of 15.6 wt/wt% for GM-LDH hybrid prepared by ion-exchange (GML-I) and 18.6 wt/wt% for GM-LDH hybrid by reconstruction (GML-R). On the other hand, bioactive substance in both GM-LDH hybrids, revealed that GML-R has higher daidzein content (0.0286 wt/wt%) compared with GML-I (0.0108 wt/wt%). According to time-dependent daidzein release, we confirmed that GML-R showed pH dependent daidzein release; a higher amount of daidzein was released in pH 4.5 physiological condition than in pH 7.4, suggesting the drug delivery potential of GML-R. Furthermore, alkaline phosphatase activity and collagen fiber formation on human osteoblast-like MG-63 cells displayed that GML-R had superior possibility of osteoblast differentiation than GML-I. From these results, we concluded that reconstruction method was more effective for extract incorporation than ion-exchange reaction, due to its pH dependent release property and alkaline phosphatase activity.

Hierarchical Ag Nanostructures Fabricated from Silver Coordination Polymers for Antibacterial Surface.

A hierarchical silver nanostructure with improved antibacterial property was fabricated utilizing silver coordination polymer. Octadecanethiolate⁻silver polymer was synthesized to have a layered structure and was coated on silicon wafer by drop-casting method utilizing hydrophobic⁻hydrophobic interaction. Thus, the silver coordination polymer was calcined under reductive condition to produce zero-valent silver with a hierarchical nanostructure. X-ray diffraction patterns revealed that layered silver coordination polymer successfully transformed to hexagonal silver upon calcination. According to scanning electron and atomic force microscopy, silver coordination polymer with ~145.5 nm size was homogeneously coated on the surface before calcination, and it evolved micrometer-sized lumps and grooves which were composed of ~58.8 nm sized Ag nanoparticles. The hierarchical structure-micrometer lump/groove consisting of Ag nanoparticles-would be advantageous to kill bacteria; micrometer-grooves provide physical condition (pocket for bacteria capture) and the Ag nanoparticles from the neighboring lump endow chemical condition (antibacterial property of released Ag⁺). The antibacterial activity test on Escherichia coli via colony forming inhibitory assay indeed exhibited an improved antibacterial activity of hierarchical Ag nanostructure compared with the surface simply coated with Ag nanoparticles. From the line profile of atomic force microscopy, the bacterium trapped in the hierarchical Ag nanostructure was shown to interact intimately with Ag surface.

A New Architecture for Fibrous Organic Transistors Based on a Double-Stranded Assembly of Electrode Microfibers for Electronic Textile Applications.

Herein, a unique device architecture is proposed for fibrous organic transistors based on a double-stranded assembly of electrode microfibers for electronic textile applications. A key feature of this work is that the semiconductor channel of the fiber transistor comprises a twist assembly of the source and drain electrode microfibers that are coated by an organic semiconductor. This architecture not only allows the channel dimension of the device to be readily controlled by varying the thickness of the semiconductor layer and the twisted length of the two electrode microfibers, but also passivates the device without affecting interconnections with other electrical components. It is found that the control of crystalline nanostructure of the semiconductor layer is critical for improving both the production yield of the device and the charge-carrier transport in the device. The resulting fibrous organic transistors show a high output current of over -5 mA at a low operation voltage of -1.3 V and a good on/off current ratio of 105 . The device performance is maintained after repeated bending deformation and washing with a strong detergent solution. Application of the fibrous organic transistors to switch current-driven LED devices and detection of electrocardiography signals from a human body are demonstrated.

Layered Double Hydroxide Nanomaterials Encapsulating Angelica gigas Nakai Extract for Potential Anticancer Nanomedicine.

We prepared hybrids consisting of Angelica gigas Nakai (AGN) root or flower extract and layered double hydroxide (LDH) for potential anticancer nanomedicine, as decursin species (DS) in AGN are known to have anticancer activity. Dimethylsulfoxide solvent was determined hybridization reaction media, as it has affinity to both AGN and LDH moiety. In order to develop inter-particle spaces in LDH, a reversible dehydration-rehydration, so-called reconstruction route, was applied in AGN-LDH hybridization. Quantitative analyses on AGN-LDH hybrids indicated that the content of DS was two times more concentrated in the hybrids than in extract itself. Using X-ray diffraction, FT-IR spectroscopy, scanning electron microscopy, and zeta-potential measurement, we found that AGN extract moiety was incorporated into inter-particle spaces of LDH nanoparticles during the reconstruction reaction. Time-dependent DS release from hybrids at pH 7.4 (physiological condition) and pH 4.5 (lysosomal condition) exhibited a pH-dependent release of extract-incorporated LDH hybrids. An anticancer activity test using HeLa, A549, and HEK293T cells showed that the AGN-LDH hybrid, regardless of extract type, showed enhanced anticancer activity compared with extract alone at an equivalent amount of DS, suggesting a nanomedicine effect of AGN-LDH hybrids.

Cytotoxicity, Intestinal Transport, and Bioavailability of Dispersible Iron and Zinc Supplements.

Iron or zinc deficiency is one of the most important nutritional disorders which causes health problem. However, food fortification with minerals often induces unacceptable organoleptic changes during preparation process and storage, has low bioavailability and solubility, and is expensive. Nanotechnology surface modification to obtain novel characteristics can be a useful tool to overcome these problems. In this study, the efficacy and potential toxicity of dispersible Fe or Zn supplement coated in dextrin and glycerides (SunActive FeTM and SunActive ZnTM) were evaluated in terms of cytotoxicity, intestinal transport, and bioavailability, as compared with each counterpart without coating, ferric pyrophosphate (FePP) and zinc oxide (ZnO) nanoparticles (NPs), respectively. The results demonstrate that the cytotoxicity of FePP was not significantly affected by surface modification (SunActive FeTM), while SunActive ZnTM was more cytotoxic than ZnO-NPs. Cellular uptake and intestinal transport efficiency of SunActive FeTM were significantly higher than those of its counterpart material, which was in good agreement with enhanced oral absorption efficacy after a single-dose oral administration to rats. These results seem to be related to dissolution, particle dispersibility, and coating stability of materials depending on suspending media. Both SunActiveTM products and their counterpart materials were determined to be primarily transported by microfold (M) cells through the intestinal epithelium. It was, therefore, concluded that surface modification of food fortification will be a useful strategy to enhance oral absorption efficiency at safe levels.

Comparison of Intra-Abdominal Pressure Among 3 Prone Positional Apparatuses After Changing From the Supine to the Prone Position and Applying Positive End-Expiratory Pressure in Healthy Euvolemic Patients: A Prospective Observational Study.

BACKGROUND: Positional apparatuses used for the prone position can affect intra-abdominal pressure (IAP). In this study, we compared the IAP after changing to the prone position and applying various positive end-expiratory pressure (PEEP) levels among 3 prone positional apparatuses. METHODS: A total of 108 healthy euvolemic patients undergoing elective prone spinal surgery were divided into 3 groups based on the positional apparatus used: the Jackson spinal table was used in group J (n=36), the Wilson frame in group W (n=36), and chest rolls in group C (n=36). The IAP was measured 2 minutes after application of 0, 3, 6, and 9 cm H2O of PEEP. RESULTS: The IAP in the supine position was 6.4±3.0, 5.9±2.8, and 7.1±2.5 mm Hg in groups J, C, and W, respectively. After the supine-to-prone positional change, the IAP in the prone position was significantly lower in group J than in groups C and W (2.7±2.9 vs. 8.9±4.0 and 12.9±4.3 mm Hg, P<0.01). In the prone position, a PEEP of 9 cm H2O increased the IAP from baseline (zero PEEP) by 1.5±1.3, 1.6±1.3, and 1.7±1.0 mm Hg in groups J, C, and W, respectively. CONCLUSIONS: The IAP in the prone position was significantly lower using the Jackson table compared with the Wilson frame and chest rolls. A PEEP up to 9 cm H2O can be safely used in healthy euvolemic patients undergoing prone spinal surgery without a clinically significant increase in IAP, irrespective of the type of prone positional apparatus.

Integrated line-by-line optical pulse shaper for high-fidelity and rapidly reconfigurable RF-filtering.

We present a 32 channel indium phosphide integrated pulse shaper with 25 GHz channel spacing, where each channel is equipped with a semiconductor optical amplifier allowing for programmable line-by-line gain control with submicrosecond reconfigurability. We critically test the integrated pulse shaper by using it in comb-based RF-photonic filtering experiments where the precise gain control is leveraged to synthesize high-fidelity RF filters which we reconfigure on a microsecond time scale. Our on-chip pulse shaping demonstration is unmatched in its combination of speed, fidelity, and flexibility, and will likely open new avenues in the field of advanced broadband signal generation and processing.

Enhanced processing gain via pulse polarity switching in an RF photonic phase filter.

Fast pulse polarity switching is proposed and demonstrated to enhance processing gain in a comb-based radio-frequency photonic phase filter. The polarity switching scheme overcomes previous limits on time bandwidth product and processing gain based on the number of optical frequency comb lines. In an experiment with broadband jamming noise, the peak signal-to-noise ratio of compressed RF output pulses is improved by ~30 dB compared to the input average signal-to-noise ratio.

Hybridization Between Natural Extract of Angelica gigas Nakai and Inorganic Nanomaterial of Layered Double Hydroxide via Reconstruction Reaction.

We have hybridized layered double hydroxide (LDH) with Angelica gigas Nakai root extract (AGNR) through reversible dehydration-rehydration reaction which is known as reconstruction. LDHs having well-ordered hydrotalcite-like crystal structure and average size 250 ± 20 nm were prepared by hydrothermal method. The root of Angelica gigas Nakai, which has been utilized in the treatment of female disorders as herbal medicine, was treated with methanol to obtain extract. Pristine LDHs were calcined at 400 °C for 8 hours to obtain layered double oxide (LDO), which was further dispersed into extract solution with various AGNR/LDO weight ratios, 0.11, 0.21 and 0.43. The extract content in each hybrid increased in proportion to initial AGNR/LDO ratio, showing the highest content of ~12%. The zeta potential of LDH shifted from +44 mV to +20 mV upon hybridization with extract, which was attributed to the adsorption of negatively charged organic moieties in AGNR on LDH surface. The scanning electron microscopic (SEM) results exhibited that the random stacking of LDH nanolayers resulted in LDH-AGNR hybrid with house-of-cards structure, of which inter-particle cavity serves nano-reservoir for natural extract. According to quantitative analyses, it was revealed that the content of active components in AGNR increased when they were hybridized with LDHs compared with those in AGNR alone.