Effect of cellulose nanofiber-montmorillonite hybrid filler on the melt blending of thermoplastic starch composites.

This study investigated the impact of cellulose nanofibers (CNFs) on montmorillonites (MMTs) exfoliation within thermoplastic starch (TPS) nanocomposites during the melt blending process. TPS nanocomposite films were manufactured using an internal mixer with a controlled ratio of CNFs and MMTs to evaluate the effect of individual and hybrid fillers on the material interactions and characteristics of the TPS composites. The incorporation of hybrid fillers resulted in notable enhancements in torque values and rheological properties, suggesting interactions between the starch, CNFs, and MMTs. The degree of MMT intercalation, obtained via X-ray diffraction analysis, decreased with the addition of CNFs, indicating that CNFs positively impacted MMT exfoliation. Scanning electron microscopy (SEM) images of cryo- and tensile-fractured samples highlighted the effectiveness of CNFs in facilitating MMT exfoliation and reinforcing interactions between the MMTs and TPS matrix. These interactions enhanced the tensile strength and Young's modulus by up to 95.8 % and 278.2 %, respectively, with a 1:1 weight ratio of CNFs to MMTs. Additionally, well-dispersed MMTs within the TPS matrix caused passivation and created tortuous paths, improving the water contact angle and decreasing the water vapor sorption. These synergistic effects of the hybrid filler, achieved through a melt blending process, indicate the potential use of TPS nanocomposites as an eco-friendly packaging material.

Estimating Free Energy Barriers for Heterogeneous Catalytic Reactions with Machine Learning Potentials and Umbrella Integration.

Predicting the rate constants of elementary reaction steps is key for the computational modeling of catalytic processes. Within transition state theory (TST), this requires an accurate estimation of the corresponding free energy barriers. While sophisticated methods for estimating free energy differences exist, these typically require extensive (biased) molecular dynamics simulations that are computationally prohibitive with the first-principles electronic structure methods that are typically used in catalysis research. In this contribution, we show that machine-learning (ML) interatomic potentials can be trained in an automated iterative workflow to perform such free energy calculations at a much reduced computational cost as compared to a direct density functional theory (DFT) based evaluation. For the decomposition of CHO on Rh(111), we find that thermal effects are substantial and lead to a decrease in the free energy barrier, which can be vanishingly small, depending on the DFT functional used. This is in stark contrast to previously reported estimates based on a harmonic TST approximation, which predicted an increase in the barrier at elevated temperatures. Since CHO is the reactant of the putative rate limiting reaction step in syngas conversion on Rh(111) and essential for the selectivity toward oxygenates containing multiple carbon atoms (C2+ oxygenates), our results call into question the reported mechanism established by microkinetic models.

Mechanisms of the Device Property Alteration Generated by the Proton Irradiation in GaN-Based MIS-HEMTs Using Extremely Thin Gate Insulator.

Recently, we reported that device performance degradation mechanisms, which are generated by the γ-ray irradiation in GaN-based metal-insulator-semiconductor high electron mobility transistors (MIS-HEMTs), use extremely thin gate insulators. When the γ-ray was radiated, the total ionizing dose (TID) effects were generated and the device performance deteriorated. In this work, we investigated the device property alteration and its mechanisms, which were caused by the proton irradiation in GaN-based MIS-HEMTs for the 5 nm-thick Si3N4 and HfO2 gate insulator. The device property, such as threshold voltage, drain current, and transconductance varied by the proton irradiation. When the 5 nm-thick HfO2 layer was employed for the gate insulator, the threshold voltage shift was larger than that of the 5 nm-thick Si3N4 gate insulator, despite the HfO2 gate insulator exhibiting better radiation resistance compared to the Si3N4 gate insulator. On the other hand, the drain current and transconductance degradation were less for the 5 nm-thick HfO2 gate insulator. Unlike the γ-ray irradiation, our systematic research included pulse-mode stress measurements and carrier mobility extraction and revealed that the TID and displacement damage (DD) effects were simultaneously generated by the proton irradiation in GaN-based MIS-HEMTs. The degree of the device property alteration was determined by the competition or superposition of the TID and DD effects for the threshold voltage shift and drain current and transconductance deterioration, respectively. The device property alteration was diminished due to the reduction of the linear energy transfer with increasing irradiated proton energy. We also studied the frequency performance degradation that corresponded to the irradiated proton energy in GaN-based MIS-HEMTs using an extremely thin gate insulator.

Van der Waals Heterostructure of Hexagonal Boron Nitride with an AlGaN/GaN Epitaxial Wafer for High-Performance Radio Frequency Applications.

While two-dimensional (2D) hexagonal boron nitride (h-BN) is emerging as an atomically thin and dangling bond-free insulating layer for next-generation electronics and optoelectronics, its practical implementation into miniaturized integrated circuits has been significantly limited due to difficulties in large-scale growth directly on epitaxial semiconductor wafers. Herein, the realization of a wafer-scale h-BN van der Waals heterostructure with a 2 in. AlGaN/GaN high-electron mobility transistor (HEMT) wafer using metal-organic chemical vapor deposition is presented. The combination of state-of-the-art microscopic and spectroscopic analyses and theoretical calculations reveals that the heterointerface between ∼2.5 nm-thick h-BN and AlGaN layers is atomically sharp and exhibits a very weak van der Waals interaction without formation of a ternary or quaternary alloy that can induce undesired degradation of device performance. The fabricated AlGaN/GaN HEMT with h-BN shows very promising performance including a cutoff frequency (fT) and maximum oscillation frequency (fMAX) as high as 28 and 88 GHz, respectively, enabled by an effective passivation of surface defects on the HEMT wafer to deliver accurate information with minimized power loss. These findings pave the way for practical implementation of 2D materials integrated with conventional microelectronic devices and the realization of future all-2D electronics.

A Study on the Oxygen Permeability Behavior of Nanoclay in a Polypropylene/Nanoclay Nanocomposite by Biaxial Stretching.

Polypropylene (PP) has poor oxygen barrier properties, therefore it is manufactured in a multi-layer structure with other plastics and metals, and has been widely used as a packaging material in various industries from food and beverage to pharmaceuticals. However, multi-layered packaging materials are generally low in recyclability and cause serious environmental pollution, therefore we have faced the challenge of improving the oxygen barrier performance as a uni-material. In this work, PP/nanoclay nanocomposites were prepared at nanoclay contents ranging from 0.8 to 6.4 wt% by the biaxial stretching method, performed through a sequential stretching method. It was observed that, as the draw ratio increased, the behavior of the agglomerates of the nanoclay located in the PP matrix changed and the nanoclay was dispersed along the second stretching direction. Oxygen barrier properties of PP/nanoclay nanocomposites are clearly improved due to this dispersion effect. As the biaxial stretching ratio and the content of nanoclay increased, the oxygen permeability value of the PP/nanoclay nanocomposite decreased to 43.5 cc·mm/m2·day·atm, which was reduced by about 64% compared to PP. Moreover, even when the relative humidity was increased from 0% to 90%, the oxygen permeability values remained almost the same without quality deterioration. Besides these properties, we also found that the mechanical and thermal properties were also improved. The biaxially-stretched PP/nanoclay nanocomposite fabricated in this study is a potential candidate for the replacement of the multi-layered packaging material used in the packaging fields.

Optical bioelectronic nose of outstanding sensitivity and selectivity toward volatile organic compounds implemented with genetically engineered bacteriophage: Integrated study of multi-scale computational prediction and experimental validation.

Genetic engineering of a bacteriophage is a promising way to develop a highly functional biosensor. Almost countless configurational degree of freedom in the manipulation, considerable uncertainty and cost involved with the approach, however, have been huddles for the objective. In this paper, we demonstrate rapidly responding optical biosensor with high selectivity toward gaseous explosives with genetically engineered phages. The sensors are equipped with peptide sequences in phages optimally interacting with the volatile organic compounds (VOCs) in visible light regime. To overcome the conventional issues, we use extensive utilization of empirical calculations to construct a large database of 8000 tripeptides and screen the best for electronic nose sensing performance toward nine VOCs belonging to three chemical classes. First-principles density functional theory (DFT) calculations unveil underlying correlations between the chemical affinity and optical property change on an electronic band structure level. The computational outcomes are validated by in vitro experimental design and testing of multiarray sensors using genetically modified phage implemented with five selected tripeptide sequences and wild-type phages. The classification success rates estimated from hierarchical cluster analysis are shown to be very consistent with the calculations. Our optical biosensor demonstrates a 1 ppb level of sensing resolution for explosive VOCs, which is a substantial improvement over conventional biosensor. The systematic interplay of big data-based computational prediction and in situ experimental validation can provide smart design principles for unconventionally outstanding biosensors.

Comprehensive Research of Total Ionizing Dose Effects in GaN-Based MIS-HEMTs Using Extremely Thin Gate Dielectric Layer.

The device performance deterioration mechanism caused by the total ionizing dose effect after the γ-ray irradiation was investigated in GaN-based metal-insulator-semiconductor high electron mobility transistors (MIS-HEMTs) for a 5 nm-thick SiN and HfO2 gate dielectric layer. The γ-ray radiation hardness according to the gate dielectric layer was also compared between the two different GaN-based MIS-HEMTs. Although HfO2 has exhibited strong tolerance to the total ionizing dose effect in Si-based devices, there is no detail report of the γ-ray radiation effects in GaN-based MIS-HEMTs employing a HfO2 gate dielectric layer. The pulsed-mode stress measurement results and carrier mobility behavior revealed that the device properties not only have direct current (DC) characteristics, but radio frequency (RF) performance has also been mostly degraded by the deterioration of the gate dielectric quality and the trapped charges inside the gate insulator. We also figured out that the immunity to the γ-ray radiation was improved when HfO2 was employed instead of SiN as a gate dielectric layer due to its stronger endurance to the γ-ray irradiation. Our results highlight that the application of a gate insulator that shows superior immunity to the γ-ray irradiation is a crucial factor for the improvement of the total ionizing dose effect in GaN-based MIS-HEMTs.

Charging Effect by Fluorine-Treatment and Recess Gate for Enhancement-Mode on AlGaN/GaN High Electron Mobility Transistors.

An enhancement-mode AlGaN/GaN metal-insulator-semiconductor high-electron- mobility-transistor was fabricated using a recess gate and CF4 plasma treatment to investigate its reliable applicability to high-power devices and circuits. The fluorinated-gate device showed hysteresis during the DC current-voltage measurement, and the polarity and magnitude of hysteresis depend on the drain voltage. The hysteresis phenomenon is due to the electron trapping at the Al2O3/AlGaN interface and charging times longer than milliseconds were obtained by pulse I-V measurement. In addition, the subthreshold slope of the fluorinated-gate device was increased after the positive gate bias stress because of the two-dimensional electron gas reduction by ionized fluorine. Our systematic observation revealed that the effect of fluorine ions should be considered for the design of AlGaN/GaN power circuits.

Hyaluronidase: An overview of its properties, applications, and side effects.

Hyaluronidase, an enzyme that breaks down hyaluronic acid, has long been used to increase the absorption of drugs into tissue and to reduce tissue damage in cases of extravasation of a drug. With the increasing popularity of hyaluronic acid filler, hyaluronidase has become an essential drug for the correction of complications and unsatisfactory results after filler injection. For this reason, when performing procedures using hyaluronic acid filler, a sufficient knowledge of hyaluronidase is required. In order for hyaluronidase to dissolve a hyaluronic acid filler, it must interact with its binding sites within the hyaluronic acid. The reaction of a filler to hyaluronidase depends on the hyaluronic acid concentration, the number of crosslinks, and the form of the filler. Hyaluronidase is rapidly degraded and deactivated in the body. Therefore, in order to dissolve a hyaluronic acid filler, a sufficient amount of hyaluronidase must be injected close to the filler. If the filler is placed subcutaneously, injection of hyaluronidase into the filler itself may help, but if the filler is placed within a blood vessel, it is sufficient to inject hyaluronidase in the vicinity of the vessel, instead of into the filler itself. Allergic reactions are a common side effect of hyaluronidase. Most allergic reactions to hyaluronidase are local, but systemic reactions may occur in infrequent cases. Since most allergic responses to hyaluronidase are immediate hypersensitivity reactions, skin tests are recommended before use. However, some patients experience delayed allergic reactions, which skin tests may not predict.

Thermochemical study for remediation of highly concentrated acid spill: Computational modeling and experimental validation.

The release of concentrated acid solutions by chemical accidents is disastrous to our environmental integrity. Alkaline agents applied to remedy the acid spill catastrophe may lead to secondary damages such as vaporization or spread out of the fumes unless substantial amount of neutralization heat is properly controlled. Using a rigorous thermodynamic formalism proposed by Pitzer to account short-range ion interactions and various subsidiary reactions, we develop a systematic computational model enabling quantitative prediction of reaction heat and the temperature change over neutralization of strongly concentrated acid solutions. We apply this model to four acid solutions (HCl, HNO3, H2SO4, and HF) of each 3 M-equivalent concentration with two neutralizing agents of calcium hydroxide (Ca(OH)2) and sodium bicarbonate (NaHCO3). Predicted reaction heat and temperature are remarkably consistent with the outcomes measured by our own experiments, showing a linear correlation factor R2 greater than 0.98. We apply the model to extremely concentrated acid solutions as high as 50 wt% where an experimental approach is practically restricted. In contrast to the extremely exothermic Ca(OH)2 agent, NaHCO3 even lowers solution temperatures after neutralization reactions. Our model enables us to identify a promising neutralizer NaHCO3 for effectively controlling concentrated acid spills and may be useful for establishment of proper strategy for other chemical accidents.

First principles computational study on hydrolysis of hazardous chemicals phosphorus trichloride and oxychloride (PCl3 and POCl3) catalyzed by molecular water clusters.

Using first principles calculations we unveil fundamental mechanism of hydrolysis reactions of two hazardous chemicals PCl3 and POCl3 with explicit molecular water clusters nearby. It is found that the water molecules play a key role as a catalyst significantly lowing activation barrier of the hydrolysis via transferring its protons to reaction intermediates. Interestingly, torsional angle of the molecular complex at transition state is identified as a vital descriptor on the reaction rate. Analysis of charge distribution over the complex further reinforces the finding with atomic level correlation between the torsional angle and variation of the orbital hybridization state of phosphorus (P) in the complex. Electronic charge separation (or polarization) enhances thermodynamic stability of the activated complex and reduces the activation energy through hydrogen bonding network with water molecules nearby. Calculated potential energy surfaces (PES) for the hydrolysis of PCl3 and POCl3 depict their two contrastingly different profiles of double- and triple-depth wells, respectively. It is ascribed to the unique double-bonding O=P in the POCl3. Our results on the activation free energy show well agreements with previous experimental data within 7kcalmol-1 deviation.

Extended negative pressure wound therapy-assisted dermatotraction for the closure of large open fasciotomy wounds in necrotizing fasciitis patients.

BACKGROUND: Necrotizing fasciitis (NF) is a rapid progressive infection of the subcutaneous tissue or fascia and may result in large open wounds. The surgical options to cover these wounds are often limited by the patient condition and result in suboptimal functional and cosmetic wound coverage. Dermatotraction can restore the function and appearance of the fasciotomy wound and is less invasive in patients with comorbidities. However, dermatotraction for scarred, stiff NF fasciotomy wounds is often ineffective, resulting in skin necrosis. The authors use extended negative pressure wound therapy (NPWT) as an assist in dermatotraction to close open NF fasciotomy wounds. The authors present the clinical results, followed by a discussion of the clinical basis of extended NPWT-assisted dermatotraction. METHODS: A retrospective case series of eight patients with NF who underwent open fasciotomy was approved for the study. After serial wound preparation, dermatotraction was applied in a shoelace manner using elastic vessel loops. Next, the extended NPWT was applied over the wound. The sponge was three times wider than the wound width, and the transparent covering drape almost encircled the anatomical wound area. The negative pressure of the NPWT was set at a continuous 100 mmHg by suction barometer. The clinical outcome was assessed based on wound area reduction after treatment and by the achievement of direct wound closure. RESULTS: After the first set of extended NPWT-assisted dermatotraction procedures, the mean wound area was significantly decreased (658.12 cm(2) to 29.37 cm(2); p = 0.002), as five out of eight patients achieved direct wound closure. One patient with a chest wall defect underwent latissimus dorsi musculocutaneous flap coverage, with primary closure of the donor site. Two Fournier's gangrene patients underwent multiple sets of treatment and finally achieved secondary wound closure with skin grafts. The patients were followed up for 18.3 months on average and showed satisfactory results without wound recurrence. CONCLUSIONS: Extended NPWT-assisted dermatotraction advances scarred, stiff fasciotomy wound margins synergistically in NF and allows direct closure of the wound without complications. This method can be another good treatment option for the NF patient with large open wounds whose general condition is unsuitable for extensive reconstructive surgery.

Continuous separation of microparticles in a microfluidic channel via the elasto-inertial effect of non-Newtonian fluid.

Pure separation and sorting of microparticles from complex fluids are essential for biochemical analyses and clinical diagnostics. However, conventional techniques require highly complex and expensive labeling processes for high purity separation. In this study, we present a simple and label-free method for separating microparticles with high purity using the elasto-inertial characteristic of a non-Newtonian fluid in microchannel flow. At the inlet, particle-containing sample flow was pushed toward the side walls by introducing sheath fluid from the center inlet. Particles of 1 µm and 5 µm in diameter, which were suspended in viscoelastic fluid, were successfully separated in the outlet channels: larger particles were notably focused on the centerline of the channel at the outlet, while smaller particles continued flowing along the side walls with minimal lateral migration towards the centerline. The same technique was further applied to separate platelets from diluted whole blood. Through cytometric analysis, we obtained a purity of collected platelets of close to 99.9%. Conclusively, our microparticle separation technique using elasto-inertial forces in non-Newtonian fluid is an effective method for separating and collecting microparticles on the basis of size differences with high purity.