Radical-Driven Crystal-Amorphous-Crystal Transition of a Metal-Organic Framework.

Self-assembly-based structural transition has been explored for various applications, including molecular machines, sensors, and drug delivery. In this study, we developed new redox-active metal-organic frameworks (MOFs) called DGIST-10 series that comprise π-acidic 1,4,5,8-naphthalenediimide (NDI)-based ligands and Ni2+ ions, aiming to boost ligand-self-assembly-driven structural transition and study the involved mechanism. Notably, during the synthesis of the MOFs, a single-crystal-amorphous-single-crystal structural transition occurred within the MOFs upon radical formation, which was ascribed to the fact that radicals prefer spin-pairing or through-space electron delocalization by π-orbital overlap. The radical-formation-induced structural transitions were further confirmed by the postsynthetic solvothermal treatment of isolated nonradical MOF crystals. Notably, the transient amorphous phase without morphological disintegration was clearly observed, contributing to the seminal structural change of the MOF. We believe that this unprecedented structural transition triggered by the ligand self-assembly magnifies the structural flexibility and diversity of MOFs, which is one of the pivotal aspects of MOFs.

In-Car Environment Control Using an SSVEP-Based Brain-Computer Interface with Visual Stimuli Presented on Head-Up Display: Performance Comparison with a Button-Press Interface.

Controlling the in-car environment, including temperature and ventilation, is necessary for a comfortable driving experience. However, it often distracts the driver's attention, potentially causing critical car accidents. In the present study, we implemented an in-car environment control system utilizing a brain-computer interface (BCI) based on steady-state visual evoked potential (SSVEP). In the experiment, four visual stimuli were displayed on a laboratory-made head-up display (HUD). This allowed the participants to control the in-car environment by simply staring at a target visual stimulus, i.e., without pressing a button or averting their eyes from the front. The driving performances in two realistic driving tests-obstacle avoidance and car-following tests-were then compared between the manual control condition and SSVEP-BCI control condition using a driving simulator. In the obstacle avoidance driving test, where participants needed to stop the car when obstacles suddenly appeared, the participants showed significantly shorter response time (1.42 ± 0.26 s) in the SSVEP-BCI control condition than in the manual control condition (1.79 ± 0.27 s). No-response rate, defined as the ratio of obstacles that the participants did not react to, was also significantly lower in the SSVEP-BCI control condition (4.6 ± 14.7%) than in the manual control condition (20.5 ± 25.2%). In the car-following driving test, where the participants were instructed to follow a preceding car that runs at a sinusoidally changing speed, the participants showed significantly lower speed difference with the preceding car in the SSVEP-BCI control condition (15.65 ± 7.04 km/h) than in the manual control condition (19.54 ± 11.51 km/h). The in-car environment control system using SSVEP-based BCI showed a possibility that might contribute to safer driving by keeping the driver's focus on the front and thereby enhancing the overall driving performance.

Design of Wearable EEG Devices Specialized for Passive Brain-Computer Interface Applications.

Owing to the increased public interest in passive brain-computer interface (pBCI) applications, many wearable devices for capturing electroencephalogram (EEG) signals in daily life have recently been released on the market. However, there exists no well-established criterion to determine the electrode configuration for such devices. Herein, an overall procedure is proposed to determine the optimal electrode configurations of wearable EEG devices that yield the optimal performance for intended pBCI applications. We utilized two EEG datasets recorded in different experiments designed to modulate emotional or attentional states. Emotion-specialized EEG headsets were designed to maximize the accuracy of classification of different emotional states using the emotion-associated EEG dataset, and attention-specialized EEG headsets were designed to maximize the temporal correlation between the EEG index and the behavioral attention index. General purpose electrode configurations were designed to maximize the overall performance in both applications for different numbers of electrodes (2, 4, 6, and 8). The performance was then compared with that of existing wearable EEG devices. Simulations indicated that the proposed electrode configurations allowed for more accurate estimation of the users' emotional and attentional states than the conventional electrode configurations, suggesting that wearable EEG devices should be designed according to the well-established EEG datasets associated with the target pBCI applications.

Titanium-Carboxylate Metal-Organic Framework Based on an Unprecedented Ti-Oxo Chain Cluster.

Titanium(IV)-based metal-organic frameworks (Ti-MOFs) have received significant attention in recent years due to their numerous photocatalytic applications. We herein prepare the single-crystalline Ti-carboxylate MOF (DGIST-1) composed of an unprecedented Ti-oxo chain cluster and the porphyrinic ligand, TCPP (tetrakis(4-carboxyphenyl)porphyrin). Preformed Ti-oxo clusters were used as Ti4+ sources to avoid the spontaneous hydrolysis and condensation reactions of traditional Ti-alkoxide precursors, thus, enabling the formation of the highly crystalline Ti-MOF. The successfully activated DGIST-1 exhibited a higher surface area (i.e., 1957.3 m2 g-1 ) than previously reported Ti-MOFs due to its high crystallinity. Furthermore, the visible-light-responsive photocatalytic activity of DGIST-1 was confirmed by the simultaneous generation of singlet oxygen (1 O2 ) and superoxide (. O2 - ) species, in addition to the highly efficient and selective oxidation of benzyl alcohol to benzaldehyde.

Structural and biochemical study of Bacillus subtilis HmoB in complex with heme.

Most bacteria have developed a hemoprotein degradation system to acquire iron from their hosts. Bacillus subtilis HmoB, a heme monooxygenase, is involved in the degradation of heme and subsequent release of iron. HmoB contains a C-terminal ABM domain, which is similar in sequence and structure to other heme monooxygenases. Heme degradation assay showed that highly conserved residues (N70, W128, and H138) near the heme-binding site were critical for activity of HmoB. However, HmoB was shown to be different from other bacterial heme oxygenases due to its longer N-terminal region and formation of a biological monomer instead of a dimer. The degradation product of B. subtilis HmoB was identified as staphylobilin from mass spectrometric analysis of the product and release of formaldehyde during degradation reaction.

Randomized clinical trial of pulpotomy using a premixed injectable calcium silicate cement on mature permanent teeth with reversible pulpitis.

The aim of this two-center randomized controlled trial was to assess the outcomes and relative factors associated with pulpotomies performed using a premixed injectable calcium silicate cement, as compared to mineral trioxide aggregate in mature permanent premolar and molar teeth with reversible pulpitis. Included teeth were randomly divided into two groups according to pulpotomy material (ProRoot MTA [PMTA] group, Endocem MTA Premixed [EPM] group). After pulp exposure, the superficial pulp was either removed to a depth of 2 mm (partial pulpotomy) or completely amputated to the level of the root canal orifice (full pulpotomy). A 3-mm layer of either material was randomly placed over the pulp wound, followed by the application of a thin layer of a light-cured glass ionomer composite liner. The restoration procedure was then carried out during the same visit. After one year of treatment, the pulpotomy success rate was 94.4% (67/71), with no significant difference between the PMTA and EPM groups. The success rate was 93.9% in the PMTA group and 97.1% in the EPM group. There were no significant factors related to the procedures. EPM is a viable alternative to PMTA for single-visit pulpotomies of permanent premolars and molars.

Design and performance evaluation of a rotary magnetorheological damper for unmanned vehicle suspension systems.

We designed and validated a rotary magnetorheological (MR) damper with a specified damping torque capacity, an unsaturated magnetic flux density (MFD), and a high magnetic field intensity (MFI) for unmanned vehicle suspension systems. In this study, for the rotary type MR damper to have these satisfactory performances, the roles of the sealing location and the cover case curvature of the MR damper were investigated by using the detailed 3D finite element model to reflect asymmetrical shapes and sealing components. The current study also optimized the damper cover case curvature based on the MFD, the MFI, and the weight of the MR damper components. The damping torques, which were computed using the characteristic equation of the MR fluid and the MFI of the MR damper, were 239.2, 436.95, and 576.78 N·m at currents of 0.5, 1, and 1.5 A, respectively, at a disk rotating speed of 10 RPM. These predicted damping torques satisfied the specified damping torque of 475 N·m at 1.5 A and showed errors of less than 5% when compared to experimental measurements from the MR damper manufactured by the proposed design. The current study could play an important role in improving the performance of rotary type MR dampers.

A novel method for the accurate evaluation of Poisson's ratio of soft polymer materials.

A new method with a simple algorithm was developed to accurately measure Poisson's ratio of soft materials such as polyvinyl alcohol hydrogel (PVA-H) with a custom experimental apparatus consisting of a tension device, a micro X-Y stage, an optical microscope, and a charge-coupled device camera. In the proposed method, the initial positions of the four vertices of an arbitrarily selected quadrilateral from the sample surface were first measured to generate a 2D 1st-order 4-node quadrilateral element for finite element numerical analysis. Next, minimum and maximum principal strains were calculated from differences between the initial and deformed shapes of the quadrilateral under tension. Finally, Poisson's ratio of PVA-H was determined by the ratio of minimum principal strain to maximum principal strain. This novel method has an advantage in the accurate evaluation of Poisson's ratio despite misalignment between specimens and experimental devices. In this study, Poisson's ratio of PVA-H was 0.44 ± 0.025 (n = 6) for 2.6-47.0% elongations with a tendency to decrease with increasing elongation. The current evaluation method of Poisson's ratio with a simple measurement system can be employed to a real-time automated vision-tracking system which is used to accurately evaluate the material properties of various soft materials.

Frictional response of normal and osteoarthritic articular cartilage in human femoral head.

We evaluated the microscale frictional response of human articular cartilage in different osteoarthritis stages using an atomic force microscope. Four human femoral heads (60-80 years old) with different osteoarthritis stages were explanted, and two cylindrical cartilage samples were sectioned from each femoral head. The microscale frictional coefficient mu of human cartilage in phosphate-buffered saline increased with increasing osteoarthritis stages, resulting in mu = 0.119 +/- 0.036 for stage 0 (normal cartilage), 0.151 +/- 0.039 for stage I, 0.158 +/- 0.041 for stage 2, and 0.409 +/- 0.119 for stage 3. Statistically significant differences of mu values for different osteoarthritis stages were detected only between stage 3 and other stages (p < 0.0001). The average surface roughness Rq significantly increased with increasing osteoarthritis stages, ranging from 137 +/- 25 nm for stage 0 to 533 +/- 196 nm for stage 3. A significant correlation between mu and Rq for different osteoarthritis stages was observed (R2 = 0.981). These results demonstrate a positive correlation between the osteoarthritis stages and cartilage surface roughness, and the dependence of the human cartilage frictional response, on osteoarthritis progression. The results could be due to a decrease in the superficial zone protein concentration during the natural progression of osteoarthritis.

Transcranial alternating current stimulation over multiple brain areas with non-zero phase delays other than 180 degrees modulates visuospatial working memory performance.

While zero-phase lag synchronization between multiple brain regions has been widely observed, relatively recent reports indicate that systematic phase delays between cortical regions reflect the direction of communications between cortical regions. For example, it has been suggested that a non-zero phase delay of electroencephalography (EEG) signals at the gamma frequency band between the bilateral parietal areas may reflect the direction of communication between these areas. We hypothesized that the direction of communication between distant brain areas might be modulated by multi-site transcranial alternating current stimulation (tACS) with specific phase delays other than 0° and 180°. In this study, a new noninvasive brain stimulation (NIBS) method called multi-site multi-phase tACS (msmp-tACS) was proposed. The efficacy of the proposed method was tested in a case study using a visuospatial working memory (VWM) paradigm in which the optimal stimulation conditions including amplitudes and phases of multiple scalp electrodes were determined using finite element analysis adopting phasor representation. msmp-tACS was applied over the bilateral intraparietal sulci (IPS) and showed that 80 Hz tACS with the phase for the right IPS leading that for the left IPS by 90° (= 3.125 ms) partialized VWM performance toward the right visual hemifield. The three stimulation conditions were synchronized, RL, and LR, which refers to stimulation condition with no phase lag, stimulation phase of right IPS (rIPS) leading left IPS (lIPS) by 90° and the stimulation of lIPS leading rIPS by 90°, respectively. The lateralization of VWM significantly shifted towards right visual hemifield under the RL condition compared to the synchronized and LR conditions. The shift in VWM was the result of the stimulation affecting both left and right visual hemifield trials to certain degrees, rather than significantly increasing or decreasing VWM capacity of a specific visual hemifield. Altered brain dynamics caused by msmp-tACS partialized VWM performance, likely due to modulation of effective connectivity between the rIPS and lIPS. Our results suggest that msmp-tACS is a promising NBS method that can effectively modulate cortical networks that cannot be readily modulated with conventional multi-site stimulation methods.

Bifurcation control of the Morris-Lecar neuron model via a dynamic state-feedback control.

In this paper, we address the control problem of bifurcations in the Morris-Lecar (ML) neuron model. With the use of a dynamic state-feedback control, two Hopf bifurcation points in the ML neuron model with Type II excitability can be relocated to new desired locations simultaneously. Also, with the proposed control law, the neuronal excitability characteristics can be transformed from Type I excitability to Type II excitability by changing the type of bifurcation, in which the neuron goes from quiescence to periodic spiking from a saddle node on an invariant circle bifurcation to a Hopf bifurcation. Simulation results are provided.

Effect of protein concentrations of bovine serum albumin and γ-globulin on the frictional response of a cobalt-chromium femoral head.

The study aims to identify the concentration-dependent role of bovine serum albumin (BSA) and γ-globulin in the lubricating ability of a cobalt-chromium femoral head. The frictional coefficients of the cobalt-chromium femoral head decreased with increasing BSA concentrations from 10 to 40 mg/ml and showed statistical differences between any of the BSA concentration groups, except between the 30 and 40 mg/ml concentration groups. In γ-globulin, the frictional coefficients significantly decreased at concentrations of 2.5 and 5.0 mg/ml as compared with the PBS control group, but significant increases were observed at 7.5 and 12.5 mg/ml. These results suggest that the friction of the cobalt-chromium femoral head is dependent on the concentration of both BSA and γ-globulin. However, there is a maximum concentration for BSA to act as an effective boundary lubricant, while the lubricating ability of γ-globulin is most effective in the physiological concentration range within human synovial fluid.

Biphasic Properties of PVAH (Polyvinyl Alcohol Hydrogel) Reflecting Biomechanical Behavior of the Nucleus Pulposus of the Human Intervertebral Disc.

PVAH is a mixture of solid and fluid, but its mechanical behavior has usually been described using solid material models. The purpose of this study was to obtain material properties that can reflect the mechanical behavior of polyvinyl alcohol hydrogel (PVAH) using finite element analysis, a biphasic continuum model, and to optimize the composition ratio of PVAH to replace the nucleus pulposus (NP) of the human intervertebral disc. Six types of PVAH specimens (3, 5, 7, 10, 15, 20 wt%) were prepared, then unconfined compression experiments were performed to acquire their material properties using the Holmes-Mow biphasic model. With an increasing weight percentage of PVA in PVAH, the Young's modulus increased while the permeability parameter decreased. The Young's modulus and permeability parameter were similar to those of the NP at 15 wt% and 20 wt%. The range of motion, facet joint force, and NP pressures measured from dynamic motional analysis of the lumbar segments with the NP model also exhibited similar values to those with 15~20 wt% PVAH models. Considering the structural stability and pain of the lumbar segments, it appears that 20 wt% PVAH is most suitable for replacing the NP.

Ti-Based porous materials for reactive oxygen species-mediated photocatalytic reactions.

Reactive oxygen species (ROS) are highly reactive oxidants that are typically generated by the irradiation of semiconducting materials with visible or UV light and are widely used for the photocatalytic degradation of toxic substances, photodynamic therapy, and selective organic transformations. In this context, TiO2 is considered to be among the most promising photocatalysts due to its high redox activity, structural stability, and natural abundance. In view of the extensive development of highly active photocatalysts, we herein briefly introduce TiO2 and the mechanisms of TiO2-mediated ROS generation, subsequently focusing on key advances in the design and synthesis of Ti-containing porous materials, such as porous TiO2, Ti-based metal-organic frameworks, and Ti-based metal-organic aerogels. In particular, this review highlights the significance of porosity and the structure-function relationship for the development of Ti-based photocatalysts. The structures, porosities, and ROS generation mechanisms of these materials as well as the related efficiencies of ROS-mediated photocatalytic organic transformations are discussed in detail to provide a useful reference for future researchers and to inspire the exploration of high-performance photocatalysts.

Novel Hybrid Brain-Computer Interface for Virtual Reality Applications Using Steady-State Visual-Evoked Potential-Based Brain-Computer Interface and Electrooculogram-Based Eye Tracking for Increased Information Transfer Rate.

Brain-computer interfaces (BCIs) based on electroencephalogram (EEG) have recently attracted increasing attention in virtual reality (VR) applications as a promising tool for controlling virtual objects or generating commands in a "hands-free" manner. Video-oculography (VOG) has been frequently used as a tool to improve BCI performance by identifying the gaze location on the screen, however, current VOG devices are generally too expensive to be embedded in practical low-cost VR head-mounted display (HMD) systems. In this study, we proposed a novel calibration-free hybrid BCI system combining steady-state visual-evoked potential (SSVEP)-based BCI and electrooculogram (EOG)-based eye tracking to increase the information transfer rate (ITR) of a nine-target SSVEP-based BCI in VR environment. Experiments were repeated on three different frequency configurations of pattern-reversal checkerboard stimuli arranged in a 3 × 3 matrix. When a user was staring at one of the nine visual stimuli, the column containing the target stimulus was first identified based on the user's horizontal eye movement direction (left, middle, or right) classified using horizontal EOG recorded from a pair of electrodes that can be readily incorporated with any existing VR-HMD systems. Note that the EOG can be recorded using the same amplifier for recording SSVEP, unlike the VOG system. Then, the target visual stimulus was identified among the three visual stimuli vertically arranged in the selected column using the extension of multivariate synchronization index (EMSI) algorithm, one of the widely used SSVEP detection algorithms. In our experiments with 20 participants wearing a commercial VR-HMD system, it was shown that both the accuracy and ITR of the proposed hybrid BCI were significantly increased compared to those of the traditional SSVEP-based BCI in VR environment.

Optimization of a lumbar interspinous fixation device for the lumbar spine with degenerative disc disease.

Interspinous spacer devices used in interspinous fixation surgery remove soft tissues in the lumbar spine, such as ligaments and muscles and may cause degenerative diseases in adjacent segments its stiffness is higher than that of the lumbar spine. Therefore, this study aimed to structurally and kinematically optimize a lumbar interspinous fixation device (LIFD) using a full lumbar finite element model that allows for minimally invasive surgery, after which the normal behavior of the lumbar spine is not affected. The proposed healthy and degenerative lumbar spine models reflect the physiological characteristics of the lumbar spine in the human body. The optimum number of spring turns and spring wire diameter in the LIFD were selected as 3 mm and 2 turns, respectively-from a dynamic range of motion (ROM) perspective rather than a structural maximum stress perspective-by applying a 7.5 N∙m extension moment and 500 N follower load to the LIFD-inserted lumbar spine model. As the spring wire diameter in the LIFD increased, the maximum stress generated in the LIFD increased, and the ROM decreased. Further, as the number of spring turns decreased, both the maximum stress and ROM of the LIFD increased. When the optimized LIFD was inserted into a degenerative lumbar spine model with a degenerative disc, the facet joint force of the L3-L4 lumbar segment was reduced by 56%-98% in extension, lateral bending, and axial rotation. These results suggest that the optimized device can strengthen the stability of the lumbar spine that has undergone interspinous fixation surgery and reduce the risk of degenerative diseases at the adjacent lumbar segments.

Brain-Controlled, AR-based Home Automation System using SSVEP-based Brain-Computer Interface and EOG-based Eye Tracker: A Feasibility Study for the Elderly End User.

Over the past decades, brain-computer interfaces (BCIs) have been developed to provide individuals with an alternative communication channel toward external environment. Although the primary target users of BCI technologies include the disabled or the elderly, most newly developed BCI applications have been tested with young, healthy people. In the present study, we developed an online home appliance control system using a steady-state visual evoked potential (SSVEP)-based BCI with visual stimulation presented in an augmented reality (AR) environment and electrooculogram (EOG)-based eye tracker. The performance and usability of the system were evaluated for individuals aged over 65. The participants turned on the AR-based home automation system using an eye-blink-based switch, and selected devices to control with three different methods depending on the user's preference. In the online experiment, all 13 participants successfully completed the designated tasks to control five home appliances using the proposed system, and the system usability scale exceeded 70. Furthermore, the BCI performance of the proposed online home appliance control system surpassed the best results of previously reported BCI systems for the elderly.

Selection of the optimal channel configuration for implementing wearable EEG devices for the diagnosis of mild cognitive impairment.

BACKGROUND: Early diagnosis of mild cognitive impairment (MCI) is essential for timely treatment planning. With recent advances in the wearable technology, interest has increasingly shifted toward computer-aided self-diagnosis of MCI using wearable electroencephalography (EEG) devices in daily life. However, no study so far has investigated the optimal electrode configurations for the efficient diagnosis of MCI while considering the design factors of wearable EEG devices. In this study, we aimed to determine the optimal channel configurations of wearable EEG devices for the computer-aided diagnosis of MCI. METHOD: We employed an EEG dataset collected from 21 patients with MCI and 21 healthy control subjects. After evaluating the classification accuracies for all possible electrode configurations for the two-, four-, six-, and eight-electrode conditions using a support vector machine, the optimal electrode configurations that provide the highest diagnostic accuracy were suggested for each electrode condition. RESULTS: The highest classification accuracies of 74.04% ± 4.82, 82.43% ± 6.14, 86.28% ± 2.81, and 86.85% ± 4.97 were achieved for the optimal two-, four-, six-, and eight-electrode configurations, respectively, which demonstrated the possibility of precise machine-learning-based diagnosis of MCI with a limited number of EEG electrodes. Additionally, further simulations with the EEG dataset revealed that the optimal electrode configurations had significantly higher classification accuracies than commercial EEG devices with the same number of electrodes, which suggested the importance of electrode configuration optimization for wearable EEG devices based on clinical EEG datasets. CONCLUSIONS: This study highlighted that the optimization of the electrode configuration, assuming the wearable EEG devices can potentially be utilized for daily life monitoring of MCI, is necessary to enhance the performance and portability.

Bis(2-phenyl-ethyl-ammonium) tetra-chloridocobaltate(II).

Crystals of the title compound, (C(6)H(5)CH(2)CH(2)NH(3))(2)[CoCl(4)], were grown by the solvent-evaporation method. This inorganic-organic hybrid compound exhibits a layered structure in which isolated CoCl(4) inorganic layers alternate with bilayers of phenylethylammonium cations. Although the inorganic anion is zero-dimensional, the layered structure is stabilized via N-H⋯Cl hydrogen bonds. The CoCl(4) tetra-hedra connect to the cations through N-H⋯Cl hydrogen bonds, building a two-dimensional network extending parallel to (010).

Estimation of Emotional Arousal Changes of a Group of Individuals During Movie Screening Using Steady-State Visual-Evoked Potential.

Neurocinematics is an emerging discipline in neuroscience, which aims to provide new filmmaking techniques by analyzing the brain activities of a group of audiences. Several neurocinematics studies attempted to track temporal changes in mental states during movie screening; however, it is still needed to develop efficient and robust electroencephalography (EEG) features for tracking brain states precisely over a long period. This study proposes a novel method for estimating emotional arousal changes in a group of individuals during movie screening by employing steady-state visual evoked potential (SSVEP), which is a widely used EEG response elicited by the presentation of periodic visual stimuli. Previous studies have reported that the emotional arousal of each individual modulates the strength of SSVEP responses. Based on this phenomenon, movie clips were superimposed on a background, eliciting an SSVEP response with a specific frequency. Two emotionally arousing movie clips were presented to six healthy male participants, while EEG signals were recorded from the occipital channels. We then investigated whether the movie scenes that elicited higher SSVEP responses coincided well with those rated as the most impressive scenes by 37 viewers in a separate experimental session. Our results showed that the SSVEP response averaged across six participants could accurately predict the overall impressiveness of each movie, evaluated with a much larger group of individuals.