Room-Temperature Superprotonic Conductivity beyond 10-1 S cm-1 in a Co(II) Coordination Polymer.

An efficient design of crystalline solid-state proton conductors (SSPCs) is crucial for the progress of clean energy applications. Developing such materials to make them work at room temperature with a conductivity of ≥10-1 S cm-1 is of significant interest in terms of technical and commercial aspects. Utilizing the recently highlighted "coordinated-water-driven proton conduction" approach, herein, we have rationally synthesized two highly stable and scalable 1D Co(II) coordination polymers (CPs) as SSPCs, PCM-2 {[Co(bpy)(H2O)2(NO3)2]·H2O}n and PCM-3 {[Co2(bpy)2(SO4)2(H2O)6].4H2O}n, with distinct alignments in coordinated water and coordinated oxo-anions (nitrate and sulfate, respectively). The acidity of the metal-bound water molecules in PCM-2 is further enhanced through cooperative long-range continuous H bonds with coordinated Brønsted basic nitrates (proton acceptors), leading to ultrahigh superprotonic conductivities even at 25 °C (1.03 × 10-1 S cm-1 under 95% RH), and reached a maximum of 2.99 × 10-1 S cm-1 at 85 °C (95% RH). The conductivity at 25 °C is even higher than that of commercial Nafion 117 (6.74 × 10-2 S cm-1 at 100% RH). The absence of such an H-bonding interaction in PCM-3 (closed loops) resulted in a lesser conductivity of 5.87 × 10-5 S cm-1 (95% RH, 85 °C). PCM-2 represents the first example of SSPC exhibiting conductivity in the order 10-1 S cm-1 at ambient temperature (25 °C) with excellent recyclability.

Intrusion Detection System CAN-Bus In-Vehicle Networks Based on the Statistical Characteristics of Attacks.

For in-vehicle network communication, the controller area network (CAN) broadcasts to all connected nodes without address validation. Therefore, it is highly vulnerable to all sorts of attack scenarios. This research proposes a novel intrusion detection system (IDS) for CAN to identify in-vehicle network anomalies. The statistical characteristics of attacks provide valuable information about the inherent intrusion patterns and behaviors. We employed two real-world attack scenarios from publicly available datasets to record a real-time response against intrusions with increased precision for in-vehicle network environments. Our proposed IDS can exploit malicious patterns by calculating thresholds and using the statistical properties of attacks, making attack detection more efficient. The optimized threshold value is calculated using brute-force optimization for various window sizes to minimize the total error. The reference values of normality require a few legitimate data frames for effective intrusion detection. The experimental findings validate that our suggested method can efficiently detect fuzzy, merge, and denial-of-service (DoS) attacks with low false-positive rates. It is also demonstrated that the total error decreases with an increasing attack rate for varying window sizes. The results indicate that our proposed IDS minimizes the misclassification rate and is hence better suited for in-vehicle networks.

Cooperative Proton and Li-ion Conduction in a 2D-Layered MOF via Mechanical Insertion of Lithium Halides.

Ionic conduction in highly designable and porous metal-organic frameworks has been explored through the introduction of various ionic species (H+ , OH- , Li+ , etc.) using post-synthetic modification such as acid, salt, or ionic liquid incorporation. Here, we report on high ionic conductivity (σ>10-2  S cm-1 ) in a two-dimensionally (2D)-layered Ti-dobdc (Ti2 (Hdobdc)2 (H2 dobdc), H4 dobdc: 2,5-dihydroxyterephthalic acid) via LiX (X=Cl, Br, I) intercalation using mechanical mixing. The anionic species in lithium halide strongly affect the ionic conductivity and durability of conductivity. Solid-state pulsed-field gradient nuclear magnetic resonance (PFG NMR ) verified the high mobility of H+ and Li+ ions in the temperature range of 300-400 K. In particular, the insertion of Li salts improved the H+ mobility above 373 K owing to strong binding with H2 O. Furthermore, the continuous increase in Li+ mobility with temperature contributed to the retention of the overall high ionic conductivity at high temperatures.

Proton Transport in Metal-Organic Frameworks.

Solid-state proton conductors (SSPCs), which are a key component for the safety and efficiency of fuel cells, have received much attention due to their broad application in electrochemical devices. In particular, the development of new materials with high conducting performance and an understanding of the conduction mechanism have become critical issues in this field. Porous metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) have recently emerged and have been extensively studied as a new type of proton conductor due to their crystallinity, designability, and high porosity. These properties are able to adsorb the guest molecules working as conducting media. During the past decade, major advances in proton-conductive MOFs have been achieved with high performance (>10-2 S cm-1), comparable to the conventional material, via various synthetic strategies, and the veiled conduction mechanism has been elucidated through structure analysis and spectroscopy tools such as NMR, X-ray diffraction, and neutron scattering measurement. This Review aims to summarize and provide a comprehensive understanding of proton transport in MOFs. Here, we discuss the fundamental principles and various design strategies and implementations aimed at enhancing proton conductivity with representative examples. We also deal with characterization methods used to investigate proton-conductive MOFs and computational/theoretical studies that aid in understanding the conduction mechanism. Finally, future endeavors are suggested regarding the challenges of research for practical SSPCs.

Rational strategies for proton-conductive metal-organic frameworks.

Since the transition of energy platforms, proton-conducting materials have played a significant role in broad applications for electrochemical devices. In particular, solid-state proton conductors (SSPCs) are emerging as the electrolyte in fuel cells (FC), a promising power generation technology, because of their high performance and safety for operating in a wide range of temperatures. In recent years, proton-conductive porous metal-organic frameworks (MOFs) exhibiting high proton-conducting properties (>10-2 S cm-1) have been extensively investigated due to their potential application in solid-state electrolytes. Their structural designability, crystallinity, and porosity are beneficial to fabricate a new type of proton conductor, providing a comprehensive conduction mechanism. For the proton-conductive MOFs, each component, such as the metal centres, organic linkers, and pore space, is manipulated by a judicious predesign strategy or post-synthetic modification to improve the mobile proton concentration with an efficient conducting pathway. In this review, we highlight rational design strategies for highly proton-conductive MOFs in terms of MOF components, with representative examples from recent years. Subsequently, we discuss the challenges and future directions for the design of proton-conductive MOFs.

Void Space versus Surface Functionalization for Proton Conduction in Metal-Organic Frameworks.

Void space and functionality of the pore surface are important structural factors for proton-conductive metal-organic frameworks (MOFs) impregnated with conducting media. However, no clear study has compared their priority factors, which need to be considered when designing proton-conductive MOFs. Herein, we demonstrate the effects of void space and pore-surface modification on proton conduction in MOFs through the surface-modified isoreticular MOF-74(Ni) series [Ni2 (dobdc or dobpdc), dobdc=2,5-dihydroxy-1,4-benzenedicarboxylate and dobpdc=4,4'-dihydroxy-(1,1'-biphenyl)-3,3'-dicarboxylate]. The MOF with lower porosity with the same surface functionality showed higher proton conductivity than that with higher porosity despite including a smaller amount of conducting medium. Density functional theory calculations suggest that strong hydrogen bonding between molecules of the conducting medium at high porosity is inefficient in inducing high proton conductivity.

Superprotonic Conductivity in Metal-Organic Framework via Solvent-Free Coordinative Urea Insertion.

Highly stable superprotonic conductivity (>10-2 S cm-1) has been achieved through the unprecedented solvent-free-coordinative urea insertion in MOF-74 [M2(dobdc), M = Ni2+, Mg2+; dobdc = 2,5-dioxido-1,4-benzenedicarboxylate] without an acidic moiety. The urea is bound to open metal sites and alters the void volume and surface functionality, which triggers a significant change in proton conductivity and diffusion mechanism. Solid-state 2H NMR revealed that the high conductivity was attributed to the strengthening of the hydrogen bonds between guest H2O induced by hydrogen bonds in the interface between H2O and the polarized coordinated urea.

A Phosphate-Based Silver-Bipyridine 1D Coordination Polymer with Crystallized Phosphoric Acid as Superprotonic Conductor.

Phosphate-based silver-bipyridine (Ag-bpy) 1D coordination polymer {[{Ag(4,4'-bpy)}2 {Ag(4,4'-bpy)(H2 PO4 )}]⋅2 H2 PO4 ⋅H3 PO4 ⋅5 H2 O}n (1) with free phosphoric acid (H3 PO4 ), its conjugate base (H2 PO4 - ) and water molecules in its lattice was synthesized by room-temperature crystallization and the hydrothermal method. An XRD study showed that coordinated H2 PO4 - , lattice H2 PO4 - anions, free H3 PO4 and lattice water molecules are interconnected by H-bonding interactions, forming an infinitely extended 2D H-bonded network that facilitates proton transfer. This material exhibits a high proton conductivity of 3.3×10-3  S cm-1 at 80 °C and 95 % relative humidity (RH). Furthermore, synthesis of this material from commercially available starting materials in water can be easily scaled up, and it is highly stable under extreme conditions of conductivity measurements. This report inaugurates the usage and design principle of proton-conducting frameworks based on crystallized phosphoric acid and phosphate.

Characterization of Proton Dynamics for the Understanding of Conduction Mechanism in Proton Conductive Metal-Organic Frameworks.

Proton conductivity has been traditionally investigated with various materials such as organic polymers, metal oxides, and other inorganic and organic compounds because of their potential application in the electrochemical devices. In particular, during the last decade, crystalline porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) have received considerable attention in recent years, as solid-state proton conductors (SSPCs). To date, proton-conductive MOFs have achieved high performance in proton conductivity (>10-2  S cm-1 ) with rational design strategies. In addition, there are dedicated efforts to define the conduction pathway and mechanism using various experimental tools. In this review, we focus on the characterization of proton conductivity and molecular dynamics in hydrated MOFs, with selected examples to provide an understanding of the overall conduction mechanism.

Modeling adsorption properties of structurally deformed metal-organic frameworks using structure-property map.

Structural deformation and collapse in metal-organic frameworks (MOFs) can lead to loss of long-range order, making it a challenge to model these amorphous materials using conventional computational methods. In this work, we show that a structure-property map consisting of simulated data for crystalline MOFs can be used to indirectly obtain adsorption properties of structurally deformed MOFs. The structure-property map (with dimensions such as Henry coefficient, heat of adsorption, and pore volume) was constructed using a large data set of over 12000 crystalline MOFs from molecular simulations. By mapping the experimental data points of deformed SNU-200, MOF-5, and Ni-MOF-74 onto this structure-property map, we show that the experimentally deformed MOFs share similar adsorption properties with their nearest neighbor crystalline structures. Once the nearest neighbor crystalline MOFs for a deformed MOF are selected from a structure-property map at a specific condition, then the adsorption properties of these MOFs can be successfully transformed onto the degraded MOFs, leading to a new way to obtain properties of materials whose structural information is lost.

A Multiple Rényi Entropy Based Intrusion Detection System for Connected Vehicles.

In this paper, we propose an intrusion detection system based on the estimation of the Rényi entropy with multiple orders. The Rényi entropy is a generalized notion of entropy that includes the Shannon entropy and the min-entropy as special cases. In 2018, Kim proposed an efficient estimation method for the Rényi entropy with an arbitrary real order α . In this work, we utilize this method to construct a multiple order, Rényi entropy based intrusion detection system (IDS) for vehicular systems with various network connections. The proposed method estimates the Rényi entropies simultaneously with three distinct orders, two, three, and four, based on the controller area network (CAN)-IDs of consecutively generated frames. The collected frames are split into blocks with a fixed number of frames, and the entropies are evaluated based on these blocks. For a more accurate estimation against each type of attack, we also propose a retrospective sliding window method for decision of attacks based on the estimated entropies. For fair comparison, we utilized the CAN-ID attack data set generated by a research team from Korea University. Our results show that the proposed method can show the false negative and positive errors of less than 1% simultaneously.

Superionic Conduction over a Wide Temperature Range in a Metal-Organic Framework Impregnated with Ionic Liquids.

Most molecules in confined spaces show markedly different behaviors from those in the bulk. Large pores are composed of two regions: an interface region in which liquids interact with the pore surface, and a core region in which liquids behave as bulk. The realization of a highly mobile ionic liquid (IL) in a mesoporous metal-organic framework (MOF) is now reported. The hybrid shows a high room-temperature conductivity (4.4×10-3  S cm-1 ) and low activation energy (0.20 eV); both not only are among the best values reported for IL-incorporated MOFs but also are classified as a superionic conductor. The conductivity reaches over 10-2  S cm-1 above 343 K and follows the Vogel-Fulcher-Tammann equation up to ca. 400 K. In particular, the hybrid is advantageous at low temperatures (<263 K), where the ionic conduction is superior to that of bulk IL, making it useful as solid-state electrolytes for electrochemical devices operating over a wide temperature range.

Differences in and correlations between cognitive abilities and brain volumes in healthy control, mild cognitive impairment, and Alzheimer disease groups.

The purpose of this study is to investigate differences in and correlations between cognitive abilities and brain volumes in healthy control (HC), mild cognitive impairment (MCI), and Alzheimer's disease (AD) groups. The Korean Version of the Consortium to Establish a Registry for Alzheimer's Disease (CERAD-K), which is used to diagnose AD, was used to measure the cognitive abilities of the study subjects, and the volumes of typical brain components related to AD diagnosis-cerebrospinal fluid (CSF), gray matter (GM), and white matter (WM)-were acquired. Of the CERAD-K subtests, the Boston Naming Test distinguished significantly among the HC, MCI, and AD groups. GM and WM volumes differed significantly among the three groups. There was a significant positive correlation between Boston Naming Test scores and GM and WM volumes. In conclusion, the Boston Naming Test and GM and WM brain volumes differentiated the three tested groups accurately, and there were strong correlations between Boston Naming Test scores and GM and WM volumes. These results will help to establish a test method that differentiates the three groups accurately and is economically feasible.

Primary and secondary gait deviations of stroke survivors and their association with gait performance.

[Purpose] Stroke survivors exhibit abnormal pelvic motion and significantly deteriorated gait performance. Although the gait of stroke survivors has been evaluated at the primary level pertaining to ankle, knee, and hip motions, secondary deviations involving the pelvic motions are strongly related to the primary level. Therefore, the aim of this study was to identify the kinematic differences of the primary and secondary joints and to identify mechanism differences that alter the gait performance of stroke survivors. [Subjects and Methods] Five healthy subjects and five stroke survivors were recruited. All the subjects were instructed to walk at a self-selected speed. The joint kinematics and gait parameters were calculated. [Results] For the stroke survivors, the range of motion of the primary-joint motions were significantly reduced, and the secondary-joint motions were significantly increased. Additionally, for the healthy subjects, the primary joint kinematics were the main factors ensuring gait performance, whereas for the stoke survivors, the secondary-joint motions were the main factors. [Conclusion] The results indicate that while increasing the range of motion of primary-joint movements is the main target to achieve, there is a strong need to constrain and support pelvic motions in order to improve the outcome of gait rehabilitation.

Formation of Frustrated Lewis Pairs in Ptx -Loaded Zeolite†NaY.

The formation of a frustrated Lewis pair consisting of sodium hydride (Na(+) H(-) ) and a framework-bound hydroxy proton O(H(+) ) is reported upon H2 treatment of zeolite NaY loaded with Pt nanoparticles (Ptx /NaY). Frustrated Lewis pair formation was confirmed using in situ neutron diffraction and spectroscopic measurements. The activity of the intrazeolite NaH as a size-selective catalyst was verified by the efficient esterification of acetaldehyde (a small aldehyde) to form the corresponding ester ethyl acetate, whereas esterification of the larger molecule benzaldehyde was unsuccessful. The frustrated Lewis pair (consisting of Na(+) H(-) and O(H(+) )) generated within zeolite NaY may be a useful catalyst for various catalytic reactions which require both H(-) and H(+) ions, such as catalytic hydrogenation or dehydrogenation of organic compounds and activation of small molecules.

Fabrication of metal nanoparticles in metal-organic frameworks.

In this review, we highlight various preparative strategies and characterization methods for metal nanoparticles fabricated in porous metal-organic frameworks (MOFs) or porous coordination polymers (PCPs), and their applications in hydrogen storage and heterogeneous catalysis.

Development of a simple pressure and heat stimulator for intra- and interdigit functional magnetic resonance imaging.

For this study, we developed a simple pressure and heat stimulator that can quantitatively control pressure and provide heat stimulation to intra- and interdigit areas. The developed stimulator consists of a control unit, drive units, and tactors. The control unit controls the stimulation parameters, such as stimulation types, intensity, time, and channel, and transmits a created signal of stimulation to the drive units. The drive units operate pressure and heat tactors in response to commands from the control unit. The pressure and heat tactors can display various stimulation intensities quantitatively, apply stimulation continuously, and adjust the stimulation areas. Additionally, they can easily be attached to and detached from the digits. The developed pressure and heat stimulator is small in total size, easy to install, and inexpensive to manufacture. The new stimulator operated stably in a magnetic resonance imaging (MRI) environment without affecting the obtained images. A preliminary functional magnetic resonance imaging (fMRI) experiment confirmed that differences in activation of somatosensory areas were induced from the pressure and heat stimulation. The developed pressure and heat stimulator is expected to be utilized for future intra- and interdigit fMRI studies on pressure and heat stimulation.

Hydrogen storage in a potassium-ion-bound metal-organic framework incorporating crown ether struts as specific cation binding sites.

To develop a metal-organic framework (MOF) for hydrogen storage, SNU-200 incorporating a 18-crown-6 ether moiety as a specific binding site for selected cations has been synthesized. SNU-200 binds K(+), NH4(+), and methyl viologen (MV(2+)) through single-crystal to single-crystal transformations. It exhibits characteristic gas-sorption properties depending on the bound cation. SNU-200 activated with supercritical CO2 shows a higher isosteric heat (Qst) of H2 adsorption (7.70 kJ mol(-1)) than other zinc-based MOFs. Among the cation inclusions, K(+) is the best for enhancing the isosteric heat of the H2 adsorption (9.92 kJ mol(-1)) as a result of the accessible open metal sites on the K(+) ion.

Development of a simple MR-compatible vibrotactile stimulator using a planar-coil-type actuator.

For this study, we developed a magnetic resonance (MR)-compatible vibrotactile stimulator using a planar-coil-type actuator. The newly developed vibrotactile stimulator consists of three units: control unit, drive unit, and planar-coil-type actuator. The control unit controls frequency, intensity, time, and channel, and transfers the stimulation signals to the drive unit. The drive unit operates the planar-coil-type actuator in response to commands from the control unit. The planar-coil-type actuator, which uses a planar coil instead of conventional electric wire, generates vibrating stimulation through interaction of the current of the planar coil with the static magnetic field of the MR scanner. Even though the developed tactile stimulating system is small, simple, and inexpensive, it has a wide range of stimulation frequencies (20 ~ 400 Hz, at 40 levels) and stimulation intensities (0 ~ 7 V, at 256 levels). The stimulation intensity does not change due to frequency changes. Since the transient response time is a few microseconds, the stimulation time can be controlled on a scale of microseconds. In addition, this actuator has the advantages of providing highly repeatable stimulation, being durable, being able to assume various shapes, and having an adjustable contact area with the skin. The new stimulator operated stably in an MR environment without affecting the MR images. Using functional magnetic resonance imaging, we observed the brain activation changes resulting from stimulation frequency and intensity changes.

Driving performance changes of middle-aged experienced taxi drivers due to distraction tasks during unexpected situations.

This study investigated the effects of distraction taskssuch as sending a text message with a cellphone and searching navigation with car navigation system-on the driving performance of 29 highly experienced taxi drivers in their 50s. All participants were instructed to drive using a driving simulator for 2 min. while maintaining a constant distance from the vehicle in front and a constant speed. Participants drove without any distractions for the first minute. For an additional minute, they performed Driving Only or performed a task while driving (Driving + Sending Text Message or Driving + Searching Navigation). An unexpected situation, in which the participant had to stop abruptly due to a sudden stop of the preceding vehicle, occurred during this period. Driving performance during the unexpected situation was evaluated by car control variables, medial-lateral coefficient of variation and brake time, and by motion variables such as the jerk-cost function. Compared to Driving Only, jerk-cost function, medial-lateral coefficient of variation, and brake time increased during Driving + Sending Text Message or Driving + Searching Navigation.