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.

Reversible ammonia uptake at room temperature in a robust and tunable metal-organic framework.

Ammonia is useful for the production of fertilizers and chemicals for modern technology, but its high toxicity and corrosiveness are harmful to the environment and human health. Here, we report the recyclable and tunable ammonia adsorption using a robust imidazolium-based MOF (JCM-1) that uptakes 5.7 mmol g-1 of NH3 at 298 K reversibly without structural deformation. Furthermore, a simple substitution of NO3 - with Cl- in a post-synthetic manner leads to an increase in the NH3 uptake capacity of JCM-1(Cl-) up to 7.2 mmol g-1.

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.

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.

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.

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.

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.

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.

Functionality in metal-organic framework minerals: proton conductivity, stability and potential for polymorphism.

Rare metal-organic framework (MOF) minerals stepanovite and zhemchuzhnikovite can exhibit properties comparable to known oxalate MOF proton conductors, including high proton conductivity over a range of relative humidities at 25 °C, and retention of the framework structure upon thermal dehydration. They also have high thermodynamic stability, with a pronounced stabilizing effect of substituting aluminium for iron, illustrating a simple design to access stable, highly proton-conductive MOFs without using complex organic ligands.

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.

MOP × MOF: Collaborative Combination of Metal-Organic Polyhedra and Metal-Organic Framework for Proton Conductivity.

We report a hybrid solid system, UMOM-100-a and UMOM-100-b, synthesized by incorporation of Cu-based metal-organic polyhedra (MOPs) into a porous metal-organic framework (MOF) host, PCN-777. The MOP guests have acid (SO3-) functional groups, acting as functionalized nanocages, whereas the porosity is still maintained for proton conductivity. The key parameter for the UMOM-100 series is the number of MOPs inside a MOF, which controls the ratio between meso- and micropores, polarity, and finally proton conductivity. This is an example demonstrating a new design strategy for porous solids to add active components into porous MOFs, opening up possibilities in other applications such as solid-state electrolytes and heterogeneous catalysts.

Proton transfer in hydrogen-bonded degenerate systems of water and ammonia in metal-organic frameworks.

Porous crystalline metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) are emerging as a new class of proton conductors with numerous investigations. Some of the MOFs exhibit an excellent proton-conducting performance (higher than 10-2 S cm-1) originating from the interesting hydrogen(H)-bonding networks with guest molecules, where the conducting medium plays a crucial role. In the overwhelming majority of MOFs, the conducting medium is H2O because of its degenerate conjugate acid-base system (H3O+ + H2O ⇔ H2O + H3O+ or OH- + H2O ⇔ H2O + OH-) and the efficient H-bonding ability through two proton donor and two acceptor sites with a tetrahedral geometry. Considering the systematic molecular similarity to water, ammonia (NH3; NH4 + + NH3 ⇔ NH3 + NH4 +) is promising as the next proton-conducting medium. In addition, there are few reports on NH3-mediated proton conductivity in MOFs. In this perspective, we provide overviews of the degenerate water (hydronium or hydroxide)- or ammonia (ammonium)-mediated proton conduction system, the design strategies for proton-conductive MOFs, and the conduction mechanisms.

Ultrafast fabrication of thermally stable protein-coated silver iodide nanoparticles for solid-state superionic conductors.

Solid-state ionic conductor is an essential and critical part of electrochemical devices such as batteries and sensors. Nano-sized silver iodide (AgI) is the most promising ionic conductor due to its superionic conductivity at room temperature. In recent years, proteins have been used as organic templates to obtain high-performance solid-state ionic conductors as well as to extend their applications in a biosensor. Here, we report the unprecedented ultrafast synthesis of thermally stable protein-coated AgI nanoparticles (NPs) through the photo-irradiation method for solid-state electrolyte. The synthesis was performed using a hyperthermostable bacterial ß-glucosidase. The protein-coated AgI NPs with an approximate diameter of 13 nm showed that the controllable transition from the α- to ß-/γ-phase was drastically suppressed down to 41 °C in the cooling process. After drying, the product represents a thermally stable organic-inorganic hybrid system with superionic conductivity. It is noteworthy that the superionic conductivity (σ ˜ 0.14 S/cm at 170 °C) of thermally stable protein-coated AgI NPs is maintained during several thermal cycles (25-170 °C). To our knowledge, this is the first report showing the diffusion of mobile Ag+ ions on the surface of the AgI NPs through a protein matrix. The facile synthesis method and high performance of the protein-coated AgI NPs may provide a latent application in the mass production of nanobatteries and other technological applications.

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.

Increase in brain activation due to sub-tasks during driving: fMRI study using new MR-compatible driving simulator.

BACKGROUND: Several studies have used functional magnetic resonance imaging (fMRI) to show that neural activity is associated with driving. fMRI studies have also elucidated the brain responses associated with driving while performing sub-tasks. It is important to note that these studies used computer mouses, trackballs, or joysticks to simulate driving and, thus, were not comparable to real driving situations. In order to overcome these limitations, we used a driving wheel and pedal equipped with an MR-compatible driving simulator (80 km/h). The subjects drove while performing sub-tasks, and we attempted to observe differences in neuronal activation. METHODS: The experiments consisted of three blocks and each block consisted of both a control phase (1 min) and a driving phase (2 min). During the control phase, the drivers were instructed to look at the stop screen and to not perform driving tasks. During the driving phase, the drivers either drove (driving only condition) or drove while performing an additional sub-task (driving with sub-task condition) at 80 km/h. RESULTS: Compared to when the drivers were focused only on driving, when the drivers drove while performing a sub-task, the number of activation voxels greatly decreased in the parietal area, which is responsible for spatial perception. Task-performing areas, such as the inferior frontal gyrus and the superior temporal gyrus, showed increased activation. Performing a sub-task simultaneously while driving had affected the driver's driving. The cingulate gyrus and the sub-lobar region (lentiform nucleus, caudate, insula, and thalamus), which are responsible for error monitoring and control of unnecessary movements (e.g., wheel and pedal movements), showed increased activation during driving with sub-task condition compared to driving only condition. CONCLUSIONS: Unlike simple driving simulators (joysticks, computer mouses, or trackballs) used in previous research, the addition of a driving wheel and pedals (accelerator and brake) to the driving simulator used in this study closely represents real driving. Thus, the number of processed movements was increased, which led to an increased number of unnecessary movements that needed to be controlled. This in turn increased activation in the corresponding brain regions.

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.

Somatotopic Map and Inter- and Intra-Digit Distance in Brodmann Area 2 by Pressure Stimulation.

The somatotopic representation of the tactile stimulation on the finger in the brain is an essential part of understanding the human somatosensory system as well as rehabilitation and other clinical therapies. Many studies have used vibrotactile stimulations and reported finger somatotopic representations in the Brodmann area 3 (BA 3). On the contrary, few studies investigated finger somatotopic representation using pressure stimulations. Therefore, the present study aimed to find a comprehensive somatotopic representation (somatotopic map and inter- and intra-digit distance) within BA 2 of humans that could describe tactile stimulations on different joints across the fingers by applying pressure stimulation to three joints-the first (p1), second (p2), and third (p3) joints-of four fingers (index, middle, ring, and little finger). Significant differences were observed in the inter-digit distance between the first joints (p1) of the index and little fingers, and between the third joints (p3) of the index and little fingers. In addition, a significant difference was observed in the intra-digit distance between p1 and p3 of the little finger. This study suggests that a somatotopic map and inter- and intra-digit distance could be found in BA 2 in response to pressure stimulation on finger joints.

An unprecedented single platform via cross-linking of zeolite and MOFs.

The unprecedented ternary nanocomposites have been synthesized as a single platform via cross-linking of two nanoporous materials, MOFs and Pt nanoparticle (NP) loaded zeolite. The heterojunction of the novel nanocomposites is anticipated to work as a chemical platform for size selective catalytic hydrogenation or deuteration of small molecules.