Effect of a "Zn Bridge" on the Consecutively Tunable Retention Characteristics of Volatile Random Access Memory Materials.

Polyimide memory materials with a donor-acceptor structure based on a charge-transfer mechanism exhibit great potential for next-generation information storage technology due to their outstanding high-temperature resistance and good dimensional and chemical stability. Precisely controlling memory performance by limited chemical decoration is one of core challenges in this field. Most reported work mainly focuses on designing novel and elaborate electron donors or acceptors for the expected memory behavior of polyimides; this takes a lot of time and is not always efficacious. Herein, we report a series of porphyrinated copolyimides coPI-Znx (x=5, 10, 20, 50, 80), where x represents the mole percentage of Zn ion in the central core of the porphyrin. Experimental and theoretical analysis indicate that the Zn ion could play a vital bridge role in promoting the formation and stabilization of a charge-transfer complex by enhancing the hybridization of local and charge transfer (HLCT) excitations of porphyrinated polyimides, endowing coPI-Znx with volatile random access memory performance and continuously tunable retention time. This work could provide one simple strategy to precisely regulate memory performance merely by altering the metal content in porphyrinated polyimides.

Zinc Ion Triggered Controllable Binary/Ternary Memory Conversion Behaviors in Polyimides Containing Pendant Porphyrin Group.

Compared with typical binary polymeric memory materials, functional polymers with ternary memory performance possess significant potential to achieve ultra-high-density data storage. The reported ternary memory polymers are normally driven by dual-mechanism. However, the involved thermodynamically unstable mechanisms (field-induced conformation change or conductive filament formation/fracture) may result in the poor reliability of memory devices under high-temperature working atmosphere. Another strategy to realize ternary memory is introducing charge trapping/de-trapping mechanism by attaching charge trap atom/group at electron donor, which is proved not always effective. Moreover, the synergistic two mechanisms may have difficulty for clarifying the relationship between memory performance and chemical structures, which is the core issue of polymer memory materials. Besides, some multi-level memory materials need the cooperative participation of artificially setting compliance current, which is the extension of typical binary memory and may cause a more complicated technique and logic circuit. Herein, based on charge-transfer mechanism, a concise and effective strategy to realize ternary memory application is proposed. By inserting a Zn ion, the charge-transfer process occurring in electron donors can lead to the novel electrical tri-stability memory behaviors. This work can provide a novel idea for achieving reliable and intrinsic ternary high-density data storage applications.

Improving Interfacial and Compressive Properties of Polyimide Fiber by Constructing Inorganic Layers on Fiber Surface.

The compressive performance of organic fiber has always been a key problem, limiting its development. In this paper, silicon oxide, alumina, and titanium oxide particles were separately deposited on the surface of high-strength and high-modulus polyimide (PI) fibers to form a structural supporting shell by using a magnetron sputtering method. The theoretical thickness was calculated by thermogravimetric analysis in good agreement with the actual thickness determined from scanning electron microscopy. The mechanics, surface, and interface properties of the measured fibers were analyzed mainly from the aspects of surface energy, interfacial shear strength (IFSS), and compression strength. The results showed that after magnetron sputtering, the inorganic shells were uniformly deposited on the surface of PI fiber, resulting in an increase in the content of inorganic elements as well as the roughness. As a result, the surface energy and IFSS of silica-coated fiber was increased by 174 and 85.6%, respectively, and compression strength was increased by 45.7%. This study provides a new approach for improving the interface property and compression strength of high-strength and high-modulus PI-fiber-reinforced composites.

Dual-functional Separators Regulating Ion Transport Enabled by 3D-Reinforced Polyimide Microspheres Protective Layer for Dendrite-Free and High-Temperature Lithium Metal Batteries.

High-energy-density lithium metal batteries (LMBs) are confronted with crucial concerns of security and a short cycle lifespan caused by the uncontrollable formation of lithium (Li) dendrites. The poor thermal stability and heterogeneous Li deposition of conventional polyolefin separators often cause battery short circuiting and thermal runaway in LMBs. Herein, a novel dual-functional PE composite separator (PI-COOH/PE) coated by carboxyl polyimide (PI) microspheres is fabricated by an etching-acidification method. The three-dimensional (3D) high-temp PI microsphere with rich carboxyl groups on the surface improve the security of LMBs at extremely high temperatures and facilitate the formation of a stable and uniform SEI layer, which contributes to accelerating the Li+ transport and stabilizing the formation of the SEI layer. Consequently, the Li symmetric cell assembled with the (PI-COOH)/PE separator exhibits stable overpotential over 3000 h, and the corresponding Li//NCM811 full cells also show a high-level discharge capacity of 146.6 mAh g-1 at 5 C. Meanwhile, it also demonstrates outstanding cycling stability and thermal safety, which can survive continuously over 160 min at 140 °C (vs 21 min for PE). The above results indicate the (PI-COOH)/PE separator constructed by a low-cost and industrial-friendly strategy simultaneously addresses high-temperature stability and dendrite resistance.

Critical role of connexin 43 in secondary expansion of traumatic spinal cord injury.

Spinal cord injury (SCI) is often complicated by secondary injury as a result of the innate inflammatory response to tissue trauma and swelling. Previous studies have shown that excessive ATP release from peritraumatic regions contributes to the inflammatory response to SCI by activation of low-affinity P2X7 receptors. Because connexin hemichannels constitute an important route for astrocytic ATP release, we here evaluated the impact on post-traumatic ATP release of deletion of connexins (Cx30/Cx43) in astrocytes. In vivo bioluminescence imaging showed a significant reduction in ATP release after weight-drop injury in mice with deletion of Cx43 compared with Cx43-expressing littermates, both on a Cx30 knockout background. Moreover, astrogliosis and microglia activation were reduced in peritraumatic areas of those mice lacking Cx43; motor recovery was also significantly improved, and the traumatic lesion was smaller. Combined, these observations are consistent with a contribution by astrocytic hemichannels to post-traumatic ATP release that aggravates secondary injury and restrains functional recovery after experimental spinal cord injury. Connexins may thereby constitute a new therapeutic target in spinal cord injury.

Retina-inspired organic neuromorphic vision sensor with polarity modulation for decoding light information.

The neuromorphic vision sensor (NeuVS), which is based on organic field-effect transistors (OFETs), uses polar functional groups (PFGs) in polymer dielectrics as interfacial units to control charge carriers. However, the mechanism of modulating charge transport on basis of PFGs in devices is unclear. Here, the carboxyl group is introduced into polymer dielectrics in this study, and it can induce the charge transfer process at the semiconductor/dielectric interfaces for effective carrier transport, giving rise to the best device mobility up to 20 cm2 V-1 s-1 at a low operating voltage of -1 V. Furthermore, the polarity modulation effect could further increase the optical figures of merit in NeuVS devices by at least an order of magnitude more than the devices using carboxyl group-free polymer dielectrics. Additionally, devices containing carboxyl groups improved image sensing for light information decoding with 52 grayscale signals and memory capabilities at an incredibly low power consumption of 1.25 fJ/spike. Our findings provide insight into the production of high-performance polymer dielectrics for NeuVS devices.

An astrocytic basis of epilepsy.

Hypersynchronous neuronal firing is a hallmark of epilepsy, but the mechanisms underlying simultaneous activation of multiple neurons remains unknown. Epileptic discharges are in part initiated by a local depolarization shift that drives groups of neurons into synchronous bursting. In an attempt to define the cellular basis for hypersynchronous bursting activity, we studied the occurrence of paroxysmal depolarization shifts after suppressing synaptic activity using tetrodotoxin (TTX) and voltage-gated Ca(2+) channel blockers. Here we report that paroxysmal depolarization shifts can be initiated by release of glutamate from extrasynaptic sources or by photolysis of caged Ca(2+) in astrocytes. Two-photon imaging of live exposed cortex showed that several antiepileptic agents, including valproate, gabapentin and phenytoin, reduced the ability of astrocytes to transmit Ca(2+) signaling. Our results show an unanticipated key role for astrocytes in seizure activity. As such, these findings identify astrocytes as a proximal target for the treatment of epileptic disorders.

Systemic administration of an antagonist of the ATP-sensitive receptor P2X7 improves recovery after spinal cord injury.

Traumatic spinal cord injury is characterized by an immediate, irreversible loss of tissue at the lesion site, as well as a secondary expansion of tissue damage over time. Although secondary injury should, in principle, be preventable, no effective treatment options currently exist for patients with acute spinal cord injury (SCI). Excessive release of ATP by the traumatized tissue, followed by activation of high-affinity P2X7 receptors, has previously been implicated in secondary injury, but no clinically relevant strategy by which to antagonize P2X7 receptors has yet, to the best of our knowledge, been reported. Here we have tested the neuroprotective effects of a systemically administered P2X7R antagonist, Brilliant blue G (BBG), in a weight-drop model of thoracic SCI in rats. Administration of BBG 15 min after injury reduced spinal cord anatomic damage and improved motor recovery without evident toxicity. Moreover, BBG treatment directly reduced local activation of astrocytes and microglia, as well as neutrophil infiltration. These observations suggest that BBG not only protected spinal cord neurons from purinergic excitotoxicity, but also reduced local inflammatory responses. Importantly, BBG is a derivative of a commonly used blue food color (FD&C blue No. 1), which crosses the blood-brain barrier. Systemic administration of BBG may thus comprise a readily feasible approach by which to treat traumatic SCI in humans.

Long non-coding RNA TUG1 promotes osteosarcoma cell proliferation and invasion through inhibition of microRNA-212-3p expression.

[This retracts the article DOI: 10.3892/etm.2018.6216.].

Thermostable and nonflammable polyimide/zirconia compound separator for lithium-ion batteries with superior electrochemical and safe properties.

Separators are applied to segregate cathode and anode, and provide ion transport channels in lithium-ion batteries (LIBs). Nevertheless, present commercial polyolefin separators represent high thermal shrinkage and inferior electrolyte wettability, seriously limiting wider development of LIBs. In this work, we prepared zirconia (ZrO2) nanolayer encapsulated polyimide (PI) nanofiber compound separator through in-situ polar adsorption and hydrolysis strategy. The obtained PI/ZrO2 compound separator has superior thermal stability, electrolyte wettability and flame retardance in comparison with polypropylene (PP) separator. The shrinkage ratio of prepared PI/ZrO2 compound separator is 0 even at 300 °C, while the PP separator significantly shrank at 160 °C. Furthermore, the ionic conductivity of PI/ZrO2 separator reaches up to 1.32 mS cm-1, far higher than 0.34 mS cm-1 of PP separator. Besides, the coin batteries of LiNi0.8Co0.1Mn0.1O2 (NCM811)/electrolyte-separator/lithium (Li) assembled with PI/ZrO2 compound separator exhibit enhanced rate performance, high discharge capacity retention rate of 88.3% after 100 cycles at 1C and excellent battery safety performance even at 140 °C. Thus, combined with its advantages, such as preparation, thermostability, electrolyte wettability, electrochemical property and safety, the PI/ZrO2 compound separator exhibits promising prospect in the application of commercial LIBs.

Dynamic random access memory effect and memory device derived from a functional polyimide containing electron donor-acceptor pairs in the main chain.

A functional polyimide, hexafluoroisopropyl bis(phthalic dianhydride)/3,6-diaminocarbazole (6FDA/DAC), in which DAC serves as electron donor and 6FDA as electron acceptor, has been synthesized in our present work. Electrical characterization results on the sandwiched polyimide memory device (ITO/Thin polyimide Layer/Au) indicate that the polyimide possesses electrical bistability and the device exhibits two accessible conductivity states, which can be reversibly switched from the low-conductivity (OFF) state to the high-conductivity (ON) state with an ON/OFF current ratio of about 10(4). Different from the widely reported write-once-read-many-times (WORM) effects, the device with the 6FDA/DAC polyimide as the active layer shows dynamic random access memory (DRAM) behavior. The ON state of the device was lost immediately after removal of the applied voltage, while by applying a constant bias (e.g., 3 V) the ON state can be electrically sustained. The roles of donor and acceptor components in the polyimide main chain were elucidated through molecular simulation.

Cortical spreading depression causes and coincides with tissue hypoxia.

Cortical spreading depression (CSD) is a self-propagating wave of cellular depolarization that has been implicated in migraine and in progressive neuronal injury after stroke and head trauma. Using two-photon microscopic NADH imaging and oxygen sensor microelectrodes in live mouse cortex, we find that CSD is linked to severe hypoxia and marked neuronal swelling that can last up to several minutes. Changes in dendritic structures and loss of spines during CSD are comparable to those during anoxic depolarization. Increasing O2 availability shortens the duration of CSD and improves local redox state. Our results indicate that tissue hypoxia associated with CSD is caused by a transient increase in O2 demand exceeding vascular O2 supply.

Enhanced Impact Properties of Hybrid Composites Reinforced by Carbon Fiber and Polyimide Fiber.

A series of hybrid fiber-reinforced composites were prepared with polyimide fiber and carbon fiber as the reinforcement and epoxy resin as the matrix. The influence of stacking sequence on the Charpy impact and flexural properties of the composites as well as the failure modes were studied. The results showed that hybrid fiber-reinforced composites yielded nearly 50% increment in Charpy impact strength compared with the ones reinforced by carbon fiber. The flexural performance was significantly improved compared with those reinforced solely by polyimide fibers and was greatly affected by the stacking sequence. The specimens with compressive sides distributed with carbon fiber possessed higher flexural strength, while those holding a sandwich-like structure with carbon fiber filling between the outer layers displayed a higher flexural modulus.

High-Temperature-Induced Shape Memory Copolyimide.

A series of polyimide (PI) films with a high-temperature-induced shape memory effect and tunable properties were prepared via the facile random copolymerization of 4,4'-oxydianiline (ODA) with 4,4'-(hexafluoroisopropyl)diphthalic anhydride (6FDA) and 4,4'-oxydiphthalic anhydride (ODPA). The trigger temperature can be controlled from 294 to 326 °C by adjusting the ratio of monomers. The effects of monomer rigidity on the chain mobility, physical properties, and shape memory performance of as-prepared copolyimide were systematically investigated. The introduction of ODPA could enhance the mobility of PI macromolecular chains, which made chain entanglement more likely to occur and increased the physical crosslinking density, thereby improving the PI's shape recovery up to 97%. Meanwhile, the existence of 6FDA enabled PI films to set quickly at low temperatures with a shape fixation of 98%. The shape memory cycling characteristics of the polyimide films are also studied, and the relationship between the PI chemical structure and the film properties are further discussed.

Astrocytic Ca2+ signaling evoked by sensory stimulation in vivo.

Although astrocytes are the most abundant cell type in the brain, evidence for their activation during physiological sensory activity is lacking. Here we show that whisker stimulation evokes increases in astrocytic cytosolic calcium (Ca(2+)) within the barrel cortex of adult mice. Increases in astrocytic Ca(2+) were a function of the frequency of stimulation, occurred within several seconds and were inhibited by metabotropic glutamate receptor antagonists. To distinguish between synaptic input and output, local synaptic activity in cortical layer 2 was silenced by iontophoresis of AMPA and NMDA receptor antagonists. The antagonists did not reduce astrocytic Ca(2+) responses despite a marked reduction in excitatory postsynaptic currents in response to whisker stimulation. These findings indicate that astrocytes respond to synaptic input, by means of spillover or ectopic release of glutamate, and that increases in astrocytic Ca(2+) occur independently of postsynaptic excitatory activity.

Astrocyte-mediated control of cerebral blood flow.

Local increase in blood flow during neural activity forms the basis for functional brain imaging, but its mechanism remains poorly defined. Here we show that cortical astrocytes in vivo possess a powerful mechanism for rapid vasodilation. We imaged the activity of astrocytes labeled with the calcium (Ca(2+))-sensitive indicator rhod-2 in somatosensory cortex of adult mice. Photolysis of caged Ca(2+) in astrocytic endfeet ensheathing the vessel wall was associated with an 18% increase in arterial cross-section area that corresponded to a 37% increase in blood flow. Vasodilation occurred with a latency of only 1-2 s, and both indomethacin and the cyclooxygenase-1 inhibitor SC-560 blocked the photolysis-induced hyperemia. These observations implicate astrocytes in the control of local microcirculation and suggest that one of their physiological roles is to mediate vasodilation in response to increased neural activity.

Loss of astrocytic domain organization in the epileptic brain.

Gliosis is a pathological hallmark of posttraumatic epileptic foci, but little is known about these reactive astrocytes beyond their high glial fibrillary acidic protein (GFAP) expression. Using diolistic labeling, we show that cortical astrocytes lost their nonoverlapping domain organization in three mouse models of epilepsy: posttraumatic injury, genetic susceptibility, and systemic kainate exposure. Neighboring astrocytes in epileptic mice showed a 10-fold increase in overlap of processes. Concurrently, spine density was increased on dendrites of excitatory neurons. Suppression of seizures by the common antiepileptic, valproate, reduced the overlap of astrocytic processes. Astrocytic domain organization was also preserved in APP transgenic mice expressing a mutant variant of human amyloid precursor protein despite a marked upregulation of GFAP. Our data suggest that loss of astrocytic domains was not universally associated with gliosis, but restricted to seizure pathologies. Reorganization of astrocytes may, in concert with dendritic sprouting and new synapse formation, form the structural basis for recurrent excitation in the epileptic brain.

The design of a multifunctional separator regulating the lithium ion flux for advanced lithium-ion batteries.

Herein, we design a controllable approach for preparing multifunctional polybenzimidazole porous membranes with superior fire-resistance, excellent thermo-stability, and high wettability. Specifically, the recyclable imidazole is firstly utilized as the eco-friendly template for micropores formation, which is an interesting finding and has tremendous potential for low-cost industrial production. The unique backbone structure of the as-prepared polybenzimidazole porous membrane endows the separator with superb thermal dimensional stability at 300 °C. Most significantly, the inherent flame retardancy of polybenzimidazole can ensure the high security of lithium-ion batteries, and the existence of polar groups of imidazole can regulate the Li+ flux and improve the ionic conductivity of lithium ions. Notably, the cell with a polybenzimidazole porous membrane presents higher capability (131.7 mA h g-1) than that of a commercial Celgard membrane (95.4 mA h g-1) at higher charge-discharge density (5C), and it can work normally at 120 °C. The fascinating comprehensive properties of the polybenzimidazole porous membrane with excellent thermal-stability, satisfying wettability, superb flame retardancy and good electrochemical performance indicate its promising application for high-safety and high-performance lithium-ion batteries.

A Janus nanofiber-based separator for trapping polysulfides and facilitating ion-transport in lithium-sulfur batteries.

Endowing separators with the polysulfide-blocking function is urgently needed for high-performance lithium-sulfur (Li-S) batteries. Thus far, most of the reported research has focused on modifying conventional polyolefin separators but with poor thermal stability and low ionic conductivity. To address these issues, herein we report a Janus separator based on a thermally stable polymeric nanofabric designed with abilities to trap polysulfides and facilitate the transport of Li+ simultaneously. This Janus separator possesses a configuration of a carbon nanofiber (CNF) layer toward the sulfur cathode and the polyimide (PI) nanofabric toward the Li metal anode. It is demonstrated that the conductive CNF layer can effectively anchor and convert the polysulfides; meanwhile, the excellent wettability with liquid electrolytes and the highly porous structure of the PI nanofiber layer significantly promote the Li+-transport. In addition, the Janus separator presents notable advantages in thermal dimensional stability benefiting from the PI nanofabric. As a result, the Li-S battery armed with the Janus separator shows a high initial capacity (1393 mA h g-1 at 0.1 A g-1), stable cycling performance (822 mA h g-1 at 1 A g-1) and high coulombic efficiency of 99.6%.

In Situ Armoring: A Robust, High-Wettability, and Fire-Resistant Hybrid Separator for Advanced and Safe Batteries.

Development of nonflammable separators with excellent properties is in urgent need by next-generation advanced and safe energy storage devices. However, it has been extremely challenging to simultaneously achieve fire resistance, high mechanical strength, good thermomechanical stability, and low ion-transport resistance for polymeric separators. Herein, to address all these needs, we report an in situ formed silica@silica-imbedded polyimide (in situ SiO2@(PI/SiO2)) nanofabric as a new high-performance inorganic-organic hybrid separator. Different from conventional ceramics-modified separators, this in situ SiO2@(PI/SiO2) hybrid separator is realized for the first time via an inverse in situ hydrolysis process. Benefiting from the in situ formed silica nanoshell, the in situ SiO2@(PI/SiO2) hybrid separator shows the highest tensile strength of 42 MPa among all reported nanofiber-based separators, excellent wettability to the electrolyte, good thermomechanical stability at 300 °C, and fire resistance. The LiFePO4 half-cell assembled with this hybrid separator showed a high capacity of 139 mAh·g-1@5C, which is much higher than that of the battery with the pristine PI separator (126.2 mAh·g-1@5C) and Celgard-2400 separator (95.1 mAh·g-1@5C). More importantly, the battery showed excellent cycling stability with no capacity decay over 100 cycles at the high temperature of 120 °C. This study provides a novel method for the fabrication of high-performance and nonflammable polymeric-inorganic hybrid battery separators.