Designing CoHCF@FeHCF Core-Shell Structures to Enhance the Rate Performance and Cycling Stability of Sodium-Ion Batteries.

Prussian blue analogs are well suited for sodium-ion battery cathode materials due to their cheap cost and high theoretical specific capacity. Nax CoFe(CN)6 (CoHCF), one of the PBAs, has poor rate performance and cycling stability, while Nax FeFe(CN)6 (FeHCF) has better rate and cycling performance. The CoHCF@FeHCF core-shell structure is designed with CoHCF as the core material and FeHCF as the shell material to enhance the electrochemical properties. The successfully prepared core-shell structure leads to a significant improvement in the rate performance and cycling stability of the composite compared to the unmodified CoHCF. The composite sample of core-shell structure has a specific capacity of 54.8 mAh g-1 at high magnification of 20 C (1 C = 170 mA g-1 ). In terms of cycle stability, it has a capacity retention rate of 84.1% for 100 cycles at 1 C, and a capacity retention rate of 82.7% for 200 cycles at 5 C. Kinetic analysis shows that the composite sample with the core-shell structure has fast kinetic characteristics, and the surface capacitance occupation ratio and sodium-ion diffusion coefficient are higher than those of the unmodified CoHCF.

Anisotropic structure deformation of ß-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine under high pressure: vibration spectra calculation and resolution based on AIMD simulation.

The phase transition of the ß-HMX crystal has been widely studied under high pressure, but the microscopic transition mechanism is not sufficiently understood. In this article, we perform a series of ab initio molecular dynamics simulations focusing on structure deformation and the corresponding vibration spectra resolution of ß-HMX at 0-40 GPa. Several typical pressure-induced phase transition processes are confirmed by analyzing the chemical bond, dihedral angle, charge transfer, and IR and Raman spectra. The corresponding relationship between molecular structure and spectral signal is constructed through the partial spectra calculations of special functional groups within the HMX molecule. The anisotropic effects of different groups on the initial structural phase transition are uncovered. The equatorial C-N and axial N-N bonds have the largest compression ratio as pressure increases, which is the intrinsic factor for the initiation of structure transformation. The C-N molecular ring plays an important role in the entire phase transition process. In addition, the phase transition of ß â†’ ζ is also closely related to the deformation of NO2, while that of ζ → ε is induced by the axial N-NO2 group. Regarding the higher-pressure phase transition, the synergetic effect of N-NO2, CH2 groups, and molecular rings becomes more considerable.

The Structure Properties of Carbon Materials Formed in 2,4,6-Triamino-1,3,5-Trinitrobenzene Detonation: A Theoretical Insight for Nucleation of Diamond-like Carbon.

The structure and properties of nano-carbon materials formed in explosives detonation are always a challenge, not only for the designing and manufacturing of these materials but also for clearly understanding the detonation performance of explosives. Herein, we study the dynamic evolution process of condensed-phase carbon involved in 2,4,6-Triamino-1,3,5-trinitrobenzene (TATB) detonation using the quantum-based molecular dynamics method. Various carbon structures such as, graphene-like, diamond-like, and "diaphite", are obtained under different pressures. The transition from a C sp2- to a sp3-hybrid, driven by the conversion of a hexatomic to a non-hexatomic ring, is detected under high pressure. A tightly bound nucleation mechanism for diamond-like carbon dominated by a graphene-like carbon layer is uncovered. The graphene-like layer is readily constructed at the early stage, which would connect with surrounding carbon atoms or fragments to form the tetrahedral structure, with a high fraction of sp3-hybridized carbon. After that, the deformed carbon layers further coalesce with each other by bonding between carbon atoms within the five-member ring, to form the diamond-like nucleus. The complex "diaphite" configuration is detected during the diamond-like carbon nucleation, which illustrates that the nucleation and growth of detonation nano-diamond would accompany the intergrowth of graphene-like layers.

Anisotropic Reaction Properties for Different HMX/HTPB Composites: A Theoretical Study of Shock Decomposition.

Plastic-bonded explosives (PBXs) consisting of explosive grains and a polymer binder are commonly synthesized to improve mechanical properties and reduce sensitivity, but their intrinsic chemical behaviors while subjected to stress are not sufficiently understood yet. Here, we construct three composites of ß-HMX bonded with the HTPB binder to investigate the reaction characteristics under shock loading using the quantum-based molecular dynamics method. Six typical interactions between HMX and HTPB molecules are detected when the system is subjected to pressure. Although the initial electron structure is modified by the impurity states from HTPB, the metallization process for HMX does not significantly change. The shock decompositions of HMX/HTPB along the (100) and (010) surface are initiated by molecular ring dissociation and hydrogen transfer. The initial oxidations of C and H within HTPB possess advantages. As for the (001) surface, the dissociation is started with alkyl dehydrogenation oxidation, and a stronger hydrogen transfer from HTPB to HMX is detected during the following process. Furthermore, considerable fragment aggregation is observed, which mainly derives from the formation of new C-C and C-N bonds under high pressure. The effect of cluster evolution on the progression of the following reaction is further studied by analyzing the bonded structure and displacement rate.

Electrode Materials of Cobaltous Fluoride for Supercapacitor and Electrocatalysis Applications.

Herein, CoF2 was synthesized by a solvothermal method. The characterization results of the phase and morphology of the sample show that it was successfully synthesized and its morphology is composed of micron particles with uneven size and shape. The electrochemical test results of SCs in different electrolytes show that CoF2 has electrochemical activity only in alkaline electrolytes. Notably, the electrochemical behavior of CoF2 in LiOH solution is different from that in other alkaline solutions in that charge-discharge curve has a quasi-isosceles triangle shape and the CV curve has no obvious redox peak. That is, it has pseudocapacitance behavior in LiOH. Furthermore, CoF2 as catalyst for HER requires an overpotential of only 168 mV to obtain current density of 10 mA cm-2 and a Tafel slope of 116 mV dec-1 in 1 M KOH solution. This research provides a novel way to explore excellent performance electrode materials for SC and HER.

Enhanced Effect of an External Electric Field on NH3BH3 Dehydrogenation: an AIMD Study for Thermolysis.

How to improve the dehydrogenation properties of ammonia borane (AB, NH3BH3) is always a challenge for its practical application in hydrogen storage. In this study, we reveal the enhanced effect of an external electric field (E ext) on AB dehydrogenation by means of the ab initio molecular dynamics method. The molecular rotation induced by an electrostatic force can facilitate the formation of the H-N···B-H framework, which would aggregate into poly-BN species and further suppress the generation of the volatile byproducts. Meanwhile, the dihydrogen bond (N-Hδ+···Î´-H-B) is favorably formed under E ext, and the interaction between relevant H atoms is enhanced, leading to a faster H2 liberation. Correspondingly, the apparent activation energy for AB dissociation is greatly reduced from 18.42 to around 15 kcal·mol-1 with the application of an electric field, while that for H2 formation decreases from 20.4 to about 16 kcal·mol-1. In the whole process, the cleavage of the B-H bond is more favorable than that of the N-H bond, no matter whether the application of E ext. Our results give a deep insight into a positive effect of an electric field on AB dehydrogenation, which would provide an important inspiration for hydrogen storage in industry applications.

Realizing high-performance and low-cost lithium-ion capacitor by regulating kinetic matching between ternary nickel cobalt phosphate microspheres anode with ultralong-life and super-rate performance and watermelon peel biomass-derived carbon cathode.

Lithium-ion capacitors (LICs) are emerging as one of the most advanced energy storage devices by combining the virtues of both supercapacitors (SCs) and lithium-ion batteries (LIBs). However, the kinetic and capacity mismatch between anode and cathode is the main obstacle to wide applications of LICs. Therefore, the effective strategy of constructing a high-performance LIC is to improve the rate and cycle performance of the anode and the specific capacity of the cathode. Herein, the nickel cobalt phosphate (NiCoP) microspheres anode is demonstrated with robust structural integrity, high electrical conductivity, and fast kinetic feature. Simultaneously, the watermelon-peel biomass-derived carbon (WPBC) cathode is demonstrated a sustainable synthesis strategy with high specific capacity. As expected, the NiCoP exhibits high specific capacities (567 mAh g-1 at 0.1 A g-1), superior rate performance (300 mAh g-1 at 1A g-1), and excellent cycle stability (58 mAh g-1 at 5 A g-1 after 15,000 cycles). The WPBC possesses a high specific surface area (SSA) of 3303.6 m2 g-1 and a high specific capacity of 226 mAh g-1 at 0.1 A g-1. Encouragingly, the NiCoP//WPBC-6 LIC device can deliver high energy density (ED) of 127.4 ± 3.3 and 67 ± 3.8Wh kg-1 at power density (PD) of 190 and 18240 W kg-1 (76.4% capacity retention after 7000 cycles), respectively.

Modification of ultra-micropore dominated carbon by O/N-containing functional groups grafted for enhanced supercapacitor performances.

In our study, a simple method was employed to prepare ultra-micropore-dominated carbon materials with controllable pore size. A mass of heteroatoms was introduced by surface functional group grafting, resulting in enhanced electrochemical performance: the maximum specific capacity of 327.5 F g-1 was obtained at 0.5 A g-1 in 6 M KOH, while that of un-grafted original ultra-microporous carbon was only 188 F g-1, with long-term cycle stability (90.5% of the initial after 10 000 cycles), and excellent rate performance (over 82% at the current density from 0.5 A g-1 to 10 A g-1). The mechanism behind the improved performance was due to the presence of the introduced functional groups that improved the surface wettability of the material and provided additional redox active sites. Their synergistic effects promoted the enhanced electrochemical performance of the ultra-microporous carbon. This study provides a basis for the study of the energy storage mechanism of ultra-microporous carbon and the grafted modification of carbon materials with heteroatom-containing functional groups.

Crystal Phase-Controlled Synthesis of the CoP@Co2P Heterostructure with 3D Nanowire Networks for High-Performance Li-Ion Capacitor Applications.

The paramount focus in the construction of lithium-ion capacitors (LICs) is the development of anode materials with high reversible capacity and fast kinetics to overcome the mismatch of kinetics and capacity between the anode and cathode. Herein, a strategy is presented for the controllable synthesis of cobalt-based phosphides with various morphologies by adjusting the time of the phosphidation process, including 3D hierarchical needle-stacked diabolo-shaped CoP nanorods, 3D hierarchical stick-stacked diabolo-shaped Co2P nanorods, and 3D hierarchical heterostructure CoP@Co2P nanorods. 3D hierarchical nanostructures and a highly conductive project to accommodate volume changes are rational designs to achieve a robust construction, effective electron-ion transportation, and rapid kinetics characteristics, thus leading to excellent cycling stability and rate performance. Owing to these merits, the 3D hierarchical CoP, Co2P, and CoP@Co2P nanorods demonstrate prominent specific capacities of 573, 609, and 621 mA h g-1 at 0.1 A g-1 over 300 cycles, respectively. In addition, a high-performance CoP@Co2P//AC LIC is successfully constructed, which can achieve high energy densities of 166.2 and 36 W h kg-1 at power densities of 175 and 17524 W kg-1 (83.7% capacity retention after 12000 cycles). Therefore, the controllable synthesis of various simultaneously constructed crystalline phases and morphologies can be used to fabricate other advanced energy storage devices.

[Analgesic effect of intrathecal injection of Herpes simplex virus type I amplicon vector-mediated human preproenkephalin gene on chronic neuropathic pain: experiment with rats].

OBJECTIVE: To investigate the antinociceptive effect of intrathecal (IT) injection of Herpes simplex virus type I (HSV-1) amplicon vector-mediated HPPE on chronic neuropathic pain. METHODS: 45 Sprague-Dawley rats underwent chronic constriction. Injury (CCI) of unilateral sciatic nerve and then were randomly divided into 3 equal groups: CCI + normal saline group, undergoing insertion of microspinal catheter into the subarachnoid space at the lumber region and intrathecal delivery of NS, CCI + pHSVIRES-LacZ (SHPZ) group undergoing intrathecal delivery of and recombinant HSV-I amplicon vector pHSVIRES-HPPE-LacZ containing human pre-proenkephalin (HPPE) gene, and CCI + blank vector (SHZ) group receiving pHSV-HPPE-LacZ. Another 15 rats underwent sham operation to be used as control group. One week after IT administration 9 rats from each group were killed with their lumber segments of spinal cord removed to detect the expression of LacZ by X-gal staining, HPPE mRNA expression by RT-PCR, and L-enkephalin (L-EK) content by radioimmunoassay. Paw mechanical withdrawal threshold (PMWT) and paw withdrawal thermal latency (PWTL) were measured before CCI (baseline) and 3 days after CCI and then once a week for 5 weeks after IT administration. RESULTS: After IT administration of SHPZ expression of HPPE mRNA was detected in the spinal cord. One week after the IT injection the L-EK level of the SHPZ group was (748 +/- 185 ng/L), significantly higher than those of the Sham operation, NS, and SHZ groups [(452 +/- 89), (453 +/- 92), and (451 +/- 99) ng/L respectively, all P < 0.05]. The PWMT and PWTL levels of the SHPZ group were significantly increased since 1 week after the IT administration in comparison with the baseline values and those of the other 3 groups (all P < 0.05), and these effects peaked in the third week and then lasted to the fifth week. However, the threshold to mechanical and thermal stimuli was not affected by intrathecal delivery of vehicle or SHZ compared with the threshold before intrathecal delivery. CONCLUSIONS: Intrathecal administration SHPZ can produce significant analgesic effects on chronic neuropathic pain in rats.

[Intrathecal injection of ketamine and clonidine for chronic neuropathic pain model in rats].

OBJECTIVE: To observe the effect of intrathecal injection of ketamine and clonidine for chronic constriction injury (CCI) in rats. METHODS: Thirty-two SD male rats weighing 220-280 g were anesthetized with intraperitoneal chloral hydrate 300 mg/kg. A catheter was implanted in the subarachnoid space at the lumbal region and CCI rat models were made successfully. On the 4th day after the surgery, the rats were randomly divided into 4 group: a control group,injecting 0.9%NS 20 microL intrathecally; a ketamine group, injecting ketamine 1 mg/kg(20 microL) intrathecally; a clonidine group (CL), injecting clonidine 20 microg/kg (20 microL) intrathecally; a combined ketamine and clonidine group, injecting ketamine 0.5mg/kg and clonidine 10 g/kg (20 microL) intrathecally, once a day for 1 week. BME-410A Plantar Analgesia Tester was used to measured pain threshold before the administration and 30 min after the administration. The rats were killed after the test was finished. And then we detected the nitric oxide synthase (NOS) activity and the NO production in the spinal cord. RESULTS: The combined injection of ketamine (0.5mg/kg)and clonidine(10 g/kg) produced significantly more potent analgesia than the injection of ketamine (1 mg/ kg) or clonidine (20 microg/ kg)alone. The NOS activity and the production of NO in the combined injection group were significantly lower than those of the single injection group (P<0.05). The weight of rats post-administration increased obviously in the 4 groups (P<0.05). CONCLUSION: The combined injection of ketamine and clonidine can produce synergistic ab-irritation without obvious side effects.

Dynamic Responses and Initial Decomposition under Shock Loading: A DFTB Calculation Combined with MSST Method for ß-HMX with Molecular Vacancy.

Despite extensive efforts on studying the decomposition mechanism of HMX under extreme condition, an intrinsic understanding of mechanical and chemical response processes, inducing the initial chemical reaction, is not yet achieved. In this work, the microscopic dynamic response and initial decomposition of ß-HMX with (1 0 0) surface and molecular vacancy under shock condition, were explored by means of the self-consistent-charge density-functional tight-binding method (SCC-DFTB) in conjunction with multiscale shock technique (MSST). The evolutions of various bond lengths and charge transfers were analyzed to explore and understand the initial reaction mechanism of HMX. Our results discovered that the C-N bond close to major axes had less compression sensitivity and higher stretch activity. The charge was transferred mainly from the N-NO2 group along the minor axes and H atom to C atom during the early compression process. The first reaction of HMX primarily initiated with the fission of the molecular ring at the site of the C-N bond close to major axes. Further breaking of the molecular ring enhanced intermolecular interactions and promoted the cleavage of C-H and N-NO2 bonds. More significantly, the dynamic response behavior clearly depended on the angle between chemical bond and shock direction.

Prognostic value of Annexin A3 in human colorectal cancer and its correlation with hypoxia-inducible factor-1α

Annexins are a family of intracellular proteins that bind membrane phospholipids in a Ca2+ concentration-dependent manner and are involved in cellular processes, including apoptosis, proliferation and differentiation. Hypoxia-inducible factor-1α (HIF-1α) has been hypothesized to be critical in the angiogenesis of tumors. We hypothesized that Annexin A3, a member of the Annexin family, and HIF-1α may be associated with each other in colorectal cancer. The expression of Annexin A3 and HIF-1α in 60 colorectal cancer tissues was assessed by immunohistochemistry to statistically analyze the association between the clinicopathological features and survival of these cases. In the present study, 65 and 47% of colorectal cancer specimens were found to show Annexin A3 and HIF-1α immunoreactivity, respectively. Annexin A3 expression was found to significantly correlate with tumor size and Dukes' stage (all P<0.05). Furthermore, Annexin A3 and HIF-1α protein expression exhibited a similar pattern in these samples, and their expression was found to correlate with poor survival in colorectal cancer patients. The results of the current study indicated for the first time that the increased expression of Annexin A3 in colorectal cancer correlates significantly with tumor growth and poor prognosis. Furthermore, Annexin A3 has been found to correlate with HIF-1α expression. These observations highlight an improved understanding of the carcinogenesis of colorectal cancer.

Intrathecal infusion of pyrrolidine dithiocarbamate for the prevention and reversal of neuropathic pain in rats using a sciatic chronic constriction injury model.

BACKGROUND AND OBJECTIVES: Recent studies have suggested that nuclear factor κB (NF-κB) may play a role in mediating nerve injury-induced neuropathic pain. Here, we examined the effects of intrathecal pyrrolidine dithiocarbamate (PDTC), a NF-κB inhibitor, on the development of neuropathic pain, spinal microglial activation, and CX3CR1 expression induced by sciatic chronic constriction injury (CCI) model in rats. METHODS: Under chloral hydrate anesthesia, male Sprague-Dawley rats (300-350 g) fitted with intrathecal catheters underwent either sciatic CCI or sham surgery. Intrathecal saline or PDTC (100 or 1000 pmol/d) was infused 1 day before or 3 days after CCI (n = 8). The rat hind-paw withdrawal threshold to mechanical stimuli and withdrawal latency to radiant heat were determined before surgery and from days 1 to 7 after CCI. Spinal microglial activation was evaluated with OX-42 immunoreactivity, and spinal CX3CR1 expression was assessed by Western blotting. RESULTS: Chronic constriction injury induced mechanical allodynia and thermal hyperalgesia and microglial activation as demonstrated by OX-42 expression. Whereas it had no apparent effect on spinal cord histology, intrathecal administration of PDTC prevented the development of the mechanical and thermal hyperalgesia and inhibited nerve injury-induced microglial activation and spinal CX3CR1 expression. CONCLUSIONS: In this study, we have shown the protective effect of intrathecal PDTC on the development of nociceptive behaviors induced by CCI in rats. The activation of NF-κB pathway may contribute to spinal microglial activation and CX3CR1 up-regulation.