Amorphous anion-rich titanium polysulfides for aluminum-ion batteries

The strong electrostatic interaction between Al3+ and close-packed crystalline structures, and the single-electron transfer ability of traditional cationic redox cathodes, pose challenged for the development of high-performance rechargeable aluminum batteries. Here, to break the confinement of fixed lattice spacing on the diffusion and storage of Al-ion, we developed a previously unexplored family of amorphous anion-rich titanium polysulfides (a-TiSx, x = 2, 3, and 4) (AATPs) with a high concentration of defects and a large number of anionic redox centers. The AATP cathodes, especially a-TiS4, achieved a high reversible capacity of 206 mAh/g with a long duration of 1000 cycles. Further, the spectroscopy and molecular dynamics simulations revealed that sulfur anions in the AATP cathodes act as the main redox centers to reach local electroneutrality. Simultaneously, titanium cations serve as the supporting frameworks, undergoing the evolution of coordination numbers in the local structure.

Quantifying vanadium-vacancy clusters in V2O3 towards ultra-long cycling aqueous zinc-ion battery

Defect engineering has been attracted widespread attention for promoting the stability of the electrodes. However, accurately quantifying and defining the effect of defects is extremely difficult. Here, the Rietveld analysis with combined neutron powder diffraction (NPD) and X-ray powder diffraction (XRD) patterns reveal vanadium defect (Vd) clusters in the V2O3 lattice up to 5.7% in aqueous zinc-ion batteries (ZIBs), further confirmed by positron annihilation spectroscopy (PAS) and synchrotron-based X-ray analysis. Benefitting from the Vd clusters, the V2O3 cathode achieves excellent cycle life with 81% capacity retention at 5.0 A g-1 after 30,000 cycles that is the most superb stable cathode for aqueous ZIBs at this current density. Besides, the density functional theory (DFT) calculations strongly indicate that the Vd clusters not only provide permanent sites for Zn2+ anchormen to enhance the integrity of V2O3 after the first discharging process, but also make Zn2+ de/intercalation in complex oxide, contributing collectively and effectively reducing the strong electrostatic interaction between host multivalent ions, resulting in the remarkable storage performance of Zn2+. This work highlights accurately quantifying and identifying the significant effect of defects for designing cathodes with ultra-long cycle life in future intelligent devices.

Nanocomposite-based dual enzyme system for broad-spectrum scavenging of reactive oxygen species

A broad-spectrum reactive oxygen species (ROS)-scavenging hybrid material (CASCADE) was developed by sequential adsorption of heparin (HEP) and poly(L-lysine) (PLL) polyelectrolytes together with superoxide dismutase (SOD) and horseradish peroxidase (HRP) antioxidant enzymes on layered double hydroxide (LDH) nanoclay support. The synthetic conditions were optimized so that CASCADE possessed remarkable structural (no enzyme leakage) and colloidal (excellent resistance against salt-induced aggregation) stability. The obtained composite was active in decomposition of both superoxide radical anions and hydrogen peroxide in biochemical assays revealing that the strong electrostatic interaction with the functionalized support led to high enzyme loadings, nevertheless, it did not interfere with the native enzyme conformation. In vitro tests demonstrated that ROS generated in human cervical adenocarcinoma cells were successfully consumed by the hybrid material. The cellular uptake was not accompanied with any toxicity effects, which makes the developed CASCADE a promising candidate for treatment of oxidative stress-related diseases.

Changes in Optical Properties upon Dye–Clay Interaction: Experimental Evaluation and Applications

The development of hybrid materials with unique optical properties has been a challenge for the creation of high-performance composites. The improved photophysical and photochemical properties observed when fluorophores interact with clay minerals, as well as the accessibility and easy handling of such natural materials, make these nanocomposites attractive for designing novel optical hybrid materials. Here, we present a method of promoting this interaction by conjugating dyes with chitosan. The fluorescent properties of conjugated dye–montmorillonite (MMT) hybrids were similar to those of free dye–MMT hybrids. Moreover, we analyzed the relationship between the changes in optical properties of the dye interacting with clay and its structure and defined the physical and chemical mechanisms that take place upon dye–MMT interactions leading to the optical changes. Conjugation to chitosan additionally ensures stable adsorption on clay nanoplatelets due to the strong electrostatic interaction between chitosan and clay. This work thus provides a method to facilitate the design of solid-state hybrid nanomaterials relevant for potential applications in bioimaging, sensing and optical purposes.

A kinetic dissection of the fast and superprocessive kinesin-3 KIF1A reveals a predominant one-head-bound state during its chemomechanical cycle

The kinesin-3 family contains the fastest and most processive motors of the three neuronal transport kinesin families, yet the sequence of states and rates of kinetic transitions that comprise the chemomechanical cycle and give rise to their unique properties are poorly understood. We used stopped-flow fluorescence spectroscopy and single-molecule motility assays to delineate the chemomechanical cycle of the kinesin-3, KIF1A. Our bacterially expressed KIF1A construct, dimerized via a kinesin-1 coiled-coil, exhibits fast velocity and superprocessivity behavior similar to WT KIF1A. We established that the KIF1A forward step is triggered by hydrolysis of ATP and not by ATP binding, meaning that KIF1A follows the same chemomechanical cycle as established for kinesin-1 and -2. The ATP-triggered half-site release rate of KIF1A was similar to the stepping rate, indicating that during stepping, rear-head detachment is an order of magnitude faster than in kinesin-1 and kinesin-2. Thus, KIF1A spends the majority of its hydrolysis cycle in a one-head-bound state. Both the ADP off-rate and the ATP on-rate at physiological ATP concentration were fast, eliminating these steps as possible rate-limiting transitions. Based on the measured run length and the relatively slow off-rate in ADP, we conclude that attachment of the tethered head is the rate-limiting transition in the KIF1A stepping cycle. Thus, KIF1A's activity can be explained by a fast rear-head detachment rate, a rate-limiting step of tethered-head attachment that follows ATP hydrolysis, and a relatively strong electrostatic interaction with the microtubule in the weakly bound post-hydrolysis state.

The fast and superprocessive KIF1A predominately resides in a vulnerable one-head-bound state during its chemomechanical cycle

ABSTRACTKinesin-3 are the fastest and most processive motors of the three neuronal transport kinesin families, yet the sequence of states and rates of kinetic transitions that comprise the chemomechanical cycle are poorly understood. We used stopped-flow fluorescence spectroscopy and single-molecule motility assays to delineate the chemomechanical cycle of the kinesin-3, KIF1A. Our bacterially expressed KIF1A construct, dimerized via a kinesin-1 coiled-coil, exhibits fast velocity and superprocessivity behavior similar to wild-type KIF1A. We established that the KIF1A forward step is triggered by hydrolysis of ATP and not by ATP binding, meaning that KIF1A follows the same chemomechanical cycle as established for kinesin-1 and-2. The ATP-triggered half-site release rate of KIF1A was similar to the stepping rate, indicating that during stepping, rear-head detachment is an order of magnitude faster than in kinesin-1 and kinesin-2. Thus, KIF1A spends the majority of its hydrolysis cycle in a one-head-bound state. Both the ADP off-rate and the ATP on-rate at physiological ATP concentration were fast, eliminating these steps as possible rate limiting transitions. Based on the measured run length and the relatively slow off-rate in ADP, we conclude that attachment of the tethered head is the rate limiting transition in the KIF1A stepping cycle. The fast speed, superprocessivity and load sensitivity of KIF1A can be explained by a fast rear head detachment rate, a rate-limiting step of tethered head attachment that follows ATP hydrolysis, and a relatively strong electrostatic interaction with the microtubule in the weakly-bound post-hydrolysis state.

Chitosan Stabilized Silver Nanoparticles for the Electrochemical Detection of Lipopolysaccharide: A Facile Biosensing Approach for Gram-Negative Bacteria

Negatively charged lipopolysaccharide (LPS), a major endotoxin and component of the outer membrane of several Gram-negative bacteria, provides a useful biomarker for the indirect detection of these pathogens. For instance, Escherichia coli (E. coli) is a pathogenic bacterium that causes infections in almost all age groups, and has been implicated in food and water contamination. Current diagnostic and detection methods tend to be labor-intensive or expensive, necessitating the need for an easy, sensitive, rapid, and low-cost method. We report on the synthesis and use of positively charged chitosan stabilized silver nanoparticles (Chi-AgNPs) as a sensitive electrochemical nanobiosensor for the detection of LPS. Chi-AgNPs were synthesized through a facile, single step protocol, and characterized for size, charge, and morphology. Glassy carbon electrodes modified with Chi-AgNPs resulted in an enhancement of signal in the presence of both LPS and E. coli. Detection was accomplished over a large concentration range (several orders of magnitude) of 0.001–100 ng/mL and 10–107 CFU/mL. The biosensors can reliably detect LPS and E. coli at very low concentrations. Chi-AgNPs have potential as low cost, sensitive nanobiosensors for Gram-negative bacteria due to strong electrostatic interaction with LPS present in their outer membranes.

Using Annealing Treatment on Fabrication Ionic Liquid-Based PVDF Films

In this study, a simple method to obtain pure β-phase directly from the melt process is proposed. A series of PVDF and ionic liquid (IL) was prepared by a solvent casting method with appropriate associated with the subsequent annealing treatment. IL plays a role of filler, which can create strong electrostatic interaction with PVDF matrix and directly induce β-phase crystallization on the PVDF during the melt. PVDF film sample is immersed in hot water for annealing treatment at different temperatures (25 °C to 70 °C). We found that annealing in high temperatures especially can not only increase more IL inserted into the amorphous region of polymer matrix to make more phase transformation, but also accelerate IL removal. Characteristics and performance of the PVDF films were investigated by use of FTIR, XRD, SEM, and AFM. Piezoelectric coefficient d33 as well as d31, degree of crystallinity, and sensitivity are measured in experiment to verify the performance of PVDF film.

Aligned fluorinated single-walled carbon nanotubes as a transmission channel towards attenuation of broadband electromagnetic waves

Highly fluorinated single-walled carbon nanotubes tend to be oriented under stress due to strong electrostatic interaction allowing directional propagation and then effective attenuation of electromagnetic waves by pristine single-walled carbon nanotube networks.

Heparin sodium-selective ‘on–off’ and lysine-selective ‘off–on’ fluorescence switching of cadmium telluride quantum dots and their analytical applications

The fluorescence quenching of CdTe QDs could be induced by heparin sodium via hydrogen bonding, which was then recovered by lysine through a strong electrostatic interaction.