ZIFs-Derived Hollow Nanostructures via a Strong/Weak Coetching Strategy for Long-Life Rechargeable Zn-Air Batteries.

Recently, zeolitic imidazolate frameworks (ZIFs) composites have emerged as promising precursors for synthesizing hollow-structured N-doped carbon-based noble-metal materials with diverse structures and compositions. Here, a strong/weak competitive coordination strategy is presented for synthesizing high-performance electrocatalysts with hollow features. During the competitive coordination process, the cubic zeolitic-imidazole framework-8 (Cube-8)@ZIF-67 with core-shell structures are transformed into Cube-8@ZIF-67@PF/POM with yolk-shell nanostructures employing phosphomolybdic acid (POM) and potassium ferricyanide (PF) as the strong chelator and the weak chelator, respectively. After calcination, the hollow Mo/Fe/Co@NC catalyst exhibits superior performance in both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Interestingly, the Mo/Fe/Co@NC catalyst exhibits efficient electrocatalytic performance for Zn-air batteries (ZABs), with a high power density (≈150 mW cm-2) and superior cycling life (≈500 h) compared to commercial platinum/carbon (Pt/C) and ruthenium dioxide (RuO2) mixture benchmarks catalysts. In addition, the density functional theory further proves that after the introduction of Mo and Fe atoms, the adsorption energy with the adsorption intermediates is weakened by adjusting the d-band center, thus weakening the reaction barrier and promoting the reaction kinetics of OER. Undoubtedly, this study presents novel insights into the fabrication of ZIFs-derived hollow structure bifunctional oxygen electrocatalysts for clean-energy diverse applications.

A Novel Framed Slotted Aloha Medium Access Control Protocol Based on Capture Effect in Vehicular Ad Hoc Networks.

The capture effect is a frequently observed phenomenon in vehicular ad hoc networks (VANETs) communication. When conflicts arise during time slot access, failure to access does not necessarily occur; instead, successful access may still be achieved. The capture effect can enhance the likelihood of multiple access and improve communication efficiency. The security of VANETs communication is undoubtedly the primary concern. One crucial approach to enhance security involves the design of an efficient and reliable medium access control (MAC) protocol. Taking into account both aspects, we propose a novel framed slotted Aloha (FSA) MAC protocol model. Firstly, we derive the closed-form expression for the capture probability in the Rician fading channel in this paper. Subsequently, we analyze how the number of vehicles and time slots influence the success probability of vehicle access channels as well as examine the impact of the capture effect on this success probability. Then, under constraints regarding vehicle access channel success probability, we derive optimal values for slot numbers, access times, and transmission power while proposing a comprehensive implementation method to ensure high access channel success probabilities. We verify both theoretical derivations and proposed methods through simulation experiments.

Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization.

The development of photo-responsive ferroelectrics whose polarization may be remotely controlled by optical means is of fundamental importance for basic research and technological applications. Herein, we report the design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)5(NO)] (1) (DMA = dimethylammonium, PIP = piperidinium) with potential phototunable polarization via a dual-organic-cation molecular design strategy. Compared to the parent non-ferroelectric (MA)2[Fe(CN)5(NO)] (MA = methylammonium) material with a phase transition at 207 K, the introduction of larger dual organic cations both lowers the crystal symmetry affording robust ferroelectricity and increases the energy barrier of molecular motions, endowing 1 with a large polarization of up to 7.6 µC cm-2 and a high Curie temperature (Tc) of 316 K. Infrared spectroscopy shows that the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. Specifically, the ground state with the N-bound nitrosyl ligand conformation can be reversibly switched to both the metastable state I (MSI) with isonitrosyl conformation and the metastable state II (MSII) with side-on nitrosyl conformation. Quantum chemistry calculations suggest that the photoisomerization significantly changes the dipole moment of the [Fe(CN)5(NO)]2- anion, thus leading to three ferroelectric states with different values of macroscopic polarization. Such optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization open up a new and attractive route to optically controllable macroscopic polarization.

Characterization and genomic analysis of a novel bacteriophage BUCT_49532 lysing Klebsiella pneumoniae.

Bacteriophages are a type of virus widely distributed in nature that demonstrates a remarkable aptitude for selectively recognizing and infecting bacteria. In particular, Klebsiella pneumoniae is acknowledged as a clinical pathogen responsible for nosocomial infections and frequently develops multidrug resistance. Considering the increasing prevalence of antibiotic-resistant bacteria, bacteriophages have emerged as a compelling alternative therapeutic approach. In this study, a novel phage named BUCT_49532 was isolated from sewage using K. pneumoniae K1119 as the host. Electron microscopy revealed that BUCT_49532 belongs to the Caudoviricetes class. Further analysis through whole genome sequencing demonstrated that BUCT_49532 is a Jedunavirus comprised of linear double-stranded DNA with a length of 49,532 bp. Comparative genomics analysis based on average nucleotide identity (ANI) values revealed that BUCT_49532 should be identified as a novel species. Characterized by a good safety profile, high environmental stability, and strong lytic performance, phage BUCT_49532 presents an interesting case for consideration. Although its host range is relatively narrow, its application potential can be expanded by utilizing phage cocktails, making it a promising candidate for biocontrol approaches.

Adsorption-reduction coupling mechanism and reductive species during efficient florfenicol removal by modified biochar supported sulfidized nanoscale zerovalent iron.

Sulfidized nanoscale zerovalent iron (S-nZVI) was a promising material for degrading halogenated contaminants, but the easy aggregation limits its application for in-situ groundwater remediation. Hence, S-nZVI was decorated onto modified biochar (mBC) to obtain better dispersity and reactivity with florfenicol (FF), a widely used antibiotic. Uniform dispersion of S-nZVI particles were achieved on the mBC with plentiful oxygen-containing functional groups and negative surface charge. Thus, the removal rate of FF by S-nZVI@mBC was 2.5 and 3.1 times higher than that by S-nZVI and S-nZVI@BC, respectively. Adsorption and dechlorination of FF showed synergistic effect under appropriate mBC addition (e.g., C/Fe mass ratio = 1:3, 1:1), probably due to the enrichment of FF facilitates its reduction. In contrast, the contact between FF and S-nZVI could be hindered under more mBC addition, significantly decrease the reduction rate of FF and the reduction capacity of per unit Fe0. In addition, sulfur dose altered the surface species of surface Fe and S, and removal rates of FF correlated well with surface reductive species, i.e., FeS (r = 0.90, p < 0.05) and Fe0 (r = 0.98, p < 0.01). These mechanistic insights indicate the importance of rational design for biochar supported S-nZVI, which can lead to more efficient FF degradation.

Capture-Aware Dense Tag Identification Using RFID Systems in Vehicular Networks.

Passive radio-frequency identification (RFID) systems have been widely applied in different fields, including vehicle access control, industrial production, and logistics tracking, due to their ability to improve work quality and management efficiency at a low cost. However, in an intersection situation where tags are densely distributed with vehicle gathering, the wireless channel becomes extremely complex, and the readers on the roadside may only decode the information from the strongest tag due to the capture effect, resulting in tag misses and considerably reducing the performance of tag identification. Therefore, it is crucial to design an efficient and reliable tag-identification algorithm in order to obtain information from vehicle and cargo tags under adverse traffic conditions, ensuring the successful application of RFID technology. In this paper, we first establish a Nakagami-m distributed channel capture model for RFID systems and provide an expression for the capture probability, where each channel is modeled as any relevant Nakagami-m distribution. Secondly, an advanced capture-aware tag-estimation scheme is proposed. Finally, extensive Monte Carlo simulations show that the proposed algorithm has strong adaptability to circumstances for capturing under-fading channels and outperforms the existing algorithms in terms of complexity and reliability of tag identification.

Low-Cost, High-Strength Cellulose-based Quasi-Solid Polymer Electrolyte for Solid-State Lithium-Metal Batteries.

Solid-state lithium-metal batteries are considered as the next generation of high-energy-density batteries. However, their solid electrolytes suffer from low ionic conductivity, poor interface performance, and high production costs, restricting their commercial application. Herein, a low-cost cellulose acetate-based quasi-solid composite polymer electrolyte (C-CLA QPE) was developed with a high Li+ transference number ( t L i + ${{t}_{{{\rm L}{\rm i}}^{+}}}$ ) of 0.85 and excellent interface stability. The prepared LiFePO4 (LFP)|C-CLA QPE|Li batteries exhibited excellent cycle performance with a capacity retention of 97.7 % after 1200 cycles at 1 C and 25 °C. The experimental results and Density Function Theory (DFT) simulation revealed that the partially esterified side groups in the CLA matrix contribute to the migration of Li+ and enhance electrochemical stability. This work provides a promising strategy for fabricating cost-effective, stable polymer electrolytes for solid-state lithium batteries.

An Exceptional Thermally Induced Four-State Nonlinear Optical Switch Arising from Stepwise Molecular Dynamic Changes in a New Hybrid Salt.

Switching materials in channels of nonlinear optics (NLOs) are of particular interest in NLO material science. Numerous crystalline NLO switches based on structural phase transition have emerged, but most of them reveal a single-step switch between two different second-harmonic-generation (SHG) states, and only very rare cases involve three or more SHG states. Herein, we report a new organic-inorganic hybrid salt, (Me3 NNH2 )2 [CdI4 ], which is an unprecedented case of a reversible three-step NLO switch between SHG-silent, -medium, -low, and -high states, with high contrasts of 25.5/4.3/9.2 in a temperature range of 213-303 K. By using the combined techniques of variable-temperature X-ray single-crystal structural analyses, dielectric constants, solid-state 13 C nuclear magnetic resonance spectroscopy, and Hirshfeld surface analyses, we disclose that this four-state switchable SHG behavior is highly associated with the stepwise-changed molecular dynamics of the polar organic cations. This finding demonstrates well the complexity of molecular dynamics in simple hybrid salts and their potential in designing new advanced multistep switching materials.

Photoresponsive Organic-Inorganic Hybrid Ferroelectric Designed at the Molecular Level.

Molecular ferroelectrics are becoming an important area of research due to their ability to form a variety of structures exhibiting the desired properties. However, the precise control over the assembly of molecular building blocks for the design and synthesis of photoresponsive molecular ferroelectrics remains a considerable challenge. Here, we report a new hybrid high-temperature ferroelectric, (Me2NH2)[NaFe(CN)5(NO)], by judiciously assembling inorganic photochromic nitroprusside anion, as the framework building block, and polar organic cation Me2NH2+, as the dipole-moment carrier, into the crystal lattice. Ferroelectricity arises through the synergetic ordering of Me2NH2+ below 408 K. Piezoresponse force microscopy witnessed the presence of 180° ferroelectric domains and evidenced polarization switching by repeatedly applying an external electric field. Irradiation of the N-bound nitrosyl ligand (ground state) leads to two different conformations: isonitrosyl O-bound (metastable state I) and side-on nitrosyl conformation (metastable state II). Such photoisomerization realized in solid-state molecular ferroelectrics allows for the photoswitching between the ferroelectric ground state and the metastable state. These results pave the way for new design approaches toward developing next-generation photostimulated ferroelectric materials at the molecular level.

Lipase-Catalyzed Reactive Extrusion: Copolymerization of ε-Caprolactone and ω-Pentadecalactone.

This study assesses the use of immobilized lipase catalyst N435 during reactive extrusion (REX) versus magnetically stirred bulk and solution reaction conditions for the copolymerization of ε-caprolactone with ω-pentadecalactone (CL/PDL 1:1 molar). N435-catalyzed REX for reaction times from 1 to 3 h results in total %-monomer conversion, Mn , and D values increase from 92.7% to 98.8%, 36.1 to 51.3 kDa, and 1.85 to 1.96, respectively. Diad fraction analysis by quantitative 13 C NMR reveals that, after just 1 h, rapid N435-catalyzed transesterification reactions occur that give random copolyesters. In contrast, for bulk polymerization with magnetic stirring in round bottom flasks, reaction times from 1 to 3 h result in the following: Mn  increases from 12.4 to 25.6 kDa, D decreases from 2.98 to 1.87, and the randomness index increases from 0.74 and 0.86 as PDL*-PDL diads are dominant. These results highlight that REX avoids problems associated with internal batch mixing that are encountered in bulk polymerizations. In sharp contrast to a previous study of 1:1 molar PDL/δ-valerolactone (VL) copolymerizations by N435-catalyzed REX, VL %-conversion increases to just 40.1% in 1 h whereas CL reaches 94.7%.

Effects of environmental factors on the removal of heavy metals by sulfide-modified nanoscale zerovalent iron.

Sulfide-modified nanoscale zerovalent iron (S-nZVI) has excellent reducing performance for heavy metals in water. The influence of environmental factors on the reactivity can be used to explore the practical feasibility of S-nZVI and analyze the reaction mechanism in depth. This study compared the removal effect and mechanism of Cu2+ and Ni2+ by nanoscale zerovalent iron (nZVI), S-nZVI, and carboxymethyl cellulose-modified nanoscale zerovalent iron (CMC-nZVI). The results show that the pseudo-first-order kinetic constant of Cu2+ removal by nZVI, S-nZVI, and CMC-nZVI was 1.384, 1.919, and 2.890 min-1, respectively, and the rate of Ni2+ removal was 0.304, 0.931, and 0.360 min-1, respectively. The removal mechanism of S-nZVI was similar to that of nZVI and CMC-nZVI. Specifically, Cu2+ was predominantly removed by reduction, while Ni2+ removal included adsorption and reduction. Environmental factors had a specific inhibitory effect on the removal of Cu2+ but had a negligible impact on Ni2+. The condition of low pH, the presence of Cl- and humic acid (HA) promoted the corrosion consumption of Fe0, in which H+ directly corroded Fe0 at low pH. At the same time, Cl- and HA inhibited the adsorption or binding of heavy metal ions on the particle surface, thereby reducing the electron transfer and utilization efficiency. The passivation of NO3- reduced the anaerobic corrosion of the material in water but suppressed the release of electrons, thereby reducing the reduction efficiency of the three types of materials. The anaerobic corrosion of S-nZVI was less affected by environmental factors, and it can still maintain more than 80% of the electronic utilization efficiency under different environmental factors, which illustrates that S-nZVI has broad prospects for practical applications in heavy metal polluted water.

Coatings super-repellent to ultralow surface tension liquids.

High-performance coatings that durably and fully repel liquids are of interest for fundamental research and practical applications. Such coatings should allow for droplet beading, roll off and bouncing, which is difficult to achieve for ultralow surface tension liquids. Here we report a bottom-up approach to prepare super-repellent coatings using a mixture of fluorosilanes and cyanoacrylate. On application to surfaces, the coatings assemble into thin films of locally multi-re-entrant hierarchical structures with very low surface energies. The resulting materials are super-repellent to solvents, acids and bases, polymer solutions and ultralow surface tension liquids, characterized by ultrahigh liquid contact angles (>150°) and negligible roll-off angles (~0°). Furthermore, the coatings are transparent, durable and demonstrate universal liquid bouncing, tailored responsiveness and anti-freezing properties, and are thus a promising alternative to existing synthetic super-repellent coatings.

A Molecular Perovskite with Switchable Coordination Bonds for High-Temperature Multiaxial Ferroelectrics.

The underlying phase transitions of ferroelectric mechanisms in molecular crystals are mainly limited to order-disorder and displacive types that are not involved in breaking of the chemical bonds. Here, we show that the bond-switching transition under ambient pressure is designable in molecular crystals, and demonstrate how to utilize the weaker and switchable coordination bonds in a novel molecular perovskite, [(CH3)3NOH]2[KFe(CN)6] (TMC-1), to afford a scarce multiaxial ferroelectrics with a high Curie temperature of 402 K and 24 equivalent ferroelectric directions (more than BaTiO3). The high-quality thin films of TMC-1 can be easily fabricated by a simple solution process, and to reveal perfect ferroelectric properties at both macroscopic and microscopic scales, suggesting TMC-1 as a promising candidate for applications in next-generation flexible electronics. The presented molecular assembly strategy, together with the achieved bond-switching ferroelectric mechanism, opens a new avenue for designing advanced ferroelectric materials.

3D Graphene Frameworks/Co3 O4 Composites Electrode for High-Performance Supercapacitor and Enzymeless Glucose Detection.

3D graphene frameworks/Co3 O4 composites are produced by the thermal explosion method, in which the generation of Co3 O4 nanoparticles, reduction of graphene oxide, and creation of 3D frameworks are simultaneously completed. The process prevents the agglomeration of Co3 O4 particles effectively, resulting in monodispersed Co3 O4 nanoparticles scattered on the 3D graphene frameworks evenly. The prepared 3D graphene frameworks/Co3 O4 composites used as electrodes for supercapacitor display a definite improvement on electrochemical performance with high specific capacitance (≈1765 F g-1 at a current density of 1 A g-1 ), good rate performance (≈1266 F g-1 at a current density of 20 A g-1 ), and excellent stability (≈93% maintenance of specific capacitance at a constant current density of 10 A g-1 after 5000 cycles). In addition, the composites are also employed as nonenzymatic sensors for the electrochemical detection of glucose, which exhibit high sensitivity (122.16 µA mM -1  cm-2 ) and noteworthy lower detection limit (157 × 10-9 M, S/N = 3). Therefore, the authors expect that the 3D graphene frameworks/Co3 O4 composites described here would possess potential applications as the electrode materials in supercapacitors and nonenzymatic detection of glucose.

Zeolite CAN and AFI-Type Zeolitic Imidazolate Frameworks with Large 12-Membered Ring Pore Openings Synthesized Using Bulky Amides as Structure-Directing Agents.

Using bulky amides as the structure-directing agents (SDAs) is an alternative synthetic strategy for the exploration of crystalline large pore (≥12-membered ring) zeolitic imidazolate frameworks (ZIFs). Specifically, by using the bulky amides, dibutylformamide (DBF) and dipropylformamide (DPF) as solvent and imidazole (Im) as a ligand, two ZIFs mimicking the CAN and AlPO-5 (AFI) zeotypes with 12-membered ring (MR) pore openings were synthesized, and denoted as CAN-[Zn(Im)2] and AFI-[Zn(Im)2], respectively. These two materials are the first known examples of Zn(Im)2 polymorphs with 12-MR pores and AFI-[Zn(Im)2] has the largest pore apertures reported to date for ZIF materials. The concept that the bulky amides used were not simply acting as the solvent, but were in fact acting as SDAs or templates during the synthesis of the large pore ZIFs, was suggested by the closeness of the geometrical fit between the guest DBF and the can cages (composite building units) of the CAN-[Zn(Im)2].

Quantitative Monitoring of Hypoxia-Induced Intracellular Acidification in Lung Tumor Cells and Tissues Using Activatable Surface-Enhanced Raman Scattering Nanoprobes.

Hypoxia is considered to contribute to pathophysiology in various cells and tissues, and a clear understanding about the relationship between hypoxia and intracellular acidification will help to elucidate the complex mechanism of glycolysis under hypoxia. However, current studies are mainly focused on overexpression of intracellular reductases accelerated by hypoxia, and the investigations focusing on the relationship between hypoxic degree and intracellular acidification remain to be explored. For this vacuity, we report herein a new activatable nanoprobe for sensing pH change under different degrees of hypoxia by surface-enhanced Raman spectroscopy (SERS). The monitoring was based on the SERS spectra changes of 4-nitrothiophenol (4-NTP)-functionalized gold nanorods (AuNR@4-NTP) resulting from the nitroreductase (NTR)-triggered reduction under hypoxic conditions while the as-generated 4-aminothiophenol (4-ATP) is a pH-sensitive molecule. This unique property can ensure the SERS monitoring of intracellular acidification in living cells and tissues under hypoxic conditions. Dynamic pH analysis indicated that the pH decreased from 7.1 to 6.5 as a function of different degrees of hypoxia (from 15 to 1%) due to excessive glycolytic activity triggered by hypoxia. Given the known advantages of SERS sensing, these findings hold promise in studies of pathophysiological pathways involving hypoxia.

Enantiomerically Pure Chiral {Cu(II)32}-Based 2D-Layered Frameworks: From the Asymmetric Octacopper(II) Subcomponents to 3D Hierarchical Supramolecular Structures.

Two new chiral copper(II) coordination polymers comprising octacopper(II) subcomponents were synthesized through investigation of the interplay among tartrate ligands, guanidinium cations, and metals. Our analysis confirms that these compounds are enantiomers exhibiting 3D hierarchical supramolecular structures that are constituted by 2D sublayers and sustained by noncovalent bonding interactions.

An Anionic Heptacopper(II) Oxo-Cluster {Cu(II)7} with an S = 7/2 Ground State.

An anionic heptacopper(II) oxo-cluster {Cu7} was obtained from a simple reaction in aqueous solution without heating. In a similar reaction, another cage compound {Sb12} with an encapsulated {Cu2} core was produced, implying the structural versatility of copper(II)-oxide assemblies constructed from potassium antimonyl tartrate as the ligand in aqueous solution. The ferromagnetic S = 7/2 ground state of {Cu7} is confirmed by magnetization measurements.

Plastic Crystals with Polar Halochromate Anion: Thermosensitive Dielectrics Based upon Plastic Transition and Dipole Rotation.

Plastic crystals functioning with rotatable components offer new opportunities in areas such as modern optoelectronic materials. Here, by taking advantage of controllable rotation of the polar component within the ion-pair plastic-crystal system, we present two such crystals, namely, (Et4N)(CrO3X) (X = Cl or Br), which are unusual examples exhibiting two-staged thermosensitive dielectric responses above room temperature. The frequency-dependent response in the first stage is due to the structural phase transitions, whereas that in the second stage is induced by dynamic rotation of the polar halochromate anions in their NaCl-type plastic-crystal phases. The intrinsic mechanisms were also explicated by molecular dynamics simulations, providing a direct insight into the dynamic characteristics of these two compounds. These studies show that ionic plastic crystals functioning with polar groups are an attractive candidate as sensitive thermoresponsive dielectric materials.

Responsiveness and Release Characteristic of Semi-IPN Hydrogels Consisting of Nano-Sized Clay Crosslinked Poly(Dimethylaminoethyl Methacrylate) and Linear Carboxymethyl Chitosan.

PH and temperature double responsive semi-IPN hydrogels consisting of poly(dimethylaminoethyl methacrylate) (PDMAEMA) network crosslinked by nano-sized inorganic clay and linear carboxymethyl chitosan (CMCS) were synthesized by in situ, free radical polymerization in aqueous solution. The effect of the mass and carboxymethyl substitution of CMCS on the responsiveness, swelling/deswelling and drug release characteristic of gels were investigated. Comparing to the gels without CMCS, the resulting gels (named as C-NC gels) showed similar LCST and temperature response behavior. However, with the increase of added CMCS, the swelling ratio of gels decreased considerably around the isoelectric point (IEP) of CMCS, while increased in both strong acidic and alkaline condition. The deswelling rate was improved significantly when the content of CMCS is high. In drug load and release test by using theophylline as target, the C-NC gels exhibited an excellent load ability and controlled-release in simulated human intestinal and stomachic condition. Additionally, all properties of gels were affected by the DS of added CMCS due to the different ratio and interaction of negative and positive ions in gels.