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An enzyme catalyzed strategy for the synthesis of a chiral hydrazine from 3-cyclopentyl-3-oxopropanenitrile 5 and hydrazine hydrate 2 is presented. An imine reductase (IRED) from Streptosporangium roseum was identified to catalyze the reaction between 3-cyclopentyl-3-oxopropanenitrile 5 and hydrazine hydrate 2 to produce trace amounts of ( R )-3-cyclopentyl-3-hydrazineylpropanenitrile 4 . We employed a 2-fold approach to optimize the catalytic performance of this enzyme. First, a transition state analogue (TSA) model was constructed to illuminate the enzyme-substrate interactions. Subsequently, the Enzyme_design and Funclib methods were utilized to predict mutants for experimental evaluation. Through three rounds of site-directed mutagenesis, site saturation mutagenesis, and combinatorial mutagenesis, we obtained mutant M6 with a yield of 98% and an enantiomeric excess (ee) of 99%. This study presents an effective method for constructing a hydrazine derivative via IRED-catalyzed reductive amination of ketone and hydrazine. Furthermore, it provides a general approach for constructing suitable enzymes, starting from nonreactive enzymes and gradually enhancing their catalytic activity through active site modifications.

Nanofibers based on high-performance polymers are much highlighted in recent studies toward advanced lithium-ion batteries. Herein, we demonstrate one scalable poly(ethylene oxide) (PEO)-assisted solution blow spinning strategy for the preparation of heterocyclic aramid (HA) nanofibers of poly( p -phenylene-benzimidazole-terephthalamide). The incorporation of PEO is essential to improve the spinnability of the HA solution achieved directly through the low-temperature-solution copolymerization process. Additionally, the flexible PEO with a strong H-bonding affinity is also utilized as the molecular zipper to adjust the pore size of the nanofiber membrane during the post-treatment process. The obtained membrane combines the good wettability of PEO to the liquid electrolytes, with outstanding mechanical strength, modulus, toughness, and environmental resistance of HA. The nonwoven separator membranes with a porosity of 83.6% exhibited excellent comprehensive performance, which could be seen not only on the high tensile strength (68.2 MPa), modulus (3.0 GPa), and toughness but also on the high thermal stability ( T d > 405 °C) and flame retardancy, as well as the high electrolyte uptake (302.4%). The ion conductivity of the porous separators reached 0.83 mS/cm, with the bulk resistance dropping to 1/4 of the reference polypropylene separator. In the assembly of the Li/LiFePO 4 half battery, the HA separators displayed improved discharge specific capacity and high retention in both rate capability and cycling tests, providing the potential industrial preparation for advanced lithium-ion batteries.

Lightweight, flexible, and noncombustible thermo-acoustic insulating (TAI) materials have great potential in vehicles, cold-chain transportation, and aerospace engineering, where weight and space savings are critical. However, the TAI capabilities of many commodities are hindered by the lack of diverse and reasonable resonant cavities with broadband and highly efficient acoustic responsiveness. This study demonstrates a layer-by-layer freeze-casting method for superelastic cellular aerogel construction from varied nanofibers and ice particulates with widely distributed resonant cavities from 0.5 to 300 μm. The method enabled the cumulative freezing of the nanofiber solution from one side to the other side, resulting in vertical pore channels with random holes across the entire freezing distance. The formed cellular networks of stable hinged ternary nanofiber membranes, functionalized as ultrathin nanofiber drums, exhibit strong resonances and efficiently dissipate sound waves in a broad frequency range. A high noise reduction coefficient of 0.65 at a frequency range of 63-6300 Hz and a low thermal conductivity of 0.026 W m -1 K -1 at room temperature was obtained. This work presents the bottom-up fabrication of high-performance TAI aerogels that are beneficial for practical energy-saving devices and buildings and broadband acoustic absorption applications.

The enhancement of the heat-dissipation property of polymer-based composites is of great practical interest in modern electronics. Recently, the construction of a three-dimensional (3D) thermal pathway network structure for composites has become an attractive way. However, for most reported high thermal conductive composites, excellent properties are achieved at a high filler loading and the building of a 3D network structure usually requires complex steps, which greatly restrict the large-scale preparation and application of high thermal conductive polymer-based materials. Herein, utilizing the framework-forming characteristic of polymerization-induced para -aramid nanofibers (PANF) and the high thermal conductivity of hexagonal boron nitride nanosheets (BNNS), a 3D-laminated PANF-supported BNNS aerogel was successfully prepared via a simple vacuum-assisted self-stacking method, which could be used as a thermal conductive skeleton for epoxy resin (EP). The obtained PANF-BNNS/EP nanocomposite exhibits a high thermal conductivity of 3.66 W m -1 K -1 at only 13.2 vol % BNNS loading. The effectiveness of the heat conduction path was proved by finite element analysis. The PANF-BNNS/EP nanocomposite shows outstanding practical thermal management capability, excellent thermal stability, low dielectric constant, and dielectric loss, making it a reliable material for electronic packaging applications. This work also offers a potential and promotable strategy for the easy manufacture of 3D anisotropic high-efficiency thermal conductive network structures.

Aerogel has been much highlighted as an emerging lightweight thermal insulation material, but problems such as fragility, low strength, liquid permeability, and lack of flexibility greatly limit further applications. In this work, a facile aramid-coating-on-aramid (ACoA) method is demonstrated to fabricate all-aramid aerogel composite films for thermal insulation. The method started from the bottom-up synthesis of polymerization-induced para -aramid nanofibers (PANF), which were easily transformed into aerogel films through the vacuum-assisted filtration followed by the freeze-drying techniques. Then, the heterocyclic aramid (HA) solution prepared through the low-temperature-solution polycondensation was used as the coating to be applied onto the PANF aerogel films, and composite films of HA/PANF aerogel were simply achieved with HA contributed to the dense and continuous surface layer. The bulk HA film is of superior mechanical and thermal properties to those of the PANF film. Moreover, reliable interfacial interlocking structures were developed beneath the outermost surface via the interpenetration of the infiltrated HA with PANF network. The comprehensive result was the 15 times enhanced tensile strength, 33 times enhanced fracture toughness, the high thermal decomposition temperature, and the additional flexibility for the foldable films of HA/PANF aerogel. The sealing of the surface macropores greatly suppressed the surface chalking and high water absorption. However, the survival of the tiny pores inside the composite maintained the low enough level of the thermal conductivity to provide effective protections against high temperature not only in air but also under wet or even liquid conditions, suggesting the broader applications for thermal insulation.

Aerogel has been widely known as a low-density and highly porous material and is closely connected with the complex processing methods, such as freeze-drying or supercritical drying. In this work, using the polymerization-induced aramid nanofiber (PANF) as a building block, we put forward a modified freezing-drying method for the high-efficiency preparation of all- para -aromatic-amide aerogels. In the preparation process, PANF hydrogel is first frozen at -18 °C and then dried at 20-150 °C for the formation of PANF aerogel. The PANF framework formed during the freezing process is crucial for the formation of the PANF aerogel. Moreover, the space-occupying effect of ice crystals is also helpful for the formation of the macroscopic pore structure in the aerogel. Aerogels with large size or well-controlled shape could be successfully obtained by this method. Through the variation of PANF concentration in the hydrogel and drying temperature, aerogels with different densities (20-185 mg/cm 3 ) could be achieved, and the lowest density is reached at 150 °C, with the PANF concentration of 0.7%. The low-density PANF aerogels show high specific compressive strengths and low thermal conductivities, which are comparable to those resulting from the freeze-drying or supercritical drying method. Furthermore, the shrinkage phenomenon in the drying process could be skillfully utilized for the preparation of PANF aerogel-coated objects. The PANF aerogels could be applied as a thermal insulating material or shock absorption material in practical applications.

Fe 3 O 4 @CNF anode material for Li-ion batteries (LIBs) was designed and fabricated using lyotropic cellulose acetate as the carbon nanofiber (CNF) phase and Fe(acac) 3 as the Fe 3 O 4 phase through the electrospinning approach. Because the CNFs could retard the change of Fe 3 O 4 volume during the electrochemical cycling and improve the electrical conductivity and the introduction of Fe 3 O 4 could offer a larger specific surface area and more mesopores to promote electrolyte penetration and Li + diffusion, the Fe 3 O 4 @CNFs electrode showed high reversible capacities (RCs) of 773.6 and 596.5 mAh g -1 after 300 cycles and capacity residuals of 98.0 and 99.0% at high current densities 1 and 2 A g -1 , respectively. This simple method to fabricate Fe 3 O 4 @CNFs composite as anode material can be widely applied to fabricate metal oxides and bio-carbon composite nanofibers for high-performance energy storage materials.

We developed a facile one-pot method to synthesize multishelled hollow mesoporous SiO 2 microspheres (HMSs) with controllable interior structures including one-shell, double-shell, and yolk-shell. Single reagent formaldehyde could fully control the morphology of HMSs, in that formaldehyde was crucial to the SiO 2 precursor's hydrolysis rate and the template pore size.

The manipulation of nanobuilding blocks into a 3D macroscopic monolith with ordered hierarchical structures has been much desired for broad and large-scale practical applications of nanoarchitectures. In this paper, we demonstrate a fully bottom-up strategy for the preparation of aramid aerogel monoliths. The process starts from the synthesis of poly( p -phenylene terephthalamide) (PPTA) through the polycondensation of p -phenylenediamine and terephthaloyl chloride, with the assistance of a nonreactive dispersing agent (polyethylene glycol dimethyl ether), which helps the dispersal of the as-synthesized PPTA in an aqueous medium for the formation of p -aramid nanofibers (ANF). Then the vacuum-assisted self-assembly (Vas) technique is skillfully connected with the ice-templated directional solidification (I) technique, and the combined VasI method successfully tailors the self-assembly of ANF to transform the 1D nanofibers into a 3D aerogel monolith with a specific long-range aligned, lasagna-like, multilaminated internal structure. The study of the aerogel microstructure revealed the dependence of the lamina orientation on the direction of the freezing front of ice crystals. This direction should be parallel to the deposition plane of the Vas process if a long-range aligned lamellar structure is desired. The anisotropy of the multilaminated aerogel was proven by the different results in the radial and axial directions in the compression and thermal conductivity tests. As a kind of organic aerogel, the ANF monolith has typical low density, high porosity, and low thermal conductivity. Additionally, the ANF monolith exhibits high compressive stress and excellent thermal stability. Considering its high performance and facile preparation process, potential applications of the ANF aerogel monolith can be expected.

The direct synthesis of polymer microspheres modified by aramid nanofibers (ANFs) is an interesting challenge. This work describes a simple aqueous process to prepare polystyrene (PS)/ANF composite microspheres, where the specific ANF network was "dressed" on PS. ANF was derived from the copolymerization of terephthaloyl chloride, p-phenylene diamine, and methoxypolyethylene glycol and could be dispersed in water stably. We applied the as-synthesized ANF as a Pickering emulsifier in the o/w emulsion of styrene monomer. Radical polymerization was subsequently initiated in the Pickering emulsion system. The combination of ANF with polymer spheres was revealed by scanning electron microscopy (SEM) and thermal gravity analysis. The role of ANF in the monomer emulsion as well as in the polymerization was studied through SEM, optical microscopy, optical stability analyzer, and pulse nuclear magnetic resonance combined with the polymerization kinetic analysis. Moreover, we investigated the effects of other synthesis parameters, such as monomer type, monomer content, pH value, and salt concentration.

Polystyrene-methacrylic core-shell nanospheres, self-assembled into face-centered-cube-like colloidal crystals with their (001) planes parallel to the substrate, have been transformed into ordered pore structures by a toluene treatment. Detailed analysis by transmission electron microscopy reveals that the morphological transformation is preceded by an internal neck formation due to selective fusion of the polystyrene-rich core material, at the contacts between the nanoparticles, followed by the selective dissolution of the polystyrene-rich cores. We have demonstrated the importance of local symmetry and compactness of the nanospheres assembly in determining the nature of the neck formation and the existence of multiscale ordered pore structures in the square facing colloidal crystals. The pseudo layer-by-layer nature of the selective dissolution of square arranged nanosphere multilayers is responsible for the observed three-dimensional pore structures.

Millimeter-sized films of (100) facing face-centered crystals (fcc) of colloidal nanoparticles have been fabricated by self-assembly on silicon substrates and studied by both optical and scanning electron microscopy. The top surface layer sometimes also reconstructs to form a 1 x n (n varies from 2-7) superstructure. Such (100) oriented regions of the colloidal film are apt to concentrate near the edge of the substrate, and changing the width of the substrate could control the areas of the (100)-oriented domains. The formation of the square packing surface pattern is related to the shape of the meniscus at the edges of the substrate, where the particles suffer additional shear force and higher evaporation, which can be used to control the location and size of the square arrangement of nanoparticles.