Insight into the Feasibility of Fatty Acyl Chlorides with 10-18 Carbons for the Ball-Milling Synthesis of Thermoplastic Cellulose Esters.

Fatty acid cellulose esters (FACE) are common cellulose-based thermoplastics, and their thermoplasticity is determined by both the contents and the lengths of the side chains. Herein, various FACE were synthesized by the ball-milling esterification of cellulose and fatty acyl chlorides containing 10-18 carbons, and their structures and thermoplasticity were thoroughly studied. The results showed that FACE with high degrees of substitution (DS) and low melting flow temperatures (Tf) were achieved as the chain lengths of the fatty acyl chlorides were reduced. In particular, a cellulose decanoate with a DS of 1.85 and a Tf of 186 °C was achieved by feeding 3 mol of decanoyl chloride per mole anhydroglucose units of cellulose. However, cellulose stearate (DS = 1.53) synthesized by the same protocols cannot melt even at 250 °C. More interestingly, the fatty acyl chlorides with 10 and 12 carbons resulted in FACE with superior toughness (elongation at break up to 94.4%). In contrast, due to their potential crystallization of the fatty acyl groups with 14-18 carbons, the corresponding FACE showed higher tensile strength and Young's modulus than the others. This study provides some theoretical basis for the mechanochemical synthesis of thermoplastic FACE with designated properties.

Investigation of the transport and metabolic patterns of oil-displacing bacterium FY-07-G in the microcosm model using X-CT technology.

AIMS: Microbial enhanced oil recovery (MEOR) is dedicated to enhancing oil recovery by harnessing microbial metabolic activities and their byproducts within reservoir rocks and fluids. Therefore, the investigation of microbial mobility and their extensive distribution within crude oil is of paramount importance in MEOR. While microscale models have been valuable for studying bacterial strain behavior in reservoirs, they are typically limited to 2D representations of porous media, making them inadequate for simulating actual reservoir conditions. Consequently, there is a critical need for 3D models and dependable visualization methods to observe bacterial transport and metabolism within these complex reservoir environments. METHODS AND RESULTS: Bacterial cellulose (bc) is a water-insoluble polysaccharide produced by bacteria that exhibits biocompatibility and biodegradability. It holds significant potential for applications in the field of MEOR as an effective means for selective plugging and spill prevention during oil displacement processes. Conditionally cellulose-producing strain, FY-07-G, with green fluorescent labeling, was engineered for enhanced oil recovery. 3D micro-visualization model was constructed to directly observe the metabolic activities of the target bacterial strain within porous media and to assess the plugging interactions between cellulose and the medium. Additionally, X-ray computed tomography (X-CT) technology was employed for a comprehensive analysis of the transport patterns of the target strain in oil reservoirs with varying permeabilities. The results indicated that FY-07-G, as a microorganism employing biopolymer-based plugging principles to enhance oil recovery, selectively targets and seals regions characterized by lower permeability and smaller pore spaces. CONCLUSIONS: This work provided valuable insights into the transport and metabolic behavior of MEOR strains and tackled the limitation of 2D models in faithfully replicating oil reservoir conditions, offering essential theoretical guidance and insights for the further application of oil-displacing bacterial strains in MEOR processes.

Recent Advances in Multiresponsive Flexible Sensors towards E-skin: A Delicate Design for Versatile Sensing.

Multiresponsive flexile sensors with strain, temperature, humidity, and other sensing abilities serving as real electronic skin (e-skin) have manifested great application potential in flexible electronics, artificial intelligence (AI), and Internet of Things (IoT). Although numerous flexible sensors with sole sensing function have already been reported since the concept of e-skin, that mimics the sensing features of human skin, was proposed about a decade ago, the ones with more sensing capacities as new emergences are urgently demanded. However, highly integrated and highly sensitive flexible sensors with multiresponsive functions are becoming a big thrust for the detection of human body motions, physiological signals (e.g., skin temperature, blood pressure, electrocardiograms (ECG), electromyograms (EMG), sweat, etc.) and environmental stimuli (e.g., light, magnetic field, volatile organic compounds (VOCs)), which are vital to real-time and all-round human health monitoring and management. Herein, this review summarizes the design, manufacturing, and application of multiresponsive flexible sensors and presents the future challenges of fabricating these sensors for the next-generation e-skin and wearable electronics.

Research on Trajectory Tracking Control of Inspection UAV Based on Real-Time Sensor Data.

In power inspection, uncertainties, such as wind gusts in the working environment, affect the trajectory of the inspection UAV (unmanned aerial vehicle), and a sliding mode adaptive robust control algorithm is proposed in this paper to solve this problem. For the nonlinear and under-driven characteristics of the inspection UAV system, a double closed-loop control system which includes a position loop and attitude loop is designed. Lyapunov stability analysis is used to determine whether the designed system could finally achieve asymptotic stability. Sliding-mode PID control and a backstepping control algorithm are applied to analyze the superiority of the control algorithm proposed in this paper. A PX4 based experimental platform system is built and experimental tests were carried out under outdoor environment. The effectiveness and superiority of the control algorithm are proposed in this paper. The experimental results show that the sliding mode PID control can achieve good accuracy with smaller computing costs. For nonlinear interference, the sliding mode adaptive robust control strategy can achieve higher trajectory tracking accuracy.

Interfacial Radiation-Absorbing Hydrogel Film for Efficient Thermal Utilization on Solar Evaporator Surfaces.

Solar water purification is a promising technology with a strong potential for producing fresh water without effluent discharge. For energy-intensive interfacial vapor generation, energy loss to air via heat radiation and convection occurs commonly but is normally ignored, which severely limits the energy efficiency. Therefore, it is necessary to precisely regulate the interfacial thermal energy for interfacial vapor generation. Here, we developed a hierarchically porous radiation-absorbing hydrogel film (hp-RAH) through an in situ gelation strategy and employed this hp-RAH on various existing solar evaporator surfaces. The hydrogel film efficiently absorbs and reutilizes the thermal radiation energy emitted by the photothermal layer and eradicates thermal convection of the photothermal layer into air. In this way, an evaporation efficiency up to 95% is obtained, and the heat radiation and convection losses are reduced from 6.6% to 0.39% under 1 sun. This strategy demonstrates a promising membrane evaporation prototype based on the evaporation surface thermal utilization.

Combining 'grafting to' and 'grafting from' to synthesize comb-like NCC-g-PLA as a macromolecular modifying agent of PLA.

The surface modification of nano particles is very important in nanotechnology. Grafting from (GF) and grafting to (GT) are two main methods to prepare surface modified nanoparticles like nanocellulose crystalline (NCC) grafted with polylactic acid (PLA) chains. In the GF method, the NCC can get high grafting degree but short side chains to improve its compatibility with the polymer matrix. The GT method can help obtain long side chains to increase the chain entanglements but owns low grafting density. To take the advantage of both methods, a mixed modification method combining GT and GF methods was put forward to synthesize comb-like NCC-g-PLA (NP) as a macromolecular modifying agent of PLA. Firstly, GT Method was used to obtain long side-chain NP to improve chain entanglement. Secondly, the GF method was applied to obtain NP-g-PLA (NPL) and NP-g-PDLA (NPD) with additional short side chains to improve its dispersion and compatibility in the PLA matrix. The products showed an enhanced nucleation effect, the degree of crystallinity (Xc) of PLA composites increased almost four times with only 1 wt% NPD or NPL. What's more, the storage modulus and loss modulus of the composite melts also increased with 1 wt% NPL or NPD. The NPD/PLA shows a higher effect than NPL/PLA owning to stronger interaction originated from the stereocomplex (SC) network of PLA matrix with PDLA short chains in NPD.

Tannic acid functionalized graphene hydrogel for organic dye adsorption.

Water purification provides a feasible way to relieve the pressure of water shortage and water pollution which we are facing and adsorption is one of the most effective ways to turn polluted water into clean water. Here, we prepared graphene-tannic acid hydrogel using graphene oxide and tannic acid, a natural green reducer and adsorbent, through one-step hydrothermal method. The composition, structure, and morphology of the compounds were systematically examined. The adsorption of dyes was mainly influenced by the morphology and chemical properties of gel. The addition of tannic acid, a molecule rich in oxygen containing functional groups, changed the surface chemistry of graphene sheets and microstructures of gels, which was beneficial for contaminate adsorption. Compared with reduced graphene oxide hydrogel, the graphene-tannic acid hydrogel showed an outstanding adsorption capacity for organic dye methylene blue, more than 500 mg/g at pH 10 and the maximum adsorption capacity was up to 714 mg/g. After adsorption, ethanol and inorganic acid solution can be used as desorption agent and there was no significant adsorption capacity loss after 5 cycles.

High Efficiency Conversion of Regenerated Cellulose Hydrogel Directly to Functionalized Cellulose Nanoparticles.

This article provides a novel and efficient method of "self-assembly/modification/dispersion" for the preparation of functionalized cellulose nanoparticles (CNPs) based on regenerated cellulose hydrogel (RCH). The process of the preparation of CNPs is simplified greatly, which contributes to broadening the utilization of CNPs. Under the given conditions, cellulose chains self-assemble into nanoparticles, which connect with each other to form strings and walls of nanoparticles inside RCH. Then, RCH acts as the hydrophilic precursor of the preparation of CNPs and is modified by oligo side chains to obtain functionalized RCH with imperfect cellulose II structures. After dispersing the functionalized RCH in dimethyl sulfoxide, individual CNPs are finally isolated from functionalized RCH as a result of the decline of the crystallinity of CNPs. Obtained CNPs possess uniform size and good thermal stability, and also exhibit excellent dispersibility in organic solvents. The particle size of CNPs can be adjusted easily by oligo content and particle size of the self-assembled cellulose nanoparticles in RCH. Prepared CNPs are promising candidates for polymer modification in terms of fillers, and for biomedical fields with respect to drug delivery.

The effect of chain mobility on the coarsening process of co-continuous, immiscible polymer blends under quiescent melt annealing.

Polypropylene (PP) and five kinds of monodisperse polystyrene (PS) with different terminal relaxation times were used to explore the relationship between the mobility of polymer molecular chains and the coarsening process of immiscible polymer blends with a co-continuous morphology under quiescent melt annealing at different temperatures. The terminal relaxation time of all neat PP and PS was determined by a rheological approach to characterize the mobility of molecular chains. A selective dissolution experiment showed that all PP/PS (50/50) blends maintained a co-continuous structure during the whole annealing process. Significant coarsening behaviors were observed for all PP/PS blends under a scanning electron microscope. A linear time dependence of the size of the PS phase was found in all PP/PS blends and the coarsening phenomenon was more obvious with the decrease of the terminal relaxation time of the PS phase because of the increase of the mobility of the polymer molecular chains. A direct relationship between the phase coarsening rate and the terminal relaxation time of the PS phase was found for the first time and it satisfied the equation . According to this equation, the formulae and k ∝ Mw-1 can be derived, which can provide significant information for the control of the phase coarsening process of immiscible polymer blends with a co-continuous morphology.

Influence of HMW tail chains on the structural evolution of HDPE induced by second melt penetration.

It is widely accepted that the role of the high molecular weight (HMW) component is cooperative in shear-induced crystallization, owing to entanglements among long chains. However, this paper demonstrates that the HMW component has a novel effect on structural evolution during the process of multi-melt multi-injection molding (M3IM), organized as follows. First, the appropriate HDPE system with an incremental concentration of HMW tails was established. Second, the crystalline morphologies and orientation behaviors of the M3IM samples were characterized using a combination of scanning electron microscopy (SEM) and two-dimensional small angle X-ray scattering (2D-SAXS), and these suggested that the amount of shish-kebabs was not monotonically promoted with an increasing content of HMW tails but tended to reduce at a certain value. Third, in order to explain this phenomenon, the special temperature and shear profiles of M3IM were depicted subsequently, and finally the mechanism of hierarchical structure formation with the influence of various amounts of HMW tail chains was discussed, based on the classical rheological viewpoint.

Effect of phase coarsening under melt annealing on the electrical performance of polymer composites with a double percolation structure.

The effect of phase coarsening on the evolution of the carbon black (CB) nanoparticle network under quiescent melt annealing and the electrical performance of polypropylene/polystyrene/carbon black (PP/PS/CB) composites with a double percolation structure was investigated. The results showed that when the CB content is low, the coarsening process of PP/PS/CB blends can be divided into two stages. In the first stage, the coarsening rate is fast before the formation of the CB nanoparticle network, and after annealing for a certain time, the evolution of the co-continuous morphology can drive the CB nanoparticles to self-assemble into a complete nanoparticle network. In the second stage, the coarsening rate is slow after the formation of the CB nanoparticle network. When the CB content is high, the CB nanoparticle network can be maintained throughout the whole annealing process, so that the conductivity and morphology of the PP/PS/CB composites are stable. Moreover, the electrical conductivity of the PP/PS/CB composites greatly increases after annealing for a certain time, and a percolation threshold as low as 0.07 vol% can be obtained. These results reveal the relationship between the evolution of the morphology and the conductivity in the conductive polymer composites with a double percolation structure, and provide a more in-depth and comprehensive understanding of the double percolation structure.

Distinct positive temperature coefficient effect of polymer-carbon fiber composites evaluated in terms of polymer absorption on fiber surface.

In this article, the positive temperature coefficient (PTC) effect was studied for high-density polyethylene (HDPE)/carbon fiber (CF) composites. All of the samples showed a significant PTC effect during the heating processes without a negative temperature coefficient (NTC) effect, even at a temperature much higher than the melting point of the polymer matrix. An ever-increasing PTC intensity with increasing thermal cycles was observed in our study that had never been reported in previous research. The absence of a NTC effect resulted from the increased binding force between the matrix and fillers that contributed to the very special structure of CF surface. We incorporated thermal expansion theory and quantum tunneling effects to explain PTC effect. From the SEM micrographs for the HDPE/CF composites before and after the different thermal cycles, we found that the surface of CF was covered with a layer of polymer which resulted in a change in the gap length between CF and HDPE and its distribution. We believed that the gap change induced by polymer absorption on the fiber surface had a great effect on the PTC effect.

Formation of various crystalline structures in a polypropylene/polycarbonate in situ microfibrillar blend during the melt second flow.

A strong shear flow was imposed on the melt of polycarbonate (PC) microfibrils with ß-nucleation agent reinforced isotactic polypropylene (iPP) during the melt second flow process, i.e. gas-assisted injection molding (GAIM). A special shell-core structure was formed in the iPP/PC microfibrils with ß-nucleation agent (PP/PC/ß-NA) composites. A lot of ß-transcrystalline and α-transcrystalline superstructures were observed in the skin and sub-skin regions, whereas ß-spherulite structures were formed in the gas channel region. There is no doubt that the distinct hierarchical structure has great potential to significantly improve the mechanical performance of the composites, and the experimental results verify this. The results of the mechanical performance testing show that the yield strength of the PP/PC/ß-NA composites reached 61.9 MPa, which is 19.7 MPa higher than that of the iPP parts molded by GAIM (G-iPP) (42.2 MPa). The tensile modulus of the PP/PC/ß-NA composites (3.3 GPa) increased by 135%, compared to that of G-iPP (1.4 GPa). The high content of ß-crystals improved the elongation at break of the composites compared to the iPP/PC microfibril (PP/PC) composites; the elongation at break of the PP/PC/ß-NA composites (13%) is over 3 times greater than that of the PP/PC composites (4%).

Strong shear-driven large scale formation of hybrid shish-kebab in carbon nanofiber reinforced polyethylene composites during the melt second flow.

The formation of a hybrid shish-kebab (HSK) structure with different degrees of lamellar orientations was first observed in the solution crystallization of polyethylene (PE) in the presence of carbon nanofibers (CNFs). In this study, PE crystal lamellae were periodically decorated on the surface of CNFs and were aligned approximately perpendicular to the long axes of the CNFs, forming aligned hybrid shish-kebab nanostructures. More importantly, the fascinating structure was directly formed in all regions of the injection molded bars of HDPE/CNF composites, via a gas-assisted injection molding (GAIM), instead of the shell-core structure. In the GAIM process, an intense shear was imposed onto the melt during the melt second flow and drove PE chains to orient along the axes of the CNFs. Then the entropy penalty for PE chains deposited on the CNF surface was drastically decreased. Although the attractive van der Waals interactions were weak, the oriented PE chains could successfully adsorb on the CNF surface due to the decrease of the entropy penalty, therewith the underlayer coating was formed along the axis based on a two-dimensional mode for early nucleation on the CNF surface. Subsequently, subglobules appeared on the ordered structure, which could be regarded as the crystal nucleus. Finally, the oriented PE chains began to epitaxially grow from the subglobules with a folded-chain shape to decrease the polymer surface energy and grew perpendicular to the CNFs long axis, abiding by the "soft epitaxy" crystallization mechanism regardless of strict lattice matching.

Suppression of phase coarsening in immiscible, co-continuous polymer blends under high temperature quiescent annealing.

The properties of polymer blends greatly depend on the morphologies formed during processing, and the thermodynamic non-equilibrium nature of most polymer blends makes it important to maintain the morphology stability to ensure the performance stability of structural materials. Herein, the phase coarsening of co-continuous, immiscible polyamide 6 (PA6)-acrylonitrile-butadiene-styrene (ABS) blends in the melt state was studied and the effect of introduction of nano-silica particles on the stability of the phase morphology was examined. It was found that the PA6-ABS (50/50 w) blend maintained the co-continuous morphology but coarsened severely upon annealing at 230 °C. The coarsening process could be divided into two stages: a fast coarsening process at the initial stage of annealing and a second coarsening process with a relatively slow coarsening rate later. The reduction of the coarsening rate can be explained from the reduction of the global curvature of the interface. With the introduction of nano-silica, the composites also showed two stages of coarsening. However, the coarsening rate was significantly decreased and the phase morphology was stabilized. Rheological measurements indicated that a particle network structure was formed when the concentration of nano-silica particles was beyond 2 wt%. The particle network inhibited the movement of molecular chains and thus suppressed the coarsening process.

Barnacle-inspired and polyphenol-assisted modification of bacterial cellulose-based wound dressings for promoting infectious wound healing.

Bacterial cellulose (BC) is an ideal candidate for wound dressings due to its natural origin, exceptional water-holding capacity, pliability, biocompatibility, and high absorption capability. However, the lack of essential antimicrobial activity limits its biomedical applications. This study reported BC-based wound dressings containing silk fibroin protein (SF), offering the potential for biomimetic properties, and (-)-epigallocatechin-3-gallate (EGCG) for polyphenol-assisted surface modification to promote infectious wound healing. Glycerol was used as the carbon source to promote the formation of an adhesive layer by facilitating the ß-sheet folding of SF, and different concentrations of EGCG were employed to interact with SF through strong hydrogen bonding facilitated by the polyphenolic groups. The functionalized membrane exhibited outstanding water-holding capacity, swelling ratio, and degradation properties, along with enhanced hydrophilicity, adhesiveness, and a remarkable free radical scavenging ability. Both in vitro and in vivo experiments confirmed its potent bacteriostatic activity. The composite membrane displayed excellent biocompatibility, including cellular and hemocompatibility. Importantly, it effectively promoted wound healing in murine back infections. These findings suggest the significant feasibility of the innovative modification approach, and that functionalized membranes have great potential as wound-dressing materials for infection management in future clinical applications.

Enhancing Wound Healing and Bactericidal Efficacy: A Hydrogel Membrane of Bacterial Cellulose and Sanxan Gel for Accelerating the Healing of Infected Wounds.

Bacterial cellulose is an extracellular polysaccharide produced by microorganisms, offering advantages such as high water-holding capacity, flexibility, and biocompatibility. However, its lack of bactericidal activity hampers its wide application. Usnic acid, a secondary metabolite derived from lichens of the Usnea genus, is recognized for its antibacterial and anti-biofilm efficiency, coupled with anti-inflammatory properties. Its water insolubility presents challenges for wide utilization and stable release. Sanxan gel, a novel polysaccharide, exhibits exceptional freeze-thaw stability, suspension properties, and high elasticity, rendering it effective as a suspending agent to improve the bioavailability of water-insoluble drugs. In this study, a hydrogel membrane is designed by combining bacterial cellulose and usnic acid suspended in sanxan gel through a simple in situ microorganism fermentation. The obtained membranes demonstrate excellent ability for sustained drug release, strong eradication capability against tested bacteria in both in vitro and in vivo experiments, effective inhibition of biofilm formation, and excellent hemocompatibility and cytocompatibility. Additionally, the composite membranes promote wound healing with reduced inflammation and bacterial infection in a full-thickness wound infection model in mice. This study provides innovative insights and strategies for the development of functional dressings for infected wounds in future clinical applications.

Multifunctional bacterial cellulose-bentonite@polyethylenimine composite membranes for enhanced water treatment: Sustainable dyes and metal ions adsorption and antibacterial properties.

Developing multifunctional materials for water treatment remains a significant challenge. Bacterial cellulose (BC) holds immense potential as an adsorbent with high pollutant-binding capacity, hydrophilicity, and biosafety. In this study, N-acetylglucosamine was used as a carbon source to ferment BC, incorporating amide bonds in situ. Bentonite, renowned for its adsorption properties, was added to the culture medium, resulting in BC-bentonite composite membranes via a one-step fermentation process. Polyethyleneimine (PEI) was crosslinked with amide bonds on the membrane via glutaraldehyde through Schiff base reactions to enhance the performance of the composite membrane. The obtained membrane exhibited increased hydrophilicity, enhanced active adsorption sites, and enlarged specific surface area. It not only physically adsorbed contaminants through its unique structure but also effectively captured dye molecules (Congo red, Methylene blue, Malachite green) via electrostatic interactions. Additionally, it formed stable complexes with metal ions (Cd²âº, Pb²âº, Cu²âº) through coordination and effectively adsorbed their mixtures. Moreover, the composite membrane demonstrated the broad-spectrum antibacterial activity, effectively inhibiting the growth of tested bacteria. This study introduces an innovative method for fabricating composite membranes as adsorbents for complex water pollutants, showing significant potential for long-term wastewater treatment of organic dyes, heavy metal ions, and pathogens.

Optimization of the Thermally Conductive Low-k Polymer Dielectrics Based on Multisource Free-Volume Effects.

Polymers/polymer matrix composites possessing low dielectric constants (low-k polymer dielectrics) contribute to the advance of electronics, for instance, microprocessor chips, mobile phone antennas, and data communication terminals. However, the intrinsic long-chain structural characteristic results in poor thermal conductivities, which draw heat accumulation and undermine the outstanding low-k performance of polymers. Herein, multisource free-volume effects that combine two novel kinds of extra free volume with the known in-cage free volume of polyhedral oligomeric silsesquioxanes (POSSs) are discussed to reduce the capacity for dielectric constant reduction. The multisource free-volume effects of POSSs are associated with the thermal conductive network formed by the hexagonal boron nitride (BN) in the polymer matrix. The results show a decent balance between low-k performance (dielectric constant is 2.08 at 1 MHz and 1.98 at 10 GHz) and thermal conductivity (0.555 W m-1 K-1, 4.91 times the matrix). The results provide a new idea to maximize the free-volume effects of POSSs to optimize dielectric properties together with other desired performances for the dielectrics.

Correction: Shi et al. Effect of Final Rolling Temperature on Microstructures and Mechanical Properties of AZ31 Alloy Sheets Prepared by Equal Channel Angular Rolling and Continuous Bending. Materials 2020, 13, 3346.

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