Addition of konjac glucomannan improves spraying efficiency on fruits and vegetables: Effect of surface hydrophilicity and molecular weight.

Biomacromolecules have attracted interest as spraying additives due to their degradability, renewability, and non-toxicity. However, microscopic mechanism of the biomacromolecules regulating the droplet behavior on fruits and vegetables is still unclear. In this study, konjac glucomannan (KGM) was used to improve the spraying efficiency and the fresh-keeping performance of tea polyphenols solution. KGM increased effective spreading ratio on hydrophilic surfaces and retention ratio of the main droplet on hydrophobic surfaces, thus improving spraying efficiency. Computational fluid dynamics and Brown dynamics simulations were implemented to investigate KGM behaviors during droplets colliding on hydrophilic and hydrophobic surfaces. Most KGM molecules extended and then collapsed in gradually weakened shear flow. Meanwhile, on the hydrophobic surface, most KGM molecules were continuously stretched by the unstable flow field. As the KGM extended, the kinetic energy of droplets converted into elastic energy stored in the KGM, promoting the stability of droplets on target surfaces and improving the spraying efficiency. The KGM molecular weight of 3.8 × 105 Da was optimal from the point of energy storage density. This study provides more understanding of the mechanism of biomacromolecules on spraying efficiency and guidance to develop biomass spraying additives for fruit and vegetable preservation.

Refinement of sensitive azides via in situ generated azole-based metal-organic frameworks towards stable energetic materials.

Energetic materials (EMs) have been widely employed in both military and civilian areas for nearly two centuries. The introduction of high-energy azide anions to assemble energetic metal-organic frameworks (EMOFs) is an efficient strategy to enhance energetic properties. However, azido-based EMOFs always suffer low stabilities to external mechanical stimulation. Herein, we employed an in situ hydrothermal reaction as a technique to refine azide anions with a neutral triazole-cyano-based ligand TrzAt (TrzAt = 2-(1H-1,2,4-triazol-1-yl)acetonitrile) to yield two tetrazole-based EMOFs, namely, [ZnBr(trmetz)]n1 and [Cd(trmetz)2]n2 (Htrmetz = 5-(1,2,4-triazol-1-ylmethyl)-1H-tetrazole). Compound 1 features a closely packed 2D layered network, while compound 2 exhibits a 3D architecture. With azide anions inlaid into a nitrogen-rich and chelating ligand in the EMOFs, compounds 1 and 2 present remarkable decomposition temperatures (Tdec ≥ 300 °C), low impact sensitivities (IS ≥ 32 J) and low friction sensitivities (FS ≥ 324 N). The calculated heat of detonation (ΔHdet) values of 1 and 2 are 3.496 and 4.112 kJ g-1, respectively. In particular, the ΔHdet value of 2 is higher than that of traditional secondary explosives such as 2,4,6-trinitrotoluene (TNT, ΔHdet = 3.720 kJ g-1). These results indicate that EMOFs 1 and 2 may serve as potential replacements for traditional secondary explosives. This work provides a simple and effective strategy to obtain two EMOFs with satisfactory energy densities and reliable stabilities through an in situ hydrothermal technique for desensitization of azide anions.

Machine Learning-Enhanced Biomass Pressure Sensor with Embedded Wrinkle Structures Created by Surface Buckling.

Flexible piezoresistive sensors are core components of many wearable devices to detect deformation and motion. However, it is still a challenge to conveniently prepare high-precision sensors using natural materials and identify similar short vibration signals. In this study, inspired by microstructures of human skins, biomass flexible piezoresistive sensors were prepared by assembling two wrinkled surfaces of konjac glucomannan and k-carrageenan composite hydrogel. The wrinkle structures were conveniently created by hardness gradient-induced surface buckling and coated with MXene sheets to capture weak pressure signals. The sensor was applied to detect various slight body movements, and a machine learning method was used to enhance the identification of similar and short throat vibration signals. The results showed that the sensor exhibited a high sensitivity of 5.1 kPa-1 under low pressure (50 Pa), a fast response time (104 ms), and high stability over 100 cycles. The XGBoost machine learning model accurately distinguished short voice vibrations similar to those of individual English letters. Moreover, experiments and numerical simulations were carried out to reveal the mechanism of the wrinkle structure preparation and the excellent sensing performance. This biomass sensor preparation and the machine learning method will promote the optimization and application of wearable devices.

Robust Single-Supermolecule Switches Operating in Response to Two Different Noncovalent Interactions.

Supramolecular electronics provide an opportunity to introduce molecular assemblies into electronic devices through a combination of noncovalent interactions such as [π···π] and hydrogen-bonding interactions. The fidelity and dynamics of noncovalent interactions hold considerable promise when it comes to building devices with controllable and reproducible switching functions. Here, we demonstrate a strategy for building electronically robust switches by harnessing two different noncovalent interactions between a couple of pyridine derivatives. The single-supermolecule switch is turned ON when compressing the junction enabling [π···π] interactions to dominate the transport, while the switch is turned OFF by stretching the junction to form hydrogen-bonded dimers, leading to a dramatic decrease in conductance. The robustness and reproducibility of these single-supermolecule switches were achieved by modulating the junction with Ångström precision at frequencies of up to 190 Hz while obtaining high ON/OFF ratios of ∼600. The research presented herein opens up an avenue for designing robust bistable mechanoresponsive devices which will find applications in the building of integrated circuits for microelectromechanical systems.

Tensile Performance Mechanism for Bamboo Fiber-Reinforced, Palm Oil-Based Resin Bio-Composites Using Finite Element Simulation and Machine Learning.

Plant fiber-reinforced composites have the advantages of environmental friendliness, sustainability, and high specific strength and modulus. They are widely used as low-carbon emission materials in automobiles, construction, and buildings. The prediction of their mechanical performance is critical for material optimal design and application. However, the variation in the physical structure of plant fibers, the randomness of meso-structures, and the multiple material parameters of composites limit the optimal design of the composite mechanical properties. Based on tensile experiments on bamboo fiber-reinforced, palm oil-based resin composites, finite element simulations were carried out and the effect of material parameters on the tensile performances of the composites was investigated. In addition, machine learning methods were used to predict the tensile properties of the composites. The numerical results showed that the resin type, contact interface, fiber volume fraction, and multi-factor coupling significantly influenced the tensile performance of the composites. The results of the machine learning analysis showed that the gradient boosting decision tree method had the best prediction performance for the tensile strength of the composites (R2 was 0.786) based on numerical simulation data from a small sample size. Furthermore, the machine learning analysis demonstrated that the resin performance and fiber volume fraction were critical parameters for the tensile strength of composites. This study provides an insightful understanding and effective route for investigating the tensile performance of complex bio-composites.

Adding Konjac Glucomannan for Enhancing the Whole Spraying Performance on Superhydrophobic and Hydrophilic Surfaces.

Spraying is a common way to coat solutions onto surfaces evenly. Improving spraying effectiveness can avoid wasting solutions and reduce pollution. In this study, a trace amount of natural polysaccharide, konjac glucomannan (KGM), was added into solutions to regulate the spraying performances including the breakup of liquid jets, size of produced droplets, and collision and spreading of droplets on both superhydrophobic and hydrophilic surfaces. The shear viscosity, extensive viscosity, and surface tension of the KGM solutions were tested. The results of spraying experiments showed that adding KGM inhibited the liquid jet from breaking into small droplets, avoided the breakage of droplets on superhydrophobic surfaces, and promoted the spreading of liquid films on hydrophilic surfaces. The numerical simulation showed the stretching of single macromolecules and quantified the energy stored in molecular chains in a shear-dominated flow field during the spreading of droplets on surfaces and an elongational-dominated flow field during the breakage of a liquid bridge. The storage and dissipation of energy during the stretching and relaxing of KMG macromolecules were important origins of the increase in the colloid viscosity and molecular mechanisms of the effect of the KGM additive on spraying performances. This study provided an understanding and a strategy for optimization and application of spraying additives.

Efficient and accurate multi-scale simulation for viscosity mechanism of konjac glucomannan colloids.

The viscosity is a foundational parameter of biomacromolecule in the food industry. The viscosity of macroscopic colloids is closely related to the dynamical behaviors of mesoscopic biomacromolecule clusters, which are difficult to be investigated at molecular resolution by common methods. In this study, based on experimental data, multi-scale simulations combining microscopic molecular dynamics simulation, mesoscopic Brownian dynamics simulation, and macroscopic flow field construction were used to investigate the dynamical behaviors of mesoscopic clusters of konjac glucomannan (KGM) colloids (~500 nm) over a long time (~100 ms). Numerical statistical parameters of the mesoscopic simulation of macroscopic clusters were proposed and proved to represent the viscosity of colloids. Based on the intermolecular interaction and macromolecular conformation, the mechanism of the shear thinning effect was revealed as both the regular arrangement of macromolecules at low shear rates (<100 s-1) and structural collapse of macromolecules at high shear rates (>500 s-1). Then, the effect of molecular concentration, molecular weight, and temperature on the colloid viscosity and cluster structure of KGM colloids was investigated by experiments and simulations. This study provides a novel multi-scale numerical method and insight into the viscosity mechanism of biomacromolecule.

Coordination polymerization of nitrogen-rich linkers and dicyanamide anions toward energetic coordination polymers with low sensitivities.

The design and synthesis of energetic materials (EMs) with high energy and reliable stabilities has attracted much attention in the field of EMs. In this work, we employed a strategy of the coordination polymerization of mild dicyanamide ions (DCA-), two isomeric ligands 1-methyl-5-aminotetrazole (1-MAT) and 2-methyl-5-aminotetrazole (2-MAT) to construct energetic coordination polymers (ECPs). Four new ECPs {[Co(DCA)2(1-MAT)2]·H2O}n1, [Cu(DCA)2(1-MAT)]n2, [Cd(DCA)2(1-MAT)2]n3 and [Cd(DCA)2(2-MAT)2]n4 were successfully synthesized through solvent evaporation routes. Compounds 1 and 4 display 1D chains, while 2 and 3 exhibit 2D-layered structures. Compounds 1-3 with the 1-MAT ligand all exhibit reliable thermal stabilities (> 200 °C). The calculated heats of detonation (ΔHdet) of 1-3 are all higher than 1.4 kJ g-1, which are higher than traditional explosive TNT (1.22 kJ g-1) and the reported ECP AgMtta (HMtta = 5-methyl-1H-tetrazole, ΔHdet = 1.32 kJ g-1). Furthermore, sensitivity testing demonstrates that 1-4 features low mechanical sensitivity to external mechanical action in contrast with the extremely sensitive azide-based ECPs [Cu3(2-MAT)2(N3)6]n. In addition, compound 2 shows hypergolic properties via an 'oxidizer-fuel' drop experiment, demonstrating its application prospects in the field of propellants. This work details an approach of synthesizing multipurpose ECPs with reliable stabilities by introducing mild dicyanamide anions into nitrogen-rich skeletons.

Flame-Retardant and Recyclable Soybean Oil-Based Thermosets Enabled by the Dynamic Phosphate Ester and Tannic Acid.

The demands of safety and sustainability have driven the development of intrinsic flame-retardant biobased polymers from renewable materials. Herein, a mechanically robust, good flame-retardant, and recyclable thermoset was developed from renewable epoxidized soybean oil (ESO) by using 2-hydroxyethyl methacrylate phosphate (HEMAP) as the reactive flame retardant and tannic acid (TA) as the charring agent. The flame resistance of the obtained ESO-based thermoset achieved the highest UL-94 of V-0 rating and a limited oxygen index value of 26.7% due to the synergistic flame-retardant effect of phosphate and TA. The flame-retardant mechanisms of the gaseous phase and condensed phase were fully investigated by thermogravimetric infrared, scanning electron microscopy-energy-dispersive spectrometry, X-ray photoelectron spectroscopy, and Raman spectra. It is confirmed that the incorporation of phosphate and TA could effectively promote the formation of dense carbon layers and delay the pyrolysis of long aliphatic chains. The ternary crosslinking of ESO, HEMAP, and TA via free-radical polymerization and epoxy-ring opening reaction resulted in a rigid network with a high crosslink density, bestowing the thermoset with superior tensile strength (20.0 MPa), flexural strength (36.3 MPa), and bonding strength (16.7 MPa on steel). Moreover, the ESO-based thermoset exhibited a fast stress relaxation behavior due to the transesterification of dynamic ß-hydroxyl phosphate esters, which enables the network with thermal-healing ability and recyclability. This study explores a feasible method to prepare an intrinsic flame-retardant polymer from commercially available and renewable vegetable oils and natural polyphenols.

Micro-structure and tensile properties of microfluidic spinning konjac glucomannan and sodium alginate composite bio-fibers regulated by shear and elongational flow: experiment and multi-scale simulation.

Microfluidic spinning has been widely used to produce bio-fibers with excellent tensile performances by regulating the conformation of biological macromolecules. However, the effect of channel shapes on fiber tensile performances is unclear. In this study, bio-fibers were prepared using konjac glucomannan and sodium alginate by five channels. The micro-morphology and tensile performance of fibers were characterized and measured. Then, the dynamical behaviours of macromolecule clusters in flow fields were simulated by multi-scale numerical methods. The results show that the elongational flow with increasing extension rates produced fibers with a tensile strength of 32.34 MPa and a tensile strain of 18.72 %, which were 1.37 and 1.55 times that for a shear flow, respectively. The difference in tensile performances was attributed to the micro-morphology regulated by flow fields. The continuously increasing extension rate of flow was more effective than the shear rate or the maximum extension rate for the stretching of macromolecule clusters. We conclude that the channel shapes significantly influence flow fields, dynamical behaviours of molecule clusters, the morphology of fibers, and tensile performances. This study provides a novel numerical method and understanding of microfluidic spinning, which will promote the optimization and applications of bio-fibers.

Highly Effective Multifunctional Solar Evaporator with Scaffolding Structured Carbonized Wood and Biohydrogel.

A solar evaporator that utilizes solar radiation energy can be a renewable approach to deal with energy crisis and fresh water shortage. In this study, a solar evaporator was prepared by assembling composite carbonized wood of Melaleuca Leucadendron L. and biobased hydrogel. The multilayer MXene (Ti3C2Tx) was embedded in the scaffolding structure of the wood to form composite carbonized wood, where the loose and ordered scaffolding structure of the carbonized wood significantly improves the efficiency of water transportation with increased capillary force. The MXene adsorbed in the carbonized wood has high binding energy with water molecules, leading to reduction of vaporization enthalpy and contact angle. Moreover, the addition of MXene can improve the light absorbance, especially for the infrared and ultraviolet light bands. The hydrogel was fabricated by crosslinking konjac glucomannan and sodium alginate polysaccharides with Ca2+, and it has a lower thermal conductivity than water and improves the evaporation efficiency by regulating the temperature distribution and concentrating the heat on the surface of the evaporator. This solar evaporator has an evaporation rate of 3.71 kg·m-2·h-1 and an evaporation efficiency of 129.64% under 2 sun illumination and is available to generate an open-circuit voltage of 1.8 mV after a 20 min hydrovoltaic, demonstrating a high performance and versatility. Also, experiments and numerical simulation were carried out to understand the mechanism and design principles of this solar evaporators.

DNA fragmentation in complicated flow fields created by micro-funnel shapes.

Micro-funnels have been widely applied to produce extensionally dominant flows for DNA manipulation, such as DNA extension for DNA mapping and DNA fragmentation for gene sequencing. However, it still lacks a systematic understanding of DNA fragmentation behaviors in complicated flow fields regulated by different funnel shapes with high flow rates. This limits the rational design and application scope of related microfluidic devices. In this study, fragmentation experiments of λ DNA were carried out in microfluidic chips with four different micro-funnel shapes, namely a sudden finish, a linear contraction, a constant acceleration, and an increasing extension rate funnel. The experimental results demonstrated a significant effect of the micro-funnel shape on the produced DNA fragment size. Then, the dynamical behaviors of DNA molecules in flow fields created by different micro-funnels were simulated using a numerical method of Brownian dynamics-computational fluid dynamics. The numerical simulation revealed that both the magnitude and distribution of the extension rate of flow fields were drastically altered by the funnel shape, and the extension rate at the micro-scale was the dominant factor of DNA fragmentation. The different DNA fragmentation behaviors in four micro-funnels were investigated from the perspectives including the fragment size distribution, fragmentation location, percentage of broken molecules, conformational type and stretched length of DNA before fragmentation. The results elucidated the significant impact of funnel shape on the dynamical behaviors of DNA fragmentation. This study offers insights into the rational design of microfluidic chips for DNA manipulation.

Photocuring Three-Dimensional Printing of Thermoplastic Polymers Enabled by Hydrogen Bonds.

The advent of 3D printing has led to a new era of highly customized products. Printing reprocessable thermoplastic polymers is limited to slow printing techniques such as fused deposition modeling. Photocuring 3D printing is a high-speed 3D printing technique suitable for photocurable thermosetting resins because the cross-linked 3D network could achieve rapid solid-liquid separation during printing. However, thermoplastics usually cannot be printed via photocuring 3D printers because rapid solid-liquid separation is hard to be achieved due to the diffusion/dissolution of linear molecular chains in their liquid precursor. Herein, we hypothesize that hydrogen bonds (H-bonds) between monomers may accelerate polymerization and reduce solubility of the polymer in liquid precursors to achieve rapid solid-liquid separation. Using this strategy, a series of UV-curable methacrylic and acrylic monomers was selected as inks to demonstrate the role of H-bonds in photocuring 3D printing. The hypothesis was further verified by using blended inks of N-vinyl-2-pyrrolidinone (NVP) and acrylic acid (AA) via experimental and molecular dynamic simulation. Oil palm occupies the top position of plantation species in southeastern Asian forests. Palm oil (PO) has the lowest price compared with other plant oils. Thus, a PO-based vinyl monomer was selected as the raw material for 3D printing thermoplastic polymers. Various biobased thermoplastics were successfully printed from the PO-based monomer and commercial monomers. The amide structure in the PO monomer formed H-bonds with polar monomers, including NVP and AA, resulting in printed 3D objects with surprising functionalities such as high stretchability and self-healing ability.

Preparation and Performance of Cement Mortar Reinforced by Modified Bamboo Fibers.

This study aims to prepare bamboo-fiber-reinforced cement composites and provide a solution to the issue of poor interfacial adhesion between bamboo fibers and cement matrix. The original bamboo fibers were modified by three moderately low-cost and easy-to-handle treatments including glycerol, aluminate ester, and silane treatments. The performance of the modified bamboo-fiber-reinforced cement composites was evaluated by a series of mechanical and durability tests, including flexural and compressive strength, water absorption, chloride ion penetration, drying shrinkage, freeze-thaw resistance, and carbonization. In addition, the microstructures of composites were characterized using a scanning electron microscope (SEM). The results showed that the composites reinforced with glycerol-modified bamboo fibers had 14% increased flexural strength and comparable compressive strength. From durability perspectives, all treatments showed similar performance in drying shrinkage, whereas aluminate ester treatment was the most effective in terms of impermeability, chloride resistance, freeze-thaw resistance, and carbonization. The results could provide insights to efficient and effective natural fiber treatment to enable better performance of natural-fiber-reinforced cement-based materials.

A Review on Styrene Substitutes in Thermosets and Their Composites.

In recent decades, tremendous interest and technological development have been poured into thermosets and their composites. The thermosets and composites with unsaturated double bonds curing system are especially concerned due to their versatility. To further exploit such resins, reactive diluents (RDs) with unsaturated sites are usually incorporated to improve their processability and mechanical properties. Traditional RD, styrene, is a toxic volatile organic compound and one of the anticipated carcinogens warned by the National Institute of Health, USA. Most efforts have been conducted on reducing the usage of styrene in the production of thermosets and their composites, while very few works have systematically summarized these literatures. Herein, recent developments regarding styrene substitutes in thermosets and their composites are reviewed. Potential styrene alternatives, such as vinyl derivatives of benzene and (methyl)acrylates are discussed in details. Emphasis is focused on the strategies on developing novel RD monomers through grafting unsaturated functional groups on renewable feedstocks such as carbohydrates, lignin, and fatty acids. This review also highlights the development and characteristics of RD monomers and their influence on processability and mechanical performance of the resulting thermosets and composites.

Preparation and Evaluation of Green Composites from Microcrystalline Cellulose and a Soybean-Oil Derivative.

The present work aimed at developing fully green composites from renewable materials, i.e., acrylated epoxidized soybean oil (AESO) and microcrystalline cellulose (MCC) by a solution casting method. The reinforcing effect of MCC on AESO resins was optimized by adjusting MCC loading from 20 to 40 wt % in terms of physical, mechanical, and thermal properties as well as water absorption of the resulting MCC/AESO composites. The interaction between MCC and AESO was characterized by Fourier transform infrared (FTIR) analysis, which revealed possible hydrogen bonds between the ⁻OH groups of MCC along with the polar components of AESO including C=O, ⁻OH, and epoxy groups. This was further evidenced by a benign interfacial adhesion between MCC and AESO resins as revealed by scanning electron microscope (SEM) analysis. The incorporation of MCC into AESO resins significantly increased the density, hardness, flexural strength, and flexural modulus of the MCC/AESO composites, indicative of a significant reinforcing effect of MCC on AESO resins. The composite with 30 wt % MCC obtained the highest physical and mechanical properties due to the good dispersion and interfacial interaction between MCC and AESO matrix; the density, hardness, flexural strength, and flexural modulus of the composite were 15.7%, 25.0%, 57.2%, and 129.7% higher than those of pure AESO resin, respectively. However, the water resistance at room temperature and 100 °C of the composites were dramatically decreased due to the inherent hydrophilicity of MCC.