Effect of hydrophobic modification of chitin nanocrystals on role as anti-nucleator in the crystallization of poly(ε-caprolactone)/polylactide blend.

Biodegradable polymer blends filled with rod-like polysaccharide nanocrystals have attracted much attention because each component in this type of ternary composites is biodegradable, and the final properties are more easily tailored comparing to those of binary composites. In this work, chitin nanocrystals (ChNCs) were used as nanofiller for the biodegradable poly(ε-caprolactone) (PCL)/polylactide (PLA) immiscible blend to prepare ternary composites for a crystallization study. The results revealed that the crystallization behavior of PCL/PLA blend matrices strongly depended on the surface properties of ChNCs. Non-modified ChNCs and modified ChNCs played completely different roles during crystallization of the ternary systems: the former was inert filler, while the latter acted as anti-nucleator to the PCL phase. This alteration was resulted from the improved ChNC-PCL affinity after modification of ChNCs, which was due to the 'interfacial dilution effect' and the preferential dispersion of ChNCs. This work presents a unique perspective on the nucleation role of ChNCs in the crystallization of immiscible PCL/PLA blends, and opens up a new application scenario for ChNCs as anti-nucleator.

Chitin nanocrystals-stabilized emulsion as template for fabricating injectable suspension containing polylactide hollow microspheres.

One of the promising applications of rod-like chitin nanocrystals (ChNCs) is the use as particle emulsifier to develop Pickering emulsions. We reported a ChNC-stabilized oil-in-water emulsion system, and developed a Pickering emulsion-templated method to prepare polylactide (PLA) hollow microspheres here. The results showed that both non-modified ChNCs and acetylated ChNCs could well emulsify the dichloromethane (DCM) solution of PLA-in-aqueous mannitol solution systems, forming very stable emulsions. At the same oil-to-water ratios and ChNC loadings, the emulsion stability was improved with increasing acetylation levels of ChNCs, accompanied by reduced size of droplets. Through the solvent evaporation, the PLA hollow microspheres were templated successfully, and the surface structure was also strongly dependent on the acetylation level of ChNCs. At a low level of acetylation, the single-hole or multi-hole surface structure formed, which was attributed to the out-diffusion of DCM caused by the solvent extraction and evaporation. These surface defects decreased with increased acetylation levels of ChNCs. Moreover, the aqueous suspension with as-obtained PLA microspheres revealed shear-thinning property and good biocompatibility, thereby had promising application as injectable fillers. This work can provide useful information around tuning surface structures of the Pickering emulsion-templated polymer hollow microspheres by regulating acetylation level of ChNCs.

An enhanced A* method incorporating an encrypted memory database for ASV efficient local path planning.

For the autonomous surface vehicle (ASV) planning problem, an enhanced A* method incorporating encrypted memory database for ASV efficient local path planning is proposed. Considering the current various path planning problems mostly use methods with high time complexity, such as neural networks, we select the A* algorithm with low time complexity as the basis. To speed up the path planning rate and further improve the real-time and realistic algorithm, this paper modifies the heuristic function of the A* algorithm by combining the motion mode of ASV. In response to the problem that the target point is far from the detection, we improve the target point design mechanism and create a new temporary target point within the detection range. In addition, the algorithm incorporates a memory database, which can record commonly used waters or retain the environmental path of navigated waters as a priori information. When the same waters are reencountered, the memory database information can be read directly to complete the navigation. Moreover, the memory database is encrypted to prevent information leakage. Finally, a simulation environment is built to verify the effectiveness of the proposed algorithm by comparison with some existing algorithms.

Using bacterial cellulose to bridge covalent and physical crosslinks in hydrogels for fabricating multimodal sensors.

Network optimization is vital for the polysaccharide based hydrogels with multiple crosslinks. In this study, we developed a 'two-step' strategy to activate synergistic effect of chemical and physical crosslinks using a poly (vinyl alcohol) (PVA)/bacterial cellulose (BC) hydrogel as a template. The BC nanofibers, on the one hand, acted as nucleating agents, participating in the crystallization of PVA, and on the other hand, were also involved in the formation of boronic ester bond, anchored with the PVA chains via chemical bonding. Therefore, the existence of BC nanofibers, as 'bridge', linked the crystalline regions and amorphous parts of PVA together, associating the two characteristic crosslinks, which was conducive to load transfer. The mechanical properties of resultant hydrogels, including the tensile elongation and strength, as well as fracture toughness, were significantly improved. Moreover, the dually cross-linked hydrogels possessed ionic conductivity, which was sensitive to the tensile deformation and environmental temperature. This study clarifies a unique role of BC nanofibers in hydrogels, and proposes an effective approach to construct multiple networks in the nanocellulose reinforced PVA hydrogels.

Continuous and Periodic Event-Triggered Sliding-Mode Control for Path Following of Underactuated Surface Vehicles.

This article develops continuous and periodic event-triggered sliding-mode control (SMC) algorithms for path following of underactuated surface vehicles (USVs). Based on the SMC technology, a continuous path-following control law is designed. The upper bounds of quasi-sliding modes for path following of USVs are established for the first time. Subsequently, both continuous and periodic event-triggered mechanisms are considered and added into the proposed continuous SMC scheme. It is demonstrated that with appropriate selecting of control parameters, the use of hyperbolic tangent functions does not affect the boundary layer of quasi-sliding mode caused by event-triggered mechanisms. The proposed continuous and periodic event-triggered SMC strategies can make the sliding variables reach the quasi-sliding modes and stay in there. Moreover, energy consumption can be reduced. Stability analysis shows that the USV can follow a reference path by using the designed method. The simulation results show the effectiveness of the proposed control methods.

Effect of surface acetylation of chitin nanocrystals on the preparation and viscoelasticity of sunflower seed oil-in-water Pickering emulsions.

Acetylated chitin nanocrystals (ChNCs) were used as stabilizer in this work to prepare sunflower seed oil-in-water emulsions for the morphological and rheological studies. The results revealed that the acetylation with moderate degree of substitution (0.38) reduced hydrophilicity and increased surface charge level of rod-like ChNCs, and as a result, significantly improved the emulsifying ability of ChNCs. At the same oil/water ratio and particle loading, the emulsions stabilized with the acetylated ChNCs had far smaller droplet size (∼3 µm) as compared to the emulsions stabilized with the pristine ChNCs (5-7 µm). The increased droplets numbers and improved surface coating level resulted in the enhanced viscous resistance and yield stress level, which improved the physical stability of the acetylated ChNC-stabilized emulsions as a result. In addition, the droplet clusters easily formed in this system, contributing to weak strain overshoot and decreased large-deformation sensitivity during dynamic shear flow. Therefore, the acetylated ChNC-stabilized system showed enhanced transient stress overshoot during startup flow and weakened thixotropy during cyclic ramp shear flow as compared to the pristine ChNC-stabilized system. The relationships between surface acetylation of ChNCs and flow behavior of emulsions were then established, which provide valuable information on the modulation of the ChNC-stabilized Pickering emulsions.

Effect of chitin nanocrystals on stereocomplexation of poly(l-lactide)/poly(d-lactide) blends.

Using polysaccharide nanocrystals such as chitin nanocrystals (ChNCs) as nanofiller for biodegradable aliphatic polymers is an attractive way of developing all-degradable nanocomposites. Crystallization study is vital for well regulating final performance of these type polymeric nanocomposites. In this work, ChNCs were incorporated with the poly(l-lactide)/poly(d-lactide) blends and as-obtained nanocomposites were used as target samples for the study. The results showed that ChNCs acted as nucleating agent, promoting the formation of stereocomplex (SC) crystallites and accelerating overall crystallization kinetics as a result. Therefore, the nanocomposites possessed higher SC crystallization temperatures and lower apparent activation energy as compared to the blend. However, the formation of homocrystallites (HC) was dominated by nucleation effect of SC crystallites and accordingly, the fraction of SC crystallites reduced more or less in the presence of ChNCs, despite the nanocomposites possessed higher rate of HC crystallization. This study also provided valuable information on accessing more applications of ChNCs to be used as SC nucleator for polylactide.

Heterogeneity Regulation of Bilayer Polysaccharide Hydrogels for Integrating pH- and Humidity-Responsive Actuators and Sensors.

Bilayer hydrogel-based actuators have attracted much interest because inhomogeneous structures are easily constructed in hydrogels. We used three kinds of polysaccharides, including anionic carboxymethyl cellulose (CMC), cationic chitosan (CS), and amphoteric carboxymethyl chitosan (CMCS), as both structure-constructing units and actuation-controlling units in this work to fabricate physically crosslinked poly(vinyl alcohol) bilayer hydrogels. The spatial heterogeneity was tuned by changing the types and concentrations of polysaccharides in different layers, to regulate pH- and humidity-driven actions of bilayer hydrogels. Based on the distortion of the ionic channel during the humidity-motivated deformation of bilayer hydrogels, a two-in-one flexible device integrating a humidity-driven actuator and humidity-responsive sensor was then developed, which could detect the alterations of environmental humidity in real time. Moreover, good tensile toughness and interfacial bonding as well as the strain-resistance effect endowed the bilayer hydrogels with the capability of identifying human motion as a strain sensor, unlocking more application scenarios. This work provides an overall insight into the heterogeneity regulation of bilayer hydrogels using polysaccharides as stimulus-responsive units and also proposes an interesting strategy of manufacturing hydrogel-based flexible devices with both actuating and sensing capabilities.

Preparation and research of PCL/cellulose composites: Cellulose derived from agricultural wastes.

For the rational use of agricultural wastes, bagasse, orange peel and wheat bran were used to fabricate bio-based polymer materials. Cellulose was extracted from the three different agricultural wastes, and poly(ε-caprolactone) (PCL) was used as the matrix material. PCL was mixed with nanocrystalline cellulose (CNC), extracted bagasse cellulose (GC), orange peel cellulose (JC) and wheat bran cellulose (MC) by solution casting. Morphology and structure of the extracted cellulose were studied by Scanning Electron Microscope, Fourier Infrared spectrometer, thermogravimetry and X-ray diffractometer. The influence of GC, JC, MC on the crystallization process and mechanical properties of PCL was investigated by DSC and tensile test. Experimental results show that the addition of CNC, GC, JC, MC increases the crystallization temperature of PCL, accelerates the crystallization process of PCL, and improves the tensile property of PCL.

BarA/UvrY differentially regulates prodigiosin biosynthesis and swarming motility in Serratia marcescens FS14.

BarA/UvrY, a two-component system and global regulator that controls expression of more than a hundred of genes involved in virulence, motility, biofilm formation, and central carbon metabolism under various stress conditions. In this study, we investigated the function of BarA/UvrY system in Serratia marcescens FS14. The disruption of barA or/and uvrY results in the yield increase of secondary metabolite prodigiosin. We further demonstrated that BarA/UvrY system represses prodigiosin production by inhibiting the transcription level of pig gene cluster with direct binding to the pigA promoter. In addition, deletion of barA or/and uvrY abolished the swarming motility of FS14, but not the swimming motility. We revealed that BarA/UvrY activates swarming through directly upregulating the expression of the biosurfactant synthesis gene swrW rather than flagella system. We also observed that BarA/UvrY positively regulates the resistance to H2O2 same as in Escherichia coli highlighting the importance of BarA/UvrY on hydrogen peroxide resistance. Our results demonstrated that the BarA/UvrY system differentially regulates the biosynthesis of the secondary metabolite prodigiosin and swarming motility in S. marcescens FS14. Comparison of our results with those observed for Serratia sp. 39006 suggests that BarA/UvrY's role in regulation of secondary metabolite production is different among Serratia species.

Ultrastretchable Composite Organohydrogels with Dual Cross-Links Enabling Multimodal Sensing.

Building multiple cross-links or networks is a favorable way of diversifying applications of the hydrogels, which is also available for the organohydrogels prepared via the solvent replacement way. However, the situations become more complicated for organohydrogels due to the presence of replaced solvents. Therefore, the correlations between the multiple cross-links and final performance need to be better understood for the organohydrogels, which is vital for tailoring their inherent properties to expand final application scenarios. Polyacrylamide (PAM)/poly(vinyl alcohol) (PVA)/MXene composite organohydrogels with dual cross-links, namely, the covalently cross-linked PAM chains as the primary network and the physically cross-linked PVA/PAM chains with MXene particles as the secondary cross-links, were developed here for the study. The occurrence of the secondary cross-links plays multiple roles as sacrificial units endowing the system with ultrastretchability with an excellent strain-resistance effect and as temperature-sensitive units endowing the system with thermosensation ability with an outstanding temperature coefficient of resistance. Thus, the optimized sample can be used as a strain sensor with excellent environmental tolerance for detecting human motion as a pressure sensor to probe compression with weak deformation and as a thermal sensor to capture environmental temperature changes. This work provides valuable information on developing organohydrogels with superior performance for multimodal sensors.

Mapping hierarchical networks of poly(vinyl alcohol)/cellulose nanofiber composite hydrogels via viscoelastic probes.

Discriminating the roles of different networks in the multiply cross-linked hydrogels is vital to optimize their overall performance. Poly(vinyl alcohol)/cellulose nanofiber composite hydrogels were used as template for the study. Three types of characteristic networks, including chemical network cross-linked with boronic ester bonds, physical network cross-linked with microcrystallites, and coexistence of these two networks, were constructed in the system, and the viscoelastic responses were used to detect the characteristic relaxation behavior of those networks. The physical network is more sensitive to stress-induced deformation, whereas the chemical network more sensitive to strain-induced one. The former has lower level of viscous dissipation and higher level of elastic storage as compared to the latter, and dominates linear viscoelasticity of hydrogels as the two networks coexist. Their synergistic effect can be well defined by the scaling behavior of hysteretic work. This work proposes an interesting method of probing networks in the multiply cross-linked hydrogels.

Nucleation roles of cellulose nanocrystals and chitin nanocrystals in poly(ε-caprolactone) nanocomposites.

Using polysaccharide nanocrystals such as chitin nanocrystals (ChNCs) or cellulose nanocrystals (CNCs) as fillers of biodegradable aliphatic polyesters is an attractive approach of fabricating completely biodegradable nanocomposites. Most aliphatic polyesters are semi-crystalline and hence to reveal the effect of nanocrystals on their crystallization behaviors is key to regulate final properties of the nanocomposites. In this work, poly(ε-caprolactone) (PCL) nanocomposites filled with ChNCs and CNCs were prepared as templates for the study. It is intriguing that these two nanocrystals play completely different roles towards crystallization of PCL. CNCs are nucleating agent, promoting nucleation of PCL and accelerating subsequent crystal growth; while ChNCs are anti-nucleation agent, retarding nucleation of PCL and depressing whole process of PCL crystallization. This difference arises from different particle-polymer affinities in the nanocomposites, which is confirmed by the thermodynamic and rheological tests. This work provides valuable information around tuning the thermal properties of polysaccharide nanocrystals filled polymeric nanocomposites.

Water-in-water Pickering emulsions stabilized by the starch nanocrystals with various surface modifications.

HYPOTHESIS: Using the platelet-like starch nanocrystals (SNCs) to stabilize emulsions is attractive because as-prepared emulsions have promising applications in cosmetics and food fields. Limited studies mainly focus on the oil-in-water system, and another important system, the water-in-water emulsions stabilized by SNCs, has not yet been unveiled. EXPERIMENTS: Two surface modification strategies, crosslinking and acetylation, were applied to tune surface property and aggregation of SNCs, and a common all-aqueous system (dextran/poly(ethylene glycol)) was used here as template. The viscoelasticity and morphology of emulsions were studied in terms of the SNC loadings and polymer ratios. FINDINGS: Crosslinking results in aggregation of SNCs, and the particle size increases (from 110 nm to 370 nm) with increased levels of substitution. This favors improving emulsifying ability of particles. Acetylation decreases the particle size (∼90 nm) and weakens the affinity of SNCs to the two aqueous phases, improving the emulsifying efficiency of SNCs. More intriguingly, the two emulsion systems show different phase inversion behaviors. The depletion-stabilization mechanism for the cross-linked SNCs and the diffusion-controlled mechanism for the acetylated SNCs are proposed using the emulsion viscoelasticity as probe. This study makes a comprehensive insight into the regulation of water-in-water emulsion morphology and types with the platelet-like SNCs.

Characterization of the molecular mechanism underlying the dwarfism of dsh mutant watermelon plants.

Developing dwarf watermelon is a major objective among breeders. The dsh dwarf watermelon germplasm developed in our laboratory is genetically stable. We previously produced preliminary evidence that Cla010726, which encodes a gibberellin 20-oxidase-like protein, is the primary gene controlling dwarfism in watermelon. However, the underlying genetic mechanism was unknown. In this study, we characterized the spontaneous recessive mutant dsh, which is a gibberellin (GA)-deficient mutant. Many of the phenotypic traits of dsh plants are similar to those of known GA-deficient mutants. The dsh plants were sensitive to exogenous bioactive GAs, which increased seedling height. Moreover, a quantitative analysis of endogenous GA3 proved that the bioactive GA3 content was substantially lower than normal in dsh. Additionally, the T5ClaGA20ox RNAi plants generally exhibited dwarfism, with short stems and internodes as well as small leaves and fruit. An examination of the transgenic plants carrying the ClaGA20ox1 promoter-GUS and mutant ClaGA20ox2 promoter-GUS constructs confirmed that two promoter sites are involved in the regulation of ClaGA20ox expression. Hence, mutations in the promoter of the GA20ox gene, which encodes a key enzyme involved in gibberellin biosynthesis, lead to the dwarfism of watermelon plants. The dsh mutant is a potentially useful germplasm resource for developing new watermelon varieties exhibiting dwarfism.

Mapping and Analysis of a Novel Genic Male Sterility Gene in Watermelon (Citrullus lanatus).

Seed production is critical for watermelon production, which mostly involves first-generation hybrid varieties. However, watermelon hybrid seed production currently requires complex procedures, including artificial isolation and pollination. Therefore, the development and use of a male-sterile system to generate watermelon hybrids can simplify the process. The scarcity of male-sterile watermelon germplasm resources necessitates the use of molecular breeding methods. Unfortunately, the genes responsible for male sterility in watermelon have not been cloned. Thus, the genetic basis of the male sterility remains unknown. In this study, two DNA pools derived from male-sterile and normal plants in the F2 population were used for whole-genome resequencing. The Illumina high-throughput sequencing resulted in 62.99 Gbp clean reads, with a Q30 of 80% after filtering. On the basis of the SNP index association algorithm, eight candidate regions (0.32 Mb) related to specific traits were detected on chromosome 6. Expression pattern analyses and watermelon transformation studies generated preliminary evidence that Cla006625 encodes a pollen-specific leucine-rich repeat protein (ClaPEX1) influencing the male sterility of watermelon. The identification and use of genic male sterility genes will promote watermelon male sterility research and lay the foundation for the efficient application of seed production technology.

Insight into melting point depression of polylactide nanocomposites with acetylated chitin nanocrystals.

Chitin nanocrystal (ChNC) was used to prepare fully biodegradable nanocomposites with polylactide (PLA). The nucleation and melting behavior of nanocomposites were studied with the objective to correlate PLA-ChNC affinity to PLA crystallization. The results disclose that the PLA nanocomposites with pristine ChNCs and the ones with acetylated ChNCs show completely different nucleation and melting behavior because the role of ChNCs is altered after acetylation. Pristine ChNC acts as inert filler, with weak nucleating activity, while acetylated ChNCs as anti-nucleation agent, restraining crystallization of PLA. Accordingly, the nanocomposites with acetylated ChNCs show melting point depression, with reduced nucleation capability. The recrystallization and self-nucleation, as well as the double-melting behaviors were then studied in terms of acetylation levels of ChNCs and annealing temperatures, in order to better understand the relations between two-phase affinity and PLA chain dynamics. This work provides interesting information around designing thermal properties of the ChNC-filled PLA nanocomposites.

Cellulosic nanofibers filled poly(ß-hydroxybutyrate): Relations between viscoelasticity of composites and aspect ratios of nanofibers.

Dispersion states are vital for fibrous nanocelluloses to be used as reinforcements for polymers, which is highly dependent on geometry of nanocelluloses. Three types of nanocelluloses with various fiber aspect ratios were used to prepare target composite samples with poly(ß-hydroxybutyrate) in this work. Viscoelasticity/elastoplasticity were used as probes to detect the flexibility-morphology relations of nanocelluloses in polymer. Cellulose nanocrystals (aspect ratio = 8) were rigid in polymer, retaining their rod-like shape, whereas bacterial celluloses (aspect ratio = 600) fully flexible, forming closely networked structure, and cellulose nanofibers (aspect ratio = 70) semi-flexible, dispersing as loosely flocculated clusters. Owing to these differences, the viscoelastic flow and elastoplastic deformation of three kinds of composites differed from one another. The strain-scaling and hysteresis work-scaling behaviors were then used to establish relaxation scale-structure correlations of target samples. This work provides interesting information around regulating the dispersion of nanocelluloses in polymer composites by tailoring aspect ratios of nanocelluloses.

Pickering emulsion stabilized with fibrous nanocelluloses: Insight into fiber flexibility-emulsifying capacity relations.

Three types of nanocelluloses, including bacterial cellulose (BC), cellulose nanofiber (CNF) and cellulose nanocrystal (CNC), were used to prepare oil-in-water Pickering emulsions with the objective to disclose the effect of fiber flexibility on emulsification. In aqueous suspensions, the shortest CNC is rigid, while the longest BC fully flexible, which result in large difference in their dilute-to-semi-dilute concentrations, and in the rheological percolations. Thus, these cellulosic nanofibers play different roles during emulsification. Flexible BC nearly has no emulsifying capacity, whereas semi-flexible CNF and rigid CNC can be well used to stabilize emulsions. For the CNF-stabilized system, depletion effect is dominant, leading to the formation of droplet clusters easily, while for the CNC-stabilized one, repulsive effect plays more important role. Visible evidence regarding relaxation of long-term structure of droplets is further disclosed by dynamic rheology. This work proposes interesting views around tailoring morphology and viscoelasticity of Pickering emulsions by regulating fiber flexibility.

Surface chain engineering of chitin nanocrystals towards tailoring the nucleating capacities for poly(ß-hydroxybutyrate).

Chitin nanocrystal (ChNC) is good nucleation agent for aliphatic polyesters because of its high-energy surface. To moderate its nucleation activity, silane coupling agents with different chain lengths or functional groups were used to modify ChNCs in this work, and biodegradable poly(ß-hydroxybutyrate) (PHB) was used as target polymer for crystallization study. Surface coupling of ChNCs improves their phase adhesion to PHB chain and weakens their nucleation activities. The alterations strongly depend on the surface chain structure of ChNCs: sulfhydryl silane-coupled ChNC shows lowered nucleation activity, whereas amino silane-coupled ChNCs even become antinucleation agents. The interfacial compatibility is vital to altered role of ChNCs and to following changes in spherulite growth and ring-banded morphology, which is further disclosed using Flory-Huggins interaction parameters and rheological responses as probes. This work provides useful information on tailoring the functions of ChNCs as nanoadditive for biodegradable aliphatic polyesters by the way of surface chain engineering.