Robust Synthesis of GO-PtNPs Nanocomposites: A Highly Selective Colorimetric Sensor for Mercury Ion (II) Detection.

Due to their high toxicity and ongoing bioaccumulation, mercury ions (Hg2+) can cause significant harm to both the environment and human health. Therefore, rapid, accurate, and selective methods for Hg2+ detection are highly desirable. Herein, we present a simple method for depositing platinum nanoparticles (PtNPs) on graphene oxide (GO) to obtain graphene oxide-PtNPs (GO-PtNPs). The fabricated GO-PtNPs exhibit excellent peroxidase-like activity and high stability. Further, the GO-PtNPs nanozymes preferentially reduced Hg2+, thereby inhibiting the catalytic activity. By monitoring the color change in the chromogenic substrate, Hg2+ can be detected within 15 min. With a detection limit of 88.3 pM, the GO-PtNPs system may be employed to detect Hg2+ in a linear range of 0.1 nM to 10 µM. The simplicity and low cost of the proposed approach as well as its applicability to complicated samples demonstrate its capacity for mercury sensing in environmental samples.

Structure and surface properties of ozone-conjugated octenyl succinic anhydride modified waxy rice starch: Towards high-stable Pickering emulsion.

In the present work, a dual-modified waxy rice starch (OOWRS) fabricated with OSA and ozone was successfully used to stabilize the O/W Pickering emulsion. The molecular structure, surface properties, and underlying stabilizing mechanism were systematically investigated. The results showed that oxidation occurring on the surface of OSA-modified waxy rice starch (OSAWRS) resulted in the presence of indentations and cracks. The relative crystallinity of starch was generally decreased with increasing degree of oxidation. Due to the introduction of carbonyl and the variation in surface structure, the hydrophobicity and acidity of OSAWRS were significantly enhanced after the ozone treatment. Remarkably, OOWRS stabilized Pickering emulsion exhibited a feature of typical O/W emulsion, and the 0.5 h and 1 h OOWRS emulsion exhibited a more uniform droplet size as well as a higher surface potential. We also noted that a weak-gel network was formed within the OOWRS emulsion system as the hydrophilic starch chains played a bridging role. Two reasons for the improved stability of the emulsion were the special gel structure and the enhanced electrical repulsion among the droplets. This research provides that ozone-conjugated OSA modification is a promising strategy for improving the emulsion ability of starch-based Pickering emulsions.

Toward function starch nanogels by self-assembly of polysaccharide and protein: From synthesis to potential for polyphenol delivery.

Nanogels formed by self-assembly of natural proteins and polysaccharides have attracted great interest as potential carriers of bioactive molecules. Herein, we reported that carboxymethyl starch-lysozyme nanogels (CMS-Ly NGs) were prepared using carboxymethyl starch and lysozyme by green and facile electrostatic self-assembly, and the nanogels served as epigallocatechin gallate (EGCG) delivery systems. The dimensions and structure of the prepared starch-based nanogels (i.e., CMS-Ly NGs) were characterized by dynamic light scattering (DLS), ζ-potential, Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD) and thermal gravimetric analyzer (TGA). FT-IR and 1H NMR spectra together confirmed the formation of CMS; FT-IR spectra confirmed the formation of CMS-Ly NGs; XRD spectra confirmed the disruption of the crystal structure of lysozyme after electrostatic self-assembly with CMS, and further confirmed the formation of nanogels. TGA demonstrated the thermal stability of nanogels. More importantly, the nanogels showed a high EGCG encapsulation rate of 80.0 ± 1.4 %. The CMS-Ly NGs encapsulated with EGCG exhibited regular spherical structure and stable particle size. Under the simulated gastrointestinal environmental conditions, CMS-Ly NGs encapsulated with EGCG showed the controlled release potential, which increased its utilization. Additionally, anthocyanins can also be encapsulated in CMS-Ly NGs and showed slow-release properties during gastrointestinal digestion in the same way. Cytotoxicity assay also demonstrated good biocompatibility between CMS-Ly NGs and CMS-Ly NGs encapsulated with EGCG. The findings of this research suggested the potential application of protein and polysaccharides-based nanogels in the delivery system of bioactive compounds.

Electrospray-Assisted Fabrication of Dextran-Whey Protein Isolation Microcapsules for the Encapsulation of Selenium-Enriched Peptide.

Selenium-enriched peptide (SP, selenopeptide) is an excellent organic selenium supplement that has attracted increasing attention due to its superior physiological effects. In this study, dextran-whey protein isolation-SP (DX-WPI-SP) microcapsules were fabricated via high-voltage electrospraying technology. The results of preparation process optimization showed that the optimized preparation process parameters were 6% DX (w/v), feeding rate Q = 1 mL/h, voltage U = 15 kV, and receiving distance H = 15 cm. When the content of WPI (w/v) was 4-8%, the average diameter of the as-prepared microcapsules was no more than 45 µm, and the loading rate for SP ranged from ~46% to ~37%. The DX-WPI-SP microcapsules displayed excellent antioxidant capacity. The thermal stability of the microencapsulated SP was improved, which was attributed to the protective effects of the wall materials for SP. The release performance was investigated to disclose the sustained-release capacity of the carrier under different pH values and an in-vitro-simulated digestion environment. The digested microcapsule solution showed negligible influence on the cellular cytotoxicity of Caco-2 cells. Overall, our work provides a facile strategy of electrospraying microcapsules for the functional encapsulation of SP and witnesses a broad prospect that the DX-WPI-SP microcapsules can exhibit great potential in the food processing field.

Multi-scale structure characterization of ozone oxidized waxy rice starch.

The elucidation of multi-scale structural variation and oxidation reaction mechanism of ozone oxidized waxy rice starch molecules remains a big challenge, limiting its development of intensive processing. In the present work, the changes in the structure of waxy rice starch after ozone treatment were systematically researched by various characterization methods. The study has shown that with the increase in ozone oxidation time, the granules of oxidized starch were polygons with multiple face depressions. It was also observed that ozone first attacked the amorphous zone of the starch granules and then penetrated the crystalline zone. Combining 1D and 2D NMR (1H NMR, 13C NMR, HSQC and HMBC) and other methods, it was proved that ozone oxidation led to ring splitting between C2 and C3 of the glucose unit. The resulting hemiacetal groups showed different types of structures. Among them, the main structures were intramolecular acetals and intermolecular hemiacetals. This research offered theoretical guidance for the utilization of ozone oxidation technology for starch modification and the development of waxy rice new foods.

Nanomaterials-Based Electrochemiluminescence Biosensors for Food Analysis: Recent Developments and Future Directions.

Developing robust and sensitive food safety detection methods is important for human health. Electrochemiluminescence (ECL) is a powerful analytical technique for complete separation of input source (electricity) and output signal (light), thereby significantly reducing background ECL signal. ECL biosensors have attracted considerable attention owing to their high sensitivity and wide dynamic range in food safety detection. In this review, we introduce the principles of ECL biosensors and common ECL luminophores, as well as the latest applications of ECL biosensors in food analysis. Further, novel nanomaterial assembly strategies have been progressively incorporated into the design of ECL biosensors, and by demonstrating some representative works, we summarize the development status of ECL biosensors in detection of mycotoxins, heavy metal ions, antibiotics, pesticide residues, foodborne pathogens, and other illegal additives. Finally, the current challenges faced by ECL biosensors are outlined and the future directions for advancing ECL research are presented.

Emerging starch composite nanofibrous films for food packaging: Facile construction, hydrophobic property, and antibacterial activity enhancement.

Polymers synthesized from green resources have many advantages in food packaging and hence their development is very important. Herein, starch/polyvinyl alcohol (PVA) nanofibrous composite films were fabricated by electrospinning technology. Steam-induced cross-linking reaction with glutaraldehyde (GTA) and silver sodium zirconium phosphate (Ag-ZrP) was employed to improve the hydrophobic and antibacterial properties of the constructed nanofibrous films, respectively. The effects of starch/PVA ratio on the micro-morphology and mechanical properties of the binary composite film were investigated. The composite film showed optimal uniformity, bead-free electrospun nanofibers, with enhanced mechanical strength for the 60/40 (v/v) starch/PVA composite. Moreover, the crystallinity of PVA was reduced during the electrospinning process, whereas the introduction of PVA strengthened the hydrogen interactions and improved the thermal stability of the composite films. After the cross-linking with GTA, the starch/PVA films became more hydrophobic. Furthermore, the starch/PVA films embedded with Ag-ZrP had outstanding antibacterial property against both Gram-negative and Gram-positive bacteria. This work demonstrated the potential prospects of electrospun starch nanofibrous films in the food packaging field.

Structural and mechanistic insights into starch microgel/anthocyanin complex assembly and controlled release performance.

We report a self-assembly method for the fabrication of multilayer-starch-based microgels used for anthocyanin encapsulation. Alcohol-heating treatment and ionization reactions were employed to reduce the crystallinity of starch and introduce ionic groups on the molecule to further cross-link it with sodium trimetaphosphate and produce a starch microgel. The molecular interactions between the starch and the anthocyanins facilitated the anthocyanin encapsulation and the starch-microgel/anthocyanin complexes with one, two, and three self-assembled layers were obtained. The Lay-1 microgel exhibited an encapsulation efficiency of 50.1% when the anthocyanin concentration, cross-linking starch concentration, contact time, and temperature were 0.25 mg/mL, 1.5 mg/mL, 3 h, and 40 °C, respectively. An increase in the number of layers resulted in a more compact microgel structure with the zeta potential presenting variations upon structural changes. Furthermore, the encapsulated anthocyanins presented a slow release from Lay-1, while the multilayered microgels (Lay-2 and Lay-3) displayed outstanding encapsulation stability. This study gives an insight on the encapsulation and release of anthocyanins by starch microgels, and provides a novel strategy for the design of starch-based encapsulation materials presenting great stability.

Functional nanoparticle reinforced starch-based adhesive emulsion: Toward robust stability and high bonding performance.

Sustainable bio-based adhesive is a promising substitute for petroleum-based adhesives to alleviate serious environmental and health problems. In this work, a nanoengineered starch-based adhesive was fabricated by grafting vinyl acetate (VAc) onto starch molecule and subsequently incorporating the functional nanoparticle [TiO2-coupling-poly(butyl acrylate, BA), TKB] to overcome the drawbacks present in conventional nanocomposite adhesive. Results showed that the presence of BA altered the surface property of TKB, leading to improved dispersion. In the adhesive with 4% (mass ratio to starch) TKB, TKB aggregates played the role as a sliding bridge, which significantly promoted the storage stability and shear strength in both dry and wet states. Additionally, the latex film with 4% TKB exhibited high compatibility and water resistance due to the promoted hydrophobicity. This study provides a fundamental insight into the improvement of functional nanoparticles on the performance of starch-based adhesive, suggesting a novel strategy for designing high-performance bio-adhesive.

Starch/tea polyphenols nanofibrous films for food packaging application: From facile construction to enhance mechanical, antioxidant and hydrophobic properties.

Starch based food packaging has been receiving increasing attention. However, the inherent poor properties of starch restrict its practical applications in the versatile material science field. In this study, a fast, simple, and environmentally friendly route to construct polyfunctional starch/tea polyphenols nanofibrous films (STNFs) by one-step temperature-assisted electrospinning was developed. The effects of introduction of tea polyphenols (TP) on the mechanical and antioxidant activity of STNFs were comprehensively investigated. Results of ABTS·+ free radical scavenging assay showed that the antioxidant activity of STNFs was endowed by addition of TP with optimum mechanical properties confirmed by tensile test. More interestingly, the hydrophobicity of STNFs was improved dramatically with increasing cross-linking time as indicated by water contact angle (WCA) measurement showing no effect on the antioxidant activity of the films. The results of this work offer a major step forward to promote functional starch-based materials for sustainable application in food packaging.

Investigating the structure and self-assembly behavior of starch-g-VAc in starch-based adhesive by combining NMR analysis and multi-scale simulation.

This work investigated the structure and self-assembly behavior of grafted starch (GS) prepared by grafting vinyl acetate (VAc) on the starch molecule. Our preliminary structure characterization, NMR, and quantum mechanical simulation demonstrated the C2 of the glucose unit as the main grafting site. The grafting frequency and chain length (starch, VAc) were calculated based on the result of gel permeation chromatography. Molecular dynamics simulation showed that, when compared with native starch, GS had less hydrogen bonding interaction, lower orderness, and higher extensibility, which were supported by the experimental results. In dissipative particle dynamics simulation, GS was shown to self-assemble into a core-shell structure (latex) and form a bridge structure with cross-linking interaction. The overall results indicate that chain entanglement and hydrogen bonding interaction of starch play a significant role in adhesive curing. This research provides a novel insight into the grafting and molecular interaction mechanism in the GS adhesive system.

Sodium dodecyl sulfate improves the properties of bio-based wood adhesive derived from micronized starch: Microstructure and rheological behaviors.

Enhancing the performance of starch-based wood adhesive is vitally important for its practical applications. Accordingly, we designed the use of micronized starch (MS) to prepare micronized starch-based wood adhesive (MSWA) by incorporating 0, 2, 4 and 6% (w/w, dry basis starch) sodium dodecyl sulfate (SDS). The results showed that 2% SDS exhibited remarkable improvement in shear strength and viscosity of MSWA. The grafted reaction was demonstrated by 1H NMR and the steady shear results indicated that the adhesive possessed a pseudoplastic behavior under yield stress conditions. Besides, dynamic rheological measurements were applied to evaluate the structure of MSWA under varying frequencies, temperatures and constant stain. The transmission electron microscopy (TEM), Zeta potential and surface tension indicated that SDS could improve the surficial properties. Meanwhile, the microstructure of adhesive films and fracture surfaces of glued wood veneers by scanning electron microscopy (SEM) demonstrated that the migration of SDS led to the formation of surfactant layer. Furthermore, element analysis revealed the distribution of S/N in latex slices. The results of this study provide the detailed information about the influence of SDS on the rheological properties and microstructures of MSWA, which may facilitate the preparation of high performance bio-based adhesive for wood applications.

A combination of coarse-grain molecular dynamics to investigate the effects of sodium dodecyl sulfate on grafted reaction of starch-based adhesive.

Graft copolymerization is a challenging step in preparation of starch-based adhesive due to the complexity and instantaneity. A combination of both experimental and simulation methodology has been employed to investigate the process at microscopic level. Through a series of characterizations of adhesives and copolymers with different SDS (sodium dodecyl sulfate) contents, 2% (w/w, 2g SDS/100 g starch) SDS demonstrated outstanding balance between the starch grafted percentage and interfacial properties. The coarse-grain molecular dynamics (CGMD) was utilized to reveal the molecular distribution and migratory mechanisms during the reaction by calculating radius distribution function (RDF) and mean square displacement (MSD). Starch chains covering the monomers surface was found to exhibit longer radius of gyration (Rg). Furthermore, the interfacial models were constructed in this study, and interfacial tension between water and VAc beads was calculated to confirm the improvement in interfacial properties and the rationality of simulation with the addition of SDS.

Effects of nano-TiO2 on bonding performance, structure stability and film-forming properties of starch-g-VAc based wood adhesive.

The nano-TiO2 was utilized to improve the bonding performance, structure stability and film-forming properties of renewable starch-based wood adhesive. The results showed that 4% nano-TiO2 (nano-TiO2:starch, w;w) resulted in 6.5 MPa of shear strength and 6437 Pa.s of viscosity. The thermal stability was measured by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Additionally, low-field nuclear magnetic resonance (NMR) and rheological results exhibited the enhancement of nano-TiO2 on the pseudoplasticity and structure which determined the state and migration of water. Besides, the structural characterization of copolymer was analyzed via fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD). Furthermore, the film-forming property was evaluated by small angle X-ray scattering (SAXS) and dynamic mechanical analysis (DMA). The morphological structures of adhesive were observed by scanning electron microscopy (SEM). In conclusion, the 4% nano-TiO2 (nano-TiO2:starch, w;w) can be employed to prepare starch-based wood adhesives with superior properties for wood application.

Endoscopic ligation compared with sclerotherapy for bleeding esophageal varices in children with extrahepatic portal venous obstruction.

Endoscopic sclerotherapy is an effective treatment for bleeding esophageal varices, but it is associated with significant complications. Endoscopic ligation, a new form of endoscopic treatment for bleeding varices, has been shown to be superior to sclerotherapy in adult patients with cirrhosis. To determine the efficacy and safety of endoscopic sclerotherapy and ligation, the 2 methods were compared in a randomized control trial in 49 children with extrahepatic portal venous obstruction who had proven bleeding from esophageal varices. Twenty-four patients were treated with sclerotherapy and 25 with band ligation. No significant differences were found between the sclerotherapy and ligation groups in arresting active index bleeding (100% each) and achieving variceal eradication (91.7% vs. 96%, P =.61). Band ligation eradicated varices in fewer endoscopic sessions than did sclerotherapy (3.9 +/- 1.1 vs. 6.1 +/- 1.7, respectively, P <.0001). The rebleeding rate was significantly higher in the sclerotherapy group (25% vs. 4%, P =.049), as was the rate of major complications (25% vs. 4%, P =.049). After eradication, esophageal variceal recurrence was not significantly different in patients treated by ligation than by sclerotherapy (17.4% vs. 10%, P =.67). In conclusion, variceal band ligation in children is a safe and effective technique that achieves variceal eradication more quickly, with a lower rebleeding rate and fewer complications compared with sclerotherapy.