Defective UiO-66/cellulose nanocomposite aerogel for the adsorption of heterocyclic aromatic amines.

Heterocyclic aromatic amines (HAAs), arising as chemical derivatives during the high-temperature culinary treatment of proteinaceous comestibles, exhibit notable carcinogenic potential. In this paper, a composite aerogel (AGD-UiO-66) with high-capacity and fast adsorption of HAAs was made with anchoring defective UiO-66 (D-UiO-66) mediated by lauric acid on the backbone of cellulose nanofibers (CNF). AGD-UiO-66 with hierarchical porosity reduced the mass transfer efficiency for the adsorption of HAAs and achieved high adsorption amount (0.84-1.05 µmol/g) and fast adsorption (15 min). The isothermal adsorption model demonstrated that AGD-UiO-66 belonged to a multilayer adsorption mechanism for HAAs. Furthermore, AGD-UiO-66 was successfully used to adsorb 12 HAAs in different food (roasted beef, roasted pork, roasted salmon and marinade) with high recoveries of 94.65%-104.43%. The intrinsic potential of AGD-UiO-66 demonstrated that it could be widely applicable to the adsorption of HAAs in foods.

In-situ growth of metal-organic frameworks on cellulose nanofiber aerogels for rapid adsorption of heterocyclic aromatic amines.

Heterocyclic aromatic amines (HAAs) are the main carcinogens produced during thermal processing of protein-rich foods. In this paper, a composite aerogel (TOCNFCa) with a stabilized dual-network structure was prepared via a template for the in-situ synthesis of UiO-66 on cellulose for the adsorption of HAAs in food. The dual-network structure of TOCNFCa provides the composite aerogel with excellent wet strength, maintaining excellent compressive properties. With the in-situ grown UiO-66 content up to 71.89 wt%, the hierarchical porosity endowed TOCNFCa@UiO-66 with the ability to rapidly adsorb HAAs molecules with high capacity (1.44-5.82 µmol/g). Based on excellent thermal stability, adsorption capacity and anti-interference, TOCNFCa@UiO-66 achieved satisfactory recoveries of HAAs in the boiled marinade, which is faster and more economical than the conventional SPE method. Moreover, TOCNFCa@UiO-66 could maintain 84.55 % of the initial adsorption capacity after 5 times of reuse.

Rapid and large-capacity adsorption of heterocyclic aromatic amines on heat resistant two-dimensional metal organic layer/cellulose nanofiber aerogels constructed by a thawing cross-linking strategy.

Composite aerogels, formed by the combination of nanoscale polymers and highly efficient adsorbents, offer the potential to deploy adsorbent distinct separation properties into a processable matrix. This paper presents a method for the fabrication of low energy bio-aerogels with high ductility, excellent wet strength and favorable heat resistance, based on cellulose nanofibers (CNFs) bound by calcium carbonate particles (CaCO3) via a simple process of ice induction, cross-linking during freezing and freeze-drying. Due to induced defects, two-dimensional metal-organic layers (MOLs) were rich in mesoporous structure and embedded in the aerogel (AGCa-MOL), which exhibited a powerful adsorption capacity. AGCa-MOL could take full advantage of their hierarchical pores and available surface area to obtain high adsorption capacity (0.694-5.470 µmol/g) and rapid adsorption kinetics (5 min) for 14 heterocyclic aromatic amines (HAAs). Moreover, the CaCO3 particles and MOLs gave the AGCa-MOL excellent thermal stability, so that it could maintain excellent adsorption capacity at a high temperature (100 °C) and be applied as an adsorbent to remove HAAs in the boiling marinade. The intrinsic potential of composite aerogels was revealed due to the synergistic properties of the various components in the composite aerogel.

Amino carboxymethyl chitosan//dialdehyde starch/polyvinyl alcohol double-layer film loaded with ε-polylysine.

To develop food packaging with good antibacterial activity and mechanical performance, four amino carboxymethyl chitosan (ACC)//dialdehyde starch (DAS) /polyvinyl alcohol (PVA) films were prepared by Schiff base and hydrogen bond interactions for efficient loading and release of ε-polylysine (ε-PL). The effects of the Schiff base reaction on the physicochemical properties of the films were explored based on the different aldehyde group contents in DAS. The ACC//DAS4/PVA film exhibited a tensile strength of 62.5 MPa, and the water vapor and oxygen permeability was 8.77 × 10-3·g·mm/m2·d·kPa and 0.15 × 103·cm3·mm/m2·d, respectively. By leveraging the Schiff base reaction, the film swelling properties were improved by adjusting the cross-link density, mesh size, and molecular mass between the cross-links. The ACC//DAS4/PVA film could efficiently load ε-PL with a value of 98.44% and long-term release in a food simulant of 10% ethanol at 25 °C for 120 min. Moreover, the ACC-ε-PL//DAS4/PVA film was successfully used for salmon preservation.

Hierarchical Porous Nanocellulose Aerogels Loaded with Metal-Organic Framework Particles for the Adsorption Application of Heterocyclic Aromatic Amines.

This work overcomes the long-standing challenge of cumbersome pretreatment methods in the detection of heterocyclic aromatic amines (HAAs). A UiO-66/nanocellulose composite aerogel (CMC-CNC-UiO-66) with layered pores and low density prepared by a self-cross-linking method is applied as a simple and rapid adsorbent for capturing 14 HAAs via strong electrostatic interactions, van der Waals force, and the steric effect. The adsorption capacity of CMC-CNC-UiO-66 to 14 HAAs reached 98.00-188.00 nmol/mg at equilibrium within 10 min. The adsorption and desorption abilities of CMC-CNC-UiO-66 were retained with values of 93.36 and 97.34% after two cycles. In the meantime, the kinetics study demonstrated the chemisorption between HAA molecules and CMC-CNC-UiO-66 due to the excellent agreement with the pseudo-second-order adsorption models. The fit with the Freundlich isotherm models suggested a multilayer adsorption mechanism between HAA molecules and materials with heterogeneous surfaces. Moreover, coupled with the ultrahigh-performance liquid chromatography-tandem mass spectrometry detection, the CMC-CNC-UiO-66 extraction process can be completed with a high average recovery ranging from 86.68 to 115.33%, indicating a potential application of CMC-CNC-UiO-66 in HAA adsorption for further quantitative analysis.

Preparation of chitosan-cellulose-benzyl isothiocyanate nanocomposite film for food packaging applications.

To improve the mechanical and barrier properties of cellulose and chitosan (CS) and to allow the application of volatile antibacterial benzyl isothiocyanate (BITC) in active packaging, a double-layer nanocomposite film was prepared. Cellulose nanofibers (CNF) were crosslinked with CS via genipin to build the substrate. Quaternized cellulose nanocrystals (QCNC) were synthesized for carrying BITC as the coating material. By the layer-by-layer self-assembly approach, CS-CNF/QCNC-BITC film was fabricated. This film possessed the tensile strength of 33.75 MPa, low permeabilities of oxygen (6.9 × 10-17 m3/s·m·Pa) and moisture (1.2 × 10-11 g/s·m·Pa), and good antibacterial activity with the inhibition zone diameters of 4.9, 4.2 and 2.7 cm against Escherichia coli, Salmonella typhimurium and Staphylococcus aureus. The total viable count, total volatile basic nitrogen and thiobarbituric acid-reactive substances of the chicken wrapped CS-CNF/QCNC-BITC were only 4.4 log CFU/g, 17.7 mg/100 g and 0.44 mg/kg at 14 days, indicating a potential application of CS-CNF/QCNC-BITC for food packaging.

Novel procyanidins-loaded chitosan-graft-polyvinyl alcohol film with sustained antibacterial activity for food packaging.

Active food packaging materials containing procyanidins (PC) exhibits outstanding antimicrobial activity, but PC is easy to be hydrolyzed by acid. A novel water-soluble chitosan (CS)-based copolymer was prepared to be used as a carrier to provide a pH-stable environment for loading PC. CS was copolymerized with polyvinyl alcohol (PVA) via a coupling reagent-mediated approach. The CS-graft-PVA film exhibited a desirable PC encapsulation efficiency of over 95% and excellent long-term release sustainability, which was better than the conventional CS and CS-blend-PVA films. Moreover, CS-graft-PVA film had satisfactory mechanical properties and barrier properties, as well possessed a desirable antibacterial activity and biofilm inhibition against foodborne pathogenic microbes and spoilage bacteria. The film was also applied in the salmon muscle perseveration and showed a potential ability to prevent microorganism contamination and texture deterioration in 10 days. These results suggested that the CS-graft-PVA film has an excellent promise for future food packaging applications.

Antibacterial Activity and Potential Application in Food Packaging of Peptides Derived from Turbot Viscera Hydrolysate.

As a good choice for food preservation, antimicrobial peptides (AMPs) have received much attention in recent years. In this paper, peptides derived from the turbot viscera hydrolysate were identified by ultraperformance liquid chromatography-quadrupole time-of-flight mass spectrometry (UPLC-Q-TOF-MS/MS), and the physicochemical properties and structural characteristics were analyzed by in silico tools. Furthermore, three cationic peptides with potential hydrophobicity and amphipathy were synthesized; their cytotoxicity, hemolysis, and antibacterial activities were investigated. In particular, Sm-A1 (GITDLRGMLKRLKKMK), a peptide with 16 amino acids, showed an outstanding antibacterial activity against both Gram-positive and Gram-negative bacteria by damaging the cell membrane integrity. Moreover, Sm-A1 was successfully loaded into hydroxyl-rich poly(vinyl alcohol) (PVA)/chitosan (CS) hydrogel to improve the antibacterial activity and biofilm inhibition effect. PVA/CS+7.5‰ Sm-A1 hydrogel can satisfactorily protect the salmon muscle from the microbiological contamination and texture deterioration.

Detection of Histamine Based on Gold Nanoparticles with Dual Sensor System of Colorimetric and Fluorescence.

Gold nanoparticles (Au-NPs), with the dual sensor system of colorimetric and fluorescence responses, were developed for the determination of histamine as a spoilage monitor for distinguishing lifetime and freshness of aquatic products. Upon addition of histamine, the absorption coefficient orders of magnitude via the interaction of free electrons and photons were affected, and the characteristic absorption peak of Au-NPs was red-shifted from 520 nm to 664 nm. Meanwhile, the large amino groups in the networks of histamine-Au-NPs with high molecular orbital exhibited excellent fluorescence behavior at 415 nm. Au-NPs offered a range of 0.001-10.0 µM and 0.01-1.0 µM with a limit of detection of 0.87 nM and 2.04 nM by UV-vis and fluorescence spectrum assay, respectively. Moreover, Au-NPs could be used to semiquantitatively analyze histamine with the naked eye, since the significant colorimetric and fluorescence reaction of Au-NPs solution that coincided with different concentrations of histamine can be observed as the histamine concentration was 0.1-1.0 µM. Both of the dual-sensor systems of Au-NPs were successfully applied to the quantitative analysis of histamine in fresh salmon muscle, suggesting the simplicity and rapidity in the dual detection approaches of Au-NPs might be suitable for spoilage assay of aquatic food to ensure food safety.

Transcriptomic Analysis, Motility and Biofilm Formation Characteristics of Salmonella typhimurium Exposed to Benzyl Isothiocyanate Treatment.

Salmonella typhimurium (S. typhimurium) is a common foodborne pathogen that not only causes diseases and contaminates food, but also causes considerable economic losses. Therefore, it is necessary to find effective and feasible methods to control S. typhimurium. In this study, changes in S. typhimurium after treatment with benzyl isothiocyanate (BITC) were detected by transcriptomics to explore the antibacterial effect of BITC at subinhibitory concentration. The results showed that, in contrast to the control group (SC), the BITC-treated group (SQ_BITC) had 197 differentially expressed genes (DEGs), of which 115 were downregulated and 82 were upregulated. We screened out eight significantly downregulated virulence-related genes and verified gene expression by quantitative Real-time Polymerase Chain Reaction (qRT-PCR). We also selected motility and biofilm formation to observe the effects of BITC on the other virulence related factors of S. typhimurium. The results showed that both swimming and swarming were significantly inhibited. BITC also had a significant inhibitory effect on biofilm formation, and showed an effect on bacterial morphology. These results will be helpful for understanding the mechanism of the antibacterial action of BITC against S. typhimurium and other foodborne pathogens.

AHLs Regulate Biofilm Formation and Swimming Motility of Hafnia alvei H4.

The aim of this study was to evaluate the role of N-acyl homoserine lactones (AHLs) in the regulation of swimming motility of Hafnia alvei H4 and its biofilm formation on 96-well plate, glass and stainless-steel surfaces. The luxI gene, which codes for an enzyme involved in AHL synthesis, was deleted to generate a luxI mutant (ΔluxI). The mutant produced no AHL, and the relative expression of the luxR gene was significantly (P < 0.05) decreased. In addition, qRT-PCR analysis showed that the relative expression of the luxR gene in ΔluxI was stimulated by the presence of exogenous AHLs (C4-HSL, C6-HSL, and 3-o-C8-HSL) added at concentrations ranging from of 50-250 µg/ml. Among the three AHLs, C6-HSL had the strongest effect. The ability of ΔluxI to form biofilm on 96-well plate, glass and stainless-steel surfaces was significantly reduced (P < 0.05) compared with the wild type (WT), but was increased when provided with 150 µg/ml C4-HSL, whereas C6-HSL and 3-o-C8-HSL had no effect. Scanning electron microscopy analysis of the biofilm revealed less bacteria adhering to the surface of stainless-steel and fewer filaments were found binding to the cells compared with the WT. Furthermore, ΔluxI also exhibited significant (P < 0.05) decrease in the expression of biofilm- and swimming motility-related genes, flgA, motA and cheA, consistent with the results observed for biofilm formation and swimming motility. Taken together, the results suggested that in H. alvei H4, C4-HSL may act as an important molecular signal through regulating the ability of the cells to form biofilm, as well as through regulating the swimming motility of the cell, and this could provide a new way to control these phenotypes of H. alvei in food processing.

Transcriptomic Analysis of Vibrio parahaemolyticus Reveals Different Virulence Gene Expression in Response to Benzyl Isothiocyanate.

Vibrio parahaemolyticus isolated from seafood is a pathogenic microorganism that leads to several acute diseases that are harmful to our health and is frequently transmitted by food. Therefore, there is an urgent need for the control and suppression of this pathogen. In this paper, transcriptional analysis was used to determine the effect of treatment with benzyl isothiocyanate (BITC) extracted from cruciferous vegetables on V. parahaemolyticus and to elucidate the molecular mechanisms underlying the response to BITC. Treatment with BITC resulted in 332 differentially expressed genes, among which 137 genes were downregulated, while 195 genes were upregulated. Moreover, six differentially expressed genes (DEGs) in RNA sequencing studies were further verified by quantitative real-time polymerase chain reaction (qRT-PCR). Genes found to regulate virulence encoded an l-threonine 3-dehydrogenase, a GGDEF family protein, the outer membrane protein OmpV, a flagellum-specific adenosine triphosphate synthase, TolQ protein and VirK protein. Hence, the results allow us to speculate that BITC may be an effective control strategy for inhibiting microorganisms growing in foods.

Influence of Oxygen-Containing Sulfur Flavor Molecules on the Stability of ß-Carotene under UVA Irradiation.

The influence of 11 kinds of oxygen-containing sulfur flavor molecules was examined on ß-carotene stability under UVA irradiation in ethanol system. Both the effects of sulfides on dynamic degradation of ß-carotene and the relation between structure and effect were investigated. The oxidation products of ß-carotene accelerated by sulfides under UVA irradiation were also identified. The results indicated that the disulfides had more obvious accelerative effects on the photodegradation of ß-carotene than mono sulfides. The degradation of ß-carotene after methyl (2-methyl-3-furyl) disulfide (MMFDS), methyl furfuryl disulfide (MFDS) and bis(2-methyl-3-furyl) disulfide (BMFDS) exposure followed first-order kinetics. Furan-containing sulfides such as MMFDS and BMFDS showed more pronounced accelerative effects than their corresponding isomers. The oxidation products were identified as 13-cis-ß-carotene, 9,13-di-cis-ß-carotene and all-trans-5,6-epoxy-ß-carotene. These results suggest that both the sulfur atom numbers and the furan group in oxygen-containing sulfides play a critical role in the photooxidation of ß-carotene.

Characteristics of N-Acylhomoserine Lactones Produced by Hafnia alvei H4 Isolated from Spoiled Instant Sea Cucumber.

This study aimed to identify N-acylhomoserine lactone (AHL) produced by Hafnia alvei H4, which was isolated from spoiled instant sea cucumber, and to investigate the effect of AHLs on biofilm formation. Two biosensor strains, Chromobacterium violaceum CV026 and Agrobacterium tumefaciens KYC55, were used to detect the quorum sensing (QS) activity of H. alvei H4 and to confirm the existence of AHL-mediated QS system. Thin layer chromatography (TLC) and high resolution triple quadrupole liquid chromatography/mass spectrometry (LC/MS) analysis of the AHLs extracted from the culture supernatant of H. alvei H4 revealed the existence of at least three AHLs: N-hexanoyl-l-homoserine lactone (C6-HSL), N-(3-oxo-octanoyl)-l-homoserine lactone (3-oxo-C8-HSL), and N-butyryl-l-homoserine lactone (C4-HSL). This is the first report of the production of C4-HSL by H. alvei. In order to determine the relationship between the production of AHL by H. alvei H4 and bacterial growth, the ß-galactosidase assay was employed to monitor AHL activity during a 48-h growth phase. AHLs production reached a maximum level of 134.6 Miller unites at late log phase (after 18 h) and then decreased to a stable level of about 100 Miller unites. AHL production and bacterial growth displayed a similar trend, suggesting that growth of H. alvei H4 might be regulated by QS. The effect of AHLs on biofilm formation of H. alvei H4 was investigated by adding exogenous AHLs (C4-HSL, C6-HSL and 3-oxo-C8-HSL) to H. alvei H4 culture. Biofilm formation was significantly promoted (p < 0.05) by 5 and 10 µM C6-HSL, inhibited (p < 0.05) by C4-HSL (5 and 10 µM) and 5 µM 3-oxo-C8-HSL, suggesting that QS may have a regulatory role in the biofilm formation of H. alvei H4.

Inhibition of Hafnia alvei H4 Biofilm Formation by the Food Additive Dihydrocoumarin.

Quorum sensing (QS) is an intercellular signaling and gene regulatory mechanism that is implicated in food spoilage caused by bacteria. Thus, blocking QS may suppress QS-controlled phenotypes of these bacteria that are responsible for food spoilage. Biofilm formation is closely related to bacterial infection, and it is also a major mechanism responsible for the increased resistance of biofilm-associated bacteria to antimicrobial drugs. Food spoilage and biofilm formation caused by food-related bacteria have posed a significant problem for the food industry. Thus, adopting an antibiofilm approach would provide an alternative to an antibiotic strategy. Dihydrocoumarin is a compound that is derived from coumarin, a known natural QS inhibitor that has been used as an additive in food. Hafnia alvei is a spoilage bacterium; H. alvei H4 was isolated from ready-to-eat sea cucumber. Considering that QS and biofilm are often closely linked, this research aimed to detect the effect of dihydrocoumarin on the production of violacein by Chromobacterium violaceum 026 and to evaluate the inhibitory effect of dihydrocoumarin on the formation of biofilm by H. alvei H4 by using violacein and crystal violet assays. C. violaceum 026 treated with dihydrocoumarin showed as much as 70.1% reduction in QS-mediated production of violacein compared with untreated cells, while exhibiting no significant change in growth. H. alvei H4 treated with dihydrocoumarin displayed 75.8% reduction in swimming motility, and as much as 89.4% reduction in biofilm formation compared with the nontreated cells, with the reduction in both cases being dependent on the concentration of dihydrocoumarin. Scanning electron microscopy showed that dihydrocoumarin could effectively destroy the biofilm structure of H. alvei H4 and decrease biofilm density. These findings indicate that dihydrocoumarin can be developed into a new QS inhibitor or antibiofilm agent for controlling food spoilage and potentially investigated to increase food safety.

Oxidative stress-mediated antiproliferative effects of furan-containing sulfur flavors in human leukemia Jurkat cells.

Antiproliferative effects of 15 sulfides were investigated in human leukemia Jurkat cells. Treatment with 5-50 µM of nine monosulfides and two linear disulfides did not induce DNA fragmentation. Whereas, furan-containing sulfur flavors including methyl 2-methyl-3-furyl disulfide (MMFDS), bis (2-methyl-3-furyl) disulfide (BMFDS), methyl furfuryl disulfide (MFDS) and difurfuryl disulfide (DFDS) induced DNA fragmentation to a varying extent in Jurkat cells. The cell viability-reduction effect of these sulfur flavors was in the following order: DFDS>BMFDS>MMFDS>>MFDS based on the IC50 values. MMFDS and BMFDS, but not DFDS, significantly increased the intracellular ROS level by 1.90- and 3.02-fold, respectively. Addition of N-acetylcysteine (NAC) or glutathione (GSH) partially suppressed induction of DNA fragmentation, apoptosis and caspase-3 activation by MMFDS and BMFDS. These results suggest that the furan-containing disulfides have a strong antiproliferative effect, and the oxidative stress and subsequent caspase-3 activation are involved in antiproliferative effect induced by MMFDS and BMFDS in Jurkat cells.