Synthesis and antibacterial properties of fluorinated biodegradable cationic polyesters.

Antimicrobial peptide-mimicking antibacterial polymers represent a practical strategy to conquer the ever-growing threat of antimicrobial resistance. Herein, we report the syntheses and antibacterial performance of degradable amphiphilic cationic polyesters containing pendent quaternary ammonium motifs and hydrophobic alkyl or fluoroalkyl groups. These polyesters were conveniently prepared from poly(3-methylene-1,5-dioxepan-2-one) via highly efficient one-pot successive thiol-Michael addition reactions. The antibacterial activity of these polyesters against S. aureus and E. coli and their hemolytic activity toward red blood cells were evaluated; some of them showed moderate antibacterial activity and selectivity against Gram-positive S. aureus. The membrane disruption mechanism of these cationic polyesters was briefly explored by monitoring the bacteria killing kinetics and SEM observations. Moreover, the effects of cationic/hydrophobic ratio and the incorporation of fluoroalkyl groups on the antibacterial activity and selectivity of the polyesters were demonstrated.

Enhancing the AI-2/LuxS quorum sensing system in Lactiplantibacillus plantarum: Effect on the elimination of biofilms grown on seafoods.

The biofilm clustered with putrefying microorganisms and seafood pathogens could cover the surface of aquatic products that pose a risk to cross-contaminating food products or even human health. Fighting biofilms triggers synchronous communication associated with microbial consortia to regulate their developmental processes, and the enhancement of the quorum sensing system in Lactiplantibacillus plantarum can serve as an updated starting point for antibiofilm-forming strategies. Our results showed that the exogenous 25 mM L-cysteine induced a significant strengthening in the AI-2/LuxS system of Lactiplantibacillus plantarum SS-128 along with a stronger bacteriostatic ability, resulting in an effective inhibition of biofilms formed by the simplified microbial consortia constructed by Vibrio parahaemolyticus and Shewanella putrefaciens grown on shrimp and squid surfaces. The accumulation of AI-2 allowed the suppression of the expression of biofilm-related genes in V. parahaemolyticus under the premise of L. plantarum SS-128 treatment, contributing to the inhibition effect. In addition, strengthening the AI-2/LuxS system is also conducive to eliminating preexisting biofilms by L. plantarum SS-128. This study suggests that the enhancement of the AI-2/LuxS system of lactic acid bacteria enables the regulation of interspecific communication within biofilms to be a viable tool to efficiently reduce and eradicate potentially harmful biofilms from aquatic product sources, opening new horizons for combating biofilms.

Exploring the effect of Lactiplantibacillus plantarum Lac 9-3 with high adhesion on refrigerated shrimp: Adhesion modeling and biopreservation evaluation.

Lactic acid bacteria (LAB) have recently become ideal candidates for developing food biopreservatives. Adhesion is critical for LAB to perform biocontrol functions in food processing and preservation. In this study, we innovatively proposed an effective adhesion evaluation model related to the surface properties of LAB to excavate a LAB strain with high adhesion on the surface of shrimp. Then, the biocontrol potential regarding the quality of refrigerated shrimp was explored, especially for protein quality. The screening of highly adherent LAB was performed using 54 LAB strains tolerant to the low temperature (4 °C) and present antimicrobial activity. Based on surface hydrophobicity, autoaggregation, and biofilm formation, a new method for predicting LAB adhesion was established by stepwise multiple linear regression. The most relevant relationship between adhesion and biofilm formation was derived from the model. Lactiplantibacillus plantarum Lac 9-3 stood out for the strongest adhesion on the shrimp surface and the highest antimicrobial activity. The preservation results showed that Lac 9-3 significantly (p < 0.05) retarded the accumulation of total volatile basic nitrogen (TVB-N) and the growth of spoilage bacteria. The damage to the texture properties of shrimp was inhibited. Meanwhile, the degradation of myofibrillar protein was alleviated, including a significant delay (p < 0.05) in sulfhydryl (SH) group reduction, surface hydrophobicity increases, and protein conformation changes. This research optimized the evaluation of the bacteria adhesion potential, providing a new idea for developing biocontrol strategies to extend the commercial life of aquatic products.

Synthesis and Post-Functionalization of Poly(conjugated ester)s Based on 3-Methylene-1,5-dioxepan-2-one.

Poly(α-methylene ester)s are an attractive type of functional aliphatic polyesters that represent a platform for the fabrication of various biodegradable and biomedical polymers. Herein, we report the controlled ring-opening polymerization (ROP) of a seven-membered α-methylene lactone (3-methylene-1,5-dioxepan-2-one, MDXO) that was synthesized based on the Baylis-Hillman reaction. The chemoselective ROP of MDXO was catalyzed by diphenyl phosphate (DPP) at 60 °C or stannous octoate (Sn(Oct)2) at 130 °C, generating α-methylene-containing polyester (PMDXO) with a linear structure and easily tunable molar mass. The ring-opening copolymerization of MDXO with ε-caprolactone or 1,5-dioxepan-2-one was also performed under the catalysis of DPP or Sn(Oct)2 to afford copolymers with different compositions and sequence structures that are influenced by the kinds of monomers and catalysts. PMDXO is a slowly crystallizable polymer with a glass transition temperature of ca. -33 °C, and its melting temperature and enthalpy are significantly influenced by the thermal history. The thermal properties of the copolymers are dependent on their composition and sequence structure. Finally, the post-modification of PMDXO based on the thiol-Michael addition reaction was briefly explored using triethylamine as a catalyst. Given the optimized condition, PMDXO could be dually modified to afford biodegradable polyesters with different functionalities.

The role of AI-2/LuxS system in biopreservation of fresh refrigerated shrimp: Enhancement in competitiveness of Lactiplantibacillus plantarum for nutrients.

Quorum sensing of lactic acid bacteria, mediated by the Autoinducer-2 (AI-2)/LuxS system, positively regulates antibacterial activity, which is an effective strategy for aquatic product preservation. This study revealed that AI-2/LuxS system regulates the nutritional competitiveness of LAB by facilitating membrane transport systems in preservation of vacuum-packaged refrigerated shrimp (VPRS), using Lactiplantibacillus plantarum SS-128 wild-type and the luxS mutant strain. In VPRS preservation, organisms that cause spoilage and total volatile basic nitrogen were significantly lower in the VPRS inoculated with L. plantarum SS-128 than those inoculated with the luxS mutant strain (L. plantarum ΔluxS/SS-128) (p < 0.05). Simulations in vitro using diluted shrimp juice showed the growth inhibitory effects of wild-type strain SS-128 on the main VPRS spoilage microorganism Shewanella baltica. This could potentially be attributed to more efficient nutrient utilization, presumably mediated by AI-2/LuxS system, as revealed by interaction analysis. In support of this, in vitro nutritional competition test showed that L. plantarum SS-128 was more competitive for nutrients when cocultured with S. baltica under conditions of limited nutrient availability. Subsequently, an integrated analysis of transcriptomic and metabolomic revealed that AI-2/LuxS enables a continuous expansion of L. plantarum SS-128 by balancing energy expenditure followed by enhancing membrane transport systems, which is the main driven forces for it to occupy a favourable niche quickly. Our results showed that the AI-2/LuxS system may regulate the nutritional competitiveness of lactic acid bacteria and may be a regulatory strategy for biological preservation of aquatic products.

Amelioration of dextran sulfate sodium-induced colitis by autoinducer-2-deficient Lactiplantibacillus plantarum is mediated by anti-inflammatory effects and alleviation of dysbiosis of the gut microbiota.

Lactic acid bacteria (LAB) attenuate dextran sulfate sodium (DSS)-induced colitis in mice by restoring gut flora homeostasis and modulating the immune response. Because synchronous behavior can be controlled by autoinducer-2 (AI-2)/LuxS-mediated quorum sensing, the Caco-2 cell model and DSS-induced model in C57BL/6 mice were used to explore the unknown effects of these communications involving AI-2 among various intestinal symbiotic species. The results of the cell viability and lactate dehydrogenase leakage assays indicated that the tested strains (the wild-type strains and AI-2-deficient mutants) were characterized by equal cytoprotection from hydrogen peroxide-induced injury independently of AI-2. The results of the assays of multiple indicators and proinflammatory cytokines characteristic for the symptoms of colitis in mice showed that oral administration of AI-2-deficient mutants for 7 days was more effective in ameliorating inflammation than the treatment with the wild-type strains. The treatment with AI-2-deficient mutants enriched potential probiotics (e.g., Lactobacillaceae) and controlled the proliferation of potentially harmful bacteria (e.g., Helicobacteraceae) to achieve the transformation of intestinal flora. These mutants regulated short-chain fatty acids and the intestinal epithelial barrier, thereby promoting the maintenance of relatively favorable intestinal homeostasis. These results demonstrated that the AI-2-deficient mutants provided a more pronounced ameliorative effect on colitis in a mouse model, suggesting that the background of the LAB effect is associated with the alterations in colonic flora induced by AI-2.

AI-2/Lux-S Quorum Sensing of Lactobacillus plantarum SS-128 Prolongs the Shelf Life of Shrimp (Litopenaeus vannamei): From Myofibril Simulation to Practical Application.

Retarding the protein deterioration of shrimp during storage is important for maintaining its quality. Lactobacillus plantarum SS-128 (L. plantarum SS-128) is a biocontrol bacterium that can effectively maintain the fresh quality of food. This research establishes a myofibril simulation system and refrigerated control system to explore the impact of L. plantarum SS-128 on the quality and shelf life of refrigerated shrimp (Litopenaeus vannamei). Through the bacterial growth assay and AI-2 signal molecule measurement, the effect of the AI-2/LuxS quorum sensing (QS) system of L. plantarum SS-128 and shrimp spoilage bacteria was established. In the myofibril simulation system, a study on protein degradation (dimer tyrosine content, protein solubility, sulfhydryl content, and carbonyl content) showed that adding L. plantarum SS-128 effectively slowed protein degradation by inhibiting the growth of food pathogens. The application to refrigerated shrimp indicated that the total volatile basic nitrogen (TVB-N) value increased more slowly in the group with added L. plantarum SS-128, representing better quality. The total viable count (TVC) and pH results exhibited similar trends. This study provides theoretical support for the application of L. plantarum SS-128 in storing aquatic products.

LuxS in Lactobacillus plantarum SS-128 Improves the Texture of Refrigerated Litopenaeus vannamei: Mechanism Exploration Using a Proteomics Approach.

This study illustrated the texture changes of Shewanella baltica-inoculated Litopenaeus vannamei during refrigerated storage with the exogenous addition of Lactobacillus plantarum SS-128. The group inoculated with SS-128 had an improved texture compared with that inoculated with the luxS-mutant group (ΔluxS). Proteomics were conducted to analyze the protein alterations in L. vannamei and supernatant, respectively. During storage, many texture-related proteins, including myosin heavy chain and beta-actin, were maintained due to luxS. Some endogenous enzymes related to the energy metabolism and hydrolysis of L. vannamei were downregulated. The luxS-induced interaction with S. baltica showed significant changes in the expression of some critical enzymes and pathways. The ATP-dependent zinc metalloprotease FtsH and protease subunit HslV were downregulated, and the oxidative phosphorylation and glycosaminoglycan degradation pathways in S. baltica were inhibited, resulting in the slow deterioration of L. vannamei. By exploring the mechanism underlying SS-128-led manipulation of the metabolism of spoilage bacteria, we clarified the texture maintenance mechanism of luxS in SS-128, providing theoretical evidence for SS-128 application in food preservation.

Combined Anti-Biofilm Enzymes Strengthen the Eradicate Effect of Vibrio parahaemolyticus Biofilm: Mechanism on cpsA-J Expression and Application on Different Carriers.

Vibrio parahaemolyticus is a human foodborne pathogen, and it can form a mature biofilm on food and food contact surfaces to enhance their resistance to antibacterial agents. In this study, the effect of anti-biofilm enzymes (combined lipase, cellulase and proteinase K) on the inhibition and eradication of pathogen biofilm was evaluated. The biofilm content of V. parahaemolyticus showed the highest level at the incubation time of 24 h, and the combined enzymes significantly inhibited the biofilm's development. The biofilm's inhibition and eradication rate at an incubation time of 24 h was 89.7% and 66.9%, respectively. The confocal laser scanning microscopic images confirmed that the microcolonies' aggregation and the adhesion of biofilm were inhibited with the combined enzyme treatment. Furthermore, combined enzymes also decreased the concentration of exopolysaccharide (EPS) and disrupted the EPS matrix network, wherein the expression of the EPS-related gene, cpsA-J, was likewise suppressed. The combined enzymes showed an excellent inhibition effect of V. parahaemolyticus biofilm on different carriers, with the highest inhibition rate of 59.35% on nonrust steel plate. This study demonstrates that the combined enzyme of lipase, cellulase and proteinase K could be a novel candidate to overcome biofilm's problem of foodborne pathogens in the food industry.

Dissecting of the AI-2/LuxS Mediated Growth Characteristics and Bacteriostatic Ability of Lactiplantibacillus plantarum SS-128 by Integration of Transcriptomics and Metabolomics.

Lactiplantibacillus plantarum could regulate certain physiological functions through the AI-2/LuxS-mediated quorum sensing (QS) system. To explore the regulation mechanism on the growth characteristics and bacteriostatic ability of L. plantarum SS-128, a luxS mutant was constructed by a two-step homologous recombination. Compared with ΔluxS/SS-128, the metabolites of SS-128 had stronger bacteriostatic ability. The combined analysis of transcriptomics and metabolomics data showed that SS-128 exhibited higher pyruvate metabolic efficiency and energy input, followed by higher LDH level and metabolite overflow compared to ΔluxS/SS-128, resulting in stronger bacteriostatic ability. The absence of luxS induces a regulatory pathway that burdens the cysteine cycle by quantitatively drawing off central metabolic intermediaries. To accommodate this mutations, ΔluxS/SS-128 exhibited lower metabolite overflow and abnormal proliferation. These results demonstrate that the growth characteristic and metabolism of L. plantarum SS-128 are mediated by the AI-2/LuxS QS system, which is a positive regulator involved in food safety. It would be helpful to investigate more bio-preservation control potential of L. plantarum, especially when applied in food industrial biotechnology.

Phycocyanin ameliorates mouse colitis via phycocyanobilin-dependent antioxidant and anti-inflammatory protection of the intestinal epithelial barrier.

Phycocyanin is a typical microalgal active compound with antioxidant and anti-inflammatory efficacy, and the pigment moiety phycocyanobilin has been recently proposed as its active structural component. Here, to explore the structural basis for phycocyanin's intestinal protective action, we evaluated the therapeutic effects and mechanism of action of phycocyanin and phycocyanobilin in dextran sodium sulphate (DSS)-induced colitis mice and in Caco-2 and RAW 264.7 cells. Phycocyanobilin was obtained by solvothermal alcoholysis of phycocyanin and characterized by spectroscopy and mass spectrometry methods. Phycocyanin, phycocyanobilin and a positive drug mesalazine were intragastrically administered to C57BL/6 mice daily for 7 days during and after 4-day DSS exposure. Clinical signs and colon histopathology revealed that phycocyanin and phycocyanobilin had an equivalent anti-colitis efficacy that was even superior to mesalazine. Based on biochemical analysis of colonic tight junction proteins, mucus compositions and goblet cells, and colonic and peripheral proinflammatory cytokines, phycocyanin and phycocyanobilin displayed equivalent intestinal epithelial barrier-protecting and anti-inflammatory potential that was evidently superior to that of mesalazine. Flow cytometry analysis of phycocyanobilin fluorescence in Caco-2 cells unveiled a similar uptake efficacy of phycocyanin and phycocyanobilin by intestinal epithelial cells. According to lactic dehydrogenase release, 2',7'-dichlorodihydrofluorescein fluorescence and methylthiazolyldiphenyl-tetrazolium bromide assay in Caco-2 cells, phycocyanin and phycocyanobilin could equally and effectively protect the intestinal epithelial barrier from oxidant-induced disruption. Phycocyanin and phycocyanobilin also showed equivalent anti-inflammatory effects in tumor necrosis factor-α-stimulated Caco-2 cells and in lipopolysaccharides- and tumor necrosis factor-α-activated RAW264.7 cells. Overall, our results demonstrate the phycocyanobilin-dependent anti-colitis role of phycocyanin via antioxidant and anti-inflammatory mechanisms.

Engineering Achiral Liquid Crystalline Polymers for Chiral Self-Recovery.

Flexible construction of permanently stored supramolecular chirality with stimulus-responsiveness remains a big challenge. Herein, we describe an efficient method to realize the transfer and storage of chirality in intrinsically achiral films of a side-chain polymeric liquid crystal system by combining chiral doping and cross-linking strategy. Even the helical structure was destroyed by UV light irradiation, the memorized chiral information in the covalent network enabled complete self-recovery of the original chiral superstructure. These results allowed the building of a novel chiroptical switch without any additional chiral source in multiple types of liquid crystal polymers, which may be one of the competitive candidates for use in stimulus-responsive chiro-optical devices.

Dynamics of the prokaryotic and eukaryotic microbial community during a cyanobacterial bloom.

Toxic cyanobacterial blooms frequently develop in eutrophic freshwater bodies worldwide. Microcystis species produce microcystins (MCs) as a cyanotoxin. Certain bacteria that harbor the mlr gene cluster, especially mlrA, are capable of degrading MCs. However, MC-degrading bacteria may possess or lack mlr genes (mlr+ and mlr- genotypes, respectively). In this study, we investigated the genotype that predominantly contributes to biodegradation and cyanobacterial predator community structure with change in total MC concentration in an aquatic environment. The 2 genotypes coexisted but mlr+ predominated, as indicated by the negative correlation between mlrA gene copy abundance and total MC concentration. At the highest MC concentrations, predation pressure by Phyllopoda, Copepoda, and Monogononta (rotifers) was reduced; thus, MCs may be toxic to cyanobacterial predators. The results suggest that cooperation between MC-degrading bacteria and predators may reduce Microcystis abundance and MC concentration.

Preparation and characterization of metal-tea polysaccharide complexes and their inhibition on α-glucosidase.

The preparation method and the sources of metal elements may affect the activity of the metal-polysaccharide complex. In this study, four Fe-tea polysaccharide complexes were prepared and three tea polysaccharides (TPSs) from different seasons were extracted. Moreover, the binding mode of TPSs with internal and external metallic elements as well as their inhibitory effect on α-glucosidase was explored. The results revealed that the binding mode (-C-O-Fe and -C-Fe) of the Fe-TPS complex prepared at pH 5.0 was closer to TPS with internal metallic elements. The TPS with the least amount of internal metallic elements (61.72 mg/g) exhibited a high inhibitory activity on α-glucosidase (37.90%). The inhibitory activity of Fe-TPS on α-glucosidase was lower than that without Fe. But the quenching effect and the inhibition type of TPSs on α-glucosidase were not affected by metallic elements. Therefore, the metallic elements have the potential to reduce the hypoglycemic activity of TPS. PRACTICAL APPLICATIONS: In this paper, TPS was extracted from crude tea in different seasons, and the effects of metallic elements in TPS on hypoglycemic activity, physicochemical properties, and structure of TPS were discussed. TPS metal complexes were prepared by adding Fe3+ or removing metallic elements, and the differences of internal metallic elements in TPS were discussed. It is of great academic significance to use tea pruned leaves and crude tea as potential resources to develop polysaccharide hypoglycemic products and to reveal the relationship between TPS metal ions and their structure and activity. In addition, it has guiding value for consumers to choose tea-producing regions and growers to choose chemical fertilizer.

Supramolecular Chirality in Azobenzene-Containing Polymer System: Traditional Postpolymerization Self-Assembly Versus In Situ Supramolecular Self-Assembly Strategy.

Recently, the design of novel supramolecular chiral materials has received a great deal of attention due to rapid developments in the fields of supramolecular chemistry and molecular self-assembly. Supramolecular chirality has been widely introduced to polymers containing photoresponsive azobenzene groups. On the one hand, supramolecular chiral structures of azobenzene-containing polymers (Azo-polymers) can be produced by nonsymmetric arrangement of Azo units through noncovalent interactions. On the other hand, the reversibility of the photoisomerization also allows for the control of the supramolecular organization of the Azo moieties within polymer structures. The construction of supramolecular chirality in Azo-polymeric self-assembled system is highly important for further developments in this field from both academic and practical points of view. The postpolymerization self-assembly strategy is one of the traditional strategies for mainly constructing supramolecular chirality in Azo-polymers. The in situ supramolecular self-assembly mediated by polymerization-induced self-assembly (PISA) is a facile one-pot approach for the construction of well-defined supramolecular chirality during polymerization process. In this review, we focus on a discussion of supramolecular chirality of Azo-polymer systems constructed by traditional postpolymerization self-assembly and PISA-mediated in situ supramolecular self-assembly. Furthermore, we will also summarize the basic concepts, seminal studies, recent trends, and perspectives in the constructions and applications of supramolecular chirality based on Azo-polymers with the hope to advance the development of supramolecular chirality in chemistry.

Effect of purity of tea polysaccharides on its antioxidant and hypoglycemic activities.

The effects of purity of tea polysaccharides (TPS) on its five antioxidant activities and hypoglycemic activities in vitro were studied. The results showed that the higher the purity of TPS, the lower the antioxidant capacity. The purity of FTPSI is the highest (sugar content 80.72%), but its antioxidant activities were lower than those of Fujian tea polysaccharides (FTPS) and FTPSII. The antioxidant activity of tea polysaccharide is related to its protein and polyphenol content (Pearson r > .90). The protective effect of Zhejiang tea polysaccharides and FTPS on human umbilical vein endothelial cells (HUVEC) was better than that of its purified fractions. The inhibition rates of FTPSII (5 and 2 mg/ml) on α-glucosidase (32.76%) and α-amylase (-11.93%) were higher than those of FTPS and FTPSII. Purification does not change the basic structure of TPS. This study has certain reference value for the study of the antioxidant activities of TPS. Meanwhile, TPS can be used as a potential resource with hypoglycemic function. PRACTICAL APPLICATIONS: A large number of studies have shown that TPS have antioxidant activity. However, several studies considered that the antioxidant activity of TPS mainly comes from the residues of tea polyphenols. Therefore, the in vitro and cell antioxidant activities of TPS were studied in this paper. We believe that both glycoprotein and tea polyphenol are antioxidants of tea, and tea polysaccharide perform preferable effect on hypoglycemic. HUVEC cell model and four in vitro antioxidant test methods were used to study the antioxidant activities of TPS, and two enzyme inhibition activities were used to study the hypoglycemic effect of TPS, in order to provide a theoretical basis for the study of biological activity of TPS.

Effects of intrinsic metal ions of lentinan with different molecular weights from Lentinus edodes on the antioxidant capacity and activity against proliferation of cancer cells.

In this study, effects of intrinsic metal ions in lentinan on its bioactivities were evaluated. Lentinan extracted from Lentinus edodes was separated to four fractions with different molecular weights with Sephadex G-200 gel chromatography, and intrinsic metal ions were removed by EDTA. The ferrous ion chelating capacity of ELWs was measured to estimate EDTA residue after extensive dialysis. Antioxidant and antitumor activities of the isolated lentinans (LWs and ELWs) were investigated in vitro and compared, respectively. The results indicated that all of the isolated lentinan contained a large amount of intrinsic metal ions and the fraction with the lowest Mw had highest metal content. After removing intrinsic metal ions, the polysaccharides showed lower ABTS and DPPH radicals scavenging capacity and the reduced inhibition of the proliferation of BXPC-3 and Hela cells. Our results indicated that the metal ions in lentinan had positive effects on its bioactivities.

Effects of metal ions in tea polysaccharides on their in vitro antioxidant activity and hypoglycemic activity.

Total tea polysaccharides (TTPS) were extracted from two kinds of pruning leaves of tea plant and fractionated into neutral tea polysaccharides (TPSI) and acidic tea polysaccharides (TPSII) by anion exchange resin D315. Some physicochemical properties, including structure, monosaccharide composition, and molecular weight distribution, as well as the 4 in vitro antioxidant activities and inhibitory effects on α-glucosidase of above polysaccharides before and after removing metal ions were investigated. By comparing TTPS and TPSII, we found that they exhibited different antioxidant activities and inhibitory actions against α-glucosidase after their metal ions were removed. However, the in vitro antioxidant activities and inhibitory effects on α-glucosidase of TPSI were substantially improved. The study can be a certain reference for tea and soil selection. At the same time, we suggested that pruning leaves of tea plant could be treated as a potential resource for the development of polysaccharide antioxidants and hypoglycemic products.