Examination of primary aromatic amines content in polylactic acid straws and migration into food simulants using SERS with LC-MS.

Polylactic acid (PLA) straws hold eco-friendly potential; however, residual diisocyanates used to enhance the mechanical strength can generate carcinogenic primary aromatic amines (PAAs), posing health risks. Herein, we present a rapid, comprehensive strategy to detecting PAAs in 18 brands of food-grade PLA straws and assessing their migration into diverse food simulants. Surface-enhanced Raman spectroscopy was conducted to rapidly screen straws for PAAs. Subsequently, qualitative determination of migrating PAAs into various food simulants (4 % acetic acid, 10 % ethanol, 50 % ethanol) occurred at 70 °C for 2 h using liquid chromatography-mass spectrometry. Three PAAs including 4,4'-methylenedianiline, 2,4'-methylenedianiline, and 2,4-diaminotoluene were detected in all straws. Specifically, 2,4-diaminotoluene in 50 % ethanol exceeded specific migration limit of 2 µg/kg, raising safety concerns. Notably, PAAs migration to 10 % and 50 % ethanol surpassed that to 4 % acetic acid within a short 2-hour period. Moreover, PLA straws underwent varying degrees of shape changes before and after migration. Straws with poly(butylene succinate) resisted deformation compared to those without, indicating enhanced heat resistance, while poly(butyleneadipate-co-terephthalate) improved hydrolysis resistance. Importantly, swelling study unveiled swelling effect wasn't the primary factor contributing to the increased PAAs migration in ethanol food simulant, as there was no significant disparity in swelling degrees across different food simulants. FT-IR and DSC analysis revealed higher PAAs content in 50 % ethanol were due to highly concentrated polar ethanol disrupting hydrogen bonds and van der Waal forces holding PLA molecules together. Overall, minimizing contact between PLA straws and alcoholic foods is crucial to avoid potential safety risks posed by PAAs.

Ammonia-responsive chitosan/polymethacrylamide double network hydrogels with high-stretchability, fatigue resistance and anti-freezing for real-time chicken breast spoilage monitoring.

Hydrogels are a promising option for detecting food spoilage in humid conditions, but current indicators are prone to mechanical flaws, posing a concern for packaging systems that require strong mechanical properties. Herein, a double network hydrogel was prepared by polymerizing methacrylamide in a chitosan system with aluminum chloride and glycerol. The resulting hydrogel demonstrated high stretchability (strain >1500 %), notch insensitivity, excellent fatigue resistance, and exceptional anti-freezing capabilities even at -21 °C. When incorporating bromothymol blue (BB) or methyl red (MR), or mixtures of these dyes into the hydrogels as indicators, they exhibited sensitive colorimetric responses to pH and NH3 levels at different temperatures. Hydrogels immobilizing BB to MR ratios of 1:1 and 1:2 displayed clearer and more sensitive color responses when packed into chicken breast, with a sensitivity level of 1.5 ppm of total volatile basic nitrogen (TVB-N). This color response correlated positively with the accumulation of TVB-N on the packaging during storage at both 25 °C and 4 °C, providing sensitive indications of chicken breast deterioration. Overall, the developed hydrogels and indicators demonstrate enhanced performance characteristics, including excellent mechanical strength and highly NH3-sensitive color responses, making significant contributions to the food spoilage detection and intelligent packaging systems field.

Extrusion-blown oxidized starch/poly(butylene adipate-co-terephthalate) biodegradable active films with adequate material properties and antimicrobial activities for chilled pork preservation.

Food safety concerns from spoilage and non-degradable packaging risk human health. Progress made in biodegradable plastic films, but limited study on biomass composite films with favorable morphological, mechanical, and inherent antibacterial properties for fresh meat preservation. Herein, we present a versatile packaging film created through the extrusion blowing process, combining oxidized starch (OST) with poly(butylene adipate-co-terephthalate) (PBAT). SEM analysis revealed even distribution of spherical OST particles on film's surface. FTIR spectra revealed new intermolecular hydrogen bonds between OST and PBAT. While combining OST slightly reduced tensile properties, all composite films met the required strength of 16.5 ± 1.39 MPa. Notably, films with 40 % OST showed over 98 % antibacterial rate against Staphylococcus aureus within 2 h. pH wasn't the main cause of bacterial growth inhibition; OST hindered growth by interfering with nutrient absorption and metabolism due to its carboxyl groups. Additionally, OST disrupted bacterial membrane integrity and cytoplasmic membrane potential. Remarkably, the OST/PBAT film excellently preserved chilled fresh pork, maintaining TVB-N level at 12.6 mg/100 g on day 6, microbial count at 105 CFU/g within 6-10 days, and sensory properties for 8 days. It extended pork's shelf life by two days compared to polyethylene film, suggesting an alternative to a synthetic material.

Sugarcane Pulp Take-Out Containers Produce More Microparticles in Acidic Foods.

In the current study, the production of microparticles released from fifteen commercial sugarcane pulp (SCP) take-out containers into different food simulants under different conditions was investigated, where deionized water (DI water), 4% acetic acid (4% HAc), and 95% ethanol (95% EtOH) were used to simulate aqueous, acidic, and fatty foods, respectively. Results showed that compared with DI water and 95% EtOH, 4% HAc caused the degradation of sugarcane fibers, thereby releasing the highest number of microparticles. The overall migration values of the sugarcane pulp take-out containers in 4% HAc were above the prescribed limit of 10 mg/dm2. Furthermore, it was estimated that consumers may intake 36,400-231,700 microparticles in a take-out container at one time, of which the proportion of particles with a particle size between 10 and 500 µm was the highest, ranging from 26,470 to 216,060 items. Moreover, the Al and Fe are the main metals in these take-out containers, ranging between 35.16 and 1244.04 and 44.71 and 398.52 mg/kg, respectively, followed by Pb, Ti, and Sr. This study provides important information that the safety of both the production of microparticles and the metallic elements should be considered for SCP take-out containers when in contact with food.

Progress in research on the safety of silicone rubber products in food processing.

Silicone rubber (SR) is widely used in the food processing industry due to its excellent physical and chemical properties. However, due to the differences in SR product production formulas and processes, the quality of commercially available SR products varies greatly, with chemical and biological hazard potentials. Residual chemicals in SR, such as siloxane oligomers and 2,4-dichlorobenzoic acid, are non-intentionally added substances, which may migrate into food during processing so the safe use of SR must be guaranteed. Simultaneously, SR in contact with food is susceptible to pathogenic bacteria growing and biofilm formation, like Cronobacter sakazakii, Staphylococcus aureus, Salmonella enteritidis, and Listeria monocytogenes, posing a food safety risk. Under severe usage scenarios such as high-temperature, high-pressure, microwave, and freezing environments with long-term use, SR products are more prone to aging, and their degradation products may pose potential food safety hazards. Based on the goal of ensuring food quality and safety to the greatest extent possible, this review suggests that enterprises need to prepare high-quality food-contact SR products by optimizing the manufacturing formula and production process, and developing products with antibacterial and antiaging properties. The government departments should establish quality standards for food-contact SR products and conduct effective supervision. Besides, the reusable SR products should be cleaned by consumers immediately after use, and the deteriorated products should be replaced as soon as possible.

Effect of neutralization treatment on properties of chitosan/bamboo leaf flavonoids/nano-metal oxide composite films and application of films in antioxidation of rapeseed oil.

Neutralization treatment improved the slow-release antioxidant food packaging function of chitosan (CS)/bamboo leaf flavone (BLF)/nano-metal oxides composite films. The film cast from the CS composite solution neutralized by KOH solution had good thermal stability. The elongation at break of the neutralized CS/BLF film was increased by about 5 times, which provided the possibility for its packaging application. After 24 h of soaking in different pH solutions, the unneutralized films swelled severely and even dissolved, while the neutralized films maintained the basic structure with a small degree of swelling, and the release trend of BLF conformed to the logistic function (R2 ≥ 0.9186). The films had a good ability to resist free radicals, which was related to the release amount of BLF and the pH of the solution. The antimicrobial neutralized CS/BLF/nano-ZnO film, like the nano-CuO and Fe3O4 films, were effective in inhibiting the increase in peroxide value and 2-thiobarbituric acid induced by thermal oxygen oxidation of rapeseed oil and had no toxicity to normal human gastric epithelial cells. Therefore, the neutralized CS/BLF/nano-ZnO film is likely to become an active food packaging material for oil-packed food, which can prolong the shelf life of packaged food.

Chemical contaminants from food contact materials and articles made from or containing wood and bamboo - a review.

Due to recently introduced 'so-called' bio- and plant-based friendly food contact materials and articles (FCM/FCA), some neglected safety issues need to be raised. In this review, potential chemical contaminants from FCM/FCA made from or containing wood and bamboo are presented. Sources, migration, and analytical issues in determining contaminants including intentionally and non-intentionally added substances (IAS and NIAS, respectively) are reviewed. Most of the contaminants are components from melamine-formaldehyde-resin (MFR), paints and coatings, preservatives, and bleaching agents. Tableware made of MFR containing bamboo fibres as a filler are not always suitable for use as tableware since harmful amounts of melamine and formaldehyde can migrate from the tableware into food and even accelerate the degradation of certain polymers with which they are mixed. In addition, in the EU bamboo in plastic FCM is not authorized under Regulation (EU) 10/2011. Paints and coatings used to provide surface coverage for bamboo and wooden articles also pose a risk of migration of heavy metals. Limits on preservatives in wood FCM are covered by legislation in many countries, nevertheless their contamination should not be ignored. Some wood species are considered 'toxic' or contain 'toxic' constituents that should not be used in contact with food, which are worth considering for legislation. IAS analyses in bamboo and wooden FCM is generally not a problem, but has proven to be more challenging for NIAS. Due to a complex mixture of substances contained in plant-based materials, there is a need to improve databases for non-target screening of such chemicals.

Method of Setting Environmental Administrative Fine Amounts.

In China, there are currently different degrees of arbitrariness in setting environmental administrative fines, and in many areas the faults are not equal to the penalties. To construct a more reasonable and feasible environmental punishment strategy where violators are fined in accordance with the severity of their actions, we use mathematical models to determine the specific range of environmental administrative fines based on the idea of realizing the appropriate balance between the interest of the violators and those of the public, meanwhile, law enforcement officers are allowed to use their discretion within a certain range. We use an example to prove that the punishment scheme provided by our models can be used to more effectively supervise violators' illegal behaviors than the penalty clause prescribed by law, and through sensitivity analysis and comparison, we prove that the described models are stable and feasible, and provide advantages over the existing methods. We hope our approach provides intellectual support for maintaining legal order, regulating the environmental administrative fine process, guiding business behaviors, and, most importantly, achieving the goal of protecting the environment.

Influence of cooking conditions on the migration of silicone oligomers from silicone rubber baking molds to food simulants.

The stability, surface micromorphology, and volatile organic compounds (VOCs) of silicone rubber baking molds (SRBMs) were tested while using the molds under severe conditions: baking at 175 °C, microwaving at 800 W, and freezing at -18 °C. Moreover, migration tests of SRBMs to food simulants (isooctane, 95% ethanol, and Tenax®) at 70 °C for 2 h (accelerated conditions) were performed. The initial total VOCs concentration was 2.53% higher than that recommended by BfR Recommendations on Food Contact Materials. Therefore, the SRBM samples were considered as badly tempered materials, and 18 different types of silicone oligomers were identified during the migration tests. The following percentage of silicone oligomers with a molecular weight lower than 1000 Da in isooctane, 95% ethanol, and Tenax® were detected: 70.7%, 91.8%, and 97.2%, respectively. It has been proven that previous baking treatments effectively reduced the content of silicone oligomers migrating from SRBMs.

Influence of factors on release of antimicrobials from antimicrobial packaging materials.

Antimicrobial packaging materials (films or coatings) (APMs) have aroused great interest among the scientists or the experts specialized in material science, food science, packaging engineering, biology and chemistry. APMs have been used to package the food, such as dairy products, poultry, meat (e.g., beef), salmon muscle, pastry dough, fresh pasta, bakery products, fruits, vegetables and beverages. Some materials have been already commercialized. The ability of APMs to extend the shelf-life of the food depends on the release rate of the antimicrobials (AMs) from the materials to the food. The optimum rate is defined as target release rate (TRR). To achieve TRR, the influencing factors of the release rate should be considered. Herein we reviewed for the first time these factors and their influence on the release. These factors mainly include the AMs, food (or food simulant), packaging materials, the interactions among them, the temperature and environmental relative humidity (RH).

Molecular dynamics simulation of three plastic additives' diffusion in polyethylene terephthalate.

Accurate diffusion coefficient data of additives in a polymer are of paramount importance for estimating the migration of the additives over time. This paper shows how this diffusion coefficient can be estimated for three plastic additives [2-(2'-hydroxy-5'-methylphenyl) (UV-P), 2,6-di-tert-butyl-4-methylphenol (BHT) and di-(2-ethylhexyl) phthalate (DEHP)] in polyethylene terephthalate (PET) using the molecular dynamics (MD) simulation method. MD simulations were performed at temperatures of 293-433 K. The diffusion coefficient was calculated through the Einstein relationship connecting the data of mean-square displacement at different times. Comparison of the diffusion coefficients simulated by the MD simulation technique, predicted by the Piringer model and experiments, showed that, except for a few samples, the MD-simulated values were in agreement with the experimental values within one order of magnitude. Furthermore, the diffusion process for additives is discussed in detail, and four factors - the interaction energy between additive molecules and PET, fractional free volume, molecular shape and size, and self-diffusion of the polymer - are proposed to illustrate the microscopic diffusion mechanism. The movement trajectories of additives in PET cell models suggested that the additive molecules oscillate slowly rather than hopping for a long time. Occasionally, when a sufficiently large hole was created adjacently, the molecule could undergo spatial motion by jumping into the free-volume hole and consequently start a continuous oscillation and hop. The results indicate that MD simulation is a useful approach for predicting the microstructure and diffusion coefficient of plastic additives, and help to estimate the migration level of additives from PET packaging.

Migration of copper from nanocopper/LDPE composite films.

Three nanocopper/low-density polyethylene (LDPE) composite films were tested in food simulants (3% acetic acid and 10% ethanol) and real food matrices (rice vinegar, bottled water and Chinese liquor) to explore the behaviours of copper migration using ICP-OES and GFAAS. The effects of exposure time, temperature, nanocopper concentration and contact media on the release of copper from nanocopper/LDPE composite films were studied. It was shown that the migration of copper into 10% ethanol was much less than that into 3% acetic acid at the same conditions. With the increase of nanocopper concentration, exposure time and temperature, the release of copper increased. Copper migration does not appear to be significant in the case of bottled water and Chinese liquor compared with rice vinegar with a maximum value of 0.54 µg mL-1 for the CF-0.25# bags at 70°C for 2 h. The presence and morphology of copper nanoparticles in the films and the topographical changes of the films were confirmed by field emission scanning electron microscope (FE-SEM) and atomic force microscope (AFM). In this manner, copper nanoparticles of different morphologies, sizes and distribution were found, and samples with higher nanocopper concentration had a more irregular topography. In the case of Fourier transform infrared spectroscopy (FTIR), no chemical bonds formed between copper nanoparticles and LDPE. Copper nanoparticles were just as physically dispersed in LDPE.

Study of the Migration of Stabilizer and Plasticizer from Polyethylene Terephthalate into Food Simulants.

This study investigates the determination and migration of stabilizers and plasticizers from polyethylene terephthalate (PET). Two methods [ultrasonic extraction with dichloromethane or methanol and total dissolution with phenol/tetrachloroethane (m:m/1:1)] for pre-concentration of additives in PET material were performed. The diffusion of these additives from PET was evaluated by immersing in deionized water, acetic acid 3% (w/v), ethanol 20% (v/v), ethanol 50% (v/v) and isooctane at 20, 40, 55 and 70°C, respectively. The amount of additives in PET and food simulants was quantified by high-performance liquid chromatography-photodiode array detector (HPLC-PDA). The optimized HPLC method showed high correlation coefficients (R ≥ 0.9993), good precision, accuracy and reproducibility. Experimental diffusion coefficients (DP) were calculated according to a mathematical model based on Fick's second law, and the DP values of considered compounds ranged from 9.8 × 10(-15) to 1.4 × 10(-8) cm(2) s(-1) The experimental DP values were also compared with that predicted by currently used diffusion models. In addition, the effect of temperature on the diffusion rate was assessed. The effect of temperature on the diffusion coefficients followed an Arrhenius-type model with active energies ranged from 40.4 to 113.8 kJ mol(-1) for the target compounds.

Determination of Polymer Additives-Antioxidants, Ultraviolet Stabilizers, Plasticizers and Photoinitiators in Plastic Food Package by Accelerated Solvent Extraction Coupled with High-Performance Liquid Chromatography.

An analytical method for the quantitative determination of 4 antioxidants, 9 ultraviolet (UV) stabilizers, 12 phthalate plasticizers and 2 photoinitiators in plastic food package using accelerated solvent extraction (ASE) coupled with high-performance liquid chromatography-photodiode array detector (HPLC-PDA) has been developed. Parameters affecting the efficiency in the process such as extraction and chromatographic conditions were studied in order to determine operating conditions. The analytical method of ASE-HPLC showed good linearity with good correlation coefficients (R ≥ 0.9833). The limits of detection and quantification were between 0.03 and 0.30 µg mL(-1) and between 0.10 and 1.00 µg mL(-1) for 27 analytes. Average spiked recoveries for most analytes in samples were >70.4% at 10, 20 and 40 µg g(-1) spiked levels, except UV-9 and Irganox 1010 (58.6 and 64.0% spiked at 10 µg g(-1), respectively), the relative standard deviations were in the range from 0.4 to 15.4%. The methodology has been proposed for the analysis of 27 polymer additives in plastic food package.

Triterpenoid saponins from the rhizome of Polygonatum sibiricum.

Three new triterpenoid saponins, polygonoides C (1), D (2), and E (3), were obtained from the ethanolic extract of the rhizome of Polygonatum sibiricum Redoute. On the basis of NMR and ESI-MS spectra, and chemical evidence, the structures of the three new compounds were elucidated as 3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-glucopyranosyl-(1→4)-ß-D-glucopyranosyl-3ß,7ß,22ß-trihydroxy-oleanolic acid (1), 3-O-α-L-rhamnopyranosyl-(1→2)-ß-D-glucopyranosyl-(1→4)-ß-D-glucopyranosyl-3ß,7ß,22ß-trihydroxy-oleanolic acid methyl ester (2), and 3-O-ß-D-glucopyranosyl-(1→3)-ß-D-glucopyranosyl-(1→4)-[α-L-rhamno-pyranosyl-(1→2)]-ß-D-glucopyranosyl-3ß,21ß-dihydroxy-oleanolic acid 28-O-ß-D-glucopyranosyl-(1→3)-ß-D-glucopyranosyl-(1→3)-ß-D-glucopyranoside (3).

[Protective effect of extractive of Dioscorea zingiberensis against ischemia/reperfusion injury in cultured neonatal rat cardiomyocytes].

OBJECTIVE: To define the structure of a water-soluble compound (SY-A) extracted from Dioscorea zingiberensis and investigate its protective effect against the neonatal rat cardiomyocytes ischemia/reperfusion (I/R) injured. METHODS: The SY-A was isolated from Dioscorea zingiberensis by utilizing column chromatograph and its structure was identified by 1H-NMR, 13C-NMR, 135DEPT. Neonatal rat cardiomyocytes were cultured and divided into 5 groups randomly. Then a model of ischemic/reperfusion (I/R) was established. Cells were divided into control group, simulated ischemia/reperfusion group (I/R group), I/R + SY-A (50 mg/L) group, I/ R + SY-A (100 mg/L) group and I/R + SY-A (150 mg/L) group. The levels of malondialdehyde and Creatine Kinase were measured. The cell viability was determined by MTT assay. RESULTS: The structure of SY-A was identified as 4-methoxybenzoic acid-2-O-glucopyranoside. Compared with I/R group, the levels of LDH and CK were decreased significantly in the SY-A group, and the cell viability was increased obviously. CONCLUSION: Extractive of Dioscorea zingiberensis showed protective effect against the neonatal rat cardiomyocytes ischemia/reperfusion injured.

[Isolation and structure determination of steroidal saponin from Dioscorea zingiberensis].

To study the chemical constituents of Dioscorea zingiberensis Wright, the EtOH extract of fresh rhizomes of D. zingiberensis was concentrated and partitioned further to produce petroleum ether-, ethylacetate-, n-butanol- and water-soluble fractions. The water-soluble fraction was subjected to column chromatography on macro resin AB-8, and the final products were obtained by repeated reversed-phase ODS and MCI gel CHP 20P column chromatography. Structures of compounds were elucidated by 1H NMR, 13C NMR, 135DEPT, HMQC, HMBC and TOCSY spectroscopic analyses. A new steroidal saponin was isolated, which was identified as (25R)-26-O-(beta-D-glucopyranosyl)-furost-5-en-3 beta, 16, 20, 26-tetraol-22-seco-3-O-beta-D-glucopyranosyl-(1--> 3)-beta-D-glucopyranosyl-(1--> 4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside. The compound is a novel skeletally steroidal saponin, named as zingiberenin F (1). It was reported for the first time from D. zingiberensis Wright.

Two new steroidal saponins from the rhizome of Polygonatum sibiricum.

Two new furostanol saponins, polygonoides A (1) and B (2), along with three known compounds, were obtained from the ethanolic extract of the rhizome of Polygonatum sibiricum Redoute. On the basis of acid hydrolysis and comprehensive spectroscopic analyses, the structures of polygonoides A and B were elucidated as (25R)-26-O-beta-D-glucopyranosyl-furost-5,22(23)-dien-3beta,26-diol-3-O-alpha-L-rhamnopyranosyl-(1 --> 3)-beta-D-glucopyranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (1) and 22 alpha-(propionyloxy)-furost-5-en-3beta,20 alpha-diol-3-O-beta-D-glucopyranosyl-(1 --> 4)-[alpha-L-rhamnopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (2).

[Isolation and structure determination of steroidal saponin from Dioscorea zingiberensis].

To study the chemical constituents of Dioscorea zingiberensis Wright, the EtOH extract of fresh rhizomes of D. zingiberensis was concentrated and partitioned further to produce petroleum ether-, ethylacetate-, n-butanol- and water-soluble fractions. The water-soluble fraction was subjected to column chromatography on macro resin AB-8, and the final products were obtained by repeated reversed-phase ODS and MCI gel CHP 20P column chromatography. Structures of compounds were elucidated by means of 1H NMR, 13C NMR, 135DEPT, HMQC, HMBC and TOCSY spectroscopic analyses. Five steroidal saponins were isolated, in which one new steroidal saponin was identified as (25R)-26-O-(beta-D-glucopyranosyl) -furost-5-en-3beta, 22xi, 26-triol-4beta-acetoxyl-3-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopy ranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (V). The compound V is a new compound, named as zingiberenin G. The compounds I, II and III were reported for the first time from D. zingiberensis Wright.