Synergistic antimicrobial activities of natural essential oils with chitosan films

The synergistic antimicrobial activities of three natural essential oils (i.e., clove bud oil, cinnamon oil, and star anise oil) with chitosan films were investigated. Cinnamon oil had the best antimicrobial activity among three oils against Escherichia coli , Staphylococcus aureus , Aspergillus oryzae , and Penicillium digitatum . The chitosan solution exhibited good inhibitory effects on the above bacteria except the fungi, whereas chitosan film had no remarkable antimicrobial activity. The cinnamon oil-chitosan film exhibited a synergetic effect by enhancing the antimicrobial activities of the oil, which might be related to the constant release of the oil. The cinnamon oil-chitosan film had also better antimicrobial activity than the clove bud oil-chitosan film. The results also showed that the compatibility of cinnamon oil with chitosan in film formation was better than that of the clove bud oil with chitosan. However, the incorporated oils modified the mechanical strengths, water vapor transmission rate, moisture content, and solubility of the chitosan film. Furthermore, chemical reaction took place between cinnamon oil and chitosan, whereas phase separation occurred between clove bud oil and chitosan.     

Water and moisture susceptibility of chitosan and paper-based materials: structure-property relationships

Environmentally friendly and potentially bioactive food packaging based on chitosan-coated papers were elaborated. The morphology and the microstructure of these new materials were characterized by infrared spectroscopy and scanning electron microscopy. These observations suggested that the chitosan penetrated deeply into the paper, embedding the cellulose fibers, instead of forming a layer as expected. Through the barrier properties against moisture, the liquid water sensitivity, and NMR-relaxometry measurements, the water interactions were evaluated on the chitosan films and the chitosan-coated papers. They revealed that the coating by a chitosan film forming solution improved the paper moisture barrier properties but the surface hydrophilicity remained high. Relaxometry studies showed that, due to its hydrophilic character, chitosan controlled the interaction with water, despite the very low amount of deposit. On the other hand, the mechanical properties of papers were unmodified by the chitosan coating, which did not fundamentally affect the solid structure of the papers.     

New bioactive biomaterials based on quaternized chitosan

Chitosan was chemically modified to produce quaternary ammonium salts in order to improve its antimicrobial activity and physicochemical properties. Quaternization of N-alkyl chitosan derivatives was carried out using alkyl iodide to elaborate water-soluble cationic polyelectrolytes ( N, N, N-trimethylchitosan, TMC). TMC was characterized by (1)H NMR spectroscopy; the quaternization degree was determined from (1)H NMR spectra and by titration of iodide ion. The antibacterial activity of hydroxypropylcellulose (HPC) films or coatings associated with chitosan or TMC as biocide was evaluated against the growth of Listeria monocytogenes and Salmonella typhimurium. The HPC-chitosan and HPC-TMC coatings exhibited a total inhibition on solid medium of both bacterial strains. Experiments conducted in liquid medium showed that the inhibitory activity against the growth of Listeria innocua was improved after chemical modification. Moreover, physicochemical properties of films were evaluated to determine their potential for food applications. The addition of the antibacterial agents showed a significant impact on the moisture barrier and mechanical properties of HPC films.     

Physicochemical, antimicrobial, and cytotoxic characteristics of a chitosan film cross-linked by a naturally occurring cross-linking agent, aglycone geniposidic acid

The purpose of this study was to evaluate the characteristics of a chitosan film cross-linked by a naturally occurring compound, aglycone geniposidic acid (aGSA). This newly developed aGSA-cross-linked chitosan film may be used as an edible film. The chitosan film without cross-linking (fresh) and the glutaraldehyde-cross-linked chitosan film were used as controls. The characteristics of test chitosan films evaluated were their degree of cross-linking, swelling ratio, mechanical properties, water vapor permeability, antimicrobial capability, cytotoxicity, and enzymatic degradability. It was found that cross-linking of chitosan films by aGSA (at a concentration up to 0.8 mM) significantly increased its ultimate tensile strength but reduced its strain at fracture and swelling ratio. There was no significant difference in the antimicrobial capability between the cross-linked chitosan films and their fresh counterpart. However, the aGSA-cross-linked chitosan film had a lower cytotoxicity, a slower degradation rate, and a relatively lower water vapor permeability as compared to the glutaraldehyde-cross-linked film. These results suggested that the aGSA-cross-linked chitosan film may be a promising material as an edible film.     

Use of dicarboxylic acids to improve and diversify the material properties of porous chitosan membranes

Several nontoxic dicarboxylic acid solutions (oxalic acid, succinic acid, malic acid, and adipic acid solutions) instead of an acetic acid solution were used as solvents for chitosan dissolution. The amount of free amino groups of the chitosan in the solution decreased due to the ionic cross-linking of the dicarboxylic acids with chitosan. These solutions were used to fabricate porous chitosan membranes. Replacing acetic acid with these dicarboxylic acids for membrane preparation improved the water uptake (by 35% at most), tensile strength (by 110% at most), and elongation capability (by 50% at most) of the membranes. These dicarboxylic acid solutions not only act as solvents but also improve the material properties of the chitosan membranes due to the ionic cross-linking and hydrogen bond formation. In brief, a nontoxic and straightforward cross-linking method has been developed for chitosan material; this method does not result in a brittle product, thus making it better than the use of toxic cross-linking reagents.     

天然花青素提取物与壳聚糖明胶复合膜的制备和表征

为了开发天然的抗氧化活性包装材料,以紫甘蓝、黑米、玫瑰、蓝莓为原料制备天然花青素提取物与壳聚糖明胶的复合膜,比较分析了不同天然花青素提取物对复合膜的物理、机械、抗氧化活性及形貌结构的影响。结果表明：天然花青素提取物的加入,增加了膜的厚度,显著（P<0.05）影响膜的含水率、水溶性及外观形貌。壳聚糖明胶复合膜的水蒸汽透过率（water vapor permeability,WVP）为10.69×10-11 g/(m·s·Pa)。玫瑰花青素提取物的加入使得WVP值降低,而其他花青素提取物的加入使得WVP值增大。玫瑰复合膜的拉伸强度最大,达到27.03 MPa,断裂伸长率最小,黑米花青素提取物可增加复合膜的延展性,断裂伸长率最大为57.67%。傅里叶红外光谱表明天然花青素提取物的羟基基团与壳聚糖的氨基基团产生相互作用。扫描电镜结果表明花青素提取物影响微观结构,而且生物相容性较好。加入天然花青素提取物后,复合膜抗氧化活性均显著（P<0.05）提高,且玫瑰复合膜有着较高的抗氧化活性,1,1-二苯基-2-苦基肼（DPPH）自由基清除能力达到95.47%。结果表明：玫瑰花青素提取物更有利于开发阻湿性能好,水溶性低,抗拉伸和抗氧化活性高的包装材料,具有良好的应用前景。     

Development and characterization of biodegradable films made from wheat gluten protein fractions

Gliadins and glutenins were extracted from commercial wheat gluten on the basis of their extractability in ethanol and used to produce film-forming solutions. Films cast using these gliadin- and glutenin-rich solutions were characterized. Glycerol was used as a plasticizer, and its effect on the films was also studied. Films obtained from the glutenin fraction presented higher tensile strength values and lower elongation at break and water vapor permeability values than gliadin films. Gliadin films disintegrated when immersed in water. The GAB isotherm model was used to describe the equilibrium moisture sorption of the films. The glycerol concentration largely modified mechanical and water vapor barrier properties of both film types.     

Methyl mercury acetate removal from waters by chromatography on chelating polymers

Chitin, chitosan and Dowex A 1 chelating polymers powders, 100 to 200 mesh, were used in column chromatography to remove methyl mercury acetate from various waters, including sea water and a dilute acetic acid - acetaldehyde solution. Methyl mercury acetate was labeled with²⁰³Hg and chromatography was followed by γ-ray spectrometry. Results show that chitosan and Dowex A 1 are particularly effective in collecting Hg, even though the metalorganic compounds are not fixed so strongly as the simple ions. Elution can be performed with hot water. A good volume reduction factor can be obtained and the results might be applied in Hg pollution prevention.     

Antimicrobial and physicochemical properties of chitosan-HPMC-based films

To prepare composite films from biopolymers with anti-listerial activity and moisture barrier properties, the antimicrobial efficiency of chitosan-hydroxy propyl methyl cellulose (HPMC) films, chitosan-HPMC films associated with lipid, and chitosan-HPMC films chemically modified by cross-linking were evaluated. In addition, the physicochemical properties of composite films were evaluated to determine their potential for food applications. The incorporation of stearic acid into the composite chitosan-HPMC film formulation decreased water sensitivity such as initial solubility in water and water drop angle. Thus, cross-linking of composite chitosan-HPMC, using citric acid as the cross-linking agent, led to a 40% reduction in solubility in water. The water vapor transfer rate of HPMC film, approximately 270 g x m(-2) x day(-1) x atm(-1), was improved by incorporating chitosan and was further reduced 40% by the addition of stearic acid and/or cross-linking. Anti-listerial activity of films was determined on solid medium by a numeration technique. Chitosan-HPMC-based films, with and without stearic acid, inhibited the growth of Listeria monocytogenes completely. On the other hand, a loss of antimicrobial activity after chemical cross-linking modification was observed. FTIR and 13C NMR analyses were then conducted in order to study a potential chemical modification of biopolymers such as a chemical reaction with the amino group of chitosan. To complete the study, the mechanical properties of composite films were determined from tensile strength assays.     

Incorporation of a high concentration of mineral or vitamin into chitosan-based films

Mineral or vitamin E was incorporated into chitosan-based films: 10-200% (w/w chitosan) Gluconal Cal (GC), a mixture of calcium gluconate and lactate; 5-20% zinc lactate (ZL); and 5-20% alpha-tocopheryl acetate (VE) with acetylated monoglyceride (AM). The functionality of film-forming solutions and dried films was analyzed with standard procedures, and mathematical equations were developed to coordinate selected film functionality with the type and concentration of incorporated mineral or vitamin E. GC incorporation significantly increased pH and decreased viscosity of film-forming solutions, but not the addition of ZL or VE. The water barrier property of the films was improved by increasing the concentration of mineral or vitamin E in the film matrix. The tensile strength of the films was more significantly affected by GC or VE addition than film elongation, puncture strength, and puncture deformation. While a major endothermic peak around 200 degrees C was observed in DSC thermograms of chitosan-based films, only 200% GC incorporation altered this endothermic peak. This study demonstrated the capability of chitosan-based film matrix to carry a high concentration of mineral or vitamin E. Such films may be used for wrapping or coating to enhance the nutritional value of foods.     

Effects of hydrophilic plasticizers on mechanical, thermal, and surface properties of chitosan films

Chitosan films were plasticized with four hydrophilic compounds, namely, glycerol (GLY), ethylene glycol (EG), poly(ethylene glycol) (PEG), and propylene glycol (PG). Our objective was to investigate the effect of plasticizers on mechanical and surface properties of chitosan films. The stability of plasticized films was observed by storage for 3 and 20 weeks in an environmental chamber at 50 +/- 5% RH and 23 +/- 2 degrees C. Plasticization improves the chitosan ductility, and typical stress-strain curves of plasticized films have the features of ductile materials, except the film made with 5% PG that exhibits as a brittle polymer and shows an antiplasticization effect. In most cases, the elongation of plasticized films decreases with the storage time, which might be due to the recrystallization of chitosan and the loss of moisture and plasticizer from the film matrix. Although at the beginning the mechanical properties of films made with PG, at high plasticizer concentration, are comparable to those of films made with EG, GLY, and PEG, their stability is poor and they tend to become brittle materials. The surface properties, analyzed by contact angle measurement, reveal that plasticization increases film hydrophilicity. It is found that GLY and PEG are more suitable as chitosan plasticizers than EG and PG by taking into account their plasticization efficiency and storage stability. Furthermore, a plasticizer concentration of 20% (w/w) with GLY or PEG seemingly is sufficient to obtain flexible chitosan film with a good stability for 5 months of storage.     

商陆不同极性、根和茎提取物的抑菌性能分析

为探究商陆不同极性、部位提取物的抑菌性能,本实验分别从商陆根和茎中提取石油醚相、乙酸乙酯相、正丁醇相和水相4种不同极性的提取物,再采用滤纸片法测量提取物对大肠杆菌（Escherichia coli）、金黄色葡萄球菌（Staphyloccocus aureus）、巨大芽孢杆菌（Bacillus megaterium）和副溶血弧菌（Vibrio parahaemolyt-icus）4种细菌的抑制性能。结果表明,部分商陆的提取物有一定的抑菌活性,如根正丁醇相对巨大芽孢杆菌和副溶血弧菌,茎水相对副溶血弧菌的抑菌圈在10mm以上,但总体上商陆的提取物的抑菌性能远不及头孢氨苄好。实验还发现商陆抑菌活性最强的物质大都存在于根中,且抑菌活性最强的物质大都存在于水和正丁醇这种极性较高的溶剂的提取物中,不同提取物对不同细菌的抑菌活性情况不一致。因此本研究结果可以为商陆提取物抑菌性能的进一步探索提供参考。     

Edible bioactive fatty acid-cellulosic derivative composites used in food-packaging applications

To develop biodegradable packaging that both acts as a moisture barrier and as antimicrobial activity, nisin and stearic acid were incorporated into a hydroxy propyl methyl cellulose (HPMC) based film. Fifteen percent (w/w HPMC) of stearic acid improved film moisture barrier. However, film mechanical resistance and film antimicrobial activity on Listeria monocytogenes and Staphylococcus aureus pathogenic strains were both reduced. This lower film inhibitory activity was due to interactions between nisin and stearic acid. The molecular interaction was modeled, and an equation was developed to calculate the nisin concentration needed to be incorporated into the film matrix to obtain a desired residual antimicrobial activity. Because the molecular interactions were pH dependent, the impact of the pH of the film-forming solution on film inhibitory activity was investigated. Adjusting the pH to 3 totally avoided stearic acid and nisin interaction, inducing a high film inhibitory activity.     

Enzymatic grafting of peptides from casein hydrolysate to chitosan. Potential for value-added byproducts from food-processing wastes

Tyrosinase was used to initiate the grafting of peptides onto the amine-containing polysaccharide chitosan. Chemical evidence for covalent grafting was obtained from electrospray mass spectrometry for products formed from reactions with glucosamine (the monomeric unit of chitosan) and the model dipeptide Tyr-Ala. When this model dipeptide was incubated with tyrosinase and chitosan, there was a marked increase in the viscosity of the solution. This viscosity increase provides physical evidence that tyrosinase can initiate peptide grafting onto the chitosan backbone. A peptide-modified chitosan derivative was generated by reacting chitosan (0.32 w/v%) with acid-hydrolyzed casein (0.5 w/v %) using tyrosinase. After reaction, the peptide-modified chitosan was partially purified and dissolved in an aqueous acetic acid solution. Low concentrations of this peptide-modified chitosan were observed to confer viscoelastic properties to the solutions. Specifically they conferred high viscosities and shear thinning properties to the solutions, and solutions containing only 1 w/w % of the peptide-modified chitosan behaved as weak gels. Thus, tyrosinase provides a simple and safe way to convert food-processing byproducts into environmentally friendly products that offer useful functional properties. The selectivity of tyrosinase and the relatively high reactivity of chitosan's amines allow grafting to be performed with uncharacterized peptide mixtures present in crude hydrolysates.     

环保地膜覆盖对土壤水分及玉米产量的影响

为了提高旱作农区降雨利用效率,并解决地膜覆盖造成的环境污染问题,在渭北旱塬进行了普通地膜、生物降解膜和液态膜玉米集雨种植栽培试验。结果表明：普通地膜和生物降解膜覆盖处理在玉米不同生育阶段较对照0～60 cm土层土壤贮水量均有所提高,与液态膜及不覆盖处理（CK）相比呈显著性差异（p＜0.05）;不同材料覆盖处理的土壤水分空间变化规律相同,普通地膜和生物降解膜覆盖处理可有效提高土壤含水率,并能增强0～200 cm土层土壤含水率的稳定性;普通地膜和生物降解膜处理的玉米籽粒产量比对照（CK）分别提高了19.96%和19.67%,水分利用效率分别比对照提高32.08%和31.81%,均与对照（CK）呈显著性差异,液态膜处理的籽粒产量及水分利用效率与对照无显著性差异。可见,生物降解膜与普通地膜在土壤保水及对玉米产量的影响方面均具有显著效果,且相互间没有明显差异,生物降解膜可以替代普通地膜应用于农业生产。     

Physicochemical properties and bioactivity of nisin-containing cross-linked hydroxypropylmethylcellulose films

Cross-linked hydroxypropylmethylcellulose (HPMC) cast films with citric acid as polycarboxylic cross-linker were elaborated to study the effect of cross-linking level on various properties. Increased amounts of cross-linking agent were not connected to statistically different tensile strength and Young's modulus. Whatever the cross-linking level of the film was, the ultimate elongation parameter decreased by approximately 60% compared to the HMPC control film. Moisture sorption isotherms and water contact angle meter showed that the effect of cross-linking degree tends to reduce the hygroscopic and hydrophilic characteristics of films. In addition, to control bacteria growth on food surfaces, the antimicrobial activity of both 98% cross-linked HPMC-nisin and control HPMC-nisin films was tested on Micrococcus luteus. Despite the incorporation of a significant content of nisin, cross-linked HPMC-nisin films were completely inactive on the microbial strain compared to the HPMC-nisin control films. Cross-linking conditions likely either denatured the nisin or irreversibly bound nisin to the cross-linked HPMC. However, nisin adsorbed into films made from previously cross-linked HPMC maintained its activity.     

无黏性土增湿-脱湿过程中接触角的特性

[目的]研究粉土颗粒的接触角滞后特性,掌握土壤增湿或脱湿过程中的界面特性,为建立离散元接触模型提供相应的试验基础。[方法]用躺滴法对土颗粒表面的初始接触角及动态接触角进行测量,用直接观测法对增湿和脱湿条件下土颗粒与孔隙水的接触角进行测量。[结果]天然粉土的平均初始接触角为41.5°,远大于0,广泛用在具有连续表面固体动态接触角测量的3种方式仅有1种能测出土颗粒表面的动态接触角,且3种土样的后退接触角都大于0。初始接触角的小大对蒸发(脱湿)过程中土颗粒与孔隙水的接触角变化规律影响不大。同一试样,不同土颗粒与孔隙水间的接触角在脱湿过程中的变化规律并不一致,甚至会出现脱湿过程中接触角由小变大的情况。亲水土与斥水土的增湿模式差异较大,亲水土在增湿过程中先形成液桥再形成包裹土颗粒的液膜,而斥水土则是先在土颗粒表面形成液滴,再由液滴连接成包裹土颗粒的液膜。[结论]土颗粒的接触角存在明显的接触角滞后现象,土颗粒表面的接触角和土颗粒间的接触角并不一致,实际应用时需要严格区分。     

香蕉纤维素-壳聚糖/聚丙烯酰胺双网络水凝胶的制备及吸附性能

纤维素、壳聚糖等天然多糖形成的水凝胶力学性能较弱,在应用中受到限制。该文利用香蕉纤维素-壳聚糖为第一层刚性网络,以聚丙烯酰胺为第二层柔性网络,通过"一锅法"制备了香蕉纤维素-壳聚糖/聚丙烯酰胺(cellulosechitosan/polyacrylamide, Ce-Cs/PAAM)双网络水凝胶,并采用傅里叶红外光谱(Fourier transform infrared spectroscopy,FTIR)、扫描电子显微镜(scanning electron microscope,SEM)、X射线衍射(X-ray diffractometer,XRD)等对双网络水凝胶结构进行了表征,并分析其力学性能、溶胀性能和吸附性能。结果表明,Ce-Cs/PAAM水凝胶是一种三维多孔、双网络状结构,具有优良的机械强度和韧性,在90%的压缩应变下,其最大压缩应力可以达到60 MPa;水中的溶胀度为9.56 mg/mg,在pH值为12的溶液中溶胀度为15.34 mg/mg;Ce-Cs/PAAM双网络水凝胶吸附Cu^2+试验结果表明,在Cu2+的初始浓度为350 mg/L、pH值为5.5、吸附时间为90 min时,最大吸附量为312.4 mg/g。该文制备的CeCs/PAAM双网络水凝胶方法简单、力学性能、吸附性能优良,在重金属离子吸附领域具有一定的应用前景。     

黄土高原山坡道路侵蚀与防治

液态地膜和植生带是2类新兴的土壤改良和覆盖保水材料。通过盆栽和田间实验,比较了液态地膜和植生带及其配合使用对土壤水分和温度及玉米成苗的效应。结果证明纤维植生带和棉质植生带及其与液态地膜配合应用保持水土效果虽好,但极大影响玉米出苗;液态地膜保水增温效果明显,玉米出苗率最高,是值得研究和推广的新型保墒抗旱成苗措施。     

草本植物根系对高液限土的加固效应

[目的]探索草本植物根系对高液限土的加固效应,为工程中合理预估植物根系在高液限土质边坡防护中的作用提供依据。[方法]以高羊茅根系及其与高液限土壤构成的根—土复合体为研究对象,通过一系列室内直剪试验分析高液限土含水率和含根量对抗剪强度的影响。[结果]在土样中掺加根系可以显著提升其黏聚力,小幅提升其内摩擦角。根系对土体的加固效果随着含水率增加呈现先上升后减小的趋势。不同含水率梯度下根—土复合体的最优含根量有所区别,对于20%和25%含水率的土样,其最优含根量大致在0.3%附近,对30%含水率土样在0.4%附近,对35%~45%含水率土样在0.5%附近。[结论]草本植物根系可以有效抑制高液限土的水敏性,且在不同含水率梯度下根系发挥的作用差异显著。