Preparation and characterization of multilayered hydroxyapatite/silk fibroin film

We prepared multilayered films consisting of silk fibroin (SF) and hydroxyapatite (HAp) by alternating lamination using untreated SF and HAp-deposited SF films. Untreated SF films were prepared from a regenerated SF solution by air drying. HAp-deposited SF films were prepared by soaking methanol-treated SF films containing >5 wt% CaCl2 in a simulated body fluid with the ion concentration 1.5-fold higher than that of the standard one. The multilayered HAp/SF films had HAp layers with approximate thicknesses of 3-5 microm and SF layers with thicknesses of 40-70 microm. The bonding strength between the SF and HAp layers was significantly affected by temperature and compression time under the lamination method. The optimal conditions for achieving the maximum T-peel strength and beta-sheet contents were determined to be 130 degrees C for 4 min. The Young's modulus of the multilayered films (133.4 MPa) was higher than that of the films consisting of SF alone (92.5 MPa) under swollen conditions. The biocompatibility of the HAp-deposited SF films was analyzed by culturing of osteoblasts (MC3T3-E1) on a film. The results indicate that HAp-deposited SF films and SF films show similar degrees of cell adhesion and alkaline phosphatase activities.     

聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)复合膜的制备及其性能

为提高聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)(PHBV)膜的抗菌性能,拓展其在食品包装领域的应用,首先利用纤维素纳米纤丝(CNF)表面的不同极性基团,采用原位还原法制备了不同形貌的CNF-Ag杂化材料;然后将其与PHBV复合制得高阻隔性抗菌复合膜材料,并对复合膜材料的微观形貌、结晶性能、热稳定性、化学结构和抗菌性能进行表征与分析。结果表明:引入柠檬酸与抗坏血酸后,CNF-Ag杂化材料表面羧基含量最高可达1.21 mmol/g;CNF-Ag杂化材料和PHBV基体形成了较强的氢键作用,改善了PHBV的结晶性能和抗菌性能,使复合膜的拉伸强度高达66.7 MPa,弹性模量达7.6 GPa,且对金黄色葡萄球菌抗菌率达到99%。     

Use of Electrospinning to Develop Antimicrobial Biodegradable Multilayer Systems: Encapsulation of Cinnamaldehyde and Their Physicochemical Characterization

In this work, three active bio-based multilayer structures, using a polyhydroxybutyrate-co-valerate film with a valerate content of 8 % (PHBV8) as support, were developed. To this end, a zein interlayer with or without cinnamaldehyde (CNMA) was directly electrospun onto one side of the PHBV8 film and the following systems were developed: (1) without an outer layer; (2) using a PHBV8 film as outer layer; and (3) using an alginate-based film as outer layer. These multilayer structures were characterized in terms of water vapour and oxygen permeabilities, transparency, intermolecular arrangement and thermal properties. The antimicrobial activity of the active bio-based multilayer systems and the release of CNMA in a food simulant were also evaluated. Results showed that the presence of different outer layers reduced the transport properties and transparency of the multilayer films. The active bio-based multilayer systems showed antibacterial activity against Listeria monocytogenes being the multilayer structure prepared with CNMA and PHBV outer layers (PHBV + zein/CNMA + PHBV) the one that showed the greater antibacterial activity. The release of CNMA depended on the multilayer structures, where both Fick’s and Case II transport—polymer relaxation explained the release of CNMA from the multilayer systems.Overall, the deposition of electrospun CNMA-loaded zein fibres on a PHBV8 layer is a promising methodology for the development of active bio-based multilayer systems, with a great potential for food packaging applications.     

熔喷非织造用聚(3-羟基丁酸-co-3-羟基戊酸共聚酯)/聚乳酸双组分生物降解材料的可纺性能

采用熔融共混法制备了质量比为100/0、75/25、50/50、25/75、0/100的熔喷非织造用PHBV/PLA共混材料,分别采用热重分析法(TG)、熔融指数法(MFI)、热台偏光镜法(POM)和毛细管流变法对共混材料的可纺性能进行了研究,并对其初生纤维的纺丝性能给予了初步评价。研究表明:PHBV的热稳定性差,加工窗口窄且熔体流动性差,PHBV/PLA共混材料的热稳定性和熔体流动性明显改善;PHBV结晶速率快,PLA对PHBV的结晶具有稀释作用;PHBV/PLA共混物为典型的切力变稀型流体,PHBV对温度和剪切速率变化敏感度高,PHBV/PLA共混材料的表观黏度随PLA含量的提高而有所增大,但均小于纯PLA;PHBV纤维发黏现象严重,纺丝困难,随着共混材料中PLA含量的提高,纺丝性能提高,初生纤维表面变得光滑。     

Adhesion and protective properties of polyvinyl alcohol nanofibrous composite fabrics

To avoid the separation of nanofiber mats and substrates during post-processing, the substrate was pretreated by plasma before electrospinning. Polyvinyl alcohol (PVA) nanofiber mats were deposited on the habutae, polyester-taffeta, and nylon-taffeta fabrics by a needless electrospinning setup with spiral disk spinnerets. The effects of plasma treatment on the adhesion of electrospun PVA nanofibrous composite fabrics were studied. The aerosol particles protective performance and wearabilities were also investigated as a function of the thickness of electrospun PVA nanofiber mat. Results showed that the surface nanoscale concave–convex roughness of substrate fabric was formed after oxygen plasma treatment. The peeling strength and peeling energy increased with the increase in surface roughness in a limited range. The peeling energy of PVA/nylon-taffeta enhanced to 2.97 times when nylon-taffeta treated by oxygen plasma at 200 W for 3 min. The aerosol particle filtration efficiency enhanced with the increase in electrospinning time, and the quality factor of PVA/nylon-taffeta was the highest with electrospinning for 10 min. Simultaneously, the air permeability and the water vapor transmission rate of PVA/nylon-taffeta decreased with the increase in electrospinning time, whereas the drape coefficient increased.     

聚乳酸-聚己内酯/丝素蛋白三元复合纳米纤维膜支架的结构与性能

通过静电纺丝技术制备出不同质量比的聚乳酸-聚己内酯/丝素蛋白(PLA-PCL/SF)复合纳米纤维膜支架,采用扫描电子显微镜、傅里叶红外光谱仪对纳米纤维膜的形貌和结构进行表征,测试纤维膜的孔隙率和吸附性能。结果表明:PLA-PCL与SF这2种组分的质量比对复合纳米纤维膜的形貌有显著影响,质量比为90∶10和70∶30的纳米纤维表面分布着密集的孔洞;PLA-PCL/SF复合纳米纤维膜中SF经甲醇处理后由无定形结构转变为β-折叠结构;随着复合纳米纤维膜中SF含量的增加,纳米纤维膜的孔隙率和吸附性也逐渐降低。接触角实验和小鼠胚胎成纤维细胞(NIH-3T3)培养结果表明,SF的加入提高了纳米纤维膜的亲水性,有利于NIH-3T3细胞的黏附和增殖。     

Production of triacylglycerol and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) by the toluene-degrading bacterium Rhodococcus aetherivorans IAR1

Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) produced by various bacteria has been intensively investigated as a promising biodegradable plastic, but required a supply of an expensive precursor as a secondary carbon source for its production. In a previous study, we identified a new bacterial strain, Rhodococcus aetherivorans IAR1, which synthesizes PHBV from toluene without the supply of a precursor. Toluene is the volatile organic compound most abundantly emitted to the environment. In the present paper, we show that R. aetherivorans IAR1 produces triacylglycerols (TAGs) simultaneously with PHBV. Both PHBV and TAGs were synthesized before the nitrogen source is completely exhausted. The cellular content of PHBV reached 10% of cell dry weight (CDW) and its synthesis ceased even during intermittent supply of toluene. However, accumulation of TAGs continued during cultivation and their cellular content reached 24% of CDW at the end of cultivation. Cerulenin inhibited TAG production and increased PHBV cellular content up to 30% of CDW. The mole fraction of 3-hydroxyvalerate (3HV) in PHBV produced from toluene increased from 60% to 80% during its accumulation. Fatty acid compositions of TAGs produced from acetate and toluene were different. At the end of cultivation, the mole fraction of C17:0, one of odd-carbon number fatty acids, was 5% on toluene or 10% on acetate while the mole fraction of 3HV in PHBV from toluene was as high as that in PHBV from acetate, suggesting that a C5 intermediate of toluene degradation might directly become a precursor of 3HV whereas propionyl-CoA is required for the incorporation of C17:0 into TAGs.     

Stabilized nanosilver based antimicrobial poly(3-hydroxybutyrate-co-3-hydroxyvalerate) nanocomposites of interest in active food packaging

Antimicrobial silver based nanocomposites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) were successfully synthesized and characterized. For the synthesis, a masterbatch of in situ stabilized silver nanoparticles (AgNPs) produced into a mixed microbial cultures based poly(3-hydroxybutyrate-co-18 mol%-3-hydroxyvalerate) (PHBV18) was used, which was diluted by melt compounding with a commercial poly(3-hydroxybutyrate-co-3 mol%-3-hydroxyvalerate) (PHBV3) material. The incorporated AgNPs (0.04 wt.%) led to a surprising oxygen permeability drop of ca. 56% compared to the neat polymer. The thermal stability and optical properties of the nanocomposites were not significantly modified as compared to the neat PHBV3. Moreover, the antimicrobial performance of the PHBVs-AgNPs films against two of the most common food borne pathogens, Salmonella enterica and Listeria monocytogenes, showed a strong and sustained (even after seven-months) antibacterial activity. This study provides an innovative route to generate fully renewable and biodegradable antimicrobial nanocomposites that could potentially be of interest in film and coating applications such as active food packaging.Industrial relevanceAs a response to the consumers for more safety foodstuffs and ecofriendly packaging materials, this work presents a novel methodology to develop antimicrobial packaging by using biodegradable materials obtained from industrial food by-products in combination of an industrially meaningful melt blending process. The methodology here applied allows the use of low doses of stabilized silver nanoparticles in the polymer matrix, without additives, which exhibits prolonged antimicrobial activity against food borne pathogens and enhanced oxygen barrier properties. These materials are of great interest in the development and design of biodegradable active food packaging materials and antibacterial food contact surfaces with the additional advantage that they can be easily scale-up.     

Transglutaminase-mediated gelatin matrices incorporating cell adhesion factors as a biomaterial for tissue engineering

The goal of this work was to develop a novel biomaterial to be used for either wound dressing or as a scaffold for tissue engineering. The biodegradable hydrogels were prepared through cross-linking of gelatin with transglutaminase (TGase) in an aqueous solution. We found that the concentrations of 5 wt% gelatin and 1 unit/ml TGase were optimum for the proliferation of NIH/3T3 fibroblasts. Then, we investigated whether the cell proliferation was enhanced by incorporation of cell adhesion factors into the gelatin hydrogels. Since vitronectin and fibronectin can bind with gelatin by the action of TGase, we added these cell adhesion proteins into the gelatin hydrogels. The hydrogels incorporating these cell adhesion proteins significantly enhanced cell proliferation compared with the gelatin hydrogels without these proteins (p<0.05). Two types of synthetic Arg-Gly-Asp (RGD) peptides, RGDLLQ and RGDLLG were also added to the gelatin solution where RGDLLQ is a substrate of TGase by virtue of a glutamine (Q) residue with an epsilon-amino group and RGDLLG is not. These two RGD peptides enhanced cell proliferation, but RGDLLQ significantly enhanced the proliferation compared with RGDLLG (p<0.05). These results suggest that T-Gase-mediated incorporation of cell adhesion factors into gelatin matrices enhanced cell proliferation and this novel biomaterial is a potent tool for wound dressing or tissue engineering.     

聚丙烯腈/改性羟基磷灰石光接枝复合材料的制备工艺

采用硅烷偶联剂KH-570对羟基磷灰石(HAp)进行改性,通过紫外光接枝法制备聚丙烯腈/改性羟基磷灰石(PAN/MHAp)-KH570接枝复合膜和复合纤维。通过正交优化分析得到具备良好吸附和拉伸性能的接枝复合膜的HAp改性工艺为:偶联剂KH-570体积分数5%、乙醇与水体积比9∶1、水解时间1 h、pH值6、偶联时间30 min、偶联温度50℃、蒸干温度50℃。采用此工艺得到的接枝复合膜的拉伸断裂强度为0.847 MPa,对Cd2+的吸附量为82.54 mg/g;复合纤维的断裂强度为3.198 cN/dtex,对Cd2+的吸附量为86.2 mg/g。通过单因素分析得到PAN/MHAp-KH570接枝复合膜的最佳接枝时间为8 min,光引发剂最佳用量为9%(对MHAp质量分数)。PAN/MHAp-KH570接枝复合纤维的拉伸断裂强度大于共混复合纤维,而吸附量略小于共混复合纤维。