Genipin交联丝素蛋白纳米纤维膜的制备与性能

利用Genipin对再生丝素蛋白进行交联改性,并通过静电纺丝法制备交联的丝素蛋白纳米纤维膜.利用场发射扫描电镜、红外光谱仪、X射线衍射仪、热重分析仪以及拉力机等对其结构与性能进行表征与测试.结果表明,随着交联剂Genipin质量比的增加,交联度增加,静电纺丝素蛋白纳米纤维平均直径增大,标准偏差增大;Genipin交联对丝素蛋白纳米纤维结晶结构影响不大,但热性能提高;常温条件下,随着Genipin质量比从2％提高至15％,丝素蛋白纳米纤维膜的力学性能逐渐增强,质量比为10％时,其力学性能较好,拉伸强度和断裂应变分别为19.6 MPa和5.9％;随着试验温度从40℃升高到200℃,丝素蛋白纳米纤维膜的拉伸强度和断裂应变先增大然后减小,当试验温度为80℃时,其力学性能较好,拉伸强度和断裂应变分别为41.6 MPa和8.6％.     

Genipin交联丝素蛋白纳米纤维膜的制备与性能

利用Genipin对再生丝素蛋白进行交联改性, 并通过静电纺丝法制备交联的丝素蛋白纳米纤维膜。利用场发射扫描电镜、 红外光谱仪、 X射线衍射仪、 热重分析仪以及拉力机等对其结构与性能进行表征与测试。结果表明, 随着交联剂Genipin质量比的增加, 交联度增加, 静电纺丝素蛋白纳米纤维平均直径增大, 标准偏差增大;Genipin交联对丝素蛋白纳米纤维结晶结构影响不大, 但热性能提高;常温条件下, 随着Genipin质量比从2%提高至15%, 丝素蛋白纳米纤维膜的力学性能逐渐增强, 质量比为10%时, 其力学性能较好, 拉伸强度和断裂应变分别为19.6 MPa和5.9%;随着试验温度从40 ℃升高到200 ℃, 丝素蛋白纳米纤维膜的拉伸强度和断裂应变先增大然后减小, 当试验温度为80 ℃时, 其力学性能较好, 拉伸强度和断裂应变分别为41.6 MPa和8.6%。     

Plasma-initiated graft polymerization of water-soluble vinyl monomers onto hydrophobic films and its application to metal ion adsorbing films

Plasma-initiated graft polymerization of water-soluble vinyl monomers such as acrylic acid, 2-hydroxyethyl methacrylate and acrylamide was carried out onto polyethylene, polypropylene and poly(ethylene terephthalate) films. It was found that these monomers could be graft polymerized quite easily to 0.5%–670% of the mass of the dry films by exposing the films to a plasma for 90s, with subsequent post-polymerization at room temperature. Thus, polyethylene films capable of adsorbing and desorbing metal ions reversibly could be prepared by grafting the monomers described.     

Preparation and characterization of magnetic nanofibrous composite membranes with catalytic activity

Magnetic nanofibrous composite membranes were electrospun from the mixtures of poly(acrylonitrile-co-acrylic acid) (PANCAA) and Fe₃O₄ nanoparticles. Field emission scanning electron microscopy (FESEM) and thermal gravimetric analysis (TGA) were used to characterize the composite membranes. TGA results indicate that the addition of Fe₃O₄ nanoparticles catalyzes the carbonization of PANCAA as well as dramatically increases the carbonization temperature. The intrinsic peroxidase-like activity of Fe₃O₄ nanoparticles was measured by the color reaction of phenol/4-amino antipyrine in the presence of H₂O₂. Under optimal conditions, the electrospun composite membranes show high peroxidase-like catalytic activity and reusability. Taking into account of the potentiality for separation, these as-prepared magnetic nanofibrous composite membranes will be applied in phenolic wastewater treatment.     

等离子体诱导接枝聚合修饰碳纳米管及其环氧树脂复合材料

以马来酸酐(MAH)为有机单体,通过等离子体诱导接枝聚合法修饰碳纳米管(CNTs),借助红外光谱、扫描电镜分析手段,对所得表面为聚合物膜修饰碳纳米管(p-CNTs)进行表征。将上述p-CNTs应用于环氧树脂(EP)固化体系,制备出p-CNT/EP纳米复合材料,研究了其对EP性能的影响。结果表明:等离子体可诱导马来酸酐在CNTs表面接枝聚合成膜。利用包覆于CNTs表面的聚马来酸酐(PMAH)薄膜功能化修饰CNTs。合适含量的p-CNTs可显著提高环氧树脂的强度和韧性,使其高度强韧化。     

Macroscopic single crystals of polymers by solid-state polymerization: a study of the monomer to polymer phase transformation of 1,6-dicarbazolyl hexadiyne

The solid-state polymerization of 1,6-di(N-carbazolyl-2,4-hexadiyne (DCH) giving rise to macroscopic single crystals of the corresponding polymer is described with regard to structural aspects. The crystal structures of the monomer and polymer are discussed with respect to the observed solid-state reactivity. An autocatalytic acceleration in the conversion-time characteristics of the radiation-induced polymerization is attributed to a non-destructive phase transition as indicated by a sudden change in the lattice parameters and the elastic constants of the polymerizing crystal. The same phase transition occurs with destruction of the parent lattice during thermal polymerization. The Young's modulus in the chain direction of radiation-polymerized crystals reaches the theoretical value expected for infinitely long polymer chains.     

CAN引发淀粉与MMA接枝共聚反应的研究

在研究玉米淀粉(corn starch,CS)与甲基丙烯酸甲酯(MMA)接枝共聚反应时发现,硝酸浓度为0.1mol/L、硝酸铈铵(CAN)/CS质量比为1/6、MMA/CS质量比为3/2是兼顾单体转化率(C)、接枝率(G)和接枝效率(GE)的最佳反应条件;同时发现,该反应中均聚物的生成不仅可由CAN直接引发,还可能因淀粉自由基或淀粉接枝物自由基的链转移而引发.     

Controllable crystal growth of Mg(OH)2 hexagonal flakes and their surface modification using graft polymerization

Mg(OH)₂ crystals with excellent flame retardance in the application of polymer materials are always in demand. Herein, regular and well-dispersed Mg(OH)₂ hexagonal flakes were hydrothermally prepared with the existence of polyethylene glycol (PEG) and then modified by surface grafting-polymerization of methyl methacrylate (MMA) monomers. The results showed that the morphology and dispersity of Mg(OH)₂ relied on the precise control of the reaction parameters including hydrothermal conditions, the molecular weight and additive amount of PEG. PEG with a molecular weight of 8000 exhibited an enhanced directing role due to its more appropriate length of molecular chains and intensive interaction with the formed Mg(OH)₂ crystallites. The molecular chains of PEG-8000 can be preferentially adsorbed onto the (0 0 1) and (1 0 1) planes of Mg(OH)₂ crystallites and sub-micro hexagonal flakes with low-polarity were consequently assembled. The optimal conditions for preparing Mg(OH)₂ hexagonal flakes with higher crystallinity and more regular morphology were determined to be hydrothermal treatment at 120 °C for 12 h with 3 wt% PEG-8000. The dimension and decomposition temperature of the end products were 400 ~ 500 nm and 388 °C, respectively. The surface graft-modified Mg(OH)₂ hexagonal flakes exhibited high hydrophobicity with a water contact angle of 148°, indicating an excellent compatibility with polymers.     

Sorption of polycyclic aromatic hydrocarbons on electrospun nanofibrous membranes: sorption kinetics and mechanism

Five types of nanofibrous membranes were prepared by electrospinning poly(?-caprolactone) (PCL), poly(d,l-lactide) (PDLLA), poly(lactide-co-caprolactone) (P(LA/CL)), poly(d,l-lactide-co-glycolide) (PDLGA) and methoxy polyethylene glycol-poly(lactide-co-glycolide) (MPEG-PLGA), respectively. These electrospun nanofibrous membranes (ENFMs) were used to adsorb anthracene (ANT), benz[a]anthracene (BaA) and benzo[a]pyrene (BaP) from aqueous solution, and the sorption kinetics and isotherms of these PAHs on the five ENFMs were investigated. The pseudo-second-order model (PSOM) can well describe the sorption kinetics of the three PAHs on five ENFMs, and the partition-adsorption model (PAM) can interpret the sorption processes of PAHs on the ENFMs. PCL ENFMs, which had the largest surface areas (8.57 m² g⁻¹), exhibited excellent sorption capacity for ANT at over 4112.3 ± 35.5 μg g⁻¹. Moreover, the hydrophobicity and pore volume of ENFMs significantly affected the sorption kinetics and sorption capacity of the PAHs. The main sorption mechanisms of three PAHs on the PDLLA ENFMs included hydrophobic interactions and pore-filling, while those of PCL, P(LA/CL) and PDLGA ENFMs were dominated by the hydrophobic interactions. The sorption mechanisms of MPEG-PLGA ENFMs primarily included pore-filling, hydrogen bonding interactions and hydrophobic interactions. Additionally, π-π bonding interaction was also deduced to be involved in all of ENFMs sorption systems.     

淀粉与丙烯酸乙酯接枝共聚物的合成与表征

以硝酸铈铵(CAN)为引发剂,研究了丙烯酸乙酯(EA)与玉米淀粉接枝共聚体系的自由基引发反应规律.实验结果得到较佳的反应条件为:单体浓度1.4939mol/L,引发剂浓度0.0293mol/L,AGU浓度1.1075mol/L,硝酸浓度0.02 mol/L,反应温度50℃,反应时间3h.在以上的反应条件下,转化率(C)可达98.64％,接枝率(G)可达34.92％,接枝效率(GE)可达74.55％.通过对接枝共聚产物的红外分析、核磁共振波谱分析、DSC分析及电镜扫描分析对产物进行了表征.结果表明,EA与淀粉发生了接枝共聚反应.     

亲水性沸石膜在异丙醇脱水中的应用及其耐酸性研究

采用二次生长法,在α-Al2O3陶瓷管上制备亲水性NaA、T型、ZSM-5沸石膜,采用SEM对其进行表征.比较3种亲水性膜在异丙醇/水体系的渗透汽化性能,考察其在不同的料液温度下对异丙醇的分离效果.通过优化膜合成液中Si/Al和F-/Si的摩尔比、合成时间等条件,提高ZSM-5沸石膜的渗透汽化性能.分析考察膜的耐酸性能,结果显示ZSM-5沸石膜具有良好的耐酸性;将ZSM-5沸石膜在pH为5.8的酸性溶液浸泡10天后,用于97%的乙酸乙酯/水体系中渗透汽化脱水,渗透液水含量可达99.59%,渗透通量可达0.12kg/(m2·h),分离因数高达7 894.     

聚乙烯亚胺包埋无色纳米银抗菌剂制备及协同抗菌效果研究

以高枝化聚乙烯亚胺(PEI)为稳定剂,硼氢化钠为还原剂,利用化学还原法制备了纳米银抗菌剂。探讨了温度、PEI与Ag+的摩尔比对纳米银抗菌剂合成的影响,利用紫外分光光度法及扫描电镜对合成纳米银抗菌剂进行了表征,利用抑菌圈实验分别对纳米银及PEI进行了抑菌性能测试,筛选出稳定性好抑菌性强的纳米银抗菌剂制备工艺。实验结果表明,在45℃,PEI与Ag+的摩尔配比在2∶1~0.6∶1条件下能制备无色透明且抑菌性强的具有核壳结构的纳米银抗菌剂,PEI对纳米银抗菌剂具有协同作用。     

Atom-transfer radical graft polymerization initiated directly from silica applied to functionalization of stationary phases for high-performance liquid chromatography in the hydrophilic interaction chromatography mode

Initiation of atom-transfer radical polymerization of a number of monomers (styrene, methyl acrylate, 3-[N,N-dimethyl-N-(methacryloyloxyethyl)ammonium] propanesulfonate, butyl methacrylate, 2,3-epoxypropyl methacrylate) directly from chlorinated porous silica particles has been performed. The grafting has been confirmed and evaluated by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. This initiation technique results in a hydrolytically stable initial Si-C bond, tethering the polymer to the silica substrate. The resulting grafted particles have been used as separation materials for both reversed-phase and hydrophilic interaction chromatography.     

聚环氧乙烷及其衍生物在超滤膜亲水化改性中的应用

依据亲水改性方法的划分从膜的表面涂覆、共混、表面接枝和成膜材料改性等4个方面进行阐述,分析比较了聚环氧乙烷及其衍生物在各种不同的疏水超滤膜亲水改性中应用的途径和特性。经过聚环氧乙烷及其衍生物改性之后,超滤膜的接触角降低,蛋白质吸附量减少,亲水性和抗污染能力明显提高,应用前景更加广阔。     

HRP-mediated graft polymerization of acrylic acid onto silk fibroins and <Emphasis Type="Italic">in situ</Emphasis> biomimetic mineralization

Silk fibroin (SF) can be extensively utilized in biomedical areas owing to its appreciable bioactivity. In this study, biocompatible composites of SF and hydroxyapatite (HAp) were fabricated through in situ biomimetic mineralization process. Graft copolymerization of acrylic acid (AA) onto SF was conducted by using the catalytic system of acetylacetone (ACAC), hydrogen peroxide (H₂O₂) and horseradish peroxidase (HRP), for enhancing the deposition of apatite onto the fibroin chains. Subsequently, biomimetic mineralization of the prepared fibroin-based membrane was performed in Ca/P solutions to synthesize the organized SF/HAp composites. The efficacies of graft copolymerization and biomimetic mineralization were evaluated by means of ATR-FTIR, GPC, EDS-Mapping, XRD and others. The results denoted that AA was successfully graft-copolymerized with fibroin and formed the copolymer of silk fibroin-graft-polyacrylic acid (SF-g-PAA), and the grafting percentage (GP) and grafting efficiency (GE) under the optimal condition reached to 23.2% and 29.4%, respectively. More mineral phases were detected on the surface of SF-g-PAA membrane after mineralization process when compared to that of the untreated fibroin membrane, companying with an improved mechanical property. According to MG-63 cell viability and fluorescent adhesion assays, the mineralized SF-g-PAA composite showed satisfactory biocompatibility and exceptional adhesive effects as well. The synthetized composite of SF-g-PAA/HAp can be potentially applied in the fields of bone tissue engineering.

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Uniform-sized molecularly imprinted polymers for 2-arylpropionic acid derivatives selectively modified with hydrophilic external layer and their applications to direct serum injection analysis

Uniform-sized molecularly imprinted polymers (MIPs) for (S)-naproxen and -ibuprofen selectively modified with hydrophilic external layer, restricted access media (RAM)-MIPs, have been prepared. First, the MIP for (S)-naproxen or -ibuprofen was prepared using 4-vinylpyridine and ethylene glycol dimethacrylate as a functional monomer and cross-linker, respectively, by a multistep swelling and thermal polymerization method. Next, a 1:1 mixture of glycerol monomethacrylate and glycerol dimethacrylate was used for hydrophilic surface modification, and it was added directly to the MIP for (S)-naproxen or -ibuprofen 4 h after the start of molecular imprinting. The obtained RAM-MIP material for (S)-naproxen or -ibuprofen was applied for direct serum injection assays of the drug by a column-switching system, consisting of a RAM-MIP material and conventional C18-silica column. However, leakage of the imprint molecule prevented accurate and precise assays of the drug. This problem has been overcome by using the RAM-MIP for (S)-naproxen for the assays of ibuprofen in rat plasma. The optimized column-switching system was applied successfully to the assay of ibuprofen in rat plasma after oral administration.     

Dual delivery of hydrophilic and hydrophobic drugs from chitosan/diatomaceous earth composite membranes

Oral administration of drugs presents important limitations, which are frequently not granted the importance that they really have. For instance, hepatic metabolism means an important drug loss, while some patients have their ability to swell highly compromised (i.e. unconsciousness, cancer…). Sublingual placement of an accurate Pharmaceutical Dosage Form is an attractive alternative. This work explores the use of the β-chitosan membranes, from marine industry residues, composed with marine sediments for dual sublingual drug delivery. As proof of concept, the membranes were loaded with a hydrophilic (gentamicin) and a hydrophobic (dexamethasone) drug. The physico-chemical and morphological characterization indicated the successful incorporated of diatomaceous earth within the chitosan membranes. Drug delivery studies showed the potential of all formulations for the immediate release of hydrophilic drugs, while diatomaceous earth improved the loading and release of the hydrophobic drug. These results highlight the interest of the herein developed membranes for dual drug delivery.

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原子转移自由基聚合与高分子膜亲水化/功能化构造

原子转移自由基聚合(ATRP)对膜的亲水化/功能化改性包括对膜基体材料的共聚改性和对膜的表面改性.膜基体材料的改性最多见于PVDF为主链的两亲性聚合物.ATRP对膜的表面改性尤其是膜的表面引发方法,可实现将不同功能性单体接枝到聚合物膜表面,得到了抗污染能力强,生物相容性好,开关响应迅速等多种功能性表面层.直接的表面引发改性是一种高效,灵活的表面修饰/功能化方法,也是目前应用最广泛的改性技术.     

Design and fabrication of imidazolium ion-immobilized electrospun polyurethane membranes with antibacterial activity

By covalently immobilizing imidazolium ion onto molecular chain, functional polyurethane (PU) is fabricated and thus an effective way is initiated to prepare electrospun membranes with antibacterial activity. In the experiment, PUs containing imidazolium ion side group (Bmim-PUs) are synthesized through a two-step polymerization process. It includes prepolymerization of isophorone diisocyanate (IPDI) with polyester glycol and chain extension polymerization using imidazolium-based ionic diol (Bmim-OH). Then, the obtained Bmim-PUs are electrospun into fibrous membranes with a diameter of ~640 nm. After a careful assessment, antibacterial activities of electrospun membranes against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli are clearly exhibited. The antibacterial efficiency of Bmim-PUs on both bacteria species improves by 60% in comparison with PU without imidazolium ion. This research suggests a simple but effective methodology to design and fabricate ultrafine fibrous membrane with significant antibacterial activity. Moreover, the obtained fibrous membranes have widely potential applications in protective textiles, filtration, and biomedical engineering.     

单体结构对聚酰胺复合纳滤膜表面形貌与性能的影响

以聚砜超滤膜为基膜，2，5-二胺基苯磺酸（DABSA）、间苯二胺（MPDA）、GO代树状聚合物聚酰胺-胺（PAMAM-GO）为水相单体，均苯三甲酰氯（TMC）为油相单体，通过界面聚合法分别制备出3种聚酰胺复合纳滤膜。采用傅立叶转换红外全反射分析膜表面化学组成的变化，用扫描电镜观察了膜的表面形貌，分别评价了3种膜对2000mg／LNaCl、Na2SO4、MgCl2、MgSO4等4种盐的脱除效果。结果表明，NF-DABSA膜表面呈疏松网络状结构，NF-MPDA膜表面由许多小的囊泡堆积成致密层，而NF-ZGO膜表面是由许多小的颗粒紧密堆积而成。其中NF-ZGO膜呈荷正电特征，对NaCl、Na2SO4、MgCl2、MgSO4的脱除顺序为MgCl2〉MgSO4〉Na2SO4〉NaCl，另两种膜则呈荷负电特征。当3种水相单体中的活性基团浓度都相同时，制备所得的纳滤膜对2000mg／LNa2SO4的脱除顺序为NF-MPDA-T〉NF-ZG0-T〉NF-DABSA-T。由此可见，单体的结构对复合纳滤膜的形貌及性能产生很大影响，其主要原因可能与单体的反应活性及在基膜表面的吸附性能有关。