N-长烷基壳聚糖季铵盐的合成及其抗菌活性研究

先用甲醛-甲酸法(eschweiler-clarke反应)合成N,N-二甲基壳聚糖(DMC),再与溴代烷进行Hoffman烷基化反应制备了N-十二烷基-N,N-二甲基壳聚糖季铵盐(DODMC)和N-十六烷基-N,N-二甲基壳聚糖季铵盐(HDMC),用FT-IR、1 H NMR、EA、TG等对产物进行表征。抗菌实验结果表明所合成产物具有较好的抗菌活性,对革兰氏阳性菌S.aureus的抗菌活性优于革兰氏阴性菌E.coli,抗菌活性随着烷基链长度的增加而增强;产物在pH值=5.5比在pH值=7.2条件下表现出更好的抗菌活性;在碱性及中性条件下,HDMC的抗菌活性随着季铵化度的提高而提高,而在酸性条件下抗菌活性则随着季铵化度提高而降低。     

季铵盐修饰有机硅改性聚氨酯的制备与杀菌性能

以制备环境友好型海洋防污涂料为目标,利用自制的双羟基封端剂、2,4,6-三(3-氯丙基)-2,4,6-三甲基-环三硅氧烷和八甲基环四硅氧烷(D4),通过开环共聚得到含氯丙基双羟基封端聚硅氧烷,然后经季铵化反应在聚硅氧烷链上引入具有杀菌性的季铵盐基团,最后通过活性基团羟基与异氰酸酯反应合成聚氨酯材料并进一步对聚氨酯的表面性能与抗菌性能进行了表征。结果表明:季铵盐含量为20%时,聚氨酯不仅具有低表面能特性,而且对革兰氏阳性菌和革兰氏阴性菌的杀菌率都能到达90%以上,而且有机硅分子量相近时,季铵盐含量越高,杀菌性越好,但疏水性越差。     

Synthesis of a novel tertiary amine containing urethane dimethacrylate monomer (UDMTA) and its application in dental resin

A novel tertiary amine containing urethane dimethacrylate monomer UDMTA was synthesized with the aim of replacing Bis-GMA as one component of dental restorative materials. The structure of UDMTA was confirmed by FT-IR and ¹H-NMR spectra. UDMTA was incorporated into Bis-GMA/TEGDMA (50 wt%/50 wt%) resin system to replace Bis-GMA partly and totally. Double bond conversion, polymerization volumetric shrinkage, water sorption and solubility, flexural strength and modulus of UDMTA containing resin formulations were studied with neat Bis-GMA/TEGDMA resin formulation as a reference. Results showed that UDMTA could be used as a coinitiator in photocurable dental resin, UDMTA containing resin had higher double bond conversion and lower polymerization shrinkage than that of Bis-GMA/TEGDMA resin, and the UDMTA containing copolymer had higher flexural strength and flexural modulus than Bis-GMA/TEGDMA copolymer. When UDMTA was used to replace more than 25 wt% of Bis-GMA, the obtained copolymer had higher water sorption and solubility. The optimized resin composition is by replacing 25 wt% of Bis-GMA in Bis-GMA/TEGDMA (50/50 by wt%), for the prepared resin had the best comprehensive properties.     

Effect of alumina,silk and ceria short fibers in reinforcement of Bis-GMA/TEGDMA dental resin

The present study is focused to investigate influence of short fibers such as Alumina Microfibers (AMFs), Silk Microfibers (SMFs) and Ceria Nanofibers (CNFs) as reinforcements in Bis-GMA/TEGDMA resin towards development of composite dental filler. Morphologies of AMFs, SMFs, CNFs and their representative fracture surfaces of the reinforced dental resins/composites were examined by SEM. X-ray Diffraction Analysis was done to analyse the phase of the fibers used in this study and degree-of-conversion of the fiber incorporated base resin was studied by FTIR. Viscosity study of fiber resin mixture, depth of cure and mass change behaviour of the fibers resin composites in artificial saliva were done to analyse the flow ability and physical properties of the fiber resin composites. Mechanical properties of the composites were tested by a universal testing machine. This study demonstrated that incorporation of 10% AMFs, 5% SMFs, and 3.33% CNFs individually in Bis-GMA/TEGDMA dental resin resulted in similar degree of conversion compared to the control. Also the fiber reinforced composites (10% AMFs, 5% SMFs, and 3.33% CNFs) demonstrated significant improvement in mechanical properties compared to Bis-GMA/TEGDMA resin (Control). However, depth of cure was significantly reduced due to incorporation of fibers in the resin. The reinforcement effect of AMFs, SMFs in dental resin was superior due to their uniform distribution and good interfacial bonding between fibers and resin matrix. In case of CNFs, rapid increase in viscosity during mixing of fibers with resin and inhomogeneous mixing were the major problem encountered during formulation, which was mainly associated with high surface to volume ration of the nanofibers. The resultant composite containing CNFs had less improvement in mechanical properties which may be due to less fiber content, formation of agglomerates and improper distribution of the fibers in the composite which subsequently resulted in reduction of adhesive strength.     

Effect of alumina particles loading on the mechanical properties of light-cured dental resin composites

The purpose of this study is to evaluate the effect of alumina (Al₂O₃) loading on the mechanical properties of dental resin composites (DRCs). The DRCs were prepared based on Al₂O₃ particles and bisphenol A-glycidyl methacrylate (Bis-GMA) was used as the base monomer. The silane-treated Al₂O₃ particles were mixed with the resin matrix in proportions of 40, 50, and 60 wt%, respectively. Resin matrix without filler was used as the control sample. The Vickers hardness (HV) and flexural modulus (FM) of the DRCs mixed with Al₂O₃ particles were found to be superior compared to the control sample; the values increased from 14.4 to 23.5 kg/mm² and 1.5 to 5.7 GPa, respectively. However, the flexural strength (FS) values of DRCs were slightly decreased as the filler loading increased i.e. from 84.5 to 74.2 MPa. The results also revealed statistically significant increases in the HV and FM. On the other hand, FS values showed significant decrease when filler loading was increased (P < 0.05).     

单体种类对季铵盐羧酸型复鞣固色剂性能的影响

以含有季铵盐和羧基的聚合物为基体,通过水溶液聚合法引入不同单体,考察单体种类对季铵盐羧酸型复鞣固色剂性能的影响。红外光谱(FT-IR)结果表明,不饱和单体成功发生了聚合;X射线衍射(XRD)结果表明,与聚合物基体相比,不同单体的引入均降低了复鞣固色剂的结晶度,提高了高分子链的柔软性;将其应用于绵羊皮服装革的复鞣工序,结果表明,在聚合物基体中引入丙烯酸-2-羟乙酯(HEA)后,坯革的K/S值达到了16.461,耐干湿擦牢度和物理机械性能良好。     

Biomineralization,antibacterial activity and mechanical properties of biowaste derived diopside nanopowders

This work reports on the preparation and characterization of mesoporous nano diopside (CaMgSi₂O₆) using a simple and cost-effective sol-gel combustion route. Stoichiometric oxidant/fuel ratio was adopted for the combustion reaction. Eggshell was used as a calcium source, glycine (fuel) as reductant, magnesium nitrate and nitric acid as oxidant were used in the preparation. The thermal behavior of the precursor was studied by thermo-gravimetric analysis (TGA) and heating microscopy. The temperature required for the transformation of the precursor into pure diopside was optimized at 1100 °C. Rietveld refinement method was utilized to confirm the phase purity of diopside. The resultant powder contains 36 nm particle with a specific surface area of 51 m²/g. The appearance of Ca, Mg, Si, and O peaks in EDX pattern confirmed the existence of essential elements. The rapid consumption of calcium and phosphorus ions from the simulated body fluid during dissolution indicated their involvement in apatite deposition on the surface of the nano diopside. FT-IR spectra showed that the SiO and SiOSi groups were replaced by phosphate bands due to hydroxyapatite deposition. The mechanical stability of the diopside after bioactivity studies was found to be superior to the cancellous bone. The release of alkaline earth ions (Ca²⁺ and Mg²⁺) from the diopside sample into the bacterial culture medium increases the pH (7.4), which inhibits the bacterial growth. The surface properties, concentration, and type of bacteria are the other factors responsible for the antibacterial activity of the nano diopside.     

玻璃纤维增强光固化树脂基齿科生物复合材料的半互穿网络结构界面的形成及力学性能

采用不同浓度的聚甲基丙烯酸甲酯(PMMA)丙酮溶液对玻璃纤维进行表面处理,并对不同处理条件下的玻璃纤维表面化学组成、PMMA的吸附量及齿科树脂基复合材料的力学和界面性能进行了分析和测试。结果表明,经过表面处理,玻璃纤维表面吸附上PMMA,且吸附量随PMMA溶液浓度的增大而增大。控制玻纤表面吸附的PMMA质量分数在1%左右,可以设计其与齿科树脂形成半互穿网络结构的良好界面。与未处理的玻纤复合材料相比,用质量分数为5%的PMMA溶液处理的玻纤/光固化树脂基复合材料的弯曲强度提高29.6%,弯曲模量提高30%,可以作为一种齿科修复用的新型生物复合材料应用。     

生物基没食子酸环氧树脂/纳米氧化锌抗菌涂层的制备与性能EI北大核心CSCD

以没食子酸为主要原料制备生物基没食子酸环氧树脂(GAER),将硅烷偶联剂KH550表面改性的纳米ZnO与GAER进行复合,以丁二酸酐为固化剂,制备KH550-nano-ZnO/GAER生物基复合涂层。对纳米ZnO改性前后微观结构的变化进行表征;采用示差扫描量热仪对丁二酸酐/GAER体系的固化过程进行研究,测试KH550-nano-ZnO的加入对GAER固化膜力学性能、热性能、动态力学性能以及抗菌性能的影响。结果表明:适量KH550-nano-ZnO的加入,可以增加GAER固化体系的玻璃化温度,提高涂层表面的抗冲击性,KH550-nano-ZnO含量的增加使得涂层的硬度增加,附着力下降,热稳定性增加。复合涂层的起始热失重温度(T5%)比纯GAER高12.6~15.4℃。当KH550-nano-ZnO含量为2%(质量分数)时,玻璃化转变温度与纯GAER树脂相比增加了30.7℃。KH550-nano-ZnO/GAER固化涂膜对大肠杆菌和金黄色葡萄球菌的抗菌率均达到99.99%。     

Polymer grafted hydroxyapatite whisker as a filler for dental composite resin with enhanced physical and mechanical properties

The objective of this study was to investigate the effect of surface graft polymerization of hydroxyapatite whisker (HW) on physical and mechanical properties of dental composite resin. Poly bisphenol A glycidyl methacrylate (Poly(Bis-GMA)) was grafted onto silanized hydroxyapatite whisker (SHW) via solution polymerization and the amount of the Poly(Bis-GMA) on the surface was effectively controlled by polymerization time. The obtained poly(Bis-GMA) grafted hydroxyapatite whisker (PGHW) with different polymer contents was filled into a resin matrix respectively, meanwhile the composites with HW and with SHW served as controls. Monomer conversion was characterized by Fourier transform infrared spectroscopy (FTIR) and volume shrinkage of the composite resin was measured with a density tester. Mechanical properties were tested with a universal testing machine. The results indicated that the composite filled with PGHW-1 h (graft ratio of poly(Bis-GMA): 8.5 wt.%) showed lower shrinkage and better mechanical properties, improving flexural strength by 6.5% and 11.9% compared with SHW filled composite and HW filled composite, respectively. However, PGHW with higher graft ratios aggregated seriously and formed defects in the composite, leading to deterioration of mechanical properties. It was revealed that the poly(Bis-GMA) on the surface of PGHW acted as a functional transition layer and enhanced interfacial compatibility and interaction between whisker and resin matrix, which facilitated the dispersion of PGHW in the composite and decreased the composite shrinkage. Thus, the graft polymerization of Bis-GMA on the surface of filler might be a promising modification method for the fabrication of dental materials.     

纳米铜/聚丙烯腈纤维抗菌性能、力学性能研究

通过对纳米铜/聚丙烯腈纤维进行抗菌性能研究,结果表明,纳米铜/聚丙烯腈纤维对大肠杆菌、枯草芽孢杆菌、金黄色葡萄球菌、白色链球菌等微生物有明显的抗菌效果,抗菌15h,抗菌率均达90%以上;纳米铜/聚丙烯腈纤维对大肠杆菌、枯草芽孢杆菌、金黄色葡萄球菌的抗菌效率高于非纳米铜/聚丙烯腈纤维对其的抗菌效率.力学性能测试表明:纳米铜/聚丙烯腈纤维的断裂强力、初始模量、应力均优越于非纳米级铜/聚丙烯腈纤维.     

Facile fabrication of superior antibacterial cotton fabric based on ZnO nanoparticles/quaternary ammonium salts hybrid composites and mechanism study

In the research for the safe and efficiently antibacterial cotton fabrics to minimize risk for human health, an organic–inorganic hybrid material of ZnO nanoparticles (NPs) and quaternary ammonium salt (QAS) was employed to modify cotton fabrics by a dipping–padding–drying method. The synergistic effects of ZnO NPs and QAS on the structure and antibacterial properties of cotton fabrics were studied in detail. Results displayed that the QAS and ZnO NPs were immobilized firmly in cotton fabric by the formation of chemical covalent bonds and silica gel structure. ZnO/QAS/cotton had a good inhibitory effect on the growth of E. coli and S. aureus, with superior antibacterial efficiency of >99.99%. ZnO/QAS/cotton preserved good mechanical property, water absorbability, and limpness. We also provided a detailed analysis of antibacterial mechanism for the hybrid materials. The contact mechanism and the Zn²⁺ release were considered as the main mechanisms for the ZnO/QAS/cotton, while the reactive oxygen species (ROS) generation only had a little contribution to the antibacterial activity. In short, the excellent integrated properties endowed the hybrid cotton fabrics as potential application in many fields, like healthcare, food packaging.     

The thermal and mechanical properties of graphite foam/epoxy resin composites

A series of epoxy resin (EP) filled graphite foam (GF) composites were prepared to explore a new material with good heat transfer property. The effects of the mass fraction of EP and the network structure of GFs on the thermal diffusivity and the compression strength of the composites were investigated. The thermal diffusivity of the GF/EP composite with EP mass fraction of 91.45% was raised to 6.541 mm²/s, which was 45.7 times higher than the pure EP. The thermal conductivity reached to 14.67 W/(m K), which was 43.1 times higher than the pure EP. The compression strength of the GF/EP increased 55% above the value of pure EP. In addition, the thermal diffusivity of GF/EP increased with the decrease of the mass fraction of EP. A model was formulated to calculate the pressure needed for a mass fraction of EP.     

Epoxy resin/liquid natural rubber system: secondary phase separation and its impact on mechanical properties

An investigation was carried out to explore the morphology and mechanical properties of diglycidyl ether of bisphenol A epoxy resin (DGEBA) with liquid natural rubber possessing hydroxyl functionality (HLNR). Though modification of epoxies by synthetic rubber has been extensively studied not much attention has been paid to liquid natural rubber. Photo depolymerisation of natural rubber enables us to synthesise low molecular weight oligomers by varying the experimental parameters. Epoxy resin was cured using nadic methyl anhydride as hardener in presence of N,N-dimethyl benzyl amine accelerator. Hydroxylated natural rubber of different concentrations is used as modifier for epoxy resin. The addition of such chemically modified liquid rubber to an anhydride hardener–epoxy resin mixture has given rise to the formation of a two-phase microstructure in the cured systems, consisting of spherical particles of liquid natural rubber strongly bonded to the surrounding matrix, there by providing the required mechanism for toughness enhancement. Subinclusions of epoxy resin were present in the elastomer domains as secondary particles (particle in particle morphology) as evidenced from the SEM (scanning electron micrograph) photomicrographs. The origin of the so-called secondary phase separation is due to the combined effect of hydrodynamics, viscoelastic effects of rubber phase, diffusion, surface tension, polymerisation reaction and phase separation. In a dynamic asymmetric system, the diffusion of the fast dynamic phase is prevented by the slow dynamic phase, and hence the growth of fast dynamic phase gets retarded due to the slow dynamic phase. In the case of low viscosity blends the growth of fast dynamic phase turns fast and hence diffusion of fast dynamic phase cannot follow geometrical growth and cannot establish local concentration equilibrium and hence double phase separation takes place. The double phase separation is responsible for the enhanced impact and toughness behaviour of the blends. The mechanical behaviour of the liquid rubber-modified epoxy resin was evaluated in terms of tensile and flexural properties.     

树脂浸渍法对炭/炭复合材料力学性能的影响

将炭纤维坯体CVD增密至不同密度,再对其进行树脂浸渍。对自制样品与英国Dunlop公司和美国Ben dix公司产品的力学性能特征进行了对比分析。结果表明:自制样的抗压强度和抗弯强度远远高于国外样品,层间剪切强度也比国外样品高;自制样品在ρCVD不超过1.45g cm3的情况下,随样品中CVD炭含量的增加,样品的抗弯强度和层间剪切强度值都随之增大,抗弯模量在ρCVD为1.06g cm3时达到最大值。同时用扫描电镜(SEM)分析了这几组试样的弯曲与剪切断口,发现除纯浸渍的样品具有明显的脆性断裂特征外,其余材料都呈假塑性断裂,且强度较高,说明树脂由于炭化后产生的树脂炭与纤维粘结太强,不适合在样品增密的初始阶段作浸渍剂。     

Effect of resin system on the mechanical properties and water absorption of kenaf fibre reinforced laminates

The objective of this study is to compare the mechanical and water absorption properties of kenaf (Hibiscus cannabinus L.) fibre reinforced laminates made of three different resin systems. The use of different resin systems is considered so that potentially complex and expensive fibre treatments are avoided. The resin systems used include a polyester, a vinyl ester and an epoxy. Laminates of 15%, 22.5% and 30% fibre volume fraction were manufactured by resin transfer moulding. The laminates were tested for strength and modulus under tensile and flexural loading. Additionally, tests were carried out on laminates to determine the impact energy, impact strength and water absorption. The results revealed that properties were affected in markedly different ways by the resin system and the fibre volume fraction. Polyester laminates showed good modulus and impact properties, epoxy laminates displayed good strength values and vinyl ester laminates exhibited good water absorption characteristics. Scanning electron microscope studies show that epoxy laminates fail by fibre fracture, polyester laminates by fibre pull-out and vinyl ester laminates by a combination of the two. A comparison between kenaf and glass laminates revealed that the specific tensile and flexural moduli of both laminates are comparable at the volume fraction of 15%. However, glass laminates have much better specific properties than the kenaf laminates at high fibre volume fractions for all three resins used.     

Optimizing the mechanical properties of electrospun polycaprolactone and nanohydroxyapatite composite nanofibers

Interest in fabrication of nanofibers using electrospinning has recently increased due to the ability to produce fibers with controlled structures, orientations, and dimensions. Tensile properties of electrospun fibers have not been widely investigated due to the difficulties in handling nanofibers and measuring low load for deformation. In this study, the effects of process parameters on the mechanical properties of electrospun composite nanofibers of polycaprolactone and nanohydroxyapatite were experimentally investigated. Response surface methodology (RSM) was utilized to design the experiments at the settings of solution concentration, voltage, spinning distance and flow rate. Mechanical properties of the electrospun fibers were correlated with these variables using a third order polynomial function. It was found that polymer concentration, voltage and spinning distance were the most effective parameters. The predicted mechanical properties were in good agreement with the experimental results.     

Singlet oxygen generation properties of Fe-OCAP and its influence on the antibacterial and mechanical properties of Fe-OCAP/PU blends

In this paper, the singlet oxygen generation properties of Fe-octacarboxyl acid phthalocyanine (Fe-OCAP)/polyurethane (PU) blends were investigated by ultraviolet–visible spectra. 1,3-diphenylisobenzofuran was used as the reaction substrate to detect the yields of the singlet oxygen of the samples. It was found that Fe-OCAP showed a high efficiency in generating singlet oxygen when it was dissolved in dimethylacetamide (DMAc), while no singlet oxygen was generated when it was in ethanol. The singlet oxygen generation properties of Fe-OCAP/PU blends were also investigated. It was found that with increasing Fe-OCAP content, Fe-OCAP/PU blends showed increased efficiency in generating singlet oxygen. The influence of wavelength of light on the singlet oxygen generation of Fe-OCAP/PU was studied. Compared with orange light, Fe-OCAP/PU had a higher efficiency in generating singlet oxygen under the illumination of red light. The generated singlet oxygen by Fe-OCAP/PU blends had a high efficiency in cell inactivation. As a result, the percentage bacterial reduction of the samples increased with increasing Fe-OCAP content. The influence of the generated singlet oxygen on the mechanical properties of PU was also investigated. The generated singlet oxygen could initiate the oxidation of PU chain and cause the degradation of PU. Therefore, after illuminated by white light, the tensile strength of the samples containing Fe-OCAP decreased, but still was higher than that of pure PU.