氧化纤维素增强胶原水凝胶

对纤维素进行氧化,得到醛基化的氧化纤维素,将其作为大分子交联剂制备了氧化纤维素改性胶原水凝胶.通过扫描电镜、力学性能及流变学测试,对改性胶原水凝胶的结构和性能进行了表征.研究结果表明,与纯胶原水凝胶相比,氧化纤维素改性胶原水凝胶的力学性能和热稳定性都得到了明显改善,其压缩破坏强度比纯胶原水凝胶提高了1个数量级以上.此外,氧化纤维素的引入,并未出现一般化学交联剂改性所带来的细胞毒性,并保持了胶原水凝胶良好的生物相容性.为改性胶原水凝胶在组织工程材料领域的应用提供依据.     

基于聚丙交酯的光固化型可生物降解聚氨酯丙烯酸酯的合成和表征

基于聚醚酯的聚氨酯丙烯酸酯具有应用于组织工程支架材料及相关生物医用材料的潜力,研究其可生物降解性及影响因素非常重要.聚醚酯是由PEG(Mw=400)引发L-丙交酯开环聚合而得到的PLLA-PEGPLLA(PLEL)嵌段共聚物.它与二异氰酸酯(异佛尔酮二异氰酸酯和六亚甲基二异氰酸酯)反应,并用甲基丙烯酸羟乙酯封端,得到聚氨酯丙烯酸酯低聚物,然后通过紫外固化得到聚氨酯丙烯酸酯材料(PUA).用NMR和GPC对PLEL二醇和预聚物进行了组成和分子量表征,用DSC和DMA对PUA进行了结构和物理性能表征以及用接触角、吸水率和质量分析方法对材料的亲水性和降解性能进行了表征.结果发现,随着PLLA疏水链段变长,PLEL软段分子量增大,材料的亲水性降低,交联度和降解速率变小.相同的软段,基于硬段HDIHEMA的PUA材料比IPDI-HEMA的PUA有较低的T_g,较高的亲水性和降解速率.因为IPDI有环状结构,降低了PUA与水的相互作用.在3种不同降解条件下,氧化降解速率最高,酶解的速率高于水解.PUA材料的氧化降解速率取决于软段中PEG的含量,PLEL1000-HDI中PEG含量最高,其氧化降解最快,13周内失重率达到82.6%.     

超声波活化处理对微晶纤维素结构和氧化反应性能的影响

采用无污染的超声波技术预处理微晶纤维素, 研究了微晶纤维素在活化前后的超分子结构、形态结构和可及度的变化, 超声波活化对微晶纤维素选择性氧化性能的影响.     

氧化淀粉的氧化度对其交联海藻酸钠/明胶互穿网络膜性能的影响

以氧化淀粉为交联剂交联明胶、以氯化钙为交联剂交联海藻酸钠,采用分步交联的方法制备了海藻酸钠/明胶互穿网络膜.通过红外光谱仪表征了氧化淀粉、海藻酸钠/明胶互穿网络膜的结构;研究了氧化淀粉的氧化度对互穿网络膜力学性能、热稳定性能、微观形貌、交联度、吸水保水性能等各种性能的影响.结果表明,随着氧化淀粉氧化度的增加,互穿网络膜的拉伸强度、断裂伸长率、交联度呈现先增加后降低的趋势,氧化度为60%的氧化淀粉交联制备的互穿网络膜的以上性能达到最大值;吸水保水性能呈现先降低后增加的趋势,这主要是因为随着互穿网络膜交联度的增加,使两相间形成了均匀、致密的网络结构,两者分子链上大量的羟基和羧基受到束缚,导致互穿网络膜吸水率、保水率的下降.同时也说明了该体系的交联度并不是随着氧化淀粉氧化度的提高而逐渐提高,对于该体系氧化淀粉存在最佳氧化度.     

溶液预凝胶化对再生纤维素水凝胶膜性能的影响

研究了溶液预凝胶化对纤维素/NaOH/尿素水溶液体系以浸没沉淀相转化法制备的再生纤维素水凝胶膜的影响.通过静态拉伸、扫描电子显微镜研究了预凝胶化温度、凝固浴温度、凝固浴组成对再生纤维素水凝胶膜结构和性能的影响.结果表明,与常规的浸没沉淀相转化法相比,使溶液预凝胶化可以提高所制备的水凝胶膜的机械性能.经60℃预凝胶30 min后制备的水凝胶膜,拉伸强度比未经预凝胶处理的水凝胶膜提高85%.凝固浴温度的升高和凝固浴中硫酸浓度的增大均会导致形成具有较大孔结构的纤维素水凝胶膜,机械性能也随之下降.     

高碘酸钠催化微晶纤维素的氧化

主要讨论了使用高碘酸钠(NaIO4)溶液氧化微晶纤维素的过程及性能,用红外光谱(IR)验证了氧化纤维素的生成;通过扫描电镜(SEM)、热重分析(TG-DSC)以及X射线衍射(XRD)对比了反应前后纤维素的变化;考察了氧化时间、氧化温度、氧化剂的浓度以及溶液的pH值对氧化纤维素的产率及醛基含量的影响;结果表明,反应前后纤维素的晶型和形貌基本没有变化,随着氧化程度的加深,氧化纤维素的热稳定性越来越差;并且随着氧化温度的提高和氧化剂浓度的增大,醛基含量相应提高,而氧化时间和pH值对醛基含量存在相对最高值。     

TEMPO氧化和高频超声下埃米级厚度纤维素纳米纤丝的制备

通过不同TEMPO氧化体系对商品竹浆进行氧化处理,经高频超声纳米纤丝化后,可以制得长度在数百纳米,宽度小于5.0 nm,厚度仅为几个埃的纤维素纳米纤丝(TEMPO-oxided cellulose nanofibrils,TOCNs).这种纳米带状(nanostrip)的TOCNs是由纤维素片层构成的.本文通过场发射扫描电子显微镜(FE-SEM)探究了原料和2组TOCNs样品的形貌变化,利用透射电子显微镜(TEM)和原子力显微镜(AFM)对2组TOCNs样品的三维尺寸(长、宽、厚)进行测量统计.通过不同氧化体系产物的TOCNs三维尺寸差异,并结合傅里叶红外吸收光谱(FTIR)、X射线衍射(XRD)及交叉极化和魔角旋转13C固态核磁共振光谱(CP/MAS 13C-NMR)揭示了不同氧化体系对纤维素Iβ层内氢键及长轴方向的作用机理.     

以纤维素/AmimCl溶液制备纤维素气凝胶

利用离子液体AmimCl溶解结合超临界CO2干燥的方法制备了纤维素气凝胶材料.研究了不同初始浓度的纤维素溶液及其在不同凝固浴中制备的纤维素凝胶的流变行为,进一步考察了纤维素溶液浓度和凝固浴种类对纤维素气凝胶材料结构的影响.结果表明,随着初始纤维素溶液浓度的增大,气凝胶的孔结构逐渐致密,比表面积随之减小;凝固浴的组成对纤维素气凝胶的结构也有较大影响.采用适当的制备条件,可以制备出高比表面积的纤维素气凝胶材料.对纤维素气凝胶的热性能进行了表征,结果表明所得到的气凝胶材料具有较好的热稳定性和较高的炭残余含量.     

介孔硅复合氧化石墨烯多孔材料的制备及其CO2吸附性能研究

以P123为模板剂,以TEOS为硅源,以氧化石墨烯为复合组分,采用溶胶-凝胶法和自组装法制备了具有较大比表面积的介孔硅复合氧化石墨烯三维多孔材料（MSM/GOs）,进一步通过物理浸渍聚乙烯亚胺（PEI）制备了固态胺吸附材料。利用扫描电子显微镜（SEM）、氮气吸附-脱附曲线、元素分析等方法表征复合材料的结构和形貌,研究了氧化石墨烯添加量对材料的比表面积和胺化效果的影响以及吸附温度对其吸附CO₂性能的影响。研究结果表明,氧化石墨烯的引入能显著提高介孔硅复合氧化石墨烯多孔材料的比表面积,当GO添加量为4.5wt%时,其比表面积可高达841m²/g。高的比表面积有利于提高材料的氨基含量。在30wt%PEI的物理浸渍胺化后,MSM/GO-4.5@30%PEI拥有最大含氮量（9.59wt%）和CO₂吸附量（1.70mmol/g）。得益于良好的多孔基体和有机胺的均匀分布,MSM/GO-4.5@30%PEI在不同温度下的吸附量较稳定,循环再生吸附后仍能保持初始吸附量的80%。动力学研究表明,准一级模型和Avrami模型均能较好地拟合其吸...     

纳米纤维素基多层级孔道结构碳气凝胶的制备及在锂电池中的应用

采用纳米精磨法对商品桉木浆进行纳米纤丝化处理,得到了高长径比、尺寸均一的纳米纤丝化纤维素(NFC),平均直径为230.10 nm,长度达数十微米.将其组装、干燥后制得具有大量介孔的纳米纤丝化纤维素气凝胶(NFCA).将NFCA在氮气氛围下高温碳化制得碳气凝胶(CNFA),或在氢氧化钾条件下辅助碳化制得具有多层级孔道结构的碳气凝胶(CNFA-A),在保留的碳气凝胶骨架结构上进行孔洞构建.通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)表征及Nanomeasure统计分析,发现NFC的平均直径经碳化后减小到53.16 nm.利用X射线衍射(XRD)、BET比表面积测试和拉曼光谱揭示了碳化处理对纳米纤维素结构、比表面积、石墨化程度和缺陷的影响.结果表明,KOH辅助碳化处理后的碳气凝胶不仅保留了纤维素气凝胶前驱体的网络结构,还在其骨架上二次构建了更多的微孔和介孔,其比表面积高达488.92 m2/g,总孔容为0.404 cm3/g,所得的碳骨架被部分石墨化,具有良好的导电性.这类源于生物质的高比表面积碳气凝胶在被用作锂离子电池(LIB)负极材料时表现出优异的电化学性能,在电流密度1 A/g下连续充放电1000次后比容量达到409 m A·h/g,在电流密度高达20 A/g下,比容量还能维持在219 m A·h/g.     

Preparation of the water-soluble chitosan-coated oxidized regenerated cellulose gauze

A water-soluble chitosan-coated oxidized regenerated cellulose (ORC) gauze was prepared by the oxidation of a viscose gauze with NO₂/CCl₄ and subsequent treatment with a solution of chitosan in aqueous acetic acid and finally neutralization with NaOH/C₂H₅OH solution. A series of C6 ORC samples with different –COOH content were prepared and coated by chitosans (CTS) with different molecular weight (Mw) of 2,000, 50,000, 100,000 (denoted as CTS1, CTS2, CTS3). FT-IR and TG suggested the formation of the amide bond between the carboxyl group of ORC and the amino group of CTS. Kjeldahl nitrogen analysis of ORC gauze treated with CTS (CTS-ORC) showed that the percentage of chitosan with the lowest Mw of 2,000 introduced on ORC surface was highest and increased with oxidation time, while chitosans with medium and high Mw showed that the maximum percentage of chitosan introduced on ORC surface occurred at the oxidation time of 8 h. The neutralized chitosan-coated ORC gauze could still maintain its original morphological form and was water-soluble, and could form a transparent gel quickly for 5 s in water. The prepared water-soluble gauze could be anticipated to possess the improved hemostatic and antibacterial properties.     

Preparation and characterization of oxidized regenerated cellulose film for hemostasis and the effect of blood on its surface

Hemostatic effects of oxidized regenerated cellulose (ORC) are well-known but its mechanism has never been demonstrated clearly. Since thrombus formation is a kind of surface phenomenon, we changed the morphology of cellulose to form a kind of membrane with ionic liquid as solution, and also we prepared ORC films with nitrogen dioxide(NO₂)/carbon tetrachloride(CCl₄) oxidation system reacting for 16, 40, 64 and 88 h, respectively. FTIR and NMR spectra showed that NO₂/CCl₄ oxidation system had a high selectivity on hydroxyl group at C6 of regenerated cellulose. With the oxidation time prolonging, the carboxyl content was enhanced and the DP was reduced. The XPS results suggested that a new carboxyl bond was formed due to the increasing of oxygen content. From contact angle analysis, the wettability of blood on the ORC film surface was better than that of the regenerated cellulose film, which was beneficial for the blood to spread. SEM photographs showed that the ORC film oxidized for 40 h could adsorb and activate more platelets and erythrocytes. Hemostatic evaluation and enzyme-linked immunosorbent assay indicated that the ORC film had a dramatic hemostatic performance, and the products of platelets release reaction, activated platelets glycoprotein and activated clotting enzymes were increased simultaneously. Moreover, the possible mechanism of the hemostasis for ORC film was discussed.     

Self-reinforced cellulose nanocomposites

A self-reinforced cellulosic material was produced exclusively from regenerated cellulose microcrystals. The level of reinforcement was controlled by tailoring the crystallinity of cellulose by controlling the dissolution of microcrystalline cellulose (MCC) before its regeneration process. After the cellulose regeneration a self-reinforced material was obtained in which cellulose crystals reinforced amorphous cellulose. This structure was produced by dissolution of MCC in a non-derivatising cosolvent N,N-dimethylacetamide/LiCl followed by subsequent cellulose regeneration in distilled H₂O. The reduction of the overall crystallinity of self-reinforced regenerated cellulose was dependent on the dissolution time of the cellulose precursor. The crystallinity of regenerated cellulose was determined by wide angle X-ray diffraction. A reduction in crystal size from microcrystalline cellulose to regenerated cellulose was observed with increasing dissolution time in DMAc/LiCl cosolvent. The reduction in degree of crystallinity of regenerated cellulose led to a decrease in the tensile mechanical performance and thermal stability of the regenerated cellulose. The controlled dissolution of microcrystalline cellulose resulted in the modification of structural, physical, thermal properties and moisture uptake behaviour of regenerated cellulose.     

Hemostatic efficacy and tissue reaction of oxidized regenerated cellulose hemostats

Oxidized regenerated cellulose (ORC) has been used as an absorbable hemostat since World War II. In the present study, hemostasis time was determined in a spleen incision model in swine. The effect of mass on absorbable hemostat efficacy and hemostasis time was evaluated by standardizing the ORC materials on a mass basis. The median hemostasis time for a single layer of the new nonwoven ORC was as much as 51 % shorter than woven ORC (P < 0.001). The mean hemostasis time for nonwoven ORC was not affected by the mass of hemostat applied to the wound. The hemostatic efficacy of woven ORC increased with the mass (layers) of hemostat applied to the wound. Nonwoven ORC is significantly faster in achieving hemostasis than woven ORC, and its hemostatic efficacy is not influenced by the mass of material applied. Tissue reaction was minimal and the material was fully absorbed by 14 days.     

新型功能化离子液体[HeEIM]Cl的合成及其对棉纤维的溶解性能

合成了离子液体氯化1-(2-羟乙基)-3-乙基-咪唑([HeEIM]Cl), 并利用FTIR和1HNMR对其化学结构进行了表征. 考察了NaOH、微波和高压等处理方式对棉纤维的结晶度、聚合度(DP)和溶解率的影响. 研究了不同的溶解温度在微波加热和传统加热条件下对棉纤维的溶解率和再生纤维素的聚合度的影响. 利用FTIR, XRD, TGA和SEM等方法分别对溶解后得到的再生纤维素的化学结构、结晶度变化、热稳定性和表观形貌进行了分析. 结果表明, 合成的离子液体对棉纤维表现出很好的溶解能力, 且在溶解和再生过程中未发生化学变化. 棉纤维在高压条件下经质量分数为30%的NaOH预处理后, 溶解性能最佳. 微波加热法的溶解效果远远优于传统加热法, 且随着温度的升高, 溶解率逐渐增大. 溶解后得到的再生纤维素的结晶度变小, 聚合度下降, 热稳定性降低.     

Loss of stability by migration and chemical reaction of Santonox R in branched polyethylene under anaerobic and aerobic conditions

Plaques of branched polyethylene stabilized with 0.1 wt.% 4,4′-thiobis(6-tert-butyl-3-methylphenol) [Santonox^® R] were aged at different temperatures between 75 and 95 °C in anaerobic (nitrogen or water) and aerobic (air or water saturated with air) media. Antioxidant concentration profiles were obtained by oxidation induction time (OIT) measurements using differential scanning calorimetry. Results obtained by high performance liquid chromatography of extracts confirmed that the gradual decrease in OIT with increasing ageing time was due to migration of antioxidant to the surrounding medium. The antioxidant concentration profiles along the plaque thickness direction were flat in the plaques aged in the non-aqueous media indicating that the migration of antioxidant to the surrounding medium was controlled by the low evaporation rate at the material boundary. Crystals of antioxidant were detected by optical microscopy on the samples exposed to nitrogen. The similarity of the antioxidant concentration profiles obtained after ageing in nitrogen and in air suggested that the fraction of the antioxidant oxidized is negligible in comparison with the loss of antioxidant by migration to the surrounding media. The antioxidant concentration profiles along the plaque thickness direction obtained after ageing in water were less flat, suggesting faster dissolution in the water phase than evaporation in the case of non-aqueous ageing. The antioxidant diffusivity could be determined from the aqueous experiments and was in reasonable agreement with data reported by Moisan. For the samples exposed to water, the loss of antioxidant was faster from the samples exposed to water saturated with air. This difference is attributed to a faster degradation of the antioxidant in the oxygen-containing water phase increasing the mass transport from the polymer phase boundary to the water phase.     

Enzymatic degradation of oxidized cellulose hydrogels

The cellulose-based hydrogel with abundant aldehyde groups was prepared by periodate oxidation of cellulose hydrogel prepared by dissolution-regeneration of cellulose by aqueous LiOH/urea solvent. Aldehyde groups could be introduced retaining the nanoporosity of the cellulose gel. The enzymatic degradation of three grades of oxidized cellulose hydrogel, with aldehyde contents of 3.3, 8.1 and 18.6 per 100 glucose unit, was carried out using solutions containing cellulase and β-glucosidase at 37 °C up to 48 h. The degradation of oxidized gels was remarkably slower than that of original cellulose gel, depending strongly on the degree of oxidation. The portion except for the amount of glucose released was greater than the degree of oxidation, but became closer to the latter with increase in the degree of oxidation. This behavior can be interpreted in terms of the enzymatic recognition of the chemically modified cellulose chains.     

Structure and properties of regenerated cellulose fibers from aqueous NaOH/thiourea/urea solution

Regenerated cellulose fibers were successfully prepared through dissolving cotton linters in NaOH/thiourea/urea aqueous solution at ?2 °C by a twin-screw extruder and wet-spinning process at varying precipitation and drawing conditions. The dissolution process of an optimized 7 wt% cellulose was controlled by polarizing microscopy and resulted in a transparent and stable cellulose spinning dope. Rheological investigations showed a classical shear thinning behavior of the cellulose/NaOH/thiourea/urea solution and a good stability towards gelation. Moreover, the mechanical properties, microstructures and morphology of the regenerated cellulose fibers were studied extensively by single fiber tensile testing, X-ray diffraction, synchrotron X-ray investigations, birefringence measurements and field-emission scanning electron microscopy. Resulting fibers demonstrated a smooth surface and circular cross-section with homogeneous morphological structure as compared with commercial viscose rayon. At optimized jet stretch ratio, acidic coagulation composition and temperature, the structural features and tensile properties depend first of all on the drawing ratio. In particular the crystallinity and orientation of the novel fibers rise with increasing draw ratio up to a maximum followed by a reduction due to over-drawing and oriented crystallites disruption. The microvoids in the fiber as analysed with SAXS were smaller and more elongated with increasing drawing ratio. Moreover, a higher tensile strength (2.22 cN/dtex) was obtained in the regenerated fiber than that of the viscose rayon (2.13 cN/dtex), indicating higher crystallinity and orientation, as well as more elongated and orientated microvoid in the regenerated fiber. All in all, the novel extruder-based method is beneficial with regard to the dissolution temperature and a simplified production process. Taking into account the reasonable fiber properties from the lab-trials, the suggested dissolution and spinning route may offer some prospects as an alternative cellulose processing route.     

Enhancement of cellulose dissolution in water-based solvent via ethanol–hydrochloric acid pretreatment

Cellulose dissolution in water-based solvents is essential for processing of regenerated cellulose products such as fibres, films and particles. Cellulose dissolution in NaOH–urea aqueous solution has emerged as a simple and attractive alternative for processing cellulose solutions. However, this solvent requires energy intensive pretreatments such as milling or refining. In this paper we investigate a one step chemical pretreatment method using ethanol–hydrochloric acid prior to the dissolution of cellulose in NaOH–urea–water. The dissolution mechanism of the pretreated sample was initially examined in diluted cupri-ethylenediamine and 7% NaOH–12% urea–water solvent using optical microscopy methods and field emission scanning electron microscopy. The apparent energy of activation for the viscous flow of ethanol–acid pretreated pulp in NaOH–urea–water was calculated using rheological methods. Our results showed that the dissolution of pretreated pulp was achieved up to 4% cellulose concentration. We suggest that the enhancement of dissolution was due to a combination of degradation of remnant primary fibre wall layer and reduction of degree of polymerization of cellulose.     

贻贝启发功能改性的明胶基海绵止血材料的制备与性能

由战争、手术等而造成的大出血通常会导致更大的伤痛或更高的死亡率,因此,非常需要及时有效的止血以减少创伤导致死亡.而目前的止血材料都存在止血速度慢、止血效果差等问题.为提高材料的止血效率,本文受贻贝启发使用多巴胺和赖氨酸接枝改性的明胶(GDL)和氧化葡聚糖(ODE)为原料,通过冷冻干燥法制备多孔海绵状止血材料(GDL/O...