盐酸羟胺-电位滴定法测定氧化海藻酸钠上的醛基浓度

本文建立了一种测定被氧化海藻酸钠上醛基浓度的方法。盐酸羟胺可与醛基反应生成肟,同时释放出HCl,通过滴定HCl的量可计算出醛基的浓度。据此,本文采用盐酸羟胺-电位滴定法测定被氧化海藻酸钠上的醛基浓度,并考察了该方法的测定条件、精密度及准确度。结果,当盐酸羟胺与样品之间的反应时间≥2 h时,被氧化海藻酸钠上的醛基浓度与氧化反应时的投料比(≤80%)基本一致,该方法的RSD<10%;当以戊二醛溶液为标准品时,其测量值和真实值之间的误差<1%。本方法可快捷准确地测定小分子或大分子多糖上的醛基浓度。     

氧化海藻酸钠的氧化度对其交联海藻酸钠/明胶(半)互穿网络膜性能的影响

以海藻酸钠(SA)为原料、高碘酸钠(SP)为氧化剂,通过调整SA与SP物质的量之比以及氧化时间,制备了不同氧化度的氧化海藻酸钠(OSA);以OSA为交联剂,制备了海藻酸钠/明胶(半)互穿网络膜(SA/Ge(semi)IPN)。通过红外光谱研究了(半)互穿网络膜的结构,推测了其交联机理;通过力学性能、交联度等测试方法研究了OSA的氧化度对(半)互穿网络膜力学性能的影响。结果表明:通过控制SA与SP物质的量之比可以制备特定氧化度的OSA;(半)互穿网络膜的力学性能随着OSA氧化度的增加呈现先增加后降低的趋势,而交联度随着OSA氧化度的增加而增加。     

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.     

利用氧化和希夫碱反应制备具有手性分离功能的滤纸

纸色谱具有微量、快速、高效和灵活程度高等特点。以滤纸为原料用高碘酸钠氧化法合成了二醛基滤纸,通过希夫碱反应接枝手性氨基酸,合成了一种具有手性分离功能的新型纸色谱材料。通过单因素试验和正交试验确定滤纸氧化的最佳合成条件为：高碘酸钠的质量分数为4%, pH值为2,反应温度45℃和反应时间4 h,该条件下氧化滤纸醛基含量为57.93%（物质的量分数）。氧化滤纸与L-谷氨酸通过微波合成得到具有手性分离功能的色谱用纸。利用该种手性滤纸分离外消旋酒石酸,展开剂配方为100 mL 50%正丁醇,50 mL乙酸和0.1000 g溴酚绿。结果显示,L-酒石酸比移值（R_f）为0.52, D-酒石酸R_f为0.40。该方法不需要使用大型设备,适合一般的教学、研究及工业应用。     

高锰酸钾氧化法合成2-甲酸吡啶

以2-甲基吡啶为原料,水为溶剂,经80℃下高锰酸钾氧化和乙醇重结晶得到2-甲酸吡啶;采用红外光谱仪和核磁共振谱仪表征了目标产物的结构;考察了高锰酸钾用量、溶剂用量和反应时间对产物收率的影响,讨论了重结晶试剂的选择,进而确定了合成2-甲酸吡啶的较优条件.结果表明:以水作反应溶剂,控制原料和高锰酸钾的摩尔比为1∶2.3时,反应时间为5~6 h,以乙醇重结晶,目标产物的总收率达79.7%.     

利用氧化和希夫碱反应制备具有手性分离功能的滤纸（英文）

纸色谱具有微量、快速、高效和灵活程度高等特点。以滤纸为原料用高碘酸钠氧化法合成了二醛基滤纸,通过希夫碱反应接枝手性氨基酸,合成了一种具有手性分离功能的新型纸色谱材料。通过单因素试验和正交试验确定滤纸氧化的最佳合成条件为:高碘酸钠的质量分数为4%,pH值为2,反应温度45℃和反应时间4 h,该条件下氧化滤纸醛基含量为57.93%(物质的量分数)。氧化滤纸与L-谷氨酸通过微波合成得到具有手性分离功能的色谱用纸。利用该种手性滤纸分离外消旋酒石酸,展开剂配方为100 mL 50%正丁醇,50 mL乙酸和0.100 0 g溴酚绿。结果显示,L-酒石酸比移值(R_f)为0.52,D-酒石酸Rf为0.40。该方法不需要使用大型设备,适合一般的教学、研究及工业应用。     

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。     

干法制备阳离子淀粉(I):反应效率的研究

在碱催化剂BZ-1存在下,以N-(2,3-环氧丙基)三甲基氯化铵(GTA)为阳离子化试剂,干法制备了高取代度季铵型阳离子淀粉.考察了碱催化剂BZ-1、水含量、反应温度和反应时间对取代度和反应效率的影响.当淀粉用量为5.5g,GTA用量为3g时,最佳反应条件为:碱催化剂BZ-1 0.8g、反应温度60℃、反应时间4h、反应体系含水量24%,取代度可达0.56,反应效率为88%.     

干法制备阳离子淀粉（Ⅰ）：反应效率的研究

在碱催化剂BZ-1存在下,以N-（2,3-环氧丙基）三甲基氯化铵（GTA）为阳离子化试剂,干法制备了高取代度季铵型阳离子淀粉。考察了碱催化剂BZ-1、水含量、反应温度和反应时间对取代度和反应效率的影响。当淀粉用量为5.5g,GTA用量为3g时,最佳反应条件为：碱催化剂BZ-10.8g、反应温度60℃、反应时间4h、反应体系含水量24%,取代度可达0.56,反应效率为88%.     

酸量法及碘量法测定氧化葡聚糖的醛基

通过高碘酸钠氧化葡聚糖,制备不同氧化度的葡聚糖,采用酸量法和碘量法测定其醛基含量,但所得结果差异大.结合葡聚糖的氧化机理,以甘油的氧化反应结果作为对照,对借助化学滴定分析的酸量法和碘量法所得数据的差异性进行了分析.结果表明这种差异是由葡聚糖氧化存在的中间反应及其分支结构造成的,当高碘酸钠与葡聚糖的糖单元的物质的量比控制在2以内,操作简单的酸量法所得结果是可靠的.     

海藻酸钠的疏水改性及释药性能研究

为了提高对疏水性药物的负载量和缓释作用,将海藻酸钠氧化后与十二胺反应使其进行疏水改性.对改性后聚合物结构进行了表征.研究了聚合物在水溶液及盐溶液中的粘度变化;将聚合物分散于NaCl/CaCl2的混合溶液中制备成凝胶微球,对药物布洛芬进行了包埋释放实验.结果表明,疏水改性后的海藻酸钠粘度增加,其凝胶微球对布洛芬负载量提高,具有较好的缓释作用.     

Preparation and controlled degradation of oxidized sodium alginate hydrogel

Degradation is often a critical property of materials utilized in tissue engineering. Although alginate, a naturally derived polysaccharide, is an attractive material due to its biocompatibility and ability to form hydrogels, its slow and uncontrollable degradation can be an undesirable feature. In this study, the degradation behavior of hydrogel based on oxidized sodium alginate (OSA) crosslinked with Ca²⁺ was studied in phosphate buffer solution (PBS, pH = 7.4) and Tris-(hydroxymethyl) aminomethane–HCl (Tris–HCl, pH = 7.4) at 37 °C. The degradation behavior of OSA hydrogels with different degrees of oxidation was evaluated as a function of degradation time by monitoring the changes of molecular weight and weight loss. It was found that the degradation behavior relied heavily on the degree of oxidation and the surrounding medium. This result indicates that the degradation rates of OSA hydrogels can be controlled by changing the degree of oxidation.     

Sodium alginate/magnesium oxide nanocomposite scaffolds for bone tissue engineering

A simple 2‐step method, consisting of film casting and polyvinyl alcohol leaching, is proposed to prepare magnesium oxide (MO) nanoparticle‐reinforced sodium alginate scaffolds with right properties for bone tissue engineering. The cytocompatibility of the as‐prepared scaffolds was also evaluated using the 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium‐bromide yellow tetrazole assay test, wherein chondrocyte cells had been considered as target cells. According to the results, the ensuing sodium alginate nanocomposites, containing 4‐wt% MO nanoparticles, demonstrated the highest physical and mechanical properties after leaching step. The Young modulus of sodium alginate/4‐wt% MO was improved about 44%, in comparison with that of the pure alginate sample. Furthermore, incorporating MO nanoparticles up to 4 wt% controlled the liquid uptake capacity of scaffolds vis‐à‐vis the resultant pure sodium alginate sample. Moreover, with increasing the nanoparticle content, the antibacterial properties of scaffolds enhanced, but their degradation rates under in vitro conditions tapered off. With the introduction of 3‐ and 4‐wt% MO, the average diameter of the bacterial zone of the scaffold samples reduced to less than 10 mm², suggesting an insensitive antimicrobial performance, compared with the pure sodium alginate and the samples with 1‐ and 2‐wt% MO content, which exhibit antimicrobial sensitivity. 3‐(4,5‐Dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium‐bromide assay test also revealed the cultivated chondrocyte cells on the 4‐wt% MO nanoparticle‐reinforced scaffold possessed better interaction as well as appropriate cell attachment and proliferation than the pristine sodium alginate sample.     

壳聚糖─海藻酸钠微囊对蛋白质控制释放的研究

采用乳化法制备了可注射用壳聚糖海藻酸钠微囊, 其粒径小于２００ μｍ ,且具有相对较窄的近似高斯分布。牛血清白蛋白作为模型药物在微囊中的包埋率可超过５０ ％ 。通过壳聚糖在海藻酸钠微囊表面的复合,牛血清白蛋白从微囊中的持续释放时间从几个小时延长到半个月以上。     

褐藻酸钠的高效凝胶色谱行为及其分子量参数测定

用高效凝胶色谱法测定褐藻酸钠的分子量参数。比较了褐藻酸钠样品与非极性标样DextranT500的高效凝胶色谱行为的差异,讨论了进样浓度和进样体积对结果的影响。     

交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络水凝胶的制备及其溶胀性能

将线性聚(N-异丙基丙烯酰胺)(PNIPAAm)和海藻酸钠(SA)分子同时引入到PNIPAAm凝胶中,制备了交联聚(N-异丙基丙烯酰胺)/(海藻酸钠/聚(N-异丙基丙烯酰胺))半互穿网络(Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN)水凝胶。在弱碱性条件下(pH=7.4),改变SA与线性PNIPAAm的质量比对Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的溶胀度没有太大的影响。在酸性条件下(pH=1.0),其溶胀度随着SA与线性PNIPAAm质量比的减小而增大。由于亲水性SA与线性PNIPAAm的协同作用,Cr-PNIPAAm/(SA/PNIPAAm)semi-IPN水凝胶的消溶胀速率得到很大提高。     

Development of Biopolymer Based Matrix Type Multiple Unit Systems for Sustained Release of Diclofenac Sodium: In vitro and In vivo Evaluation

The objective of the present study was to investigate the applicability of matrix type chitosan treated alginate multiple unit systems (MUS) for sustained release of diclofenac sodium. The multiple unit systems (MUS) were prepared by the ionotropic gelation method. Spherical MUS with 1.852±0.041–2.173±0.265 mm diameter range and 66.66±3.21 to 78.55±6.49% entrapment efficiency were produced. The addition of chitosan increased the swelling of MUS in acidic conditions and reduced the drug release from MUS. The fluoroscopic study reveals that the MUS retained in gastrointestinal tract (GIT) for more than 12 h and distributed throughout the GIT. The in vivo evaluation in healthy human volunteers of the MUS and that of Voveran SR tablets each containing 100 mg drug revealed that the MUS was bioequivalent to Voveran SR producing a non‐significantly different (p>0.05) AUC. This study demonstrates that the matrix type chitosan treated alginate MUS can be a good alternative to sustained release tablets to deliver diclofenac sodium and expected to be less of an irritant to gastric and intestinal mucosa.     

Influence of Polyglycerol Polyricinoleate and Biopolymers on Physical Properties and Encapsulation Efficiency of Water-in-Oil-in-Water Emulsions Containing Mango Seed Kernel Extract

The influence of polyglycerol polyricinoleate (PGPR) and biopolymers (gelatin and sodium alginate) on the stabilization of water-in-oil (W/O) emulsions was investigated to improve the encapsulation efficiency (EE) of water-in-oil-in-water (W/O/W) emulsions containing mango seed kernel extract (MSKE). The physical properties and EE of the emulsions were found to depend more strongly on PGPR than on biopolymers. High EE values of MSKE were obtained when W/O emulsions stabilized by 4–8 wt% PGPR were incorporated with 1–5 wt% gelatin, or by 6–8 wt% PGPR incorporated with 0.5–1.5 wt% sodium alginate in the inner aqueous phase.     

Synthesis and rheological investigation of self‐healable deferoxamine grafted alginate hydrogel

Deferoxamine grafted alginate (SA‐DFA) was successfully synthesized via amidation of sodium alginate with deferoxamine mesylate as determined by H‐NMR and elemental analysis. SA‐DFA with different graft yield was obtained by adjusting the ratio of sodium alginate and deferoxamine mesylate. It was found that aqueous solution of SA‐DFA could form hydrogel spontaneously due to hydrogen bonding interactions, which also endowed the SA‐DFA hydrogel with self‐healing capability. The healing efficiency of SA‐DFA hydrogels ranged from 53.64 to 90.16%. In addition, surface morphologies of SA‐DFA hydrogels before/after self‐healing process were demonstrated by SEM images. We anticipated that such self‐healable alginate hydrogel would be applied in the field of wound healing. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 856–865     

二乙基三胺五乙酸用于示波极谱络合滴定法的研究

本文对二乙基三胺五乙酸（ＤＴＰＡ）用于示波极谱络合滴定的方法进行了研究，同时测定了多种金属离子和藻酸双酯钠新药，该法快速、准确、终点直观。