漆酶/TEMPO体系氧化棉纤维接枝壳聚糖制备抗菌纤维

利用漆酶/TEMPO体系选择性将纤维素C-6伯羟基氧化成醛基,得到单醛纤维素,再将壳聚糖通过席夫碱反应接枝到单醛纤维素上,制得接枝产物。将接枝产物进行红外光谱分析、SEM及能谱分析及壳聚糖含量的分析,确定接枝产物结构的变化和壳聚糖含量,并进一步对其抗菌性进行研究。结果表明,经漆酶/TEMPO体系氧化后,纤维素C-6伯羟基被选择性的氧化成醛基,与壳聚糖接枝反应后,壳聚糖的氨基与醛基反应生成CN;接枝产物表面出现了明显的变化且有壳聚糖存在;接枝产物中壳聚糖含量为4.55%;与棉纤维相比,接枝产物对大肠杆菌和金黄色葡萄球菌均具有抗菌性,且对大肠杆菌的抑制作用强于金黄色葡萄球菌。     

漆酶-TEMPO体系选择性氧化壳聚糖C-6伯羟基提高其抗氧化性能的研究

利用漆酶-TEMPO体系选择性地氧化壳聚糖C-6伯羟基,对氧化产物分别进行红外光谱、13C NMR、离子色谱和热失重分析,确定产物结构的变化,并进一步对其抗氧化性进行研究。结果表明,经漆酶-TEMPO体系氧化后,壳聚糖分子结构中的C-6伯羟基被选择性地氧化成羧基,其它结构基本不变,其产物为氧化壳聚糖钠盐;壳聚糖氧化产物与原样相比,热稳定性得到了提高;壳聚糖经漆酶-TEMPO体系氧化后的ABTS自由基清除率5min后达到66.36%,抗氧化性能得到改善。     

壳聚糖-脱氧胆酸及其叶酸偶联体的表征及自组装特性研究

以1-乙基-(3-二甲基氨基丙基)碳酰二亚胺(EDC)为催化剂,将脱氧胆酸接枝到壳聚糖主链的氨基上,得到疏水改性的双亲性壳聚糖;再将叶酸连接于壳聚糖氨基,可得到具有肿瘤靶向潜力的双亲性共聚物.利用红外光谱、1H核磁、X射线晶体衍射图谱对其结构进行表征.脱氧胆酸-壳聚糖、叶酸-壳聚糖-脱氧胆酸在水相中通过透析处理均能形成自聚集体,利用荧光探针技术研究其自聚集行为.制得的两种自聚集体均具有较低的临界胶束浓度(10-2mg/ml),透射电镜和粒径分析测试显示制得的自聚集体为纳米级颗粒.随着脱氧胆酸取代度的增加,粒径降低,临界胶束浓度下降,但叶酸直接偶联壳聚糖导致自组装阻力增加.     

端氨基聚乙二醇-聚乳酸嵌段共聚物的合成及表征

以聚乙二醇为原料,采用四步反应,合成了二碳酸二叔丁酯单保护的氨基聚乙二醇(BOC-PEG-NH2);并以DOe-PEG-NH2为引发剂,引发丙交酯开环聚合,得到了叔丁氧基酰胺基聚乙二醇-聚乳酸嵌段共聚物(BOC-PEG-PLA).在三氟乙酸二氯甲烷溶液中,脱去保护基团,得到了端氨基聚乙二醇-聚乳酸嵌段共聚物(NH2-PEG-PLA).采用核磁共振氢谱(1H-NMR)、紫外光度仪(UV)表征各聚合物的结构,由凝胶色谱仪(GPC)测定嵌段共聚物的分子量以及分子量分布.结果表明:合成的氨基引发在无催化剂条件下能够引发丙交酯开环聚合,制得分子量高、分子量分布窄的双亲性共聚物.通过三氟乙酸脱保护得到了端氨基聚乙二醇-一聚乳酸(NH2-PEG-PLA),且对分子量没有影响.     

含双噻唑聚合物的合成与性能

以丁二酮、液溴和硫脲为原料合成了2,2-二氨基-4,4-联噻唑(DABT);将DABT与对氨基苯甲酸和多聚甲醛共聚制得对氨基苯甲酸缩聚DABT聚合物,然后与铁、镍、铜的硫酸盐配合得到金属配合物。表征了产物结构,测试了产物的热性能、电导率、磁性能和荧光特性。结果表明,对氨基苯甲酸缩聚DABT聚合物的电导率优于配合有金属离子的聚合物,其值为3.12×10-6S/cm,处于半导体范围;配合Fe2+的聚合物具有一定的磁性能,表明配合Fe2+聚合物是一种有机软铁磁体;而配合Cu2+的聚合物能激发产生荧光,具有发射紫外-蓝光特性,可作为新型有机光功能材料。     

含1,4-戊二烯-3-酮结构的光敏性二胺合成

报道了由硝基苯甲醛和丙酮经Claisen-Schmidt缩合而制得1,5-二硝基苯基-1,4-戊二烯-3-酮,然后在SnCl2·2H2O-HCl还原体系下,得到1,5-二胺基苯基-1,4-戊二烯-3-酮,同时讨论了影响产率的几个因素.与文献报道相比,此方法具有反应条件温和、操作简便和收率高(91.7%)等优点.产物结构通过元素分析、熔点、IR 和1H NMR证实.     

以环糊精为核的星形七臂官能化聚己内酯的制备与表征及生物素修饰

以含有7个羟基的乙酰化β-环糊精为引发剂,开环聚合4-氨基甲酸苄酯-ε-己内酯(CABCL)单体,得到星形七臂官能化聚己内酯(CDSPCABCL)。并使用酸脱法与钯碳氢解法对CDSPCABCL的甲酸苄酯保护基脱保护,得到星形聚氨基己内酯(CDPACL)。同时,探索了投料比、聚合温度、聚合时间对CDSPCABCL聚合度的影响,以及酸脱法的酸倍数与反应时间、钯碳氢解法的反应时间对CDPACL断链率与脱保护率的影响。通过1 H NMR、GPC、FT-IR与TGA表征各步骤产物。最后通过CDPACL的氨基与生物素的羧基发生酯化反应,得到生物素化的星形聚己内酯,其在癌细胞靶向、生物探针等领域有潜在的应用前景。     

1,1,4,4-四苯基-1,3-丁二烯衍生物的合成

以苯乙酮和溴代苯为原料,通过格氏反应先制得1,1-二苯基乙醇(1),收率为91.3%;(1)经脱水和氯甲基化得到1,1-二苯基-3-氯丙烯(2),收率为92.9%;(2)再与二苯甲酮衍生物经格氏反应制得了1,1,4,4-四苯基-1,3-丁二烯衍生物(3a)和(3b),收率高于54.0%,并对各步合成的工艺条件进行了研究.HPLC测得(3a)和(3b)质量分数均高于99.0%.通过紫外光谱、红外光谱、质谱、1H NMR和元素分析对产物的组成和结构进行了鉴定.     

ODPA/BAPP型聚异酰亚胺及其衍生物的合成与性能表征

首先由二苯醚四酸二酐(0DPA)与4,4′-双(氨基苯氧基)丙烷(BAPP)经两步反应制得聚异酰亚胺(PⅡ),然后分别用丙烯酸羟乙酯(HEA)和正辛醇对所得PⅡ进行开环反应得到光敏的和非光敏的聚酰胺酯(PAE1和PAE2)。对聚异酰亚胺(PⅡ)的制备过程用红外进行了跟踪,并对聚异酰亚胺的热异构化、聚异酰亚胺衍生物的合成和产物的溶解性、热性能及膜性能进行了表征。     

4-羟基苯甲酸-2′-辛酯的合成

以对羟基苯甲酸为起始原料 ,经羟基保护、酯化和脱羟基保护三步反应 ,合成了难以用传统酯化法制备的 4 羟基苯甲酸 2′ 辛酯 ,总收率 6 5 % ,产物结构经IR及MS鉴定。     

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。     

Chitosan derivatives with thickening properties obtained by reductive alkylation

Chitosan derivatives were prepared by reductive alkylation using glutaraldehyde and 3-amino-1-propanol. The reducing agent used was sodium borohydride. Tests of solubility, stability and viscosity were performed to evaluate the effect of the molar ratio of the reactants and the presence of nitrogen in the reaction system. The ¹H NMR characterization of chitosan derivatives confirmed the presence of hydrophobic groups grafted onto the chitosan backbone. The rheological behavior of the polymers was studied as a function of polymer concentration, temperature and ionic strength of the medium. It was observed that the chemical modification of chitosan resulted in derivatives with thickening action, and the polymer solubility in acetic acid aqueous solution decreased with the increase of the glutaraldehyde and 3-amino-1-propanol molar ratio in relation to chitosan. The atmosphere of nitrogen and a larger amount of reducing agent in the reaction system contributed to the increase in solubility, stability and viscosity of the polymer in solution. The chitosan derivative solutions were significantly more viscous than the chitosan solution and showed higher thermal stability in the presence of salt, which could be explained by the hydrophobic groups grafted onto the chitosan backbone.     

胆碱磷酰化偶联壳聚糖仿生衍生物的合成及表征

采用Antherton-Todd反应合成了两种胆碱磷酰化偶联壳聚糖衍生物——带双正电荷的N-二胆碱磷酰化偶联壳聚糖(N-PC+Cs)和两性的N-磷酸胆碱磷酰化偶联壳聚糖(N-PCCs),并用核磁共振波谱(NMR)和红外光谱(IR)表征其化学结构。由1H-NMR谱得到N-PC+Cs的取代度为30.9%,N-PCCs的取代度为32.6%。X射线衍射谱(XRD)和热分析的结果表明,与壳聚糖相比,N-PC+Cs和N-PCCs的结晶性和热稳定性都显著降低。水溶性试验表明,两种仿生衍生物在中性水溶液中都表现出良好的溶解性,有望用于药物/基因传输系统载体。     

Synthesis and characterization of chitosan–carbon nanotube composites

Acid functionalized single walled carbon nanotubes were covalently grafted to chitosan by first reacting the oxidized carbon nanotubes with thionyl chloride to form acyl-chlorinated carbon nanotubes which are subsequently dispersed in chitosan and covalently grated to form composite material, CNT–chitosan, 1, which was washed several times to remove un-reacted materials. This composite has been characterized by FTIR, 13C NMR, TGA, SEM and TEM and has been shown to exhibit enhanced thermal stability. The reaction of 1, with poly lactic acid has also been accomplished to yield CNTchitosan–g-poly(LA), 2 and fully characterized by the above techniques. Results showed covalent attachment of chitosan and chitosan–poly lactic acid to the carbon nanotubes.     

Sludge ash/hydrated lime on the geotechnical properties of soft soil

Modified chitosan such as chitosan alpha-ketoglutaric acid (KCTS) and hydroxamated chitosan alpha-ketoglutaric acid (HKCTS) are successfully prepared. The resulting polymers were characterized by 13C NMR and X-ray diffraction (XRD), respectively. A adsorption system was applied to study the adsorption of Zn(II) ion onto chitosan derivatives. The isothermal sorption kinetics of chitosan derivatives for Zn(II) ion has been investigated. The kinetics experimental data correlated well with the second-order kinetic model, indicating that the chemical sorption was the rate-limiting step. The adsorption mechanism of chitosan derivatives with Zn(II) was studied by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The results indicated that the nitrogen in amino group and the oxygen in carboxyl group of KCTS were coordination atoms. N atom of amino group, O atom of hydroxamic acid and O atom of carbonyl group in HKCTS coordinated with Zn(II).     

Preparation and characterization of a quaternized chitosan

A novel method was developed to obtain N-(2-hydroxy)-propyl-3-trimethylammonium chitosan chloride (HTCC) using glycidyl trimethyl ammonium chloride (GTMAC) and chitosan in a homogeneous system. The factors affecting the degree of substitution (DS) of HTCC, including the amount of perchloric acid, the reaction temperature, and the reaction time, were especially investigated. Under optimal conditions (i.e., with 2.0, 1.9, and 15 g of chitosan, perchloric acid, and GTMAC, respectively), chitosan was pre-reacted with GTMAC at 60 °C, and then the reaction was continued at 80 °C for 8 h. The as-produced HTCC had a DS of 86.9%. Its structure was characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Moreover, it had a good solubility in water within a wide pH range. Besides, the composite was formed from HTCC loaded on bentonite surface.     

Precise quantification of the antibacterial activity of chitosan by NB medium neutralizer

In the present research,nutrient broth(NB)medium was identified to be able to neutralize the antibac-terial activity of chitosan and its derivatives.Therefore,an improved test method independent of NB medium was proposed to precisely quantify the antibacterial effectiveness and efficiency of chitosan.The minimum bactericidal concentration(MBC)of chitosan was 60 μg mL-1 against S.aureus and E.coli,and 0.01％(w/v)chitosan could kill 100％of bacteria within 3 min.From another point of view,the neutralizing efficiency of NB could be tripled by adding 25 g L-1 of sodium chloride.Then the neutraliz-ing mechanism of NB medium was ascribed to flocculation between chitosan and protein.Adding extra sodium chloride could significantly reduce the size of floccules,and smaller floccules would lose the ability of binding with bacteria directly,showing higher neutralizing rate on the macro scale.     

壳寡糖季铵盐型基因载体制备的新方法研究

首次以甲醇/水为溶剂合成壳寡糖季铵盐型基因载体,并采用1 H NMR表征技术对合成条件进行了研究。结果表明,反应溶剂、NaOH浓度、CH3I用量、反应时间、一步法/两步法合成步骤等都会影响壳寡糖季铵盐的合成。甲醇/水溶剂比NMP溶剂更有利于壳寡糖季铵盐产品的控制、减少副反应的发生;适量的NaOH浓度,有利于壳寡糖季铵盐的合成,NaOH浓度过低,不利于季铵盐的生成,NaOH浓度过高,易发生壳寡糖3,6位-OH的甲醚化副反应;足够量的CH3I和反应时间及两步法合成步骤有利于壳寡糖季铵盐的合成。本研究为具有潜在临床应用价值的壳寡糖季铵盐基因载体提供了一种低碳、绿色、经济、环境友好的合成新方法。     

Synthesis of metallic nanoparticles protected with N,N,N-trimethyl chitosan chloride via a relatively weak affinity

A water-soluble cationic chitosan derivative, N,N,N-trimethyl chitosan chloride (TMC), was synthesized and used as a stabilizing reagent for the synthesis of highly stable Au, Ag and Pt nanoparticles in a single-phase of neutral aqueous solution. The morphology and stability of metallic nanoparticles were evaluated by transmission electron microscopy and UV-vis spectroscopy. The results showed that well-dispersed metallic nanoparticles have a spherical morphology with diameters of about 3 ± 0.5?nm. The prepared gold nanoparticles are stable in the aqueous solution (no significant changes in their morphology and size within 10?months) due to repulsion between the charged polymer shell coatings around the metallic nanoparticles. The relatively low affinity of TMC on gold nanoparticles was confirmed by using a ligand exchange experiment. The mechanism stabilizing the chitosan derivative and the neighbouring gold nanoparticles was identified by FTIR, (1)H NMR and (13)C NMR measurements.     

The crossover of (Ba<Subscript>1−x</Subscript>Ca<Subscript>x</Subscript>)(Ti<Subscript>0.9</Subscript>Sn<Subscript>0.1</Subscript>)O<Subscript>3</Subscript> piezoelectric ceramics from single-phase to composite with studying the structural and dielectric properties

Lead-free (Ba_1?xCa_x)(Ti_0.9Sn_0.1)O₃ perovskite ceramics (x?=?0.02–0.5) (BCTS) were synthesized using the solid-state reaction technique. X-ray diffraction was used to identify the formed phases of the prepared compositions. The morphology of ceramics has been studied using a scanning electron microscope equipped with an energy dispersive spectrometer. Field emission scanning electron microscope was used to examine the morphology of sensing film calcined powder. The crossover from BCTS single-phase (x?=?0.02) to BCTS composite(x?=?0.5) was obtained via coexistence of both (x?=?0.3) of Ca addition. The composite powder was sintered at higher temperature rather than the single-phase powder. The calcined powder sensing film was prepared by the screen-printing technique as humidity sensors. Thereafter, DC resistance measurements were performed in the presence of relative humidity RH at room temperature. All the compositions exhibited a poor sensitivity toward the humidity sensing in the range of 0–98% RH. The compositions 0.02 and 0.06 have shown orthorhombic–tetragonal phase transition (T_O?T) below the room temperature, while the other compositions have shown a pure tetragonal phase. The highest value of permittivity at Curie temperature (ε?=?29241 at 100 Hz) and piezoelectric coefficient (d₃₃?=?495 pC/N) at room temperature were obtained at Ca?=?0.06 due to present polymorphic phase transition. The effect of frequency on the dielectric constant and dielectric loss at room temperature were investigated. All the prepared compositions exhibited small values of dielectric loss from 50 Hz up to 100 KHz, which indicates a good reliability for electronic applications such as capacitors or memory devices.