低浓度部分水解聚丙烯酰胺/柠檬酸铝交联体系剪切稳定性研究

采用粘度法、核孔膜过滤和动态光散射(DLS)法,研究了高分子量低浓度的部分水解聚丙烯酰胺(HPAM)与柠檬酸铝(AlCit)反应所形成的交联体系的剪切稳定性和HPAM剪切降解后与AlCit反应所形成的体系的封堵性能及降解机理.研究结果表明,低浓度的HPAM与AlCit反应所形成的交联聚合物体系随剪切速率增加,其对1.2μm的核孔膜的封堵能力降低.HPAM稀溶液剪切降解后再与AlCit反应,低剪切速率对其封堵性能影响较小,而高剪切速率会使得其封堵性能大大降低.HPAM/AlCit交联体系和HPAM剪切降解后形成的交联体系的封堵性能下降的原因是HPAM/AlCit交联体系中交联聚合物线团(LPC)尺寸和HPAM中高分子线团的尺寸变小.     

聚[芳基二甲酸(聚四亚甲基醚二醇)酯]分子间激基缔合作用的研究

合成了聚[2,6-萘二甲酸(聚四亚甲基醚二醇)酯](1)和聚[对苯二甲酸(聚四亚甲基醚二醇)酯](2);研究了它们在溶液和本体中的荧光光谱;论证了链间和链内非相邻生色团间有激基缔合作用存在。观察了聚合物1由稀到浓的氯仿溶液的激基缔合物荧光强度与单生色团荧光强度比值的变化,得到溶液中高分子线团的动态接触浓度C_s=0.26g/dL;亚浓区到浓区的转变浓度C~+=7g/dL。在聚合物1的本体中得到基态芳环层叠缔合物直接激发到激基缔合物的实验证据。     

可溶解的聚氨酯脲微凝胶的合成及其分子尺寸的测定

以聚氧化四亚甲基二醇、4,4′ 二苯甲烷二异氰酸酯和己二胺为原料 ,利用高分子在溶液中基本形态是无规线团的特征 ,设计了一个含有分子内和分子间反应的交联聚合体系 ,由于分子内反应与分子间反应是一对竞争反应 ,使得交联过程得以控制 ,在溶液聚合体系中合成了可溶解的微凝胶 .在分子尺寸测定过程中 ,发现了这种高分子在溶液中非常容易形成分子簇 ,且分子簇的形成与解离处于不平衡之中 ,这可能是交联高分子的一种特殊的溶液行为     

部分水解聚丙烯酰胺柠檬酸铝体系临界交联浓度的研究

采用落球粘度计、核孔膜过滤、动态光散射 (DLS)和2 7Al NMR法 ,研究了高分子量、低浓度的部分水解聚丙烯酰胺 (HPAM)与柠檬酸铝 (AlCit)体系形成交联聚合物溶液 (LPS)的临界交联浓度 .研究结果表明 ,HPAM AlCit体系在聚合物浓度较低时 ,溶液中主要发生形成交联聚合物线团 (LPC)的交联反应 ,此时形成的是LPS ,聚合物浓度增加到某一临界值后 ,体系中形成线团后 ,存在线团间的交联 ,此时形成的是弱凝胶 .不同方法所测得的HPAM AlCit体系的临界交联浓度基本相同 ,对于粘均相对分子质量为 1 4× 10 7的HPAM ,在NaCl浓度为 2 0 0 0mg L ,交联比 2 0∶1时形成的交联体系 ,其临界交联浓度在 2 0 0～ 30 0mg L间 .     

低浓度HPAM/AlCit交联聚合物溶液性质研究

采用粘度法、扫描电镜（SEM）、核孔膜过滤、动态光散射（DLS）和27Al NMR法，研究了高分子量低浓度的部分水解聚丙烯酰胺（HPAM）与柠檬酸铝（AlCit）体系交联反应过程溶液性质变化.结果表明，HPAM与AlCit反应在低剪切速率时体系粘度随反应进行而降低，在剪切速率较高时具有剪切稠化现象，HPAM与AlCit反应过程中交联态Al的自旋 晶格弛豫时间随反应进行变短.低浓度的HPAM与AlCit发生分子内交联反应形成交联聚合物线团（LPC）在水中的分散体系，即交联聚合物溶液（LPS）.交联聚合物溶液中LPC的平均流体力学半径约为238 nm，其形态接近球形，具有多分散性. LPS对1.2 μm核孔膜的封堵程度与其反应时间有关.     

交联聚合物线团的形态和尺寸研究

通过建立低压差下核孔膜过滤稀释液的方法 ,研究了低浓度HPAM与AlCit形成的交联聚合物溶液(LPS)中交联聚合物线团 (LPC)的形态和尺寸 .实验结果表明 ,LPC为球形结构 ,由于交联作用 ,其剪切变形程度有限 .低压差下核孔膜过滤法与动态光散射法 (DLS)和扫描电镜法 (SEM)相结合 ,可较为准确地判断LPC的尺寸范围 ,HPAM相对分子质量为 1 1× 10 7～ 1 4× 10 7、浓度为 0 0 2 % ,NaCl浓度 0 2 % ,交联比 2 0∶1的LPS中LPC的直径小于 1 38μm ,相当多的LPC直径在 4 5 0nm以上 ,平均流体力学直径约为 4 92nm .在一定聚合物浓度范围内 ,相同实验条件下 ,随着聚合物相对分子质量的增大 ,LPC尺寸逐渐增大 .LPS制成干片后 ,LPC的尺寸收缩有限 ,利用SEM法直接观测其形态 ,具有一定的准确性 ,可用此法对其进行研究 .     

I-3-MB-AES体系分光光度法测定面粉中过氧化苯甲酰

在磷酸介质中,过氧化苯甲酰(BPO)氧化I<'->离子形成I<'-><,3>络阴离子,I<'-><,3>络阴离子进一步与亚甲基蓝形成离子缔合物,在烷基聚氧乙烯醚硫酸钠(AES)中,缔合物呈清亮的蓝紫色溶液,以试剂空白为参比,最大吸收波长位于530nm,吸光度A与过氧化苯甲酰浓度呈线性关系,BPO含量在2.0×10<'-...     

几种聚合物分子间激基缔合作用的研究

作者合成并纯化了聚[对苯二甲酸(聚四亚甲基醚二醇)酯](PPTMGTP)、聚[2、6-萘二甲酸(聚四亚甲基醚二醇)酯](PPTMGNDC)和聚[2,6-萘二甲酸(环氧丙烷-四氢呋喃共聚醚二醇)酯](PCPEGNDC)等三个新聚合物,测定了它们的凝胶渗透色谱和数均分子量,对它们在良溶剂和不良溶剂溶液中的荧光进行了研究, 严格地用实验证明了PPTMGTP溶液中链内非相邻激基缔合作用的存在, 进一步以链内非相邻攀基缔合作用为探针研究了高分子在溶液中的形态随溶剂和浓度的变化, 用激基缔合物荧光相对强度的浓度依赖性测出高分子线团开始感觉到邻近有其它线团存在而收缩的浓度C_s(PPTMGNDC氯仿溶液的C_s = 2.61×10^-3g/ml, PPTMGNDC乙酸乙醋溶液的C_s =4.0×10^-2g/ml)。首次提出用C.划分高分子溶液稀浓区和亚浓区的界限的新欢点,以链内非相邻和链间激基缔合作用为探针确定了高分子溶液链段空间密度趋于均一的浓度C⁺(PPTMGNDC级仿溶液C⁺ = 7.02×10^-2g/ml),认为C⁺是高分子溶液由亚浓区到浓区的转变浓度。     

聚[芳基二甲酸(聚四亚甲基醚二醇)酯]的激基缔合物荧光谱和结晶形态

以聚苯乙烯为例研究了柔性链高聚物在亚浓溶液区激基缔合物荧光的浓度依赖性。发现M_W6.09×10⁶线形窄分布聚苯乙烯θ溶液中的激基缔合物与单生色团荧光的比值I_E/I_M的浓度依赖性在亚浓溶液区是分数幂的,它应归因于动态接触之后相邻线团链段间的硬心体积效应。     

亚甲基蓝褪色分光光度法测定藻酸双酯钠

在pH为2.3的盐酸介质中,藻酸双酯钠与亚甲基蓝反应形成离子缔合物,使亚甲基蓝溶液褪色,最大褪色波长位于665nm。藻酸双酯钠的浓度在2~8mg/L范围内遵守郎伯-比尔定律,测定藻酸双酯钠的百分之一吸光系数ε0.01为6.39×102。该褪色体系操作简便,有较好的稳定性、选择性与准确度。据此直接测定了片剂中藻酸双酯钠的含量取得满意结果。     

CPF/ZnO纳米复合催化材料的制备

通过原位聚合-热转化两步法,利用ZnO纳米微粒和糠醇(F)制备出了具有大共轭结构的高分子(CPF)和ZnO的纳米复合催化材料(CPF/ZnO);用TG-DTA、TEM、XRD、XPS、IR和UV-Vis等技术对其热稳定性、形貌、尺寸、结构及吸光特性等进行了表征,以亚甲基蓝(MB)溶液的催化降解研究了该材料在自然光条件下的催化性能。结果表明,由该方法可以得到平均尺寸约为 50 nm的CPF/ZnO纳米复合催化材料;其中的CPF为具有极性基团和大共轭结构的高分子;ZnO与CPF化学键合在一起;CPF的引入将ZnO的光谱响应拓展到了整个紫外-可见区,从而极大地改善了ZnO在自然光条件下的催化性能。如在460 ℃下处理40 min所得的纳米复合材料,在自然光条件下,10 min即可使MB溶液完全脱色,而在相同条件下,纯纳米ZnO仅能使MB的脱色率为10%左右;该催化材料重复使用3次仍可使MB溶液的脱色率保持在80%以上。     

ZnTiO3-TiO2纳米复合材料的光催化性能

通过溶胶 凝胶（Sol-Gel）法制备了ZnTiO3-TiO2纳米复合光催化剂,利用透射电子显微镜、X射线衍射、紫外-可见吸收光谱和ζ电位等测试技术对其形貌、晶体结构及其光谱响应特性进行了表征。 以亚甲基蓝（MB）溶液的脱色降解为模型反应,考察了光源和焙烧温度对该纳米复合材料光催化性能的影响。 结果表明,所得纳米复合材料的催化性能与材料的尺寸、在介质中的分散性能、表面荷电性质等有关。 600 ℃下焙烧3 h所得的ZnTiO3-TiO2纳米复合材料尺寸小（约60 nm）、分散性能好、表面荷负电荷量最高、催化性能最好,且在太阳光下的活性高于紫外光下的。 如太阳光下7 h可使亚甲基蓝（MB）溶液的脱色降解率达到93%,而在紫外光下只有82%;并且其催化活性高于纯TiO2和ZnO的。 该纳米复合催化剂重复使用4次仍能使亚甲基蓝（MB）溶液的脱色降解率在80%以上。 因此,具有较好的光催化稳定性能。     

Removal of methylene blue dye from an aqueous media using superabsorbent hydrogel supported on modified polysaccharide

The removal of methylene blue (MB) in water with the superabsorbent hydrogel (SH) formed by modified gum arabic, polyacrylate, and polyacrylamide was investigated. The SH exhibited excellent performance in MB absorption. The maximum absorption capacity was 48 mg of the dye per g of SH, representing 98% of the MB removed. Experimental parameters were used as follows: pH 8, hydrogel mass 50 mg, and initial concentration of MB 50 mg L(-1). In a procedure with an individual solution of orange II, an opposite effect related to the MB was observed: the hydrogel only absorbed water, resulting in an orange II-richer solution. The orange II concentration in solution increased about 50 times (relative to the initial concentration). In another experiment using an aqueous mixture of orange II and MB, the SH absorbed the MB exclusively. Compared to the MB, the orange II is separated from water by SH selectivity-absorption through an inverse process. This effect was attributed to the formation of a ionic complex between the imine groups of MB and the ionized carboxylic groups of SH.     

Dynamic analysis of aggregation of methylene blue with polarized optical waveguide spectroscopy

Polarized optical waveguide (POW) spectroscopy permits analysis of the changing molecular state of methylene blue (MB), including aggregate order and orientation at the waveguide surface. Monomer or dimer, dissolved randomly in MB aqueous solution, tends to aggregate at the waveguide surface during air drying. Furthermore, POW spectroscopy dynamically revealed that MB molecules became oriented vertically to the waveguide surface with increasing aggregation order.     

溶剂诱导的聚乳酸/聚乳酸衍生物共结晶行为

通过溶液浇铸法制备不同组分的左旋聚乳酸(PLLA)和聚(L-2-羟基-3-甲基丁酸)(PL-2H3MB)共混物.运用差示扫描量热仪(DSC)、偏光显微镜(POM)、广角X射线衍射(WAXD)和热重分析仪(TGA)分析共混物的结晶、熔融行为和热稳定性.通过观察到DSC加热曲线中新的熔融峰判断PLLA和PL-2H3MB共晶...     

Study of catalytic reduction and photodegradation of methylene blue by heterogeneous catalyst

The photocatalytic degradation of methylene blue is investigated in aqueous solution containing CoS/nanoAl-MCM-41 photocatalyst under visible light. The catalyst is characterized by X-ray diffraction (XRD), UV-vis diffused reflectance spectra (UV-vis DRS) and transmission electron microscopy (TEM) techniques. The effect of CoS, nanoAl-MCM-41 support and different wt% of CoS over the support on the photocatalytic degradation and influence of parameters such as CoS loading, catalyst amount, pH and initial concentration of methylene blue on degradation are evaluated. Hypsochromic effects (i.e. blue shifts of spectral bands) resulting from N-demethylation of the dimethylamino group in methylene blue occurs in presence of CoS/nanoAl-MCM-41 under ambient condition. Meanwhile, the bleaching of methylene blue MB, by sulfide ion, in an aqueous solution is studied in the presence nanoAl-MCM-41 catalyst. In the presence of sulfide ions, MB is bleached to its colorless leuco (LMB) and MBH(2)(+) forms. In an acidified solution (pH<2) the bleaching process generates LMB and by changing pH between 2.0 and 7.0 bleaching of MB dye to MBH(2)(+) form is observed. Using nanoAl-MCM-41 with encapsulated CoS nanoparticles only causes demethylation of MB in aqueous solution.     

Cyclic methacrylic acid oligomer as a novel pH‐sensitive carrier material

The pH effect of inclusion of methylene blue (MB) in cyclic methacrylic acid oligomer (CMAA) with degree of polymerization 14, which was a novel cationic host material with pK_a 4.83, was investigated in methanol. The self‐diffusion coefficients of MB in methanol at pH 7.0 and 4.0 with and without CMAA were measured by ¹H‐NMR spectrometry with pulsed‐field‐gradient stimulated‐echo pulse (PGSE) analysis. At both pH values, the addition of CMAA to MB solution resulted in the complex formation between CMAA and MB. MB was included in CMAA in methanol at a wide range of pH. The molar fraction of the slow diffusion component corresponding to the complex increased by varying the pH from 7.0 to 4.0. Then, SiO–CMAA was synthesized by immobilization of CMAA on silica gel beads. The time dependence of adsorption of MB to SiO–CMAA was investigated by UV–Vis spectrometry. At pH 7.0, the absorbance of MB–methanol solution gradually decreased by the addition of SiO–CMAA. The absorbance drastically decreased on varying the pH from 7.0 to 4.0, and the absorbance quickly increased on varying the pH from 4.0 to 7.0. The inclusion of MB in CMAA was fast and reversible on changing the pH of the solution. CMAA was the novel pH sensitive host material. Inclusion of MB in CMAA enhanced at pH 4.0 rather than at pH 7.0. Copyright © 2008 John Wiley & Sons, Ltd.     

Signal-on electrochemical Y or junction probe detection of nucleic acid

A methylene-blue (MB)-labeled molecular beacon junction probe allows for a signal-on electrochemical detection of nucleic acids via target recycling using endonucleases. Electron transfer is reduced when the MB is intercalated in the stem of the molecular beacon, but then electron transfer from MB to a gold electrode is enhanced upon cleavage of the junction probe due to increased probability of MB approaching the electrode when attached to the more flexible ssDNA.     

Removal of methylene blue from aqueous solution by graphene oxide

Graphene oxide (GO) is a highly effective absorbent of methylene blue (MB) and can be used to remove MB from aqueous solution. A huge absorption capacity of 714 mg/g is observed. At initial MB concentrations lower than 250 mg/L, the removal efficiency is higher than 99% and the solution can be decolorized to nearly colorless. The removal process is fast and more efficient at lower temperatures and higher pH values. The increase of ionic strength and the presence of dissolved organic matter would further enhance the removal process when MB concentration is high. The results indicate that GO can be applied in treating industrial effluent and contaminated natural water. The implications to graphene-based environmental technologies are discussed.