含氟共聚物与钴卟啉复合膜的制备及促进氧输送性能

研究了甲基丙烯酸八氟戊酯-乙烯基咪唑共聚物与钴卟啉复合膜的制备及钴卟啉与氧络合、促进输送性能.共聚物中的咪唑基与钴卟啉的第五配位点在溶液中络合,制得的复合膜具有快速和可逆的氧结合特性.温度降低,钴卟啉与氧络合的平衡常数增加;膜中的钴卟啉与氧络合平衡常数大于N,N-二甲基甲酰胺(DMF)溶液中的平衡常数.钴卟啉与氧络合和选择性地促进氧的输送使共聚物/钴卟啉复合膜的氧渗透系数和氧/氮选择系数提高.     

氟涂层对聚合物-钴卟啉膜氧气输送性能及其寿命的影响

采用在聚合物-钴卟啉(CoP)膜表面旋转涂覆氟涂料法,制备了氧/氮分离膜.研究表明,与未涂层膜相比,氟涂层膜中的CoP与氧表观结合平衡常数、膜的氧渗透系数和氧/氮选择性没有发生明显变化.随氟涂层厚度增加,氧渗透系数稍有降低,但水蒸汽渗透系数显著降低.由于氟涂层的憎水性,使涂层膜的水蒸汽渗透系数显著降低,氧载体CoP与氧结合寿命延长了4倍.     

钴卟啉的不可逆氧化及含氟聚合物对钴卟啉复合膜氧络合寿命的影响

研究了甲基丙烯酸八氟戊酯 乙烯基咪唑共聚物 (PFIm)与 5 ,1 0 ,1 5 ,2 0 四 (邻 三甲基乙酰胺苯基 )钴卟啉 (TPPCo)复合膜的氧络合百分率随环境湿度和时间的变化 ,讨论了钴卟啉不可逆氧化的机理、动力学 ,及钴卟啉与氧络合的寿命 .空气中的水分子进攻与氧络合的钴卟啉 ,生成过氧化氢自由基和三价钴卟啉 ,是钴卟啉失去与氧络合能力的主要原因 .发现PFIm的憎水性可抑制由水分子引起的钴卟啉的不可逆氧化反应 ,可显著延长钴卟啉与氧络合的寿命 ,从而使含氟的PFIm TPPCo膜与氧络合的寿命要比甲基丙烯酸辛酯 乙烯基咪唑共聚物 (POIm)与钴卟啉复合膜的寿命长     

氧在甲基丙烯酸辛酯-乙烯基咪唑共聚物/钴卟啉复合膜中的溶解和扩散过程

讨论了氧在甲基丙烯酸辛酯 乙烯基咪唑共聚物 钴卟啉复合膜中的溶解和扩散过程,用二元输送模型分析了间α,α,α,α-四(邻三甲基乙酰胺苯基)钴卟啉(CoP)作为氧载体的复合膜氧输送性能.研究发现,固定在聚合物中的CoP与氧可逆地络合和解络合,其络合平衡常数K为14mol- 1 L ,根据吸附实验结果计算出氧在基体聚合物中的物理溶解度系数kD 为4 4×10 - 5cm3(STP)cm- 3Pa- 1 .聚合物 载体复合膜除了物理渗透外,氧还可通过与载体的络合和解络合而扩散,从而促进氧的输送.氧通过载体的扩散系数(DC)和通过基体聚合物的物理扩散系数(DD)的比值为0 0 8.     

聚合物网络分散液晶复合膜的制备与性能研究

报道了一种新型树脂基的聚合物网络分散晶复合膜材料。研究了基体材料的组成，液晶种类，液晶含量，聚合温度，紫外光强度及聚合时间等聚合物网络分散液晶复合膜性能的影响。扫描电子显微镜观测，发现这种材料是由两个连相互穿构成了属于聚合物球型。     

卟啉钴分子筛的制备,表征和催化性能的研究

用液－固相分步合成法将新型四卤四甲基卟啉诱捕在经Ｃｏ＾２＋交换的ＮａＸ分子筛超笼内，利用索式提取器洗净分子筛外表面吸附的卟啉后，采用ＵＶ－Ｖｉｓ、ＩＲ、ＳＥＭ、ＤＴＡ、Ｘ射线衍射分析、吸附等手段对诱捕在超笼内的卟啉予以表征。进一步对比研究了卟啉、分子筛和诱捕卟啉分子筛的催化性能。结果表明，卟啉与分子筛结合后，催化活性大大提高。     

钴卟啉络合物的氧结合性能及其在功能材料中的应用

钴卟啉可与氧发生迅速、可逆的结合反应,是有效的氧载体,已被用于氧气吸收、光学传感器和氧气选择性分离膜。综述了钴卟啉的立体结构、配住体、环境等对其与氧可逆结合性能的影响,以及钴卟啉在功能材料中的应用。     

二硫桥键钴卟啉二聚体的合成与电催化氧还原性能

成功合成了二硫桥键相连的钴卟啉二聚体2Co。通过循环伏安电化学方法测试,在无水二氯甲烷溶剂中,钴卟啉二聚体展示了3个氧化和2个还原峰,表明此钴卟啉二聚体可以稳定多重负/正电荷。详细研究了在酸性条件下的钴卟啉二聚体的电催化氧还原性能。钴卟啉二聚体的电催化氧还原显示了高稳定性和高活性,测得转移电子数为3.5~3.6之间。钴卟啉二聚体的电催化氧还原性能说明通过二硫键对钴卟啉单体二聚化可以提高钴卟啉的电催化氧还原性能。     

钴卟啉的合成及其对氧还原的电催化性能

 合成了四苯基卟啉及其钴配合物,考察了催化剂、溶剂及反应温度等因素对四苯基卟啉收率的影响,并用红外光谱和核磁共振氢谱对合成产物进行了结构表征. 以X射线光电子能谱为主要手段,研究了不同热处理温度对钴卟啉结构的影响,通过测定空气电极极化曲线研究了热处理对钴卟啉催化活性的影响. 结果表明,在200 ℃, 以对硝基苯甲酸为催化剂,硝基苯为溶剂时,四苯基卟啉收率达32%. 热处理能提高金属卟啉的催化活性, 600 ℃热处理后,钴卟啉环中的 Co-N4 结构趋于键断裂的临界状态,催化活性点增多,催化活性较好; 而800 ℃处理的钴卟啉中部分 Co-N4 键破裂,催化活性下降.     

Effect of carrier concentration on the facilitated oxygen transport in a polymer membrane

Facilitated transport of oxygen in a solid Polymer membrane containing cobaltporphyrin (CoP) which carries oxygen specifically and reversibly, leads to permselectivity of oxygen against nitrogen in the membrane. The increase in concentration of the CoP carrier is expected to enhance the oxygen transport. The membranes of poly(octylmethacrylate-co-vinylimidazole) containing 0.8 ～ 10 wt% CoP were prepared, and the effects of the CoP-concentration on the transport and the diffusion constants of oxygen are studied. Although the induction period before the steady state of oxygen permeation was prolonged with the CoP concentration in the polymer membrane, the glass transition temperature (T_g) of the membrane was increased and the diffusion constants of oxygen were decreased with the CoP concentration to yield unexpected reduction of the oxygen permeation in the highly CoP loaded membrane.     

Oxygen dissolution and transport in cobaltporphyrin-bound organophosphazene membranes

Rubbery poly(organophosphazene)s were synthesized, and were combined with cobaltporphyrin (CoP) which binds molecular oxygen rapidly and reversibly. The apparent oxygen-binding equilibrium constant (K_app) is in proportion to the physical solubility coefficient of oxygen in the polymer, although the reduced equilibrium and thermodynamic parameters are not dependent on the polymer matrix species. Diffusivity of oxygen via the fixed CoP(D_C) is enhanced for poly(organophosphazene) membranes with a larger oxygen diffusion constant. Poly(organophosphazene) membranes with both a large K_app and D_C yield high oxygen permeability.     

Facilitated Transport of Penicillin G by Bulk Liquid Membrane with TBP as Carrier

The facilitated transport of penicillin G from aqueous solutions to the stripping phase through bulk liquid membrane (BLM) containing TBP in 3% iso-octanol and n-butyl acetate was studied. Na₂CO₃ solution was used as the stripping phase. Experiments were performed as a function of stirring rate, TBP concentration and type of diluent in the liquid membrane phase, pH, and initial penicillin G concentration in the feed phase, Na₂CO₃ concentration in the stripping phase, etc. The results showed that the BLM process could carry out the simultaneous separation and concentration of penicillin G from dilute aqueous solutions, and arise “up-hill” effect due to the characteristic of non-equilibrium mass transfer. The diffusion of penicillin G complex in the liquid membrane phase played an important role in BLM process. The mass transfer mechanism of BLM for this system was also discussed.     

Porphyrin Network Polymers Prepared via a Click Reaction and Facilitated Oxygen Permeation Through Their Membranes

Network polymers of cobaltporphyrin derivatives are prepared by a facile click reaction via the Michael addition of acetoacetate‐substituted tetraphenyl cobaltporphyrin and tri‐ or tetra‐acrylates. The conversion is saturated for 1 h in the presence of a catalyst, which almost reaches the same gelation point of the formed network polymers. Deeply and homogeneously red‐colored membranes with a sub‐micrometer thickness are yielded on a porous supporting membrane. They are still tough even with a very high content of the rigid porphyrin residue. The oxygen permeability is high, at 10–100 Barrer, and the oxygen/nitrogen permselectivity (P_O2/P_N2) is significantly enhanced with the porphyrin content reaching 30, for the membranes with ca. 70 wt% porphyrin content.

     

Facilitated Transport Through Liquid Membranes

Liquid membranes, developed by Li,¹ offer a new and effective means for separation of mixtures. In order to maximize the utility of this concept, it is necessary to maximize the concentration gradient of the diffusion, species across the membrane.     

有机金属络合物用于高分子富氧膜的研究进展

本文介绍了能够可逆吸附分子氧的有机金属络合物用于高分子富氧膜的研究进展，以及以双重吸附理论进行的膜的促进输送机理。     

易化输运过程的简单化学模型及其在Wyman-Murray扩散中的应用(英文)

A simple chemical kinetic model is developed which describes the behavior of small ligands that can bind reversibly with large carrier molecules with slower intrinsic rates of transport. Under certain conditions, which we describe, the presence of the slower carriers in fact enhances the transport of the ligand. This is the chemical version of Wyman-Murray′ s facilitated diffusion. The simple model illuminates the driven nature of the enhancement of the transport by the carrier molecules: we show that the facilitated transport depends crucially on a"grand canonical" setting in which the free ligand concentrations are kept constant in the presence of the facilitating protein, in contrast to a canonical setting with constant total ligand concentrations. Results from the simple model are compared to previous experimental and theoretical results for Wyman-Murray facilitated diffusion of oxygen and carbon monoxide in muscle. A relation is established between the association-dissociation rates and the down-stream ligand concentration, or back pressure for oxygen, required for the facilitation effect to occur.     

Reversible Oxygen Binding to the Polymeric Cobalt Tetraazaporphyrin Complex and Oxygen‐Facilitated Transport through Its Membrane

Summary: A membrane of a cobalt tetraazaporphyrin polymer complex was prepared with a nanometer thickness and used as an oxygen‐facilitated transport membrane. Rapid and reversible oxygen binding to the cobalt tetraazaporphyrin complex with a polymeric imidazole ligand was observed at low temperature. Oxygen transport through the membrane was facilitated and a high (oxygen/nitrogen) permselectivity of 28 was obtained.

Oxygen‐facilitated transport through a cobalt tetraazaporphyrin complex‐polymer membrane of nanometer thickness.