基于环糊精/卟啉包络物荧光猝灭的二氧化碳光学敏感膜的研究

全 -( 2 ,6-二 -O-异丁基 ) -β-环糊精 ( DOB-β-CD)对固定于增塑 PVC膜中的 meso-四 ( 4-甲氧基苯基 )卟啉( TMOPP)有明显的荧光增强效应 ,且该荧光可被溶液中的二氧化碳可逆猝灭 .本文据此研制了一种可用于测定水溶液中二氧化碳含量 ,即 [H2 CO3]浓度的荧光敏感膜 .研究了最佳膜的组成 .经过组成优化的敏感膜测定 [H2 CO3]浓度的范围为 4 .75× 1 0 - 7～ 3.9× 1 0 - 5 mol/L.该传感器响应迅速、重现性好 ,常见的离子无明显干扰 .     

卟啉共价有机框架化合物的研究进展

共价有机框架化合物(COFs)是一类新兴的具有多孔结构的晶态有机聚合物,在储存与分离、催化、能量转化等领域具有广泛应用。本文介绍了一类基于卟啉单元的COFs,从框架构筑及应用开发两方面综述了这类材料的研究进展。     

Highly Active Electrocatalyst Derived from ZIF-8 Decorated with Iron(III) and Cobalt(III) Porphyrin Toward Efficient Oxygen Reduction in Both Alkaline and Acidic Media

Zeolite imidazole frameworks 8(ZIF-8) and modified ones after pyrolysis are highly promising toward oxygen reduction reaction(ORR). Especially, the compositional modification of ZIF-8 is crucial to the enhancement of ORR performance, yet limited to the substitution of skeletal Zn(II) with other cations or simple physical adsorption of cations. Herein, we report the decoration of ZIF-8 with ORR active hemin(FeP) and Co(III) protoporphyrin(CoP) via the coordination between the peripheral carboxylic group of FeP and CoP with skeletal Zn(II). This allows well control over the quantity of loaded FeP and CoP, critical to the synthesis of advanced electrocatalysts. Subsequent pyrolysis of FeP and CoP co-decorated ZIF-8 leads to highly active ORR electrocatalysts with a half-wave potential(E_1/2) of 0. 913 V(vs. RHE) in 0.1 mol/L KOH aq. and an E_1/2 of 0.803 V(vs. RHE) in 0.1 mol/L HClO₄ aq. Moreover, our electrocatalyst shows much more improved and comparable durability in alkaline and acidic media, respectively, during 3000 cycles of cyclic voltammetry(CV) scanning relative to commercial Pt/C.     

新水溶性卟啉季铵盐的合成及与锌的显色反应研究

合成了-种新型水溶性卟啶卟啉季铵盐即溴化5-[(4-N-芐基)吡啶基]10,15,20-(4-N-吡啶基)卟啉,研究了该试剂与锌的显色反应.在pH2.5的邻苯二甲酸氢钾-盐酸缓冲溶液中,形成了配位比为1:1的配合物,基最大吸收波长λ=424nm,表现摩尔吸光系数ε=2.03×105L·mol-1·cm-1.在0-1.2μg/10mL范围内吸光度与锌质量浓度关系符合比耳定律,该法灵敏度高、选择性好.本法应用于环境水试样中痕量锌离子的分析,结果令人满意.     

锰卟啉/钒取代杂多酸配合物的合成、表征和性能研究

利用碘化四对(4-三甲氨基苯基)锰卟啉与钒取代杂多酸H5 PMo10 V2O40,在水溶液中,室温下反应合成了锰卟啉/钒取代杂多酸配合物,用红外和紫外光谱技术对其结构进行了表征,发现该配合物中包含着金属卟啉的环状结构与杂多酸的笼状结构,并且二者以化学键的形式键合在一起.以该化合物作为催化剂,以过氧化氢水溶液为氧化剂,在温和的条件下研究了锰卟啉/钒杂多酸配合物对苯的羟基化反应的影响,考察了催化剂的催化活性,探讨了催化剂对苯羟基化反应的活性中心.研究结果表明,杂多酸中的钒原子是其主要的催化活性中心,锰卟啉的存在可以有效地提高其催化活性.     

铁卟啉/钒取代杂多酸新型催化剂的合成、表征和性能研究

文章以水溶性碘化四对(4-三甲氨基苯基)铁卟啉和钒取代杂多酸H5PMo10V2O40为原料,采用离子交换方法在水溶液中合成了一种铁卟啉/钒取代杂多酸新型无机-有机复合催化剂,并使用红外和紫外光谱技术对其结构进行了表征,结果表明,这种新型复合催化剂仍然保持着卟啉的大环共轭结构和杂多酸的笼状多电子结构。同时研究了以30%过氧化氢水溶液为绿色氧化剂,初步探讨了这种铁卟啉杂多酸催化剂对苯的羟基化反应的的影响,考察了催化剂的催化活性。催化氧化实验表明,制备的铁卟啉/杂多酸配合物可用作苯直接氧化羟基化成苯酚的催化剂,并且表现出较高的催化活性。     

两种新型卟啉吡啶季铵盐的合成

合成了两种新型卟啉吡啶季铵盐:溴化5-[4-N-(对硝基)苄铵基吡啶基]-10,15,20-三(4-N吡啶基)卟啉和氯化5-[4-N-(对甲氧基)苄铵基吡啶基]-10,15,20-三(4-N-吡啶基)卟啉.这两种化合物尚未见文献报道,它们的结构分别由紫外可见光谱、红外光谱、核磁共振谱、质谱、元素分析得到确证.     

Synthesis of phenothiazine-functionalized porphyrins with high fluorescent quantum yields

Two porphyrins with oligo-phenothiazine arms have been synthesized by a combination of Heck and Adler reaction, and their photophysical properties have been investigated by absorption and steady-state fluorescence spectroscopy. It is found that the excitation energy transfer occurs from the phenothiazine units to the porphyrin core, and that the porphyrins can emit intense red light with high fluorescent quantum yields.     

One-dimensional porphyrin H-aggregates induced by solvent polarity

A series of new porphyrin derivatives possessing the side arms of alkyl-substituted thiophene oligomer were synthesized. The effects of solvent polarity on the formation of supramolecular assembly have been studied by UV-vis absorption, fluorescence emission, and TEM measurement. The linear-shape porphyrin derivatives bearing two thiophene pentamers at meso-position showed the significant spectral changes in both blue-shift and band broadening of Soret bands which indicate the formation of a relatively larger porphyrin H-aggregate that occurred in nonpolar solvent such as n-hexane.     

Soluble porphyrin-bisindolylmaleimides dyad and pentamer as saturated red luminescent materials

Novel soluble porphyrin-bisindolylmaleimides dyad and pentamer have been prepared conveniently by coupling of amino-porphyrins and bisindolylmaleic anhydride. The bisindolylmaleimide groups function as the antenna to efficiently enhance the intramolecular energy transfer to the porphyrin core. These compounds may serve as good candidates of red-light emitting materials for organic light-emitting diodes.