Investigation of Light-harvest Material： Synthesis and Characterization of Nanometer Porphyrin Trimer

ω-Bromopropylporphyrin ether synthesized from the raction of 1,3-dibromopropane as the bridge-linkedreagent and 5- (4-hydroxyphenyl)-10,15,20-triphenylporphyrin (H2MHTPP) as the matrix reacts with 5, 15-di(4- hydroxyphenyl)-10, 20-diphenyl porphyrin(trans-H2DHDPP) to give the title nanometer porphyrintrimer. The characterization was carried out by means of elemental analyses, UV-Vis, IR, ^1H NMR andXRD.     

Facile Synthesis,Characterization, and Fluorescence Studies of Novel Porphyrin Appended Thiazoles

A facile and high yielding synthesis of porphyrin appended thiazoles 5 from the reaction of 5‐(4‐thiocarboxamidophenyl)‐10,15,20‐triphenylporphyrin with α‐bromo ketones has been described. The fluorescence studies of synthesized porphyrin appended thiazoles 5 in chloroform indicate that porphyrin π system is not greatly perturbed by substitution of a thiazole moiety at meso‐phenyl ring even in the excited state.     

Fluorescence Properties of Porphyrin Dimers Incorporating an Anhydride Linker

IntroductionOligomeric porphyrins play a number of criticalbiological roles in many processes, such as energytransfer and electron transfer, molecular binding, mul-tielectron redox catalysis and light harvest[1,2]. Amongthe arrays of covalently linked por…     

卟啉纳米材料的新法合成

采用液体分子嵌入法将卟啉分子引入到孔径为几十纳米的硅藻土孔内,制得了粒径在10～20nm左右的卟啉微晶.通过紫外、红外、X射线衍射、透射电镜和表面光电压谱等手段证实卟啉微晶被固载在硅藻土孔径内.     

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 .     

5-氟尿嘧啶卟啉化合物的合成和光谱性质

首次合成并用元素分析、红外光谱、核磁和质谱等表征了6种新的5 氟尿嘧啶卟啉化合物. 对其紫外吸收、荧光性质和荧光寿命进行了研究,并与未修饰卟啉化合物光谱性质进行了比较. 5 氟尿嘧啶卟啉化合物荧光寿命为7 ns,受环境取代基和溶剂的影响较小.     

系列羟基苯基卟啉化合物荧光性质的研究

对照紫外光谱的变化分析了5种卟啉周边羟基的数目、位置及其在不同溶剂条件下的荧光光谱的变化情况.研究表明,利用控制卟啉周边取代基的数目、对称性及选择溶剂可获得不同强度的荧光物质.     

TDI三聚体的合成研究

以一种碱金属羧酸盐K-1000作为甲苯二异氰酸酯(TDI)三聚反应的催化剂合成了以TDI三聚体为主要成分的多异氰酸酯固化剂。对合成工艺条件进行了探讨。结果表明,将反应温度控制在35℃,催化剂K-1000用量为0.06%时,用苯甲酰氯作为阻聚剂可得到性能基本稳定的TDI三聚体产品。     

苯环上取代基的性质对双卟啉分子内能量转移的影响

金属卟啉在光合作用中起重要作用,合成其聚合物并作为光合作用模拟体系研究其能量转移和电子转移过程,已成为化学领域的重要研究课题之一.用于光合作用活性中心模拟体的金属卟啉聚合物种类很多,本文参考Little方法合成2种未见报道的苯环上分别带推电子和拉电子取代基和以柔韧碳氢链相连的中位双卟啉p-ZnTPP/p-H_2TMPP和p-ZnTPP/p-H_2TCPP(图1),探索了取     

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。     

照相明胶荧光特性的研究

利用荧光分析法研究了照像明胶的荧光特性,结果表明,除了公认的苯丙氨酸和酪氨酸两种荧光物质外,还存在一种未知的荧光杂质,其最大激发峰为240 nm,荧光峰为395 nm,性能试验表明,该荧光杂质可能为卟啉类络合物或某种色素物质。     

卟啉化合物的聚集作用

从静电作用、μ-氧配位、边基配位、π－π键合等结合方式概述了卟啉化合物的聚集作用。     

5,10,15,20-四(对-十四酰亚胺基苯基)卟啉及其锰、锌配合物的合成及性质

合成了5,10,15,20-四(对-十四酰亚胺基苯基)卟啉配体(TMPPH2)及其锰、锌金属配合物(TMPPMnCl, TMPPZn), 并通过紫外-可见光谱、红外光谱、核磁共振氢谱、元素分析等技术对化合物的结构加以确认, 研究了配体和配合物的拉曼光谱、光电子能谱和荧光光谱的变化及电化学性质. 结果表明, 配体和配合物的紫外光谱、红外光谱、拉曼光谱、荧光光谱及光电子能谱都有很大区别, 锰配合物的循环伏安曲线与配体和锌配合物不同, 除了卟啉环发生氧化还原外, 还发生了金属离子的氧化还原反应.     

A Five‐layer π‐Aromatic Structure Formed through Self‐assembly of a Porphyrin Trimer and Two Aromatic Guests

In this study we synthesized two‐ and four‐armed porphyrins – bearing two carboxyl and four 2‐aminoquinolino functionalities, respectively, at their meso positions – as a complementary hydrogen bonding pair for the self‐assembly of a D₂‐symmetric porphyrin trimer host. Two units of the two‐armed porphyrin and one unit of the four‐armed porphyrin self‐assembled quantitatively into the D₂‐symmetric porphyrin trimer, stabilized through ammidinium‐carboxylate salt bridge formation, in CH₂Cl₂ and CHCl₃. The porphyrin trimer host gradually bound two units of 1,3,5‐trinitrobenzene between the pair of porphyrin units, forming a five‐layer aromatic structure. At temperatures below ?40 °C, the rates of association and dissociation of the complexes were slow on the NMR spectroscopic time scale, allowing the 1 : 1 and 1 : 2 complexes of the trimer host and trinitrobenzene guest(s) to be detected independently when using less than 2 eq of trinitrobenzene. Vis titration experiments revealed the values of K₁ (2.1±0.4×10⁵ M^?1) and K₂ (2.2±0.06×10⁴ M^?1) in CHCl₃ at room temperature.     

N-(11-羧基十一烷基)马来酰亚胺及其三聚体的合成

以顺丁烯二酸酐和12-氨基十二酸为原料,硫酸、三乙胺为脱水催化剂,经两步反应合成了N-(11-羧基十一烷基)马来酰亚胺.再在三苯基膦和苯酚作用下,N-(11-羧基十一烷基)马来酰亚胺进一步发生三聚反应合成了相应的马来酰亚胺三聚体.采用红外光谱和核磁共振谱对三聚体的结构进行了表征.     

Fluorescence ratiometric pH sensor prepared from covalently immobilized porphyrin and benzothioxanthene

A fluorescence ratiometric sensor for pH determination is described in this paper. The sensor incorporated the pH-sensitive dye meso-5,10,15,20-tetra-(4-allyloxyphenyl)porphyrin (TAPP) as an indicator and a pH-insensitive dye N-(2-methacryloxyethyl)benzo[k,l]thioxanthene-3,4-dicarboximide (MBTD), a benzothioxanthene derivative, as a reference for fluorescence ratiometric measurement. To prevent leakage of the dyes, both were photocopolymerized with acrylamide, hydroxyethyl methacrylate, and triethylene glycol dimethacrylate on the silanized glass surface. The reproducibility and response time of the prepared sensor were sufficient. Most common coexisting inorganic ions and organic compounds did not interfere with pH sensing. In the acidic pH range from 1.5 to 5.0 the fluorescence intensity ratio of the two dyes varied linearly as a function of pH. The sensing membrane was found to have a lifetime of at least one month. The sensor was applied to the analysis of waste water and artificial samples.     

SiO2表面硅钼酸的稳定性和还原性

采用ＦＴ－ＩＲ、ＸＲＤ、ＢＥＴ、ＴＰＲ等方法,研究了ＳｉＯ２负载硅钼杂多酸的热稳定性和还原性。结果表明,虽然ＳｉＭｏ的负载量达到２个理论单层,但仍以非晶形态高度分散在ＳｉＯ２上;负载的硅钼酸稳定性提高,热分解温度在３５０～６００℃,同时,可还原性能降低,杂多酸的稳定性和ＴＰＲ性能相关。     

新型桥连双卟啉化合物的合成及结构表征

通过将4,4′-二羧基-2,2′-联吡啶、2,6-二溴甲基吡啶、2,6-二羟甲基吡啶和1,8-二氨基萘分别与5-(4-羟基苯基)-10,15,20-三苯基卟啉(1a)、5-(4-甲酰苯基)-10,15,20-三苯基卟啉(1b)和5-[4-(4′-溴代丁氧基)苯基]-10,15,20-三苯基卟啉(1c)反应,合成了3类新型的双卟啉化合物2a-2e,经IR,¹HNMR,MS,UV-Vis光谱及元素分析对中间体和目标化合物的结构进行了表征.     

钛硅分子筛挤条成型催化剂热稳定性能的研究

采用在空气中程序升温焙烧的方式考察了钛硅分子筛挤条成型催化剂的热稳定性能．对不同温度焙烧得到的样品进行了XRD、IR、UV Raman和SEM表征．结果表明，在高温焙烧时，由于载体结构的改变引起载体与分子筛之问相互作用发生变化，导致成型催化剂中分子筛骨架破坏．随着焙烧温度的提高，IR谱图中960cm^-1处代表钛进入骨架的特征峰的强度迅速减弱，当焙烧温度达到1000℃时，960cm-1处的骨架钛特征峰移至948cm^-1．在紫外拉曼谱图中，骨架位钛物种的特征拉曼谱峰-1125cm^-1谱峰在加入SiO2载体后，高温下峰强度明显降低，这说明载体的加入降低了钛硅分子筛挤条成型催化剂的热稳定性能．     

Tunneling Electron Induced Fluorescence from Single Porphyrin Molecules Decoupled by Striped-Phase Octanethiol Self-assembled Monolayer

We investigate tunneling electron induced luminescence from isolated single porphyrin molecules that are decoupled by striped-phase self-assembled monolayer of octanethiol from the underneath Au(111) substrate. Intrinsic single-molecule electroluminescence has been realized by such decoupling at both bias polarities. The photon emission intensity acquired from the molecular lobe is found stronger than that from the molecular center. These re-sults provide useful information on the understanding of electroluminescent behavior and mechanism in molecular tunnel junctions.