Spectra and Transport in Almost Periodic Dimers

We study spectral properties of discrete Schrödinger operators with potentials obtained via dimerization of a class of aperiodic sequences. It is shown that both the nature of the autocorrelation measure of a regular sequence and the presence of generic (full probability) singular continuous spectrum in the hull of primitive and palindromic (four block substitution) potentials are robust under dimerization. Generic results also hold for circle potentials. We illustrate these results with numerical studies of the quantum mean square displacement as a function of time. The numerical techniques provide a very fast algorithm for the time evolution of wave packets.     

A novel and efficient synthesis of porphine

meso-Tetra(n-hexyloxycarbonyl)porphyrin was found to be converted into porphine, the mother compound of porphyrins, in a 77% yield when heated in aqueous sulfuric acid at 180 °C over 30 min under an inert atmosphere. The observation demonstrates that the substituted porphyrin serves as a novel and useful precursor for porphine.     

A Large Conformational Change of a Bridged b-Cyclodextrin Dimer in Aqueous Solution

As artificial enzymes, the binding constants of cyclodextrins (CDs) and their substrates are expected to be high1. For this purpose, many kinds of bridged cyclodextrin dimers2 whose two cyclodextrins are linked by various spacers have been constructed. It was of interest to make the dimers, whose binding constants would exceed 108dm3/mol3. Up to date, the bridged cyclodextrin dimers have been extensively studied as enzyme models and as molecular receptors4-6. Recently, we synthesized a brid…     

Synthesis and Photocytotoxicity of Mono-functionalised Porphyrin with Valine Moiety

A mono-funtionalised tetraphenylporphyrin (TPP) bearing valine moiety at the phenyl ring was synthesized for photocytotoxicity examination in four steps, starting from regiospecific mono-nitration of TPP at the phenyl ring. The in vitro photocytotoxicitic effect against SPC-Al adenocarcinona cell line was tested.     

TTF-porphyrin dyads as novel photoinduced electron transfer systems

A TTF-linked porphyrin dyad and its zinc complex have been synthesized as novel photosystems with a redox-active pendant. The two chromophores of these dyads are not interactive in the absorption spectra, but the fluorescence of the porphyrin chromophore is dramatically quenched by intramolecular electron transfer from the TTF pendant.     

四（对-羟基苯基）卟啉氧合配合物的室温固相合成，表征及氧合能力

采用固相反应合成了四羟基苯基卟啉与与Fe^2＋,Co^2＋金属离子的配合物,在室温下,将其与分子O2作用,提纯后得到两种固态氧合配合物．通过元素分析、红外光谱（IR）、核磁共振氢谱（^1HNMR）、电导、热分析（TG／DTA）、紫外光谱（UV）等测试手段确定了氧合配合物的组成为[Co·THPP·O2]（NO3）2·2H2O、[Fe·THPP·O2]Cl2·2H2O]，可知1mol配合物吸收了1molO2,采用失重法测定了氧合配合物中的配位氧,确定1mol金属配合物吸收1molO2形成超氧配合物．     

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

A tin(IV) porphyrin was combined with two axial NCN‐pincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCN‐pincer platinum derived benzoic acid. The solid‐state structure determined by X‐ray crystallography revealed some close contacts between the pincer complexes and the meso‐p‐tolyl subsitutents of the porphyrin. It was shown by ¹H NMR spectroscopy that these close contacts were not present in solution and that this compound can potentially act as a novel building block for supramolecular architectures.     

Fluorescence line narrowed spectra of Zn and metal-free cytochrome c

Fluorescence line narrowing (FLN) spectroscopy was used to study the role of the polypeptide chain in influencing the spectrum of Zn-substituted cytochrome c (Zn cyt c) and metal-free cyt c (porphyrin cyt c). For both derivatives the spectra show characteristics of relaxed fluorescence from an inhomogeneously broadened sample. Zero phonon lines and phonon wings can be clearly distinguished, and vibrational frequencies of the ground and excited states were identified. The inhomogeneous distribution width for porphyrin cyt c is slightly wider than that of Zn cyt c and a second population of molecules was apparent in the porphyrin cyt c. The phonon coupling was greater for Zn cyt c than for porphyrin cyt c, which may be due to the extra coupling to the polypeptide chain by metal ligation.This work has been done in partial fulfillment of the requirements for the Doctor of Philosophy degree.