Effect of C7-Substituent on Self-Assembly of Chlorosomal Chlorophylls

Abstract

Bacteriochlorophyll d analogues that possessed a series of bulky substituents of OMe, OCOMe, and OCO ^t Bu at the C7¹-position were synthesized (Zn-complexes of methyl 7¹-substituted-3-(1-hydroxy-methyl)pyropheophorbide a). Aggregation behavior of these pigments was examined in comparison with a natural-type compound (C7¹-H) to elucidate the effects of size of the C7¹-moiety on self-assembly of the chlorins. These C7¹-substituted Zn-chlorins formed self-aggregates in 1% THF/hexane. The aggregates gave almost the same visible absorption bands, especially a ca. 2000-cm^?1 red-shifted Q_y peak; the spectra were essentially similar to those of the natural-type Zn-chlorin (C7¹-H). All the aggregates of the C7¹-substituted compounds showed similar exciton-type CD couplets in the red-shifted Q_y region, which were different from the feature of the couplet of the C7¹-H Zn-chlorin aggregate. These spectral data suggested that the C7¹-moiety did not interrupt the intermolecular linkages between chlorin molecules but altered the supramolecular structure which influences the long-range chirality.     

The potential use of electrospun polylactic acid nanofibers as alternative reinforcements in an epoxy composite system

This pilot study elaborates the development of novel epoxy/electrospun polylactic acid (PLA) nanofiber composites at the fiber contents of 3, 5, and 10 wt % to evaluate their mechanical and thermal properties using flexural tests and differential scanning calorimetry (DSC). The flexural moduli of composites increase remarkably by 50.8 and 24.0% for 5 and 10 wt % fiber contents, respectively, relative to that of neat epoxy. Furthermore, a similar trend is also shown for corresponding flexural strengths being enhanced by 31.6 and 4.8%. Fractured surface morphology with scanning electron microscopy (SEM) confirms a full permeation of cured epoxy matrix into nanofiber structures and existence of nondestructive fibrous networks inside large void cavities. The glass transition temperature (T_g) of composites increases up to 54–60 °C due to embedded electrospun nanofibers compared to 50 °C for that of epoxy, indicating that fibrous networks may further restrict the intermolecular mobility of matrix in thermal effects. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 618–623     

Enhancement of Light Absorption Ability of Synthetic Chlorophyll Derivatives by Conjugation with a Difluoroboron Diketonate Group

The enhancement of the light absorption ability of synthetic chlorophyll derivatives is demonstrated. Chlorophyll derivatives directly conjugated with a difluoroboron 1,3‐diketonate group at the C3 position were synthesized from methyl pyropheophorbide‐d through Barbier acylmethylation of the C3‐formyl moiety, oxidation of the C3‐carbinol, and difluoroboron complexation of the diketonate. Electronic absorption spectra in a diluted solution showed that the synthetic conjugates gave an absorption band at λ=400–500 nm, with a Qy band shifted to a longer wavelength of λ≈700 nm. DFT calculations demonstrated that the absorption bands and redshifts were ascribable to the coupling of the LUMO of chlorin with that of the difluoroboron diketonate moiety. The introduction of a pyrenyl group at the C3³‐position of the conjugate afforded an additional charge‐transfer band over λ=500 nm, producing a pigment that bridged the green gap in standard chlorophylls.     

Radiation-induced polymerization of 3-octylthiophene

In order to develop a new synthetic method and to study mechanism of oxidative polymerization of conducting polymers, polymerization of 3-octylthiophene in several organic solvents by γ-irradiation was examined. Polymers bimodal distribution with molecular weights at 500–1000 and 2000–3000 were generated by the irradiation of chloroform solutions. The values of monomer conversion (G(?M)) decreased from 445 to 10 with doses from 0.99 kGy to 594 kGy. The large G(?M) values and dose dependence of G(?M) cannot be explained with widely accepted mechanism for electrochemical polymerization or chemical oxidative polymerization. Another mechanism, which proceeds through chain reactions, is proposed. This mechanism explains the large G(?M) and the dependence on the dose.     

The Structure of Nickel(Ii) and Copper(Ii) Complexes with 1,4,8,11-Tetraazacyclotetradecanein Aqueous Solution as Studied by the X-Ray Diffraction Method

The structure of 1,4,8,11-tetraazacyclotetradecane (cyclam) complexes with nickel(II) and copper(II) ions in aqueous solution has been determined by the x-ray diffraction method at 25°C. The [Ni-(cyclam)]²⁺ complex has a square-planar structure with four nitrogen atoms of the cyclam, and the Ni-N bond length has been determined to be 198 pm. Upon the addition of ammonia, the color of the nickel(II)-cyclam solution turns to deep purple and the [Ni(NH₃)₂(cyclam)]²⁺ complex is formed. The complex has a regular octahedral structure with an additional two NH₃ molecules along the axis vertical of the cyclam plane, and the Ni-N (NH₃ and cyclam) bond lengths are 209 pm. The copper(II)-cyclam complex in the aqueous solution is a distorted octahedron with two water molecules along the elongated axis. The axial Cu—O and equatorial Cu—N bond lengths are 277 and 210 pm, respectively.     

Fully automated reagent peak‐free liquid chromatography fluorescence analysis of highly polar carboxylic acids using a column‐switching system and fluorous scavenging derivatization

In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control.     

Cycloaddition to a C3-ethynylated chlorophyll derivative and self-aggregation of zinc chlorin–pyrazole/triazole conjugates

Several kinds of cycloaddition reactions were applied to C3-ethynylated pyropheophorbide-a methyl ester to develop C3-functionalized chlorophyll derivatives. Its [2+2] cycloaddition with tetracyanoethylene, [2+3] cycloaddition with diazomethane, [2+3] Huisgen reaction with trimethylsilyl azide, and [2+4] Diels–Alder reaction with tetraphenylcyclopentadienone gave the expected products in moderate to high yields. Zinc complex of the resulting 3-pyrazolyl-chlorin was found to show self-aggregation in a less polar solvent, in an aqueous micelle, and in the solid thin films more readily than the corresponding zinc 3-triazolyl-chlorin.