Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

Intramolecular photocycloaddition of β-stilbazoles tethered by silyl chains

Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity.     

Ion-transfer voltammetry at a polarized room-temperature molten salt/water interface.

Tetraoctylammonium cation forms a room-temperature molten salt (RTMS) with 2,4,6-trinitrophenolate anion. The RTMS is immiscible with water (W) and forms a stable RTMS/W interface. It has been shown that the RTMS/W interface can be electrochemically polarized. A well-defined voltammetric wave due to the transfer of thiocyanate ion across the RTMS/W interface was observed within the potential window. This is the first example of a polarized RTMS/W interface.     

Rapid and sensitive determination of the conversion of UV-cured acrylic ester resins by pyrolysis-gas chromatography in the presence of an organic alkali.

The double-bond conversion of UV-cured resins prepared from pentaerythritol triacrylate (PETA) was determined by pyrolysis-gas chromatography in the presence of an organic alkali, tetramethylammonium hydroxide (TMAH). The pyrogram of the uncured prepolymer compound, consisting of PETA and a photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, contained specific products reflecting the original acrylate structure, such as methyl acrylate (MA) and methyl ethers of pentaerithritol. Meanwhile, in pyrograms of the UV-cured PETA, the yields of MA considerably decreased. The double-bond conversions of the cured resins, irradiated with various UV dosages, were calculated based on the relative yields of MA among specific products in the pyrograms. The conversions determined by this approach were analyzed by comparing them with those estimated by Fourier-transform infrared spectroscopy.     

Phase Measurement Algorithm in Wavelength Scanned Fizeau Interferometer

Wavelength scanned interferometry allows the simultaneous measurement of top surface shape and optical thickness variation of a transparent object consisting of several parallel surfaces. Interference signals from these surfaces can be separated in frequency space, and their phases are detected by discrete Fourier analysis. However, these signal frequencies are shifted from the detection frequency by the refractive index dispersion of the object and a nonlinearity of the wavelength scanning. The Fourier analysis is sensitive to the detuning of the signal frequency and suffers from the multiple-beam interference noise. Conventional error-compensating algorithms cannot be applied to an object consisting of more than three reflecting surfaces. We derive a new 2N-1 sample error-compensating algorithm, which allows the phase detection of any order of harmonic frequency among the interference signals. The new algorithm suppresses the effect of signal frequency detuning as well as the multiple-beam interference noise and can be applied to the measurement of complex objects consisting of more than three reflecting surfaces.     

Polymorphy in the stereostructure of periodic polymer backbones

We theoretically investigated the polymorphy of the stereostructures of a periodic polymer. Using the polymer's internal conformation parameters of bond lengths, bond angles, and internal rotation angles, we extended the mathematical treatment for designing polymer backbones. We considered those periodic polymers whose unit cell consists of one (m = 1), two (m = 2), or three (m = 3) kinds of atoms. Moreover, for these three types of polymers, we supposed two catenation types for the skeleton atoms; one is a “homorotatory” sequence and the other is a “heterorotatory” one. To specify the backbone's stereostructure, we introduced several conformation parameters such as the helical pitch number n, the translation distance d, and the inclination angle of the skeleton plane Θ. By combining these parameters, we can systematically understand the variety and the possible polymorphy in the stereostructure of a periodic polymer backbone. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2829–2849, 2003     

New features in the catalytic cycle of cytochrome P450 during the formation of compound I from compound 0

Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe).