Convenient Method of Chain‐Growth Polycondensation for Well‐Defined Aromatic Polyamides

Summary: For the convenient synthesis of well‐defined poly(N‐octyl‐p‐benzamide)s with low polydispersities, the polycondensation of methyl 4‐octylaminobenzoate ( 1 ) was investigated. Methyl ester monomer 1 polymerized with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) in the presence of an initiator in tetrahydrofuran at −10 °C. The highly pure polyamide with a defined molecular weight and a low polydispersity is obtained after simple treatment of the reaction mixture with aqueous NaOH solution, followed by evaporation.

The chain‐growth polycondensation of 4‐octylaminobenzoic acid methyl ester ( 1 ) with lithium 1,1,1,3,3,3‐hexamethyldisilazide (LHMDS) to yield poly(N‐octyl‐p‐benzamide).     

Aerobic Dehydrogenation of N-Heterocycles with Grubbs Catalyst: Its Application to Assisted-Tandem Catalysis to Construct N-Containing Fused Heteroarenes

An aerobic dehydrogenation of nitrogen-containing heterocycles catalyzed by Grubbs catalyst is developed. The reaction is applicable to various nitrogen-containing heterocycles. The exceptionally high functional group compatibility of this method was confirmed by the oxidation of an unprotected dihydroindolactam V to indolactam V. Furthermore, by taking advantage of the oxygen-mediated structural change of the Grubbs catalyst, we integrated ring-closing metathesis and subsequent aerobic dehydrogenation to develop the novel assisted-tandem catalysis using molecular oxygen as a chemical trigger. The utility of the assisted-tandem catalysis was demonstrated by the concise synthesis of N-containing fused heteroarenes including a natural antibiotic, pyocyanine.     

Synthesis and peripheral substituent effects of bay-annulated indigo derivatives

In this study, indolo-naphthyridine-6,13-diones (5a–d) with four different peripheral substituents were prepared via bay-annulation reactions of indigo. The resulting compounds (5a–d) exhibited fluorescence in the red to near-IR region, while the parent indigo molecule showed no fluorescence. Although the peripheral substituents were oriented to the exterior of the π-conjugated system, the electronic structure affected the absorption and fluorescence spectra. Moreover, calculated molecular orbitals and absorption spectra successfully reproduced the experimental absorption spectra and cyclic voltammograms.     

Novel surface-modification techniques for polymer-based separation media. Stimulus-responsive phenomena based on double polymeric selectors

A pair of polymeric selectors potentially responding to stimulation was introduced onto monosized porous polymer particles to be evaluated as a packing material for HPLC. Possible complexes formed between polyacrylamide (PAAm) and poly(methacrylic acid) (PMAA) were utilized as stimulus responsive polymeric selectors. Uniformly sized base polymer particle was prepared by multi-step swelling and polymerization method, while the introduction of PAAm and PMAA was done by newly invented modification technique. In this technique, a solvent in which both acrylamide (AAm) and methacrylic acid (MAA) monomers are soluble, but PAAm and PMAA are insoluble, was utilized as a modification medium. The polymer particle doubly modified with PAAm and PMAA was utilized as packing material for HPLC and the stimulus responses were evaluated by changing temperature or pH to check change of the slope of a Van't Hoff plot. By using water as a mobile phase, the expected inflection point of the Van't Hoff plot was observed at upper critical solution temperature (UCST) of the polymer complexes and the temperature responsive ability was observed. Moreover, pH responsive ability was studied by using buffer of either pH 4 or 10 as mobile phase. Slope of the plot was changed in buffer of pH 4, but no change of slope was observed in the buffer of pH 10.     

Photodissociation of polycrystalline and amorphous water ice films at 157 and 193 nm

The photodissociation dynamics of amorphous solid water (ASW) films and polycrystalline ice (PCI) films at a substrate temperature of 100 K have been investigated by analyzing the time-of-flight (TOF) mass spectra of photofragment hydrogen atoms at 157 and 193 nm. For PCI films, the TOF spectrum recorded at 157 nm could be characterized by a combination of three different (fast, medium, and slow) Maxwell-Boltzmann energy distributions, while that measured at 193 nm can be fitted in terms of solely a fast component. For ASW films, the TOF spectra measured at 157 and 193 nm were both dominated by the slow component, indicating that the photofragment H atoms are accommodated to the substrate temperature by collisions. H atom formation at 193 nm is attributed to the photodissociation of water species on the ice surface, while at 157 nm it is ascribable to a mixture of surface and bulk photodissociations. Atmospheric implications in the high latitude mesopause region of the Earth are discussed.     

Regioselective N-acetylation as a route of nitro-9-phenylenediamine metabolism by rat liver cytosol

Regioselectivity in N-acetylation of nitro-0-phenylenediamine, a widely used hair dye component, by rat liver cytosolic N-acetyltransferases was studied in relation to its substituent effects on enzymatic N-acetylation of mono-substituted anilines. Nitro-p-phenylenediamine was acetylated specifically at the N4-position to afford the N4-monoacetate, a major urinary metabolite in the rat, when incubated with rat liver cytosol fortified with acetyl-coenzyme A. N1-Acetylation of nitro-p-phenylenediamine did not take place even when the N4-monoacetate was used as a substrate, suggesting a strong steric hindrance effect of the ortho nitro group on the enzymatic N1-acetylation. The steric hindrance effect of the nitro group on the cytosolic N-acetylation of the ortho amino group was revealed by a comparative study carried out by using aniline, three respective regioisomers of nitroanilines and phenylenediamines as model substrates. The comparative study also indicated the enzymatic N-acetylation of the mono-substituted anilines to be strongly influenced by the electronic effect of the substituents. Regioselective N-acetylation in the hepatic cytosol was also investigated with N1- and N4-monoacetates of 1,2,4-triaminobenzene. The monoacetates yielded the N1,N4-diacetate, another major urinary metabolite of the hair dye component, in the rat, without concomitant formation of the N2,N4-diacetate or the N1,N2,N4-triacetate. The triacetate was formed only from the N1,N2-diacetate in the enzymatic reactions. A comparative study, carried out by using N-mono-acetates of three regioisomeric phenylenediamines, indicated that the N-acetyl group had a potent steric hindrance effect on the primary amino group at the ortho position.(ABSTRACT TRUNCATED AT 250 WORDS)     

Structures of new alkaloids sessilifoliamides A-D from Stemona sessilifolia

Four new Stemona alkaloids, sessilifoliamides A-D (1-4), were isolated from the roots of Stemona sessilifolia, along with five known alkaloids, stenine (5), 2-oxostenine (6), stemoninoamide (7), tuberostemonone (8), and neotuberostemonol (9). The structures and absolute configurations of the new alkaloids were determined by the spectral studies (HRMS, IR, ¹H, ¹³C, and 2D NMR), single-crystal X-ray analyses, and chemical correlations. The absolute configuration of 7 was also determined by the modified Mosher's method.     

FTIR detection of protonation/deprotonation of key carboxyl side chains caused by redox change of the Cu(A)-heme a moiety and ligand dissociation from the heme a3-Cu(B) center of bovine heart cytochrome c oxidase

FTIR spectral changes of bovine cytochrome c oxidase (CcO) upon ligand dissociation from heme a(3)() and redox change of the Cu(A)-heme a moiety (Cu(A)Fe(a)()) were investigated. In a photosteady state under CW laser illumination at 590 nm to carbonmonoxy CcO (CcO-CO), the C-O stretching bands due to Fe(a3)()(2+)CO and Cu(B)(1+)CO were identified at 1963 and 2063 cm(-)(1), respectively, for the fully reduced (FR) state [(Cu(A)Fe(a)())(3+)Fe(a3)()(2+)Cu(B)(1+)] and at 1965 and 2061 cm(-)(1) for the mixed valence (MV) state [(Cu(A)Fe(a)())(5+)Fe(a3)()(2+)Cu(B)(1+)] in H(2)O as well as in D(2)O. For the MV state, however, another band due to Cu(B)(1+)CO was found at 2040 cm(-)(1), which was distinct from the alpha/beta conformers in the spectral behaviors, and therefore was assigned to the (Cu(A)Fe(a)())(4+)Fe(a3)()(3+)Cu(B)(1+)CO generated by back electron transfer. The FR-minus-oxidized difference spectrum in the carboxyl stretching region provided two negative bands at 1749 and 1737 cm(-)(1) in H(2)O, which were apparently merged into a single band with a band center at 1741 cm(-)(1) in D(2)O. Comparison of these spectra with those of bacterial enzymes suggests that the 1749 and 1737 cm(-)(1) bands are due to COOH groups of Glu242 and Asp51, respectively. A similar difference spectrum of the carboxyl stretching region was also obtained between (Cu(A)Fe(a)())(3+)Fe(a3)()(2+)Cu(B)(1+)CO and (Cu(A)Fe(a)())(5+)Fe(a3)()(2+)Cu(B)(1+)CO. The results indicate that an oxidation state of the (Cu(A)Fe(a)()) moiety determines the carboxyl stretching spectra. On the other hand, CO-dissociated minus CO-bound difference spectra in the FR state gave rise to a positive and a negative peaks at 1749 and 1741 cm(-)(1), respectively, in H(2)O, but mainly a negative peak at 1735 cm(-)(1) in D(2)O. It was confirmed that the absence of a positive peak is not caused by slow deuteration of protein. The corresponding difference spectrum in the MV state showed a significantly weaker positive peak at 1749 cm(-)(1) and an intense negative peak at 1741 cm(-)(1) (1737 cm(-)(1) in D(2)O). The spectral difference between the FR and MV states is explained satisfactorily by the spectral change induced by the electron back flow upon CO dissociation as described above. Thus, the changes of carboxyl stretching bands induced both by oxidation of (Cu(A)Fe(a)()) and dissociation of CO appear at similar frequencies ( approximately 1749 cm(-)(1)) but are ascribed to different carboxyl side chains.