Novel photodegradation of the antifungal antibiotic pyrrolnitrin in anhydrous and aqueous aprotic solvents

The UV irradiation of pyrrolnitrin (1a), which is an antibiotic clinically useful against dermatophytosis and possesses a unique 2-(pyrrol-3-yl)nitrobenzene moiety in the molecule, in an anhydrous aprotic solvent resulted in the exclusive formation of transient 7,4'-dichlorospiro[1,3-dihydrobenzo(c)isoxazole-3,3'-pyrrolin-2'-one] (2a) via the intramolecular oxidation of the juxtaposed pyrrole ring by the triplet-excited nitro group. The irradiation in an aqueous aprotic solvent, however, allowed the concurrent occurrence of intramolecular cyclization by the singlet-excited nitro group in 1a and the hydroxylation at the 2-position of the pyrrole ring by water to afford 3,7-dichloro-8-hydroxy-8,8a-dihydropyrrolo[2,3-b]indol-2-one (3a), accompanied by the formation of 2a. Elongation of the irradiation time in these photoreactions caused a rapid consumption of the products, 2a and 3a, to give undetermined polar polymeric products. The present results indicate that the photodegradation of 1a is significantly influenced by the presence of water in the reaction media and by the nature of its excited state. Thus, the loss of the antifungal activities by the photosensitive antibiotic 1a was chemically proved.     

Oligo(octithienylene-diethynylene)s as unprecedentedly long conjugated nanomolecules

[reaction: see text] A series of oligo(octithienylene-diethynylene)s alternately composed of octithiophene and diacetylene units have been prepared by a random Eglinton coupling reaction among mono- and diethynyloctithiophenes. The largest compound isolated in the oligomeric series is comprised of twelve octithiophene units and eleven diacetylene units, and its molecular length reaches ca. 43 nm, which is the longest among single-component conjugated nanomolecules.     

Total synthesis of ecteinascidin 743

The total synthesis of ecteinascidin 743 (1), an extremely potent antitumor agent, has been accomplished. The synthesis features Ugi's 4CC reaction, intramolecular Heck reaction, phenol-aldehyde cyclization, and acid-induced intramolecular sulfide formation.     

Determination of sulphide ion at trace levels by ethylation and gas chromatography

Summary A method is described for the determination of sulphide ion in aqueous samples by gas chromatography. Sulphide is ethylated with diethyl sulphate and the resulting diethyl sulphide is extracted with chloroform and determined with a gas chromatograph equipped with a flame ionization or a flame photometric detector. In the case of a flame photometric detector, the detection limit for sulphide ion is 0.05 g/ml. Other anions commonly found with sulphide ion do not interfere. Sulphide ion in spring waters was analysed by this new method and for comparison also by colorimetry (methylene blue). The results revealed the reliability of the new method.

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Bestimmung von Sulfidspuren durch Ethylierung und Gas-Chromatographie

Zusammenfassung Sulfid wird mit Diethylsulfat ethyliert, das gebildete Diethylsulfid mit Chloroform extrahiert und gaschromatographisch mit Hilfe eines Flammenionisationsoder eines flammenphotometrischen Detektors bestimmt. Die Nachweisgrenze beträgt 0,05 g S/ml für den FPD. Anionen, die üblicherweise mit Sulfid zusammen vorkommen, stören nicht. Das Verfahren wurde, im Vergleich mit der colorimetrischen Methylenblaumethode, auf Quellwasser angewendet. Es wurde gute Übereinstimmung der Ergebnisse erzielt.

     

Effect of temporal resolution on the estimation of left ventricular function by cardiac MR imaging

The aim of this study was to investigate the effect of temporal resolution on the estimation of left ventricular (LV) function by cardiac magnetic resonance (MR) imaging using a steady-state free precession (SSFP) sequence. Left ventricular function was assessed by cine MR imaging using a segmented SSFP sequence in 10 healthy volunteers. Views per segment (VPS) were set at 8 and 20, resulting in high and low true temporal resolution, respectively. Irrespective of VPS, images were reconstructed at 40 cardiac phases, providing high apparent temporal resolution. Data were analyzed using 40, 20 and 10 phases to simulate different apparent temporal resolutions. Increasing the cardiac phases used for analysis slightly decreased mean end-systolic volume (ESV) and slightly increased mean ejection fraction (EF). No substantial difference in estimates of end-diastolic volume (EDV) was found between VPSs of 8 and 20. Imaging with a VPS of 20 yielded a larger ESV and smaller EF than imaging with a VPS of 8 when 40 phases were used. In conclusion, low true temporal resolution causes overestimation of ESV and underestimation of EF. Improvement of apparent temporal resolution mildly reduces but does not eliminate the errors caused by low true temporal resolution.     

Rationality, regularity, and -cofiniteness

We demonstrate that, for vertex operator algebras of CFT type, -cofiniteness and rationality is equivalent to regularity. For -cofinite vertex operator algebras, we show that irreducible weak modules are ordinary modules and -cofinite, is -cofinite, and the fusion rules are finite.

     

Nearest-neighbor configuration in (GaIn)(NAs) probed by x-ray absorption spectroscopy

Ga(1-x)In(x)N(y)As(1-y) is a promising material system for the fabrication of inexpensive "last-mile" optoelectronic components. However, details of its atomic arrangement and the relationship to observed optical properties is not fully known. Particularly, a blueshift of emission wavelength is observed after annealing. In this work, we use x-ray absorption fine structure to study the chemical environment around N atoms in the material before and after annealing. We find that as-grown molecular beam epitaxy material consists of a nearly random distribution of atoms, while postannealed material shows segregation of In toward N. Ab initio simulations show that this short-range ordering creates a more thermodynamically stable alloy and is responsible for blueshifting the emission.     

Synthesis of (--)-Muricatacin via alpha- and alpha'-C-H bond functionalization of tetrahydrofuran

(--)-Muricatacin, a potent cytotoxic (4R,5R)-5-hydroxyheptadecan-4-olide, has been synthesized through alpha-C--H hydroxyalkylation and alpha'-C--H oxidation of tetrahydrofuran. This study presents a novel method for C--H bond functionalization as a means for preparing gamma-(hydroxyalkyl)-gamma-butyrolactones.     

Electrolytic synthesis of ammonia in molten salts under atmospheric pressure

Ammonia was successfully synthesized by using a new electrochemical reaction with high current efficiency at atmospheric pressure and at lower temperatures than the Haber-Bosch process. In this method, nitride ion (N3-), which is produced by the reduction from nitrogen gas at the cathode, is anodically oxidized and reacts with hydrogen to produce ammonia at the anode.     

Two types of diffusions at the cathode/electrolyte interface in IT-SOFCs

Analytical transmission electron microscopy, in particular with the combination of energy dispersive X-ray spectroscopy (EDX) and electron energy-loss spectroscopy (EELS), has been performed to investigate the microstructure and microchemistry of the interfacial region between the cathode (La_0.6Sr_0.4Co_0.8Fe_0.2O₃, LSCF) and the electrolyte (Gd-doped ceria, GDC). Two types of diffusions, mutual diffusion between cathode and electrolyte as well as the diffusion along grain boundaries, have been clarified. These diffusions suggest that the chemical stability of LSCF and GDC are not as good as previously reported. The results are more noteworthy if we take into consideration the fact that such interdiffusions occur even during the sintering process of cell preparation.