Synthesis of 7-aryl/heteraryl-1,3-diphenyl-1,2,4-benzotriazinyls via palladium catalyzed Stille and Suzuki-Miyaura reactions

Stille and Suzuki-Miyaura reactions of 7-iodo-1,3-diphenyl-1,4-dihydro-1,2,4-benzotriazin-4-yl are presented as rare examples of cross-coupling reactions with stable organic radicals. Both the Stille and Suzuki-Miyaura reactions are in most cases high yielding but the latter are cleaner while the former are faster and are accompanied by 1,3-diphenyl-1,2,4-benzotriazin-7(H)-one as by-product. A range of 7-aryl and 7-heteroaryl-1,2,4-benzotriazinyls have been synthesized and characterized using standard spectroscopic and spectrometric means.     

Studies on the Air Oxidation of Some Arsenic(III) Compounds

The air oxidation of As(III) oxides [(PhAsO) _x and Ph₂As-O-AsPh₂] and thioesters [Ph-As(SPh)₂, Ph₂As-SPh Me-As(SPh)₂, Me₂As-SPh], in chloroform and in methanol was studied. The air oxidation in chloroform was faster probably because the solubility of dioxygen is greater than in methanol, and it is favored by the electron-withdrawing phenyl groups bound to As(III). The products obtained were the arsonic or arsinic acids and diphenyl disulfide. In one case, diphenyl disulfide and thiophenol were produced. The results can be rationalized by assuming first hydrolysis of the As(III) compounds to arsonous or arsinous acids followed by their oxidation to arsonic and arsinic acids, which should involve the binding of dioxygen to As(III). The other hypothesis assumes first the binding of dioxygen to As(III) of these oxides and thioesters followed by the decomposition of the adducts. The binding of the ground state dioxygen to As(III) may have biochemical implications for toxicity or chemotherapy of arsenic(III) compounds.     

Low-frequency dipolar electromagnetic scattering by a solid ellipsoid in lossless environment

Electromagnetic wave scattering phenomena for target identification are important in many applications related to fundamental science and engineering. Here, we present an analytical formulation for the calculation of the magnetic and electric fields that scatter off a highly conductive ellipsoidal body, located within an otherwise homogeneous and isotropic lossless medium. The primary excitation source assumes a time-harmonic magnetic dipole, precisely fixed and arbitrarily orientated that operates at low frequencies and produces the incident fields. The scattering problem itself is modeled with respect to rigorous expansions of the electromagnetic fields at the low-frequency regime in terms of positive integral powers of the real wave number of the ambient. Obviously, the Rayleigh static term and a few dynamic terms are sufficient for the purpose of the present work, as the additional terms are neglected due to their minor contribution. Therein, the classical Maxwell's theory is suitably modified, leading to intertwined either Laplace's or Poisson's equations, accompanied by the impenetrable boundary conditions for the total fields and the limiting behavior at infinity. On the other hand, the complete spatial anisotropy of the three-dimensional space is secured via the introduction of the genuine ellipsoidal coordinate system, being appropriate for tackling incrementally such scattering boundary value problems. The nonaxisymmetric fields are obtained via infinite series expansions in terms of ellipsoidal harmonic eigenfunctions, providing handy closed-form solutions in a compact fashion, whose validity is verified by a straightforward reduction to simpler geometries of the metal object. The main idea is to demonstrate an efficient methodology, according to which the constructed analytical formulae can offer the appropriate environment for a fast numerical estimation of the scattered electromagnetic fields that could be useful for real data inversion.     

Luminescent poly(phenylene vinylene) derivatives with m‐terphenyl or 2,6‐diphenylpyridine kinked segments along the main chain: Synthesis,characterization, and stimulated emission

Two new poly(phenylene vinylene)s containing m‐terphenyl or 2,6‐diphenylpyridine kinked units along the main chain were synthesized and were used as luminescent and laser materials. They were prepared from Heck coupling of 2,5‐didodecyloxy‐1,4‐divinylbenzene with 4,4″‐dibromo‐3′‐phenyl‐m‐terphenyl or 2,6‐di(4‐bromophenyl)‐4‐phenylpyridine. The kinked units along the main chain caused a partial interruption of the conjugation leading to emission at a shorter wavelength as compared with poly(p‐phenylene vinylene). The polymers presented blue‐green emission in solution and green‐yellow emission in the solid state with photoluminescence maxima at 465–497 and 546–550 nm, respectively. Polymer containing 2,6‐diphenylpyridine segments emitted at a longer wavelength than that containing m‐terphenyl and displayed higher quantum yields in solution (0.61 and 0.40, respectively). The influence of the solvent and polymer concentration on the photoluminescence characteristics was investigated. The photoluminescence properties of protonated polymer containing 2,6‐diphenylpyridine segments were investigated both in solution and in film. Amplified spontaneous emission and tunable laser action were also obtained from the two polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2214–2224, 2004     

Synthesis of poly(n‐hexyl isocyanate‐b‐N‐vinylpyrrolidone) block copolymers by the combination of anionic and nitroxide‐mediated radical polymerizations: Micellization properties in aqueous solutions

A combination of anionic and nitroxide‐mediated radical polymerizations (dual initiator) was employed for the synthesis of poly(n‐hexyl isocyanate‐b‐N‐vinylpyrrolidone) (PHIC‐b‐PNVP) block copolymers. The samples were characterized with a size exclusion chromatograph equipped with refractive‐index and light scattering detectors as well as ¹H NMR spectroscopy. Relatively good control over the molecular weights was achieved. However, rather broad molecular weight distributions were obtained. The micellar properties of the PHIC‐b‐PNVP block copolymers were studied in water, which is a selective solvent for the poly(N‐vinylpyrrolidone) blocks. Static and dynamic light scattering revealed the presence of equilibrium between the micelles and clusters. The clusters partially deaggregated with increasing temperature. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5719–5728, 2006     

A plausible explanation of the b-value in the Gutenberg-Richter law from first Principles

It is explained, from first Principles, why in the Gutenberg-Richter law (stating that the cumulative number of earthquakes N(>M) with magnitude greater than M is given by N(>M) ~ 10^−bM) the so called b-value is usually found to be around unity varying only slightly from region to region. The explanation is achieved just by applying the analysis in the natural time domain, without using any adjustable parameter.     

3,4,5-triarylisothiazoles via C-C coupling chemistry

The regiocontrolled preparation of triarylisothiazoles is presented. 3-Halo-5-phenylisothiazole-4-carbonitriles, 1 (hal=Cl) and 18 (hal=I), are converted into the corresponding 4-bromo derivatives 5 (3-hal=Cl) and 24 (3-hal=I) via a Hunsdiecker strategy while the 4-iodo analogues 7 (3-hal=Cl) and 22 (3-hal=I) are prepared via a Hoffmann and Sandmeyer strategy. Regioselective Suzuki, Stille and Negishi reactions occur at C-4 with both the 4-bromo- and 4-iodoisothiazoles 5 and 7 , the latter being more reactive than the former. 3-Iodoisothiazoles 22 and 24 fail to give regiocontrolled Suzuki, Stille or Negishi couplings, however, 4-bromo-3-iodo-5-phenylisothiazole 24 gives the regiospecific palladium catalysed Ullmann-type reaction product 3,3'-bi(4-bromo-5-phenylisothiazole) 25 . Alkali hydrolysis of 3-chloro-4,5-diphenylisothiazole 8 gives the 3-hydroxy analogue 12 which is converted into 3-bromo-4,5-diphenylisothiazole 13 with POBr(3). 3-Bromoisothiazole 13 reacts with phenylzinc chloride to give 3,4,5-triphenylisothiazole 17 but fails to undergo effective Suzuki or Stille couplings. 3,5-Diphenylisothiazole-4-carbonitrile 26 is converted into the 4-bromo- and 4-iodo-3,5-diphenylisothiazoles 30 and 34 both of which are effective for Suzuki and Stille couplings. A series of triarylisothiazoles are prepared in this manner and fully characterised.     

Identification of redox sensitive thiols of protein disulfide isomerase using isotope coded affinity technology and mass spectrometry

Regulation of the redox state of protein disulfide isomerase (PDI) is critical for its various catalytic functions. Here we describe a procedure utilizing isotope-coded affinity tag (ICAT) technology and mass spectrometry that quantitates relative changes in the dynamic thiol and disulfide states of human PDI. Human PDI contains six cysteine residues, four present in two active sites within the a and a' domains, and two present in the b' domain. ICAT labeling of human PDI indicates a difference between the redox state of the two active sites. Furthermore, under auto-oxidation conditions an approximately 80% decrease in available thiols within the a domain was detected. Surprisingly, the redox state of one of the two cysteines, Cys-295, within the b' domain was altered between the fully reduced and the auto-oxidized state of PDI while the other b' domain cysteine remained fully reduced. An interesting mono- and dioxidation modification of an invariable tryptophan residue, Trp-35, within the active site was also mapped by tandem mass spectrometry. Our findings indicate that ICAT methodology in conjunction with mass spectrometry represents a powerful tool to monitor changes in the redox state of individual cysteine residues within PDI under various conditions.     

Traces of self-organisation and long-range memory in variations of environmental radon in soil: comparative results from monitoring in Lesvos Island and Ileia (Greece)

This paper addresses issues of self-affinity, long-memory and self-organisation in variations of radon in soil recorded in Lesvos Island, Greece. Several techniques were employed, namely (a) power-law wavelet spectral fractal analysis, (b) estimation of Hurst exponents through (b1) rescaled-range, (b2) roughness-length, (b3) variogram and (a), (c) detrended fluctuation analysis, (d) investigation of fractal dimensions and (e) analysis of five block entropies: (e1) Shannon entropy, (e2) Shannon entropy per letter, (e3) conditional entropy, (e4) Tsallis entropy, and (e5) normalised Tsallis entropy. Long-lasting antipersistency was identified during a period of anomalous radon variations following fractional Brownian modelling. Remaining variations did not exhibit analogous behaviour and followed fractional Gaussian modelling. Antipersistent power-law-beta-exponent-values between 1.5 and 2.0 were detected during anomalies. Persistent values were also found. Hurst exponents were mainly within 0 < H < 0.5. Some persistent exponents (0.5 < H < 1) were also observed. Fractal dimensions were within 1.5 < D < 2. Radon anomalies presented lower fractal dimensions. Shannon entropy ranged between 0.77 ≤ H(n) ≤ 2.38, Shannon entropy per letter, between 0.19 ≤ h ⁽ⁿ⁾ ≤ 0.59, conditional entropy, between 0.01 ≤ h _(n) ≤ 0.58, Tsallis entropy, between 0.55 ≤ S _q  ≤ 1.01 and normalised Tsallis entropy between, 0.98 ≤  $\hat{S}$  ≤ 5.42 (block-size n = 4). Entropies were lower during anomalies, indicating strong self-organisation. Persistency–antipersistency switching was observed, consistent with long-memory dynamics. Potential geological sources were discussed. The asperity-model was proposed. Findings were compared to results obtained under analogous methodologies in Ileia, Greece.