Phenol Photonitration and Photonitrosation upon Nitrite Photolysis in basic solution

Nitrophenols have been detected in some Antarctic lakes, the water of which is basic and rich in nitrate, nitrite and other nutrients. Nitrate or nitrite photolysis could be a possible reaction to explain the presence of these compounds. This work presents evidence for the formation of 2-nitrophenol (2NP), 4-nitrophenol (4NP) and 4-nitrosophenol (4NOP) upon UV irradiation of phenol and nitrite in aerated basic solutions.

The pH dependence of the 2NP initial formation rate is different from those of 4NP and 4NOP. The dependence of the first mainly reflects the phenol/phenolate equilibrium, with phenol yielding 2NP at a higher rate than phenolate. In the case of 4NOP, the initial formation rate vs pH has a maximum at pH 9.5. The pH dependence of 4NOP formation rate suggests that three pathways are likely to operate: nitrosation of undissociated phenol by N₂O₃, prevailing at pH<8.7, nitrosation of phenolate by N₂O₃, prevailing in the pH interval 8.7–10.8, and reaction between phenoxyl radical and ^?NO, prevailing at pH>10.8. Phenol nitrosation by N₂O₃ is favoured when phenol is negatively charged (phenolate), but it is also disfavoured at alkaline pH values, owing to the depletion of N₂O₃ (the nitrosating agent) by basic hydrolysis. Differently from 2NP, the initial formation rate vs pH of 4NP is very similar to that of 4NOP, suggesting that 4NP may originate from the oxidation of 4NOP. Moreover, while in neutral and acidic solutions the formation rate of 2NP is slightly higher than that of 4NP, in the pH interval 8–12 the formation of 4NP is much more rapid than that of 2NP. This indicates that the pH of natural waters influences the ratio of nitroisomers.     

Thiocarbonylthio end group removal from RAFT‐synthesized polymers by a radical‐induced process

The removal of thiocarbonylthio end groups by radical‐addition‐fragmentation‐ coupling from polymers synthesized by RAFT polymerization has been studied. We found that a method, which involves heating the polymer with a large excess (20 molar equivalents) of azobis(isobutyronitrile) (AIBN), while successful with methacrylic polymers, is less effective with styrenic or acrylic polymers and provides only partial end group removal. This is attributed to the propagating radicals generated from the latter polymers being poor radical leaving groups relative to the cyanoisopropyl radical. Similar use of lauroyl peroxide (LPO) completely removes the thiocarbonylthio groups from styrenic or acrylic polymers but, even with LPO in large excess, produces a polymer with a bimodal molecular weight distribution. The formation of a peak of double molecular weight is indicative of the occurrence of self‐termination and ineffective radical trapping. We now report that by use of a combination of LPO (2 molar equivalents) and AIBN (20 molar equivalents) we are able to completely remove thiocarbonylthio end groups of styrenic or acrylic polymers and minimize the occurrence of self termination. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6704–6714, 2009     

An ecogenetic model

A model for the effects of a predator on a genetically distinguished prey population is formulated and investigated. The predator-free system settles at an equilibrium which can be destabilized by the predators if a suitably defined parameter, the predator invasion number, exceeds a threshold. The system can then coexist at a stable equilibrium or via persistent oscillations.     

Plane algebraic curves with many cusps,with an appendix by Eugenii Shustin

The maximum number \(k(d)\) of cusps on a plane algebraic curve of degree \(d\) is an open classical problem that dates back to the nineteenth century. A related open problem is the asymptotic value ( \(a.v.\) ) of the number of cusps on plane curves, that is \(a.v.=\limsup _{d\rightarrow \infty } k(d)/{d^2}\) . In this paper, we improve the best known lower bound for the asymptotic value by constructing curves with the largest known number of cusps for infinitely many degrees. Some particular curves of relatively low degree with many cusps are constructed too. The “Appendix” to this paper is devoted to the case of degree 11 and it is due to E. Shustin.     

Method development for simultaneous multi-element determination of hydride forming elements (As, Bi, Ge, Sb, Se, Sn) and Hg by microwave induced plasma-optical emission spectrometry using integrated continuous-microflow ultrasonic nebulizer-hydride generator sample introduction system

The analytical potential of a coupled continuous-microflow ultrasonic nebulizer dual capillary system (µ-USN/DCS)–Ar/He mixed gas microwave induced plasma-optical emission spectrometry (MIP-OES) has been evaluated for the purpose of determination of hydride forming elements (As, Bi, Ge, Sb, Se, Sn) and a vapor element (Hg). A univariate approach and the simplex optimization procedure were used to achieve optimized conditions and derive analytical figures of merit. Analytical performance of the ultrasonic nebulization system was characterized by determination of the limits of detection (LODs) and precision (RSDs) with the µ-USN/DCS observed at a 15 µL min^{− 1} flow rate. At flows of ≤ 15 µL min^{− 1}, solvent loading in the plasma is sufficiently low to make desolvation unnecessary. The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times of the standard deviation of the blank (LOD, 3σ_blank criterion, peak height) were 1.2, 5.4, 6.3, 1.8, 3.3, 2.4 and 3.0 ng mL^{− 1} for As, Bi, Ge, Sb, Se, Sn and Hg, respectively. The method offers relatively good precision (RSD ranged from 8 to 11%) for liquid analysis and microsampling capability. Interference effects by transition metals have been shown to be corrected by the addition of thiourea, as a pre-reducing agent and masking agent. The accuracy of the method was verified using certified reference materials (DOLT-2, GBW 07302, SRM 2710, and SRM 1643e) and by the aqueous standard calibration technique. The measured contents of elements in reference materials were in satisfactory agreement with the certified values.     

A New Light on Nets of C*-Algebras and Their Representations

The present paper deals with the question of representability of nets of C*-algebras whose underlying poset, indexing the net, is not upward directed. A particular class of nets, called C*-net bundles, is classified in terms of C*-dynamical systems having as group the fundamental group of the poset. Any net of C*-algebras has a canonical morphism into a C*-net bundle, the enveloping net bundle, which generalizes the notion of universal C*-algebra given by Fredenhagen to nonsimply connected posets. This allows a classification of nets; in particular, we call injective those nets such that the canonical morphism is faithful. Injectivity turns out to be equivalent to the existence of faithful representations. We further relate injectivity to a generalized Čech cocycle of the net, and this allows us to give examples of nets exhausting the above classification.     

Representations of Nets of C*-Algebras over S 1

In recent times a new kind of representations has been used to describe superselection sectors of the observable net over a curved spacetime, taking into account the effects of the fundamental group of the spacetime. Using this notion of representation, we prove that any net of C^*-algebras over S ¹ admits faithful representations, and when the net is covariant under Diff(S ¹), it admits representations covariant under any amenable subgroup of Diff(S ¹).     

Sigmoidal transformations and the Euler-Maclaurin expansion for evaluating certain Hadamard finite-part integrals

Summary. Starting with some results of Lyness concerning the Euler-Maclaurin expansion of Cauchy principal value integrals over it is shown how, by the use of sigmoidal transformations, good approximations can be found for the Hadamard finite-part integral where The analysis is illustrated by some numerical examples. Received March 13, 1996     

New Tetracyclic Colchicinoids from the Reaction of N‐Deacetylthiocolchicine and N‐Deacetylcolchicine with Nitrous Acid and tert‐Butyl Nitrite

Reaction of N‐deacetylthiocolchicine ( 3 ) and N‐deacetylcolchicine ( 4 ) with nitrous acid (HONO) furnished the new tetracyclic colchicinoids 5 and 6 , as well as the Demyanov‐rearrangement products 7 and 8 . Starting from 3 , the pyrazole‐containing tetracycle 9 was obtained. The novel compounds were characterized spectroscopically, and an X‐ray crystal‐structure analysis of 5 allowed us to establish the absolute configurations at the stereogenic centers.     

REACTIVITY OF MACROMONOMERS IN FREE RADICAL POLYMERIZATION

Abstract

Macromonomers are linear polymeric o r oligomeric species which, because of the presence of a reactive end group, have the potential either to polymerize with themselves or with comonomers. The reactive group is most commonly a vinyl group that can participate in free radical polymerization, but any polymerizable end group, such as epoxy, bis-hydroxy, etc., is sufficient for the molecule to be classified as a macromonomer. The words “macromer” and “macromonomer” are often used interchangeably, although the former term was introduced originally as a trademark of CPC International to describe the macromonomers discovered by Milkovich [1].