New Synthetic Route and Characterisation of Phosphorus and Arsenic Heterocyclic Compounds

Herein we report synthetic routes for the preparation of 2-chloro-1,3,2-dioxarsenane 1 , O,O'-bis(5,5-dimethyl-1,3,2-dioxarsenane)-2,2-dimethyl-1,3-propanediol 3 , 2-chloro-1,3,2-dioxaphosphorinane 4 , and 2-fluoro-1,3,2-dioxaphosphorinane 5 . The new synthetic routes described here have the advantage to be simple, very clean and to lead to the desired compounds in very good yields. Compound 2-fluoro-1,3,2-dioxarsenane 2 also was prepared in good yield and is described here for the first time. Compounds 1-5 were fully characterized on the basis of NMR spectroscopic studies. Semi-empirical structural studies have been carried out and the results show that 1 and 2 exist as a mixture of two conformers, whereas only one conformer for 4 and 5 have been found. Variable temperature 1 H NMR studies reveal a fluxional behaviour for 1 and a mechanism for the inter-conversion between its two conformers is proposed.     

Self-organisation of female menopause in populations with child-care and reproductive risk

In this paper, by using a computer model for the evolution of age-structured populations, we show that in a sexual population subject to: (i) senescence, (ii) age-increasing reproductive risks, and (iii) long juvenile dependence, menopause arises spontaneously, in order to guarantee the survival of the offspring. Received: 12 September 1998 / Accepted: 14 September 1998     

Bioremediation of Marine Sediments Impacted by Petroleum

The aim of this work was to optimize the bioremediation of crude oil-contaminated sand sediment through the biostimulation technique. The soil was obtained in the mid-tide zone of Guanabara Bay, Rio de Janeiro, Brazil and was artificially contaminated with crude oil at 14 g kg^?1. Bioremediation optimization was performed using an experimental design and statistical analysis of the following factors: supplementation with commercial biosurfactant Jeneil® IBR 425 and commercial mineral NPK fertilizer. The response variable used was the biodegradation of the heavy oil fraction, HOF. The analysis of the studied factors and their interactions was executed using contour plots, Pareto diagram and ANOVA table. Experimental design results indicated that the supplementation with fertilizer at 100:25:25 C/N/P ratio and biosurfactant at 2 g kg^?1 yielded biodegradation of HOF at about 30% during 30 days of process. Some experiments were carried out using the experimental design results, yielding 65% of biodegradation of HOF and 100% of n- alkanes between C15 and C30 during 60 process days. Intrinsic biodegradation test was carried out, yielding 85% of biodegradation of n-alkanes between C15 and C30 during 30 days of process.     

Spontaneous CO Release from RuII(CO)2–Protein Complexes in Aqueous Solution,Cells, and Mice

We demonstrate that Ru^II(CO)₂–protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac‐RuCl(κ²‐H₂NCH₂CO₂)(CO)₃] (CORM‐3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO‐responsive turn‐on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM‐3. CO released from a synthetic bovine serum albumin (BSA)–Ru^II(CO)₂ complex leads to downregulation of the cytokines interleukin (IL)‐6, IL‐10, and tumor necrosis factor (TNF)‐α in cancer cells. Finally, administration of BSA–Ru^II(CO)₂ in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of Ru^II(CO)₂–protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo.     

Deciphering the Non‐Equivalence of Serine and Threonine O‐Glycosylation Points: Implications for Molecular Recognition of the Tn Antigen by an anti‐MUC1 Antibody

The structural features of MUC1‐like glycopeptides bearing the Tn antigen (α‐O‐GalNAc‐Ser/Thr) in complex with an anti MUC‐1 antibody are reported at atomic resolution. For the α‐O‐GalNAc‐Ser derivative, the glycosidic linkage adopts a high‐energy conformation, barely populated in the free state. This unusual structure (also observed in an α‐S‐GalNAc‐Cys mimic) is stabilized by hydrogen bonds between the peptidic fragment and the sugar. The selection of a particular peptide structure by the antibody is thus propagated to the carbohydrate through carbohydrate/peptide contacts, which force a change in the orientation of the sugar moiety. This seems to be unfeasible in the α‐O‐GalNAc‐Thr glycopeptide owing to the more limited flexibility of the side chain imposed by the methyl group. Our data demonstrate the non‐equivalence of Ser and Thr O‐glycosylation points in molecular recognition processes. These features provide insight into the occurrence in nature of the APDTRP epitope for anti‐MUC1 antibodies.     

Astrophysical S-factors from asymptotic normalization coefficients

S-factors for direct capture reactions can be found at astrophysical energies from asymptotic normalization coefficients which provide the normalization of the tail of the overlap function. For example the overlap for ⁸B → ⁷Be+p defines the S-factor for ⁷Be (p, γ)⁸B. Peripheral transfer reactions offer a technique to determine these asymptotic normalization coefficients. As a test of the technique, the ¹⁶O(³He, d)¹⁷F reaction has been used to determine asymptotic normalization coefficients for transitions to the ground and first excited states of ¹⁷F. The S-factors for ¹⁶O(p, γ)¹⁷F calculated from these ¹⁷F → ¹⁶O+p asymptotic normalization coefficients are found to be in very good agreement with recent measurements. Following the same technique, the ¹⁰B(⁷Be, ⁸B)⁹Be and ¹⁴N(⁷Be, ⁸B)¹³C reactions have been used to measure the asymptotic normalization coefficient for ⁷Be(p, γ)⁸B. This result provides an indirect determination of S ₁₇(0).     

Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.     

Isolation of NO(3)(-)-N as 1-phenylazo-2-naphthol (Sudan-1) for measurement of delta(15)N

The conversion of nitrate (NO(3)(-)) to 1-phenylazo-2-naphthol (Sudan-1) has been examined as a method for natural abundance measurement of delta(15)N of NO(3)(-). The reaction results in dilution of NO(3)(-)-N with only one reagent-derived N and the product is readily concentrated from dilute samples by reverse phase chromatography. There is systematic isotopic fractionation during the reaction, but this can be allowed for by analysing known NO(3)(-) standards along with each sample set. Sudan-1 prepared from surface water samples containing approximately 50 &mgr;g NO(3)(-)-N can be analysed by automated continuous flow isotope ratio mass spectrometry with a precision of 0.2 per thousand (one standard deviation) and the accuracy is not affected by interference from other nitrogenous species in the sample or reagents. Copyright 1999 John Wiley & Sons, Ltd.