Road traffic pollution and childhood leukemia: a nationwide case-control study in Italy

Background The association of childhood leukemia with traffic pollution was considered in a number of studies from 1989 onwards, with results not entirely consistent and little information regarding subtypes. Aim of the study We used the data of the Italian SETIL case-control on childhood leukemia to explore the risk by leukemia subtypes associated to exposure to vehicular traffic. Methods We included in the analyses 648 cases of childhood leukemia (565 Acute lymphoblastic–ALL and 80 Acute non lymphoblastic-AnLL) and 980 controls. Information on traffic exposure was collected from questionnaire interviews and from the geocoding of house addresses, for all periods of life of the children. Results We observed an increase in risk for AnLL, and at a lower extent for ALL, with indicators of exposure to traffic pollutants. In particular, the risk was associated to the report of closeness of the house to traffic lights and to the passage of trucks (OR: 1.76; 95% CI 1.03–3.01 for ALL and 6.35; 95% CI 2.59–15.6 for AnLL). The association was shown also in the analyses limited to AML and in the stratified analyses and in respect to the house in different period of life. Conclusions Results from the SETIL study provide some support to the association of traffic related exposure and risk for AnLL, but at a lesser extent for ALL. Our conclusion highlights the need for leukemia type specific analyses in future studies. Results support the need of controlling exposure from traffic pollution, even if knowledge is not complete

Rheological properties of guar and its methyl, hydroxypropyl and hydroxypropyl-methyl derivatives in semidilute and concentrated aqueous solutions

We report on a comparative study of the theological properties of guar [GG], methyl guar [MG], hydroxypropyl guar [HPG] and hydroxypropyl-methyl guar [MHPG] polymers aqueous solutions in semidilute (both unentangled and entangled) and concentrated regimes, using oscillatory and steady-shear techniques. In the dilute regime, molecular weights and radii of gyration have been investigated by means of light scattering measurements. Data obtained from steady-shear rheology were satisfactorily analyzed according to Cross model and the effects of polymer concentration and temperature on the theological behaviour of guar and guar derivatives have been investigated and discussed in terms of theological parameters, such as the zero-shear viscosity eta(0), the characteristic time tau and critical coil-overlap concentration C*. The storage and loss moduli of guar and guar derivatives aqueous solutions have been measured using angular frequencies in the range between 10(-3) and 10 rad/s. The data have been analyzed using the "blob" model for semidilute solutions and the scaling approach proposed by Rubinstein, Dobrynin and Colby for concentrated solutions. These theological parameters obey a time-concentration superposition principle, so that master curves can be constructed over a wide frequency range. Moreover, we show that, at lower temperatures, these systems behave as thermo-rheological simple systems, in that the oscillatory shear response at different temperatures can be superimposed according to the empirical time- temperature superposition principle. Although these systems can be conveniently described within a unifying scaling model, the behaviour of guar derivatives are somewhat different. At higher temperatures, relatively small deviations from the scaling behaviour of the storage modulus of MG and MHPG polymers were observed. These findings can be justified by a structural re-organization of the macromolecular network, due to the hydrophobic interactions. (C) 2010 Elsevier Ltd. All rights reserved

Acid gel formation in (pseudo) alginates with and without G blocks produced by epimerising mannuronan with C5 epimerases

The main scope of this paper is the characterization, in terms of viscoelastic and mechanical properties, of acid gels formed from solutions of mannuronan ALG (0%G/0%GG) and its enzymatically epimerised products. The epimerised products were obtained using recombinantly produced mannuronan C5 epimerases named AlgE1 and AlgE4, which catalyse the conversion of mannuronic residues into guluronic (G) and guluronic-mannuronic (GM) blocks, respectively. The products used in this study resulted from either the action of AlgE1 on mannuronan for 5 and 24 h (named ALG(44%G/32%GG) and ALG (68%G/59%GG), respectively) or AlgE4 on mannuronan (named ALG (47%G/0%GG)). d-gluconic acid-δ-lactone (GDL) was used as H+-donor to produce acidic gels. ALG (0%G/0%GG) yields strong, stable solid-like structures. As predicted by circular dichroism measurements performed at different pH, gelation of ALG (47%G/0%GG) occurs at lower values of pH (∼1) than those obtainable using GDL. Hydrochloric acid was therefore added to ALG (47%G/0%GG) solutions yielding rapid sol-gel transitions and gels with a remarkable resistance to thermal treatment. The introduction of guluronic residues along the chain (ALG (44%G/32%GG)) causes a reduction in the storage modulus at the equilibrium with respect to that of ALG (0%G/0%GG) and the occurrence of negligible syneresis at the highest polymer concentrations. The increase in the average length of the G blocks (ALG (68%G/59%GG)) is accompanied by a further increase in the storage modulus without the occurrence of any significant syneresis. © 2006 Elsevier Ltd. All rights reserved.The main scope of this paper is the characterization, in terms of viscoelastic and mechanical properties, of acid gels formed from solutions of mannuronan ALG (0%G/0%GG) and its enzymatically epimerised products. The epimerised products were obtained using recombinantly produced mannuronan C5 epimerases named AlgE1 and AlgE4, which catalyse the conversion of mannuronic residues into guluronic (G) and guluronic–mannuronic (GM) blocks, respectively. The products used in this study resulted from either the action of AlgE1 on mannuronan for 5 and 24 h (named ALG(44%G/32%GG) and ALG (68%G/59%GG), respectively) or AlgE4 on mannuronan (named ALG (47%G/0%GG)). Dgluconic acid-d-lactone (GDL) was used as HC-donor to produce acidic gels. ALG (0%G/0%GG) yields strong, stable solid-like structures. As predicted by circular dichroism measurements performed at different pH, gelation of ALG (47%G/0%GG) occurs at lower values of pH (w1) than those obtainable using GDL. Hydrochloric acid was therefore added to ALG (47%G/0%GG) solutions yielding rapid sol–gel transitions and gels with a remarkable resistance to thermal treatment. The introduction of guluronic residues along the chain (ALG (44%G/32%GG)) causes a reduction in the storage modulus at the equilibrium with respect to that of ALG (0%G/0%GG) and the occurrence of negligible syneresis at the highest polymer concentrations. The increase in the average length of the G blocks (ALG (68%G/59%GG)) is accompanied by a further increase in the storage modulus without the occurrence of any significant syneresis

Comparative studies on solution characteristics of mannuronan epimerized by C-5 epimerases

Both dilute and concentrated solutions of bacterial Mannuronan (MANNA) and its epimerized products by AlgE1 at 5 and 24 h, named MANNAEp1t5h and MANNAEp1t24h, respectively, and AlgE4 (MANNAEp4) have been studied as a function of variables such as polymer concentration and ionic strength (NaCl) in order to investigate the macromolecular solution properties of these innovative polyuronic acids having the same charge density but different composition and sequence of b-D-mannuronic acid (-M-), a-L-guluronic acid (-G-) or MGblocks. Measurements of intrinsic viscosity [h] as a function of ionic strength, I, by capillary viscometry has led to an estimate of the Smidsrød- Haug parameter B, an index useful to characterize the stiffness of polymeric chains. The results are largely consistent with much of the published data relative to chain extension and conformational freedom around the torsional angles of the glycosidic linkages occurring in alginates. Steady shear rheometry provided information about the coil-overlapping parameter c*, which marks the transition from dilute to concentrated solution. The slopes of the double logarithmic plots of hsp vs. c[h] both at low and high degrees of coil overlap suggest that all samples solutions behave like linear polymer entangled network systems. The value of c* is strictly influenced by the stiffness of the chains, and hence by the primary structure. Dynamic shear rheometry shows that the frequency dependence of dynamic viscosity is only partially superimposable to the shear rate dependence of viscosity. Such behaviour may be ascribed to the presence of semiflexible polymeric coils in a non-totally destructured entangled state. By solvent/non-solvent (H2O/isopropanol) fractionation carried out on mannuronan, a set of samples with different average molecular weights and narrow polydispersities were obtained. Triple detection GPC allowed the evalutation of the Mark–Houwink–Sakurada parameters as well as of the characteristic ratio CN for one of the fractionated MANNA samples. The chain persistence length was estimated by the wormlike chain model

Ionic gel formation of a (pseudo)alginate characterised by an alternating MG sequence produced by epimerising mannuronan with AlgE4

The scope of this paper is the characterization, in terms of viscoelastic and mechanical properties, of ionic gels obtained from solutions of pseudoalginates characterized by a strictly alternating MG sequence (ALG(47%, 0%GG)) in the presence of calcium ions. ALG(47%, 0%GG) was obtained using a recombinantly produced mannuronan C-5 epimerase, named AlgE4 which catalyses the conversion of mannuronic residues into guluronic–mannuronic (GM) blocks. It was established that the kinetics of gelation as well as the mechanical properties and degree of syneresis of the ensuing gels are markedly dependent on both polymer concentration and Ca2+ content. The molecular dynamic investigation was carried out on a comparative basis between poly(MG) vs. poly(G) and demonstrated that in the case of poly(MG) the structural unit composed by two calcium paired MG oligomer enjoy a higher degree of Xexibility in comparison to the equivalent structure based on GG sequence. Furthermore, the electrostatic interaction between Ca2+ ions and carboxylate groups of M and G units is the main driving force to gel formation

C(6)-oxidation followed by C(5)-epimerization of guar gum studied by high field NMR

Guar gum, a a-D-(1f4)-linked D-mannan with R-D galactopyranosyl units attached as side groups, was treated with R-galactosidase, an enzyme that splits off the R-D-galactosyl units to obtain a galactomannan with a low galactose content. The galactose-depleted polysaccharide was then selectively oxidized in C(6) position and epimerized using mannuronan C(5)-epimerases, namely AlgE1, AlgE4, AlgE6, and their mixtures, obtaining new pseudo-alginates. In this paper, we report a full high field 1D and 2D NMR study of guar gum as such and of the galactose-depleted, oxidized and epimerized compounds, respectively. From the 1H NMR spectra, the degree of epimerization, the distribution of mannuronic acid (M) and guluronic acid (G)residues and the average G-block length, NG>1, were obtained. By means of NMR diffusion experiments, it was also shown that no significant degradation of the polysaccharide occurs as a consequence of the epimerization reaction