Mixed micellar aggregates of nonionic and anionic surfactants with short hydrophobic tails: a microcalorimetric study

Apparent molar relative enthalpies were measured for the nonionic ethoxylated surfactant CH(3)-(CH(2))(5)-(OCH(2)-CH(2))(5)OH (C(6)E(5)) in aqueous solution at constant molality of the ionic surfactant CH(3)-(CH(2))(5)-SO(-)(3)Na(+)(C(6)SNa) at 25 degrees C. The experimental data obtained by a stepwise dilution process allowed evaluation of the C(6)E(5) first interaction parameter at several constant molalities of C(6)SNa. The C(6)E(5) critical micelle composition as a function of the C(6)SNa molality was also estimated. The experimental calorimetric data, together with the mixed micelles composition computed in the past by some of us [Ciccarelli et al., Langmuir 14, 7130 (1998)], allowed computation of the Deltah(Mic) of micellization. The experimental data are compared to those predicted by the ideal solution model and regular solution model of mixed micellization. From a calorimetric study performed on the water-hexanol-C(6)SNa and water-penthaethylene glycol-C(6)SNa model systems, it can be argued that the interactions among the hydrophilic heads in the C(6)E(5)-C(6)SNa mixed micelles prevail on the contribution of the hydrophobic tails in ruling the enthalpic properties of the system.     

Deformation behavior of thin,compliant layers under tensile loading conditions

In this article, a connection is made between the behavior of thin layers of Newtonian liquids under tensile loading conditions and the behavior of highly deformable elastic or viscoelastic solids, which are more commonly used as adhesives. The behavior of Newtonian liquids is understood in the most quantitative detail and serves as a starting point for understanding the origins of fingering and cavitation instabilities that appear when the tensile deformation rates applied to these layers are sufficiently large. Similar instabilities appear in solid systems and can be attributed to common features of the stress distribution for incompressible liquids and solids. A unifying treatment is presented that can be used to understand the overall deformation behavior and adhesive performance of a wide variety of solid and liquid systems that are typically applied as thin layers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4023–4043, 2004     

Intercalation of α,ω-alkyldiamines in layered α-zirconium phosphate and the inclusion behaviour of some of the intercalates obtained

The paper reports a study on the intercalation mechanism of NH₂(CH₂) _n NH₂ (withn=2, 4, 6, 8, 10) diamines in layered Zr(HOPO₃)₂·H₂O, performed by titrating the host with aqueous solutions of amines at 80°C. The intercalation reactions occur stepwise according to the ‘moving boundary’ model, with the formation of a number of intermediate intercalation compounds of formula Zr(HOPO₃)₂·xNH₂(CH₂) _n NH₂ (0<x<1) before obtaining the fully intercalated ones (x=1). For each diamine the batch titration curve and a diagram of the phases involved in the interaclation reaction are reported. Twenty-two intercalation compounds have been isolated and characterized by their composition, XRD patterns and thermal behaviour, and information on the disposition of the guests within the interlayer region have been derived. At full intercalation the diamines form a monolayer of extended molecules with their axis inclined at 58° to the plane of the sheet. The terminal amino groups are protonated by the —POH groups of the host, thus each diamine binds adjacent layers and, in a sense, transforms a layered structure into a framework structure that may have an accessible or potentially accessible porosity. The intercalation compound Zr(HOPO₃)₂·0.5NH₂(CH₂)₈NH₂ is indeed able to include polar molecules such as water and short chain alkanols.     

Coordinating properties of C2-symmetric chiral bis(oxazolinylpyridinyl)dioxolane ligands

Metal complexes of general formula M(L)X₂ and M(L)X₃ [L = (4S,5S)-2,2-dimethyl-4,5-bis{6-[(4,5-dihydro-4-(S)-(1-methylethyl)oxazol-2-yl)pyridin-2-yl]}-1,3-dioxolane] were obtained by reacting, respectively, Co^II, Cu^II, Ni^II, and Zn^II nitrate salts and the Rh^III chloride salt, with a chiral C₂-symmetric bis(oxazolinylpyridinyl)dioxolane (L) ligand, in MeOH/CHCl₃ solution. A single crystal X-ray analysis was carried out on [Ni(L)(OH₂)₂](NO₃)₂ · 2H₂O and the molecular structure of L was also determined. In the free ligand the two symmetric arms are essentially planar and oriented nearly perpendicular to the dioxolane average plane. In the Ni complex one seven-membered and two five-membered chelation rings are formed. The metal atom also lies on the C₂ axis, and two symmetry-related water molecules complete the octahedral coordination environment. Both compounds crystallize in chiral space groups; the ligand crystallizes in orthorhombic system, space group C 2 2 2₁, Z = 4; the nickel complex crystallizes in tetragonal system, space group P 4₃ 2₁ 2, Z = 4.     

Human Y‐chromosome SNP characterization by multiplex amplified product‐length polymorphism analysis

We designed an allele‐specific amplification protocol to optimize Y‐chromosome SNP typing, which is an unavoidable step for defining the phylogenetic status of paternal lineages. It allows the simultaneous highly specific definition of up to six mutations in a single reaction by amplification fragment length polymorphism (AFLP) without the need of specialized equipment, at a considerably lower cost than that based on single‐base primer extension (SNaPshot?) technology or PCR‐RFLP systems, requiring as little as 0.5 ng DNA and compatible with the small fragments characteristic of low‐quality DNA. By designation of two primers recognizing the derived and ancestral state for each SNP, which can be differentiated by size by the addition of a noncomplementary nucleotide tail, we could define major Y clades E, F, K, R, Q, and subhaplogroups R1, R1a, R1b, R1b1b, R1b1c, J1, J2, G1, G2, I1, Q1a3, and Q1a3a1 through amplification fragments that ranged between 60 and 158bp.     

Preparation,characterization, and structure of zirconium fluoride alkylamino-N,N-bis methylphosphonates: a new design for layered zirconium diphosphonates with a poorly hindered interlayer region

This paper reports the preparation and characterization of the homologous series of layered zirconium fluoride n-alkylamino-N,N-bis methylphosphonates, of general formula ZrF(O(3)PCH(2))(2)NHC(n)H(2n+1) (n = 1, 2, 3, 4, 5, 6, 8, 9, 10), in which the two phosphonic groups of each diphosphonate building block participate in the assembly of a single lamella, because they are joined to zirconium atoms belonging to the same layer. The crystal structure of one of the series of these zirconium diphosphonates, ZrF(O(3)PCH(2))(2)NHC(5)H(11), has been solved "ab initio" by X-ray powder diffraction data. The structure is monoclinic, space group P2(1)/c. The zwitterionic character of the diphosphonate moiety is a distinctive feature which acts as a structure-orienting factor, generating a layer framework which is different from the other structures known for zirconium phosphates and phosphonates. This compound undergoes a phase transition at 117 degrees C which involves a rearrangement of the interlayer alkyl chains. The structure of the high-temperature phase has been refined by the Rietveld method. Because only one organic residue is associated with two phosphonate tetrahedra, a poorly hindered interlayer region is formed, and alkyl chains bonded to adjacent layers are interdigitated. Preliminary experiments have shown that these compounds are able to intercalate organic molecules, such as n-alkanols, from very dilute water solutions.     

Spatial trapping of short pulses in Ti-indiffused LiNbO(3) waveguides

We show numerically and experimentally that spatial trapping can be induced in quadratic media even if the pump pulse's duration is shorter than the group-delay mismatch between fundamental wave and second-harmonic components. The influence of phase mismatch and pulse power on the trapping effect is discussed. Spatial, temporal, and spectral behaviors that accompany self-trapped propagation are highlighted.     

Enhancement of shake-up structure in alkali-metal-ion exchanged forms of α-Zr(HPO4)2 by sputtering

Mg Kα ESCA spectra of several α-Zr(PO₄)₂M₂ compounds (M = Li⁺, Na⁺, K⁺, Cs⁺) have been obtained. Satellite structure is observed at ～7–8 eV from the main P 2s peak (corresponding to ～15–16 eV from the main Zr 3d_{$\text{5}\text{2}$} peak). The intensity of the satellite depends on the counter-ion intercalated. For a given counter-ion it is strongly increased by sputtering, the rate of increase being also dependent on the counter-ion. This observation is interpreted mainly in terms of electron-defect formation similar to that involved in the formation of colour centres by radiation damage, and subsequent charge-transfer shake-up of the trapped electrons to the electron-deficient phosphorus or Zr(IV) centres.     

Transport numbers of sodium polyacrylate in aqueous solutions

The moving boundary technique has been used to measure independently the transference numbers of macroion and counterions in water solutions of sodium polyacrylate at 25° and in the concentration range 0·050-0·8 eq/l. The experimental results allow us to compute, without any arbitrary assumption, the fraction of counterions which contribute to the transport of current towards the cathode and which may be called the “fraction of free ions”.     

Diffraction engineering in arrays of photonic crystal waveguides

Light propagation in uniform arrays of photonic crystal waveguides is studied. We demonstrate that, in stark contrast to the case of conventional waveguide arrays, diffraction can be tailored both in magnitude and sign by varying only the spacing between adjacent waveguides. Diffraction management in ultracompact arrays of straight photonic crystal waveguides is demonstrated by solving Maxwell's equations through the time-domain finite-element method.