Surface active ionic liquids: Study of the micellar properties of 1-(1-alkyl)-3-methylimidazolium chlorides and comparison with structurally related surfactants

The impetus for the increasing interest in studying surface active ionic liquids (SAILs; ionic liquids with long-chain ""tails"") is the enormous potential for their applications, e.g., in nanotechnology and biomedicine. The progress in these fields rests on understanding the relationship between surfactant structure and solution properties, hence applications. This need has prompted us to extend our previous study on 1-(1-hexadecyl)-3-methylimidazolium chloride to 1-(1-alkyl)-3-methylimidazolium chlorides, with alkyl chains containing 10, 12, and 14 carbons. In addition to investigating relevant micellar properties, we have compared the solution properties of the imidazolium-based surfactants with: 1-(1-alkyl)pyridinium chlorides, and benzyl (2-acylaminoethyl)dimethylammonium chlorides. The former series carries a heterocyclic ring head-group, but does not possess a hydrogen that is as acidic as H2 of the imidazolium ring. The latter series carries an aromatic ring, a quaternary nitrogen and (a hydrogen-bond forming) amide group. The properties of the imidazolium and pyridinium surfactants were determined in the temperature range from 15 to 75 degrees C. The techniques employed were conductivity, isothermal titration calorimetry, and static light scattering. The results showed the important effects of the interactions in the interfacial region on the micellar properties over the temperature range studied. (C) 2011 Elsevier Inc. All rights reserved.

Micellar properties of surface active ionic liquids: A comparison of 1-hexadecyl-3-methylimidazolium chloride with structurally related cationic surfactants

Ionic liquids, ILs, carrying long-chain alkyl groups are surface active, SAIIs. We investigated the micellar properties of the SAIL 1-hexadecyl-3-methylimidazolium chloride, C(16)MeImCl, and compared the data with 1-hexadecylpyridinium chloride, C(16)PYCl, and benzyl (3-hexadecanoylaminoethyl)dimethylammonium chloride, C(15)AEtBzMe(2)Cl. The properties compared include critical micelle concentration, cmc; thermodynamic parameters of micellization; empirical polarity and water concentrations in the interfacial regions. In the temperature range from 15 to 75 degrees C, the order of cmc in H(2)O and in D(2)O is C(16)PYCl > C(16)MeImCl > C(15)AEtBzMe(2)Cl. The enthalpies of micellization, Delta H(mic)(degrees), were calculated indirectly from by use of the van`t Hoff treatment; directly by isothermal titration calorimetry, ITC. Calculation of the degree of counter-ion dissociation, alpha(mic), from conductivity measurements, by use of Evans equation requires knowledge of the aggregation numbers, N(agg), at different temperatures. We have introduced a reliable method for carrying out this calculation, based on the volume and length of the monomer, and the dependence of N(agg) on temperature. The N(agg) calculated for C(16)PyCl and C(16)MeImCl were corroborated by light scattering measurements. Conductivity- and ITC-based Delta H(mic)(degrees) do not agree; reasons for this discrepancy are discussed. Micelle formation is entropy driven: at all studied temperatures for C(16)MeImCl; only up to 65 degrees C for C(16)PyCl; and up to 55 degrees C for C(15)AEtBzMe(2)Cl. All these data can be rationalized by considering hydrogen-bonding between the head-ions of the monomers in the micellar aggregate. The empirical polarities and concentrations of interfacial water were found to be independent of the nature of the head-group. (C) 2010 Elsevier Inc. All rights reserved.

A class of improved heteroskedasticity-consistent covariance matrix estimators

The heteroskedasticity-consistent covariance matrix estimator proposed by White (1980), also known as HC0, is commonly used in practical applications and is implemented into a number of statistical software. Cribari–Neto, Ferrari & Cordeiro (2000) have developed a bias-adjustment scheme that delivers bias-corrected White estimators. There are several variants of the original White estimator that also commonly used by practitioners. These include the HC1, HC2 and HC3 estimators, which have proven to have superior small-sample behavior relative to White’s estimator. This paper defines a general bias-correction mechamism that can be applied not only to White’s estimator, but to variants of this estimator as well, such as HC1, HC2 and HC3. Numerical evidence on the usefulness of the proposed corrections is also presented. Overall, the results favor the sequence of improved HC2 estimators.

Reach: is such regulation WTO consistent?

This present study analyses the Regulation on Chemicals of the European Union – so called REACH, and some of its main features. Technical barriers to trade have become the new instrument of distorting international trade benefits and creating protection for domestic industry, on the basis of protection of human health and the environment. It aims at identifying REACH’s most primary and controversial element and its consistency under the World Trade Organization System, in context of the Agreement on Technical Barriers to Trade

Different origins of green-light photoluminescence emission in structurally ordered and disordered powders of calcium molybdate

A strong greenish-light photoluminescence (PL) emission was measured at room temperature for disordered and ordered powders of CaMoO4 prepared by the polymeric precursor method. The structural evolution from disordered to ordered powders was accompanied by XRD. Raman spectroscopy, and TEM imagery. High-level quantum mechanical calculations in the density functional framework were used to interpret the formation of the structural defects of disorder powders in terms of band diagram and density of states. Complex cluster vacancies [MoO3 center dot V-O(z)] and [CaO7 center dot V-O(z)] (where V-O(z) = V-O(X), V-O(center dot), V-O(center dot center dot)) were suggested to be responsible to the appearance of new states shallow and deeply inserted in the band gap. These defects give rise to the PL in disordered powders. The natural PL emission of ordered CaMoO4 was attributed to an intrinsic slight distortion of the [MoO4] tetrahedral in the short range.

Relationship between global structural parameters and Enzyme Commission hierarchy: Implications for function prediction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Consistent modified gravity: dark energy, acceleration and the absence of cosmic doomsday

We discuss modified gravity which includes negative and positive powers of curvature and provides gravitational dark energy. It is shown that in GR plus a term containing a negative power of curvature, cosmic speed-up may be achieved while the effective phantom phase (with w less than -1) follows when such a term contains a fractional positive power of curvature. Minimal coupling with matter makes the situation more interesting: even 1/R theory coupled with the usual ideal fluid may describe the (effective phantom) dark energy. The account of the R(2) term (consistent modified gravity) may help to escape cosmic doomsday.

Lessons of spin and torsion: Reply to Consistent coupling to Dirac fields in teleparallelism

In reply to the criticism made by Mielke in the preceding Comment on our recent paper, we once again explicitly demonstrate the inconsistency of the coupling of a Dirac field to gravitation in the teleparallel equivalent of general relativity. Moreover, we stress that the mentioned inconsistency is generic for all sources with spin and is by no means restricted to the Dirac field. In this sense the SL(4,R)-covariant generalization of the spinor fields in the teleparallel gravity theory is irrelevant to the inconsistency problem.

Consistent gravitationally coupled spin-2 field theory

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Towards a Realization of the Condensed-Matter-Gravity Correspondence in String Theory via Consistent Abelian Truncation of the Aharony-Bergman-Jafferis-Maldacena Model

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On an Active Control for a Structurally Nonlinear Mechanical System, Taking Into Account an Energy Pumping

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Glucose and Fructose Fermentation by Wine Yeasts in Media Containing Structurally Complex Nitrogen Sources

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of Brazilian ethanol production yeasts for maltose fermentation in media containing structurally complex nitrogen sources

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)