The influence of cosolvent polarity on the flow properties of hydroalcoholic gels: empirical models

The aim of this study was to investigate the influence of cosolvent polarity on the rheological flow properties of aqueous and hydroalcoholic gels obtained from the Carbopol Ultrez 10 base and used for topical applications. Specifically, we have examined the effect of pH (range 4.0--7.0) on the consistency and flow properties of dispersed systems in water and mixtures--15 : 85% v/v of methanol : water, ethanol : water, n-propanol : water and n-butanol : water--at a constant polymer concentration of 0.3% w/w. The gels, which had decreasing polarity values in the jellifying medium, showed qualitatively similar flow behavior, characteristic of pseudoplastic systems, and all of the flow curves were adjusted to the Ostwald model. Sigmoidal dose response functions were calculated to describe the flow and consistency indexes as a function of pH. As a result, the influence of alcohol polarity on the polymer network has been assessed meaningfully using the empirical parameters obtained: maximum consistency index value (k(max)), pH value required for 50% development of polymer network (pH(50)), and asymptotic flow index value (n(min)) for the fully structured gels.     

Electrospray ionization mass spectrometry studies of noncovalent myosin VI complexes reveal a new specific calmodulin binding site

Among the myosin superfamily, myosin VI differs from all others by a reverse directionality and a particular motility. Little structural information is available for myosin VI. It is known that it binds one calmodulin (CaM) by means of a single "IQ motif" and that myosin VI contains a specific insert located at the junction between the motor domain (MD) and the lever arm, likely to play a critical role for the unusual motility previously observed. Electrospray ionization mass spectrometry (MS) was used to determine the CaM and Ca2+ stoichiometries in several myosin VI constructs. In particular, the experimental conditions required for the observation of multiprotein/Ca2+ noncovalent assemblies are detailed for two truncated MD constructs (less than 20 kDa) and for three full MD constructs (more than 90 KDa). The specificity of the detected stoichiometries is discussed for each construct and the resolving power of Time of Flight mass spectrometry is stressed, in particular for the detection of metal ions binding to high molecular weight complexes. MS reveals a new CaM binding site for myosin VI and highlights a different behavior for the five myosin VI constructs versus Ca2+ binding. In addition to these stoichiometry based experiments, gas-phase dissociation analyses on intact complexes are described. They reveal that Ca2+ transfer between protein partners occurs during the dissociation process for one construct with a full MD. Charge-transfer and dissociation behavior has allowed to draw structural assumptions for the interaction of the MD with the CaM N-terminal lobe.     

Unprecedented, fully recyclable, solid-supported reagent for the kinetic resolution of racemic amines through enantioselective N-acetylation

The high-yielding synthesis and application of the first polymer supported reagent for the kinetic resolution (KR) of amines through enantioselective acetylation is described; this new supported chiral reagent allows the KR of primary amines with excellent selectivities at room temperature; moreover, this supported approach is highly efficient as the Merrifield-supported chiral scaffold can be quantitatively recovered and recycled.     

The effect of pyridinecarboxylate chelating groups on the stability and electronic relaxation of gadolinium complexes

The ligand N,N'-bis[(6-carboxy-2-pyridylmethyl]ethylenediamine-N,N'-diacetic acid (H(4)bpeda) was synthesised using an improved procedure which requires a reduced number of steps and leads to a higher yield with respect to the published procedure. It was obtained in three steps from diethylpyridine-2,6-dicarboxylate and commercially available ethylenediamine-N,N[prime or minute]-diacetic acid with a total yield of approximately 20%. The crystal structure of the hexa-protonated form of the ligand which was determined by X-ray diffraction shows that the four carboxylates and the two amines are protonated. The crystal structure of the polynuclear complex [Gd(bpeda)(H(2)O)(2)](3)[Gd(H(2)O)(6)](2)Cl(3)(2), isolated by slow evaporation of a 1:1 mixture of GdCl(3) and H(4)bpeda at pH approximately 1, was determined by X-ray diffraction. In complex three [Gd(bpeda)(H(2)O)(2)] units, containing a Gd(III) ion ten-coordinated by the octadentate bpeda and two water molecules, are connected in a pentametallic structure by two hexa-aquo Gd(3+) cations through four carboxylato bridges. The protonation constants (pK(a1)= 2.9(1), pK(a2)= 3.5(1), pK(a3)= 5.2(2), and pK(a4)= 8.5(1)) and the stability constants of the complexes formed between Gd(III) and Ca(II) ions and H(4)bpeda (log beta(GdL)= 15.1(3); log beta(CaL)= 9.4(1)) were determined by potentiometric titration. The unexpected decrease in the stability of the gadolinium complex and of the calcium complex of the octadentate ligand bpeda(4-) with respect to the hexadentate ligand edta(4-) has been interpreted in terms of an overall lower contribution to stability of the metal-nitrogen interactions. The EPR spectra display very broad lines (apparent DeltaH(pp) approximately 800-1200 G at X-band and 90-110 G at Q-band depending on the temperature), indicating a rapid transverse electron spin relaxation. At X-band, Gd(bpeda) is among the fastest relaxing Gd(3+) complexes to date suggesting that the presence of pyridinecarboxylate chelating groups in itself does not lead to slow electron relaxation.     

Electrochemical evidences of morphological transformation in ordered mesoporous titanium oxide thin films

We provide the first electrochemical evidence of permeability changes in continuous mesoporous TiO2 thin film electrodes induced by nanocrystallisation.     

Comments on selected fundamental aspects of microarray analysis

Microarrays are becoming a ubiquitous tool of research in life sciences. However, the working principles of microarray-based methodologies are often misunderstood or apparently ignored by the researchers who actually perform and interpret experiments. This in turn seems to lead to a common over-expectation regarding the explanatory and/or knowledge-generating power of microarray analyses. In this note we intend to explain basic principles of five (5) major groups of analytical techniques used in studies of microarray data and their interpretation: the principal component analysis (PCA), the independent component analysis (ICA), the t-test, the analysis of variance (ANOVA), and self organizing maps (SOM). We discuss answers to selected practical questions related to the analysis of microarray data. We also take a closer look at the experimental setup and the rules, which have to be observed in order to exploit microarrays efficiently. Finally, we discuss in detail the scope and limitations of microarray-based methods. We emphasize the fact that no amount of statistical analysis can compensate for (or replace) a well thought through experimental setup. We conclude that microarrays are indeed useful tools in life sciences but by no means should they be expected to generate complete answers to complex biological questions. We argue that even well posed questions, formulated within a microarray-specific terminology, cannot be completely answered with the use of microarray analyses alone.     

Biomimetic zinc funnel complexes based on calix[6]N3ArO ligands: an acid-base switch for guest binding

The coordination chemistry of Zn in an N(3)ArOH environment has been explored. The ligands are based on calix[6]arenes that present two imidazole arms and an amino phenol moiety at the narrow rim. Three different types of complexes have been characterized. One is dicationic with Zn(2+) coordinated to the three nitrogen atoms and to the oxygen of the phenol group of the calix[6]ligand. This complex is very sensitive to exogenous coordinating molecules and exists as a 5-coordinate species due to the endo-complexation of a guest. The second species is a monocationic complex for which the phenol group has been deprotonated. The resulting N(3)ArOZn complex can also bind a guest ligand albeit with a lower affinity than the dicationic complex. The third species is neutral. It can be obtained upon reaction with a base to yield a hydroxo complex or with an anion such as a chloride that coordinates the metal center from the outside of the calixarene cavity. The simultaneous binding of two anionic donors decreases the Zn Lewis acidity, allowing an impressive conformational reorganization of the system. One imidazole arm is released by the metal center. The other one undergoes self-inclusion into the pi-basic calixarene cavity because the low affinity of the metal center for neutral ligand does not allow the endo-coordination of an exogenous guest. Hence, the calix[6]N(3)ArOH-based Zn complexes act as an acid-base switch for guest binding. Several aspects of this system appear reminiscent of Zn-peptidases of the astacin and serralisin families.     

PFGSE-NMR study of the self-diffusion of sucrose fatty acid monoesters in water

The micellization of pure monosubstituted sucrose fatty acid esters in water, namely sucrose octanoate, sucrose decanoate, sucrose laurate, sucrose dodec-5-cis-enoate, sucrose myristate, and sucrose palmitate, has been investigated by means of two NMR methods, pulsed field gradient spin-echo NMR (PFGSE-NMR), giving access to the self-diffusion coefficients of free molecules and micelles in solution, and the ERETIC method (electronic reference to access in vivo concentrations) for the measurement of concentrations by external calibration of a synthetic NMR signal. The early micellar regions and, when possible, the premicellar regions were investigated. By this method, we obtained the hydrodynamic radii of micelles, displaying a linear progression in relation to the chain length and an accurate determination of critical micellar concentration (CMC) for each sucrose ester. The effect of the regiochemistry of fatty chain grafting has been investigated, showing special behavior for 1'-O-sucrose palmitate.     

Tuning the enantioselective N-acetylation of racemic amines: a spectacular salt effect

We have described a spectacular salt effect in the kinetic resolution of (+/-)-1-phenylethylamine, which leads to an increase in reactivity, high levels of selectivity, and a complete reversal of the stereoselectivity. By tuning the reaction conditions, we were able to increase the selectivity factor of (1S,2S)-1 to s = 115.     

Weak Coupling and Continuous Limits for Repeated Quantum Interactions

We consider a quantum system in contact with a heat bath consisting in an infinite chain of identical sub-systems at thermal equilibrium at inverse temperature β. The time evolution is discrete and such that over each time step of duration τ, the reference system is coupled to one new element of the chain only, by means of an interaction of strength λ. We consider three asymptotic regimes of the parameters λ and τ for which the effective evolution of observables on the small system becomes continuous over suitable macroscopic time scales T and whose generator can be computed: the weak coupling limit regime λ → 0, τ = 1, the regime τ → 0, λ²τ → 0 and the critical case λ²τ = 1, τ → 0. The first two regimes are perturbative in nature and the effective generators they determine is such that a non-trivial invariant sub-algebra of observables naturally emerges. The third asymptotic regime goes beyond the perturbative regime and provides an effective dynamics governed by a general Lindblad generator naturally constructed from the interaction Hamiltonian. Conversely, this result shows that one can attach to any Lindblad generator a repeated quantum interactions model whose asymptotic effective evolution is generated by this Lindblad operator.