Easy access to diastereomerically pure platinacycles

The synthesis of the first examples of diastereomerically pure platinacycles having simultaneously a chiral carbon and a sigma[Pt-C(sp(2), ferrocene)] bond is described.     

Enantioseparation of basic pharmaceutical compounds by capillary electrophoresis using sulfated cyclodextrins. Application to E-6006, a novel antidepressant

In this study, a chiral capillary electrophoresis method was optimized and validated for E-6006, a thienylpyrazolylethanamine derivative (pK_a 8.9). Enantioselectivity of neutral and anionic cyclodextrins (CDs) was evaluated at acid pH (3), obtaining cathodic and anodic migration, respectively. Hydroxypropyl-β-CD, carboxymethyl-β-CD and sulfobutyl ether-β-CD led to similar and partial selectivity, whereas sulfate (S)-β-CD produced baseline separation of the enantiomers. Four types of sulfated CDs were compared considering: cavity size (, β, γ) and random substitution versus unique derivative (S-β-CD, 6-heptakis-S-β-CD). Complete peak separation was obtained in all cases, but with different affinity and binding strength. Some factors that play a role in the complex formation include: position/region/degree of substitution, size of CD cavity and proportion of derivatives in mixtures. Enantioaffinity and enantioselectivity increased with the average of sulfate groups/mol. β Cavity size complexed better, although and γ cavities did not compromise separation. 6-Heptakis-S-β-CD had less affinity and separation efficiency, attributed to its lower degree and unique position of substitution. The method was optimized with S-β-CD (Aldrich, randomly substituted, 7–11 groups/mol). With this selector, the effect of pH value (3–9) was evaluated. Around pH 7 the cross-over point with change in the direction and order of migration was observed, associated with great enantioselectivity and long migration times. Fine tuning was done by adjusting the CD concentration and the buffer counterion. Definitive conditions were: uncoated silica capillary, 10 mM S-β-CD–25 mM sodium phosphate, pH 3. Validation parameters are included.     

Evidence of Native Metal–S2−–Metallothionein Complexes Confirmed by the Analysis of Cup1 Divalent‐Metal‐Ion Binding Properties

It has previously been shown that recombinant synthesis, under metal‐supplemented conditions, of diverse metallothioneins (MTs) results in the recovery of a subpopulation of S^2?‐containing complexes in addition to the S^2?‐devoid canonical metal–MT species. Further significance of this finding has remained veiled by the possibility of it being a mere consequence of synthesis in a heterologous bacterial system. Herein, we present definitive evidence that S^2? ligands are also constituents of native metal–MT complexes. Because, although practically universal, the highest S^2? content is incorporated by copper‐thioneins when coordinating divalent metal ions, we adapted the Saccharomyces cerevisiae Cup1 protein, which is the most paradigmatic copper‐thionein, as an experimental model. Most significantly, native Cd–Cup1 complexes were purified and fully spectroscopically and spectrometrically characterized from the 301N mutant yeast strain, which allows Cup1 synthesis even in the absence of copper. These results undoubtedly revealed the presence of a Cd–S^2?–Cup1 species in native preparations, which were only recovered when carefully avoiding the use of ion‐exchange chromatography in the purification protocol. Furthermore, complete analysis of recombinant (Escherichia coli) Zn–Cup1, Cd–Cup1, and Cu–Cup1 and those complexes that result from Zn/Cd and Zn/Cu replacements in vitro and acidification/renaturalization processes yielded a comprehensive and comparative overview of the metal‐binding abilities of Cup1. Overall, we consider the main conclusions of this study to go beyond the mere study of the particular Cup1 MT, so that they should be considered to delineate a new point of view on the interaction between copper‐thioneins and divalent metal ions, still an unexplored aspect in MT research.     

A teacher education experiment to challenge conceptions and practices

This study describes a teacher education experience with grade 5–6 teachers, based on a calculator module within a national program for mathematics in-service teacher education. The aim was to challenge the teachers’ conceptions about the role of the calculator in mathematics teaching and to promote their reflection about professional practices. The research methodology was qualitative and interpretive, with data collection through interviews and observation of teacher education and classroom supervision sessions, as well as analysis of teachers’ portfolios. The results indicate that some teachers are clearly against the use of the calculator in the mathematics classroom, while others allow students to use it in a passive way and some others are very affirmative about its use. The teachers who argue against the use of the calculator seem to predominate, suggesting a great distance between the curriculum orientations and classroom practice. The methodology of the course, combining collective sessions and individual classroom supervision, proved to be fruitful, providing new information, practice and discussion that allowed teachers to analyze different kinds of tasks in which the calculator might be useful, experiment using them in the classroom and reflect about the students’ work. The no imposing and questioning approach used in collective discussions encouraged teachers to assume their own positions; sharing and discussing in the collective reflections during the course stimulated a deeper reflection of their practice. Therefore, in this course, in-service teacher education focused on practice contributed to teachers to reflect on their conceptions and practices.     

Observation and mechanistic study of facile C-O bond formation between a well-defined aryl-copper(III) complex and oxygen nucleophiles

A well-defined macrocyclic aryl–Cu(III) complex (2) reacts readily with a variety of oxygen nucleophiles, including carboxylic acids, phenols and alcohols, under mild conditions to form the corresponding aryl esters, biaryl ethers and alkyl aryl ethers. The relationship between these reactions and catalytic C-O coupling methods is demonstrated by the reaction of the macrocyclic aryl–Br species with acetic acid and p-fluorophenol in the presence of 10 mol% Cu(I). An aryl-Cu(III)-Br species 2(Br) was observed as an intermediate in the catalytic reaction. Investigation of the stoichiometric C-O bond-forming reactions revealed nucleophile-dependent changes in the mechanism. The reaction of 2 with carboxylic acids revealed a positive correlation between the log(k(obs)) and the pK(a) of the nucleophile (less-acidic nucleophiles react more rapidly), whereas a negative correlation was observed with most phenols (more-acidic phenols react more rapidly). The latter trend resembles previous observations with nitrogen nucleophiles. With carboxylic acids and acidic phenols, UV-visible spectroscopic data support the formation of a ground-state adduct between 2 and the oxygen nucleophile. Collectively, kinetic and spectroscopic data support a unified mechanism for aryl-O coupling from the Cu(III) complex, consisting of nucleophile coordination to the Cu(III) center, deprotonation of the coordinated nucleophile, and C-O (or C-N) reductive elimination from Cu(III).     

Partial permutation decoding for binary linear and $$Z_4$$-linear Hadamard codes

In this paper, s-\({\text {PD}}\)-sets of minimum size \(s+1\) for partial permutation decoding for the binary linear Hadamard code \(H_m\) of length \(2^m\), for all \(m\ge 4\) and \(2 \le s \le \lfloor {\frac{2^m}{1+m}}\rfloor -1\), are constructed. Moreover, recursive constructions to obtain s-\({\text {PD}}\)-sets of size \(l\ge s+1\) for \(H_{m+1}\) of length \(2^{m+1}\), from an s-\({\text {PD}}\)-set of the same size for \(H_m\), are also described. These results are generalized to find s-\({\text {PD}}\)-sets for the \({\mathbb {Z}}_4\)-linear Hadamard codes \(H_{\gamma , \delta }\) of length \(2^m\), \(m=\gamma +2\delta -1\), which are binary Hadamard codes (not necessarily linear) obtained as the Gray map image of quaternary linear codes of type \(2^\gamma 4^\delta \). Specifically, s-PD-sets of minimum size \(s+1\) for \(H_{\gamma , \delta }\), for all \(\delta \ge 3\) and \(2\le s \le \lfloor {\frac{2^{2\delta -2}}{\delta }}\rfloor -1\), are constructed and recursive constructions are described.     

$${\mathbb{Z}_2\mathbb{Z}_4}$$-linear codes: rank and kernel

A code C{{\mathcal C}} is \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-additive if the set of coordinates can be partitioned into two subsets X and Y such that the punctured code of C{{\mathcal C}} by deleting the coordinates outside X (respectively, Y) is a binary linear code (respectively, a quaternary linear code). The corresponding binary codes of \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-additive codes under an extended Gray map are called \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear codes. In this paper, the invariants for \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear codes, the rank and dimension of the kernel, are studied. Specifically, given the algebraic parameters of \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear codes, the possible values of these two invariants, giving lower and upper bounds, are established. For each possible rank r between these bounds, the construction of a \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear code with rank r is given. Equivalently, for each possible dimension of the kernel k, the construction of a \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear code with dimension of the kernel k is given. Finally, the bounds on the rank, once the kernel dimension is fixed, are established and the construction of a \mathbbZ₂\mathbbZ₄{{\mathbb{Z}_2\mathbb{Z}_4}}-linear code for each possible pair (r, k) is given.