Monitoring of the metal displacement from the recombinant mouse liver metallothionein Zn(7)-complex by capillary zone electrophoresis with electrospray MS detection

A solution of a Zn-complex of recombinant mouse MT-1 isoform (Zn(7)-MT-1) was prepared and titrated with Cd(2+) ions. A method based on the coupling of capillary zone electrophoresis (CZE) with electrospray MS detection was developed for the analysis of the stoichiometry of the species formed during the titration. The method offered the possibility of the on-line removal of up to 100 mM Tris or phosphate buffer solutions that would otherwise suppress the electrospray signal. By allowing the determination of the metal stoichiometry of the complex species present in solution the method was shown to be complementary to circular dichroism and UV-VIS spectrophotometry conventionally used for similar studies. The titration of the Zn(7)-MT complex with Cd(II) showed the sequential displacement of the Zn by Cd. The unusually high stability of the Cd(6)Zn(1)-MT species was observed which suggests a structural role of the remaining Zn(II) ion.     

Modular bis(oxazoline) ligands for palladium catalyzed allylic alkylation: unprecedented conformational behaviour of a bis(oxazoline) palladium eta3-1,3-diphenylallyl complex

New families of enantiopure bis(oxazolines) with 4,5-trans (5 a-g) or 4,5-cis (6 c) stereochemistry at the individual rings have been prepared in high yield. Their eta(3)-allyl palladium complexes (8 a-g, 9 c and 10) have been used as catalytic precursors in allylic alkylation reactions with excellent enantioselectivities (up to 96 %) for the trans oxazoline derivatives, while Pd/6 c system was inactive. NMR studies on palladium eta(3)-1,3-diphenylallyl intermediates (11 a, c and e) showed the presence of syn/syn- and syn/anti-allyl isomers in solution; this resembles the first example of eta(3)-eta(1)-eta(3) isomerism in Pd allylic complexes containing bis(oxazolines) derived from malonic acid.     

Influence of Carboxylic Acids on the Synthesis of Chlorohydrin Esters from 1,3‐Butanediol

The influence of diverse carboxylic acid on the preparation of chlorohydrin esters using a one‐pot esterification–chlorination reaction, in which one of the reagents (chlorotrimethylsilane) acts as solvent, is described. Whereas the acid with low pKa provided higher amounts of the 2‐chloro regioisomer, the ones with higher pKa rendered the 1‐chloro regioisomer in 80% yield. These results are in accordance with the mechanism proposed in a previous article.     

S=1/2 One‐Dimensional Random‐Exchange Ferromagnetic Zigzag Ladder,Which Exhibits Competing Interactions in a Critical Regime

The synthesis, crystal structure, and magnetic properties (from a combined experimental and First‐Principles Bottom‐Up theoretical study) of the new compound catena‐dichloro(2‐Cl‐3Mpy)copper(II), 1 , [2‐Cl‐3Mpy=2‐chloro‐3‐methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest‐neighbor (J_NN) interactions and antiferromagnetic next‐nearest neighbor (J_NNN) interactions, in which α=J_NNN/J_NN <?0.25. These magnetic interactions give rise to a unique magnetic topology: a two‐leg zigzag ladder composed of edge‐sharing up‐down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2‐Cl‐3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the J_NN magnetic interactions can randomly take one of the following three values: 53, 36, and 16 cm^?1. The structural disorder does not affect the J_NNN value, which in all cases is approximately ?9 cm^?1. A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data.     

$${\mathbb{Z}_2\mathbb{Z}_4}$$-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.     

Luminescent PtII and PtIV Platinacycles with Anticancer Activity Against Multiplatinum-Resistant Metastatic CRC and CRPC Cell Models

Platinum-based chemotherapy persists to be the only effective therapeutic option against a wide variety of tumours. Nevertheless, the acquisition of platinum resistance is utterly common, ultimately cornering conventional platinum drugs to only palliative in many patients. Thus, encountering alternatives that are both effective and non-cross-resistant is urgent. In this work, we report the synthesis, reduction studies, and luminescent properties of a series of cyclometallated (C,N,N′)Pt^IV compounds derived from amine–imine ligands, and their remarkable efficacy at the high nanomolar range and complete lack of cross-resistance, as an intrinsic property of the platinacycle, against multiplatinum-resistant colorectal cancer (CRC) and castration-resistant prostate cancer (CRPC) metastatic cell lines generated for this work. We have also determined that the compounds are effective and selective for a broader cancer panel, including breast and lung cancer. Additionally, selected compounds have been further evaluated, finding a shift in their antiproliferative mechanism towards more cytotoxic and less cytostatic than cisplatin against cancer cells, being also able to oxidize cysteine residues and inhibit topoisomerase II, thereby holding great promise as future improved alternatives to conventional platinum drugs.     

From Bowls to Capsules: Assembly of Hexanuclear NiII Rings Tailored by Alkali Cations

An anionic hexanuclear Ni^II metallamacrocycle with endo and exo linking sites has been employed as a building block to generate a series of capsules and bowls of nanometric size. The supramolecular arrangement of the {Ni₆} rings was tailored by the size of the alkali cations, showing the transition from {Ni₆-M₂-Ni₆} capsules (M=Li^I and Na^I) to {Ni₆-M} bowls (M=K^I and Cs^I). The alkyl co-cations are determinant to stabilize the assemblies by means of CH⋅⋅⋅π interactions on the exo side of the metallamacrocycles. The effect on the topology of the supramolecular assemblies of the cation size, cation charge, Et₃NH⁺ or Me₄N⁺ counter cations has been analyzed. Magnetic measurements reveal the presence of ferromagnetic and antiferromagnetic interactions inside the rings that allow a S=0 ground state.     

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.     

Kinetico‐Mechanistic Insights on the Assembling Dynamics of Allyl‐Cornered Metallacycles: The PtNpy Bond is the Keystone

The square‐like homo‐ and heterometallamacrocycles [{Pd(η³‐2‐Me‐C₃H₄)( L ⁿ )₂}₂{M(dppp)}₂](CF₃SO₃)₆ (dppp=1,3‐bis(diphenylphosphino)propane) and [{Pd(η³‐2‐Me‐C₃H₄)( L¹ )₂}₂{M(PPh₃)₂}₂](CF₃SO₃)₆ [py=pyridine, M=Pd, Pt, L ^{n =}4‐PPh₂py ( L¹ ), 4‐C₆F₄PPh₂py ( L² )] containing allyl corners were synthesised by antisymbiotic self‐assembly of the different palladium and platinum metallic corners and the ambidentate N,P ligands. All the synthesised assemblies displayed a complex dynamic behaviour in solution, the rate of which is found to be dependent on the electronic and/or steric nature of the different building blocks. A kinetico‐mechanistic study by NMR line shape analysis of the dynamics of some of these assemblies was undertaken in order to determine the corresponding thermal activation parameters. Both an enhanced thermodynamic stability and slower dynamics were observed for platinum‐pyridine‐containing species when compared with their palladium analogues. Time‐dependent NMR spectroscopy in combination with ESI mass spectrometry was used to study the exchange between the assemblies and their building blocks, as well as that occurring between different metallamacrocycles. Preliminary studies were carried out on the activity of some of the metallamacrocyclic compounds as catalytic precursors in the allylic substitution reaction, and the results compared with that of the monometallic allylic corner [Pd(η³‐2‐Me‐C₃H₄)( L¹ )₂]⁺.