Ultrasoft pseudopotentials for lanthanide solvation complexes: core or valence character of the 4f electrons

The 4f electrons of lanthanides, because of their strong localization in the region around the nucleus, are traditionally included in a pseudopotential core. This approximation is scrutinized by optimizing the structures and calculating the interaction energies of Gd(3+)(H(2)O) and Gd(3+)(NH(3)) microsolvation complexes within plane wave Perdew-Burke-Ernzerhof calculations using ultrasoft pseudopotentials where the 4f electrons are included either in the core or in the valence space. Upon comparison to quantum chemical MP2 and CCSD(T) reference calculations it is found that the explicit treatment of the 4f electrons in the valence shell yields quite accurate results including the required small spin polarization due to ligand charge transfer with only modest computational overhead.     

Glycol-based sol-gel process for the fabrication of ferroelectric PZT thin films

A new sol-gel system using ethylene glycol was developed for the fabrication of PZT thin films with compositions near the morphotropic phase boundary Pb(Zr_0.52Ti_0.48)O₃. Ethylene glycol was used as both a chelating agent and a solvent to replace the highly toxic methoxyethanol used in previous formulations. Thin films were deposited by spin coating the solutions onto platinized silicon substrates. Films were completely crystallized by about 600°C and contained the ferroelectric perovskite phase. A dielectric constant of about 750–800 at 1 KHz was obtained for thin films of 0.3 µm thickness. The hysteresis measurements revealed a remanent polarization of 15 mC/cm² with a coercive field of 60 kV/cm.     

Validation of a new method using the reactivity of electrogenerated superoxide radical in the antioxidant capacity determination of flavonoids

This article lays out a new method to measure the antioxidant capacity of some flavonoids. The methodology developed is based on the kinetics of the reaction of the antioxidant substrate with the superoxide radical (O(2)(*-)). A cyclic voltammetric technique was used to generate O(2)(*-) by reduction of molecular oxygen in aprotic media. In the same experiment the consumption of the radical was directly measured by the anodic current decay of the superoxide radical oxidation in the presence of increasing concentrations of antioxidant substrate. The method was statistically validated on flavonoid monomers and on the standard antioxidants: trolox, ascorbic acid and phloroglucinol. The linear correlations between the anodic current of O(2)(*-) and the substrate concentration allowed the determination of antioxidant index values expressed by the substrate concentration needed to consume 30% (AI(30)) and 50% (AI(50)) of O(2)(*-) in given conditions of oxygen concentration and scanning rate. The fidelity of the method was examined intraday and interlaboratories.     

Spectral tuning by switching C-H[...]O hydrogen bonds: rotation-induced spectral shifts of 7-hydroxyquinoline HCOOH isomers

Spectral tuning effects on visible chromophores by hydrogen bonds are central to the chemistry of vision and of photosynthesis. A model for large spectral tuning effects by hydrogen bond switching is provided by the 7-hydroxyquinoline x HCOOH complex, which forms two isomers, CTN1 and CTN2, both with an HCOOH[...]N hydrogen bond but with different (quinoline)C-H[...]O=C hydrogen bonds. A 180 degrees rotation of the HCOOH moiety around the O-H[...]N hydrogen bond exchanges the C-H[...]O hydrogen bonds, rotates the dipole moment of HCOOH, and leads to an approximately 850 cm(-1) shift of the electronic spectrum. Mass-selected S1<--S0 resonant two-photon ionization, UV-UV holeburning, S1-->S0 fluorescence spectra, and photoionization efficiency curves of the two 7-hydroxyquinoline x HCOOH isomers were measured in supersonic expansions. Comparison to ab initio calculations allow us to determine the H-bond connectivity and structure of the two isomers and to assign their inter- and intramolecular vibrations. The Franck-Condon factors of the intermolecular shear vibration chi in the S1<--S0 spectra indicate that the weak C-H[...]O hydrogen bond contracts markedly in the CTN1 isomer but expands in the CTN2 isomer. These changes of H-bond lengths agree with the spectral shifts. In contrast, the strong O-H[...]N hydrogen bond undergoes little change upon S1[...]S0 excitation.     

Structure of sodiated octa-glycine: IRMPD spectroscopy and molecular modeling

The structure of the sodiated peptide GGGGGGGG-Na⁺ or G₈-Na⁺ was investigated by infrared multiple photon dissociation (IRMPD) spectroscopy and a combination of theoretical methods. IRMPD was carried out in both the fingerprint and N—H/O—H stretching regions. Modeling used the polarizable force field AMOEBA in conjunction with the replica-exchange molecular dynamics (REMD) method, allowing an efficient exploration of the potential energy surface. Geometries and energetics were further refined at B3LYP-D and MP2 quantum chemical levels. The IRMPD spectra indicate that there is no free C-terminus OH and that several N—Hs are free of hydrogen bonding, while several others are bound, however not very strongly. The structure must then be either of the charge solvation (CS) type with a hydrogen-bound acidic OH, or a salt bridge (SB). Extensive REMD searches generated several low-energy structures of both types. The most stable structures of each type are computed to be very close in energy. The computed energy barrier separating these structures is small enough that G₈-Na⁺ is likely fluxional with easy proton transfer between the two peptide termini. There is, however, good agreement between experiment and computations in the entire spectral range for the CS isomer only, which thus appears to be the most likely structure of G₈-Na⁺ at room temperature.     

Crystal structures and magnetic properties of two low-dimensional materials constructed from [Mn(III)(salen)H2O]+ and [M(CN)8](3-/4-) (M = Mo or W) precursors

The syntheses, X-ray structures, and magnetic behaviors of two new cyano-bridged assemblies, the molecular [Mn(III)(salen)H2O]3[W(V)(CN)8].H2O (1) and one-dimensional [Mn(salen)(H2O)2]2[[Mn(salen)(H2O)][Mn(salen)]2[Mo(CN)(8)]].0.5ClO4.0.5OH.4.5H2O (2), are presented. Compound 1 crystallizes in the monoclinic system, has space group P2(1)/c, and has unit cell constants a = 13.7210(2) A, b = 20.6840(4) A, c = 20.6370(2) A, and Z = 4. Compound 2 crystallizes in the triclinic system, has space group P, and has unit cell dimensions a = 18.428(4) A, b = 18.521(3) A, c = 18.567(4) A, and Z = 2. The structure of 1 consists of the asymmetric V-shaped Mn-NC-W-NC-Mn-O(phenolate)-Mn molecules, where W(V) coordinates with [Mn(salen)H2O] and singly phenolate-bridged [Mn(salen)H2O]2 moieties through the neighboring cyano bridges. The [W(V)(CN)8]3- ion displays distorted square-antiprism geometry. The structure of 2 consists of the cyano-bridged [Mn3(III)Mo(IV)]n- repeating units linked by double phenolate bridges into one-dimensional zigzag chains. The Mn(III) centers are bound to Mo(IV) of square-antiprism geometry through the neighboring cyano bridges. The magnetic studies of 1 reveal the antiferromagnetic intramolecular interactions through the CN and phenolate bridges and the relatively weak intermolecular interactions. Compound 1 becomes antiferromagnetically ordered below TN = 4.6 K. The presence of the magnetic anisotropy is documented with the MH measurements carried out for both polycrystalline and single-crystal samples. At T = 1.9 K, the spin-flop transition is observed in the field of 18 kOe applied parallel to the bc plane, which is the easy plane of magnetization. Field dependence of magnetization of 1 shows field-induced metamagnetic behavior from the antiferromagnetic ground state of ST = 3/2 to the state of ST = 5/2. The magnetic properties of 2 indicate a weak antiferromagnetic interaction between Mn(III) centers in double-phenolate-bridged [Mn(III)(salen)]2 dinuclear subunits and a very weak ferromagnetic interaction between them through the diamagnetic [Mo(IV)(CN)8]4- spacer.     

Influence of micromixer characteristics on polydispersity index of block copolymers synthesized in continuous flow microreactors

The influence of interdigital multilamination micromixer characteristics on monomer conversions, molecular weights and especially on the polydispersity index of block copolymers synthesized continuously in two microtube reactors is investigated. The micromixers are used to mix, before copolymerization, a polymer solution with different viscosities and the second monomer. Different geometries of micromixer (number of microchannels, characteristic lengths) have been studied. It was found that polydispersity indices of the copolymers follow a linear relationship with the Reynolds number in the micromixer, represented by a form factor. Thus, beside the operating conditions (nature of the first block and comonomer flow rate), the choice of the micromixer geometry and dimension is essential to control the copolymerization in terms of molecular weights and polydispersity indices. This linear correlation allows the prediction of copolymer features. It can also be a new method to optimize existing micromixers or design other geometries so that mixing could be more efficient.     

Development and validation of a multiplex real-time PCR method to simultaneously detect 47 targets for the identification of genetically modified organisms

Considering the increase of the total cultivated land area dedicated to genetically modified organisms (GMO), the consumers’ perception toward GMO and the need to comply with various local GMO legislations, efficient and accurate analytical methods are needed for their detection and identification. Considered as the gold standard for GMO analysis, the real-time polymerase chain reaction (RTi-PCR) technology was optimised to produce a high-throughput GMO screening method. Based on simultaneous 24 multiplex RTi-PCR running on a ready-to-use 384-well plate, this new procedure allows the detection and identification of 47 targets on seven samples in duplicate. To comply with GMO analytical quality requirements, a negative and a positive control were analysed in parallel. In addition, an internal positive control was also included in each reaction well for the detection of potential PCR inhibition. Tested on non-GM materials, on different GM events and on proficiency test samples, the method offered high specificity and sensitivity with an absolute limit of detection between 1 and 16 copies depending on the target. Easy to use, fast and cost efficient, this multiplex approach fits the purpose of GMO testing laboratories.

Benzothiadiazole- and pyrrole-based polymers bearing thermally cleavable solubilizing groups as precursors for low bandgap polymers

We report the design, synthesis and characterization of new benzothiadiazole- and pyrrole-based copolymers whose solubility and bandgap drastically change after thermal treatment of their thin films.