Molybdenum- and tungsten(II) monometallic 3-(2-pyridyl)pyrazole and bimetallic 3-(2-pyridyl)pyrazolate complexes

Molybdenum and tungsten complexes containing the pypzH (3-(2-pyridyl)pyrazole) ligand as a chelating bidentate are prepared: [Mo(CO)(4)(pypzH)], cis-[MoBr(η(3)-allyl)(CO)(2)(pypzH)], cis-[MoCl(η(3)-methallyl)(CO)(2)(pypzH)], [MI(2)(CO)(3)(pypzH)] (M = Mo, W) from [Mo(CO)(4)(NBD)] or the adequate bis(acetonitrile) complexes. The deprotonation of the molybdenum allyl or methallyl complexes affords the bimetallic complexes [cis-{Mo(η(3)-allyl)(CO)(2)(μ(2)-pypz)}](2) or [cis-{Mo(η(3)-methallyl)(CO)(2)(μ(2)-pypz)}](2) (μ(2)-pypz = μ(2)-3-(2-pyridyl-κ(1)N)pyrazolate-2κ(1)N). The allyl complex was subjected to an electrochemical study, which shows a marked connection between both metallic centres through the bridging pyridylpyrazolates.     

Copper(II) complexes of bis(amino amide) ligands: effect of changes in the amino acid residue

A family of ligands derived from bis(amino amides) containing aliphatic spacers has been prepared, and their protonation and stability constants for the formation of Cu(2+) complexes have been determined potentiometrically. Important differences are associated to both the length of the aliphatic spacer and the nature of the side chains derived from the amino acid. In general, ligands containing aliphatic side chains display higher basicities as well as stability constants with Cu(2+). In the same way, basicities and stability constants tend to increase when decreasing the steric hindrance caused by the corresponding side-chain. FT-IR, UV-vis and ESI-MS were used for analyzing the complex species detected in the speciation diagram. UV-vis studies showed the presence of different coordination environments for the copper(II) complexes. Complexes with different stoichiometries can be formed in some instances. This was clearly highlighted with the help of ESI-MS experiments.     

CaSO4 and its pressure-induced phase transitions. A density functional theory study

Theoretical investigations concerning possible calcium sulfate, CaSO(4), high-pressure polymorphs have been carried out. Total-energy calculations and geometry optimizations have been performed by using density functional theory at the B3LYP level for all crystal structures considered. The following sequence of pressure-driven structural transitions has been found: anhydrite, Cmcm (in parentheses the transition pressure) → monazite-type, P2(1)/n (5 GPa) → barite-type, Pnma (8 GPa), and scheelite-type, I4(1)/a (8 GPa). The equation of state of the different polymorphs is determined, while their corresponding vibrational properties have been calculated and compared with previous theoretical results and experimental data.     

NMR and X‐ray crystallographic studies of linear and cyclic aminomethanephosphinates

We report the preparation of four diastereoisomeric pairs of ethyl {[(3‐hydroxypropyl)‐ amino](aryl)methyl}phenylphosphinates. In two cases, the phosphinates were transformed to 1,4,2‐oxazaphosphepane heterocycles through one‐pot intramolecular esterification. The analogous reaction with formaldehyde gave the six‐membered ethyl (1,3‐oxazinan‐3‐ylmethyl)phenylphosphinate, which could be transformed in a posterior reaction to the corresponding aminomethanephosphinic acid. The new compounds were characterized by IR, ¹H, ¹³C, and ³¹P NMR. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:81–87, 2006; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20179     

Direct Organocatalytic Polymerization from Cellulose Fibers

Summary: We have developed the first direct, organocatalytic, bulk ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) with solid cotton and paper cellulose as the initiators. The mild ROPs were performed without solvent, and are operationally simple, inexpensive and environmentally benign. Organic‐acid‐catalyzed heterogeneous derivatization of cellulose provides a novel route to valuable cellulose‐based biocompatible nanomaterials. The furnished polymerization products were characterized by FTIR, ¹H and ¹³C NMR spectroscopy, MALDI‐TOF mass spectrometry and electron microscopy.

Organic acid‐catalyzed ring‐opening polymerization from cellulose fiber.     

The Application of Ultrasound in Honey: Antioxidant Activity,Inhibitory Effect on α-amylase and α-glucosidase,and In Vitro Digestibility Assessment

In the present study, the effects of ultrasound (10, 20, and 30 min) on the bioactive compounds, antioxidant capacity, enzymatic inhibition, and in vitro digestion of six honey extracts from the Oaxaca state, Mexico, were analyzed. Significant differences were found in each honey extract with respect to the ultrasonic treatment applied (p < 0.05). In the honey extract P-A1 treated with 20 min of ultrasound, the phenols reached a maximum concentration of 29.91 ± 1.56 mg EQ/100 g, and the flavonoids of 1.92 ± 0.01 mg EQ/100 g; in addition, an inhibition of α-amylase of 37.14 ± 0.09% was noted. There were also differences in the phases of intestinal and gastric digestion, presenting a decrease in phenols (3.92 ± 0.042 mg EQ/100 g), flavonoids (0.61 ± 0.17 mg EAG/100 mg), antioxidant capacity (8.89 ± 0.56 mg EAG/100 mg), and amylase inhibition (9.59 ± 1.38%). The results obtained from this study indicate that, in some honeys, the processing method could increase the concentration of bioactive compounds, the antioxidant capacity, and the enzymatic inhibition; however, when subjected to in vitro digestion, the properties of honey are modified. The results obtained could aid in the development of these compounds for use in traditional medicine as a natural source of bioactive compounds.     

When not to rely on Boltzmann populations. Automated CASE-3D structure elucidation of hyacinthacines through chemical shift differences

An Akaike Information Criterion (AIC) procedure (CASE-3D) has been successfully applied to the NMR based configurational assignment of reported hyacinthacines ( 1 – 3 , 5 – 8 ), recently target of configurational analysis using the popular DP4+ methodology. The present analysis makes use of reported ¹H and ¹³C shifts and, in some particular cases, a few ³J_HH couplings. The difficulty in proper computational prediction of relative energies, in molecules capable of inter-molecular hydrogen bonding, introduces large errors in the prediction of conformationally averaged NMR properties in methods based on Boltzmann averaging such as DP4 or DP4+. In contrast CASE-3D conformational amplitudes are free parameters in the model. Here we show that the CASE-3D conformational model selection strategy, when combined with a larger energy cutoff in the molecular-modelling conformational exploration, was sufficient to correctly assign the relative configuration in five of seven cases. Introduction of more information, either by supplementing ¹H and ¹³C data with a few J-couplings, or using a cutoff based on computed DFT energies for the definition of the conformational ensembles, allowed the safe assignment of configuration for all compounds.     

Template-Free Self-Assembly of Artificial De Novo Viral Coat Proteins into Nanorods: Effects of Sequence,Concentration, and Temperature

The self-assembly of protein polymers is a promising route to prepare sophisticated functional nanostructures. However, the interplay between protein self-assembly by itself and its co-assembly with a template is not well understood. Silk-based protein polymers that co-assemble with DNA to form rod-like artificial viruses are herein developed and the effects of silk block length, concentration, and temperature in the self-assembly of the proteins alone are characterized by using a combination of bulk dynamic light scattering (DLS) and single-molecule atomic force microscopy (AFM). Protein nanorods were slowly formed (up to hours) through the interaction of the silk-like blocks. The proteins present a silk-length dependent critical elongation concentration, and above it the amount and size of nanorods rapidly increase. Temperature-dependent light scattering data was adequately fitted into a cooperative model of nucleation–elongation. These results are also important to understand the self-assembly of designed viral coat proteins with DNA templates to form artificial virus-like particles and help us to define general guidelines to design proteins with the ability to precisely organize matter at the nanoscale.     

How large a 3JHCCH coupling can be? Prediction of giant vicinal couplings in quinonoid systems

Second-order polarization propagator approximation (SOPPA) and density functional theory (DFT) B3LYP computations revealed the presence of giant ³J_HCCH couplings, up to more than 60 Hz, in conjugated quinonoid systems, very far above the typical limit of ~15 Hz. Strong hyperconjugative interactions of the C–H σ orbitals with the quinonoid 8-e⁻ π system, which allows effective propagation of the spin polarization, seem to be responsible for those extraordinarily large couplings. Computation on several model systems showed the additive nature of the contributions from the available coupling paths to the total coupling.