Fe(II) Spin Crossover/Polymer Hybrid Materials: Investigation of the SCO Behavior via Temperature-Dependent Raman Spectroscopy,Physicochemical Characterization and Migration Release Study

Polymeric composites constitute an appealing class of materials with applications in various fields. Spin crossover (SCO) coordination complexes are switchable materials with potential use in data storage and sensors. Their incorporation into polymers can be considered an effective method for their wider practical application. In this study, Fe(II) SCO/polylactic acid hybrid polymeric composites have been prepared by film casting. The mononuclear coordination complex [Fe{N(CN)₂}₂(abpt)₂] was incorporated into polylactic acid. The morphological, structural and thermoanalytical characterization of the composite films were performed via scanning electron microscopy (SEM), attenuated total reflectance (ATR/FTIR), Raman spectroscopy and differential scanning calorimetry (DSC). In addition, the migration release study (MRS) of the SCO compound from the polymeric matrix into the food simulant 50% v/v water/ethanol solution was also examined via UV/Vis absorption. Of particular interest was the investigation of the SCO behavior of the coordination complex after its incorporation into the polymer matrix; it was accomplished by temperature-dependent micro-Raman spectroscopy. The described attempt could be considered a preparatory step toward the development of SCO-based temperature sensors integrated into food packaging materials.     

A Comparative Study of Various Pretreatment Approaches for Bio-Ethanol Production from Willow Sawdust,Using Co-Cultures and Mono-Cultures of Different Yeast Strains

The effect of different pretreatment approaches based on alkali (NaOH)/hydrogen peroxide (H₂O₂) on willow sawdust (WS) biomass, in terms of delignification efficiency, structural changes of lignocellulose and subsequent fermentation toward ethanol, was investigated. Bioethanol production was carried out using the conventional yeast Saccharomyces cerevisiae, as well as three non-conventional yeasts strains, i.e., Pichia stipitis, Pachysolen tannophilus, Wickerhamomyces anomalus X19, separately and in co-cultures. The experimental results showed that a two-stage pretreatment approach (NaOH (0.5% w/v) for 24 h and H₂O₂ (0.5% v/v) for 24 h) led to higher delignification (38.3 ± 0.1%) and saccharification efficiency (31.7 ± 0.3%) and higher ethanol concentration and yield. Monocultures of S. cerevisiae or W. anomalus X19 and co-cultures with P. stipitis exhibited ethanol yields in the range of 11.67 ± 0.21 to 13.81 ± 0.20 g/100 g total solids (TS). When WS was subjected to H₂O₂ (0.5% v/v) alone for 24 h, the lowest ethanol yields were observed for all yeast strains, due to the minor impact of this treatment on the main chemical and structural WS characteristics. In order to decide which is the best pretreatment approach, a detailed techno-economical assessment is needed, which will take into account the ethanol yields and the minimum processing cost.     

Lanthanide(III)/pyrimidine-4,6-dicarboxylate/oxalate extended frameworks: a detailed study based on the lanthanide contraction and temperature effects

Detailed structural, magnetic, and luminescence studies of six different crystalline phases obtained in the lanthanide/pyrimidine-4,6-dicarboxylate/oxalate system have been afforded: {[Ln(μ-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·3H(2)O}(n) (1-Ln), {[Ln(μ-pmdc)(μ-ox)(0.5)(H(2)O)(3)]·2H(2)O}(n) (2-Ln), {[Ln(μ(3)-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·~2.33H(2)O}(n) (3-Ln), {[Ln(2)(μ(3)-pmdc)(μ(4)-pmdc)(μ-ox)(H(2)O)(3)]·5H(2)O}(n) (4-Ln), {[Ln(μ(3)-pmdc)(μ-ox)(0.5)(H(2)O)(2)]·H(2)O}(n) (5-Ln), and [Ln(pmdc)(1.5)(H(2)O)(2.5)] (6-Ln). The slow generation of the oxalate (ox) anion, obtained from the in situ partial hydrothermal decomposition of the pyrimidine-4,6-dicarboxylate (pmdc) ligand, allows us to obtain good shaped single crystals, while direct addition of potassium oxalate provides the same compounds but as polycrystalline samples. The crystal structures of all compounds are based on the double chelation established by the pmdc and ox ligands to provide distorted 2D honeycomb layers that, in some cases, are fused together, leading to 3D systems, by replacing some of the coordinated water molecules that complete the coordination sphere of the lanthanide by uncoordinated carboxylate oxygen atoms of the pmdc. The presence of channels occupied by crystallization water molecules is also a common feature with the exception of compounds 5-Ln. It is worth noting that compounds 3-Ln present a commensurate crystal structure related to the partial occupancy of the crystallization water molecules placed within the channels. Topological analyses have been carried out, showing a previously nonregistered topology for compounds 4-Ln, named as jcr1. The crystal structures are strongly dependent on the lanthanide ion size and the temperature employed during the hydrothermal synthesis. The lanthanide contraction favors crystal structures involving sterically less hindranced coordination environments for the final members of the lanthanide series. Additionally, reinforcement of the entropic effects at high temperatures directs the crystallization process toward less hydrated crystal structures. The magnetic data of these compounds indicate that the exchange coupling between the lanthanide atoms is almost negligible, so the magnetic behavior is dominated by the spin-orbit coupling and the ligand field perturbation. The luminescence properties that exhibit the compounds containing Nd(III), Eu(III), and Tb(III) have been also characterized.     

Molecular recognition of adeninium cations on anionic metal-oxalato frameworks: an experimental and theoretical analysis

Reactions of adenine with water-soluble oxalato complexes at acidic pH give the compounds (1H,9H-ade)2[Cu(ox)2(H2O)] (1) [H2ade=adeninium cation (1+), ox=oxalato ligand (2-)] and (3H,7H-ade)2[M(ox)2(H2O)2].2H2O [M(II)=Co (2), Zn (3)]. The X-ray single crystal analyses show that the supramolecular architecture of all compounds is built up of anionic sheets of metal-oxalato-water complexes and ribbons of cationic nucleobases among them to afford lamellar inorganic-organic hybrid materials. The molecular recognition process between the organic and the inorganic frameworks determines the isolated tautomeric form of the adeninium cation found in the crystal structures: the canonical 1H,9H for compound 1, and the first solid-state characterized 3H,7H-adeninium tautomer for compounds 2 and 3. Density functional theory calculations have been performed to study the stability of the protonated nucleobase forms and their hydrogen-bonded associations by comparing experimental and theoretical results.     

Porous MII/Pyrimidine‐4,6‐Dicarboxylato Neutral Frameworks: Synthetic Influence on the Adsorption Capacity and Evaluation of CO2‐Adsorbent Interactions

The understanding of the factors that affect the real pore‐network structure for a given bulk material due to different synthetic procedures is essential to develop the material with the best adsorption properties. In this work, we have deeply studied the influence of the crystallinity degree over the adsorption capacity on three new isostructural MOFs with the formula {[CdM(μ₄‐pmdc)₂(H₂O)₂] ? solv}_n (in which, pmdc=pyrimidine‐4,6‐dicarboxylate; solv=corresponding solvent; M^II=Cd ( 1 ), Mn ( 2 ), Zn ( 3 )). Compared with other methods, the solvent‐free synthesis stands as the most effective route because, apart from enabling the preparation of the heterometallic compounds 2 and 3 , it also renders the adsorbents with the highest performance, which is indeed close to the expected one derived from Grand Canonical Monte Carlo (GCMC) calculations. The structural analysis of the as‐synthesised and evacuated frameworks reveals the existence of a metal atom exposed to the pore. The accessibility of this site is limited due to its atomic environment, which is why it is considered as a pseudo‐open‐metal site. The chemical and physical characterisation confirms that this site can be modified as the metal atom is replaced in compounds 2 and 3 . To assess the effect of the metal replacement on the adsorption behaviour, an exhaustive study of CO₂ experimental isotherms has been performed. The affinity of the pseudo‐open metal sites towards CO₂ and the distribution of the preferred adsorption sites are discussed on the basis of DFT and GCMC calculations.     

Rational design of 1-D metal-organic frameworks based on the novel pyrimidine-4,6-dicarboxylate ligand. New insights into pyrimidine through magnetic interaction

Single crystal X-ray analysis of compounds H2pmdc.2H2O (1), KHpmdc (2), and K2pmdc (3) shows that the pyrimidine-4,6-dicarboxylate (pmdc) dianion presents an almost planar geometry which confers a potential capability to act as a bis-bidentate bridging ligand, and therefore, to construct 1-D metal complexes. Based on this assumption, we have designed the first six transition metal complexes based on this ligand of formula {[M(micro-pmdc)(H2O)2].H2O}n [M(II) = Fe (4), Co (5), Ni (6), Zn (7), Cu (8)] and {[Cu(micro-pmdc)(dpa)].4H2O}n (9) (dpa = 2,2'-dipyridylamine). The crystal structure of all of these complexes has been determined by single crystal X-ray measurements, except for compound whose X-ray powder diffraction pattern reveals that it is isostructural to compounds 4-7. The bis-chelating pmdc ligand bridges sequentially octahedrally coordinated M(II) centres leading to polymeric chains. The hexacoordination of the metal centres is completed by two water molecules in compounds 4-8 and by the two endocyclic-N atoms of a terminal dpa ligand in compound . Cryomagnetic susceptibility measurements show the occurrence of antiferromagnetic intrachain interactions for compounds and (J = -2.5 (4), -5.2 (6), -32.7 (8), and -0.9 (9) cm(-1)). Model calculations and analyses of the available experimental data have been used to examine the influence of several factors on the nature and magnitude of the magnetic coupling constants in pyrimidine bridged complexes, showing that metal deviation from the pyrimidine mean plane could lead to ferromagnetic behaviour.     

Quantitative surface enhanced Raman scattering measurements at the early stage of active agent release processes

The surface enhanced Raman scattering spectroscopy (SERS) is introduced as a new method to probe the initial release of active agents from controlled delivery systems. As a model system, mitoxantrone‐loaded polypropylene specimens immersed in water have been utilized. Surface enhanced resonance Raman scattering (SERRS) measurements allowed the quantitative delineation of the initial drug release profile. SERRS was also compared in early stage release processes with UV–vis absorption often used in traditional quantitative analysis via HPLC, a common technique for controlled release evaluation. More and above the high selectivity of the Raman Effect, SERS has been proved as a highly sensitive method to quantitatively monitor the initial release of the medicine even at the very early stage of the delivery process; UV–vis absorbance was unable to respond accordingly. Copyright © 2012 John Wiley & Sons, Ltd.     

High Catalytic Efficiency of a Nanosized Copper-Based Catalyst for Automotives: A Physicochemical Characterization

The global trend in restrictions on pollutant emissions requires the use of catalytic converters in the automotive industry. Noble metals belonging to the platinum group metals (PGMs, platinum, palladium, and rhodium) are currently used for autocatalysts. However, recent efforts focus on the development of new catalytic converters that combine high activity and reduced cost, attracting the interest of the automotive industry. Among them, the partial substitution of PGMs by abundant non-PGMs (transition metals such as copper) seems to be a promising alternative. The PROMETHEUS catalyst (PROM100) is a polymetallic nanosized copper-based catalyst for automotives prepared by a wet impregnation method, using as a carrier an inorganic mixed oxide (CeO₂-ZrO₂) exhibiting elevated oxygen storage capacity. On the other hand, catalyst deactivation or ageing is defined as the process in which the structure and state of the catalyst change, leading to the loss of the catalyst’s active sites with a subsequent decrease in the catalyst’s performance, significantly affecting the emissions of the catalyst. The main scope of this research is to investigate in detail the effect of ageing on this low-cost, effective catalyst. To that end, a detailed characterization has been performed with a train of methods, such as SEM, Raman, XRD, XRF, BET and XPS, to both ceria–zirconia mixed inorganic oxide support (CZ-fresh and -aged) and to the copper-based catalyst (PROM100-fresh and -aged), revealing the impact of ageing on catalytic efficiency. It was found that ageing affects the Ce–Zr mixed oxide structure by initiating the formation of distinct ZrO₂ and CeO₂ structures monitored by Raman and XRD. In addition, it crucially affects the morphology of the sample by reducing the surface area by a factor of nearly two orders of magnitude and increasing particle size as indicated by BET and SEM due to sintering. Finally, the Pd concentration was found to be considerably reduced from the material’s surface as suggested by XPS data. The above-mentioned alterations observed after ageing increased the light-off temperatures by more than 175 °C, compared to the fresh sample, without affecting the overall efficiency of the catalyst for CO and CH₄ oxidation reactions. Metal particle and CeZr carrier sintering, washcoat loss as well as partial metal encapsulation by Cu and/or CeZrO₄ are identified as the main causes for the deactivation after hydrothermal ageing.     

Supramolecular architectures assembled by the interaction of purine nucleobases with metal-oxalato frameworks. Non-covalent stabilization of the 7H-adenine tautomer in the solid-state

The synthesis, crystal structure and variable-temperature magnetic measurements of the compounds [Mn(mu-ox)(H2O)(7H-pur-kappaN9)]n (1), {[Mn(mu-ox)(H2O)2].(7H-ade).(H2O)}n (2) and {[Cu(mu-ox)(H2O)(7H-ade-kappaN9)][Cu(mu-ox)(mu-H2O)(7H-ade-kappaN9)]. approximately 10/3H2O}n (3), (where ox: oxalato dianion, pur: purine, and ade: adenine) are reported. Compounds 1and 2 contain one-dimensional chains in which manganese(II) atoms are bridged by bis-bidentate oxalato ligands. The distorted octahedral geometry around each metal centre is completed in compound 1 by one water molecule and the imidazole N9 donor site of the purine ligand, which is a rare example of direct binding between the Mn(II) ion and the N donor site of an isolated nucleobase. Unlike 1, the adenine moiety in compound 2 is not bonded to manganese atoms and the metal coordination polyhedron is filled by two water molecules in a cis-arrangement. Its crystal building is constructed from pi-stacked layers of Watson-Crick hydrogen-bonded adenine...(H2O2)...adenine aggregates and zig-zag Mn(II)-oxalato chains held together by means of a strong network of hydrogen bonding interactions. The nucleobase exists in the lattice as the 7H-adenine tautomer which represents an unprecedented solid-state characterization of this minor tautomer as free molecule (without metal coordination) stabilized through non-covalent interactions. Compound consists of two slightly different [Cu(ox)(H2O)(7H-ade-kappaN9)] units in which the nucleobase coordinates through the imidazole N9 atom. The planar complex entities are parallel stacked and joined by means of long Cu-O bonds involving oxygen atoms from the oxalato and the aqua ligands, giving one-dimensional chains with a [4 + 1] square-planar pyramidal and a [4 + 2] octahedral coordination around the metal centre, respectively. Self-assembled process of compound 3 is further driven by an in-plane network of hydrogen bonding interactions to generate a porous 3D structure containing parallel channels filled by guest water molecules. Variable-temperature magnetic susceptibility measurements of all the complexes show the occurrence of antiferromagnetic interactions between the paramagnetic centres. DFT calculations have been performed to check the influence of packing in the stability of the 7H-amino tautomer of 2 and in the complex geometry of 3.     

Dielectric and conductivity processes in poly(ethylene terephthalate) and poly(ethylene naphthalate) homopolymers and copolymers

Electrical relaxation and conductivity processes in amorphous and semicrystalline poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) homopolymers and certain PET/PEN copolymers have been studied by means of dielectric spectroscopy. Homopolymers and copolymers able to crystallize were subjected to successive thermal runs to investigate the influence of the thermal history upon the morphology and the electrical behavior of the polymeric systems. The morphology of the untreated as well as the heat‐treated specimens was determined by means of Differential Scanning Calorimetry (DSC). All samples exhibit β‐relaxation process, due to local motions of the C?O polar side groups, and α‐relaxation process associated to the glass/rubber transition. In the PEN spectrum an additional, subglass, mode was recorded, most probably attributed to cooperative motions of the naphthalene groups. Finally, the dynamic nature of the crystallization process is expressed via the over glass transition mode and the temperature dependence of dc conductivity recorded in amorphous PET, PEN, and PET/PEN (85/15) (wt/wt) samples. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3078–3092, 2006