Synthesis, spectral and thermal studies on pyrazolate-bridged palladium(II) coordination polymers

Synthesis, spectroscopic characterization and thermal behavior of pyrazolate-bridged palladium complexes [Pd(mu-Pz)(2)](n) (1), [Pd(mu-mPz)(2)](n) (2), [Pd(mu-dmPz)(2)](n) (3), [Pd(mu-IPz)(2)](n) (4) {pyrazolate (Pz(-)), 4-methylpyrazolate (mPz(-)), 3,5-dimethylpyrazolate (dmPz(-)), 4-iodopyrazolate (IPz(-))} have been described in this work. The exobidentate coordination mode of pyrazolato ligands in 1-4 was inferred on basis of IR spectroscopic evidences. TG investigations indicated that the introduction of substituents at the 4 position in the pyrazolyl moiety into coordination polymers do not affect significantly their thermal stability, whereas at the 3 and 5 position reduced the stability of the main chain. Metal palladium was the final product of the thermal decompositions, which was identified by X-ray powder diffraction.

THERMAL ANALYSES OF COORDINATION-COMPOUNDS .2. THERMAL-DECOMPOSITION OF PALLADIUM COMPLEXES WITH TRIPHENYLPHOSPHINE, TRIPHENYLARSINE AND TRIPHENYLSTIBINE

The compounds [PdCl(2)L(2)] and [PdL(4)] (L=PPh(3), AsPh(3), SbPh(3)) were studied by thermogravimetric and differential thermal analyses in air. The residues of thermal decomposition consist of metallic palladium, except in the case of the complexes containing SbPh(3), when the residues are palladium and antimony mixtures in appropriate proportions with respect to the stoichiometry of the related complexes.

Thermal analysis of coordination compounds. Part 1. Thermodecomposition of nickel(II) triphenylphosphine complexes with halides, nitrate, and thiocyanate

The compounds [NiX 2(PPh 3) 2] (where X is Cl -, Br -, I -, NO - 3, NCS -; and PPh 3 is triphenylphosphine) were prepared and characterized by infrared and atomic absorption spectroscopies and by carbon and hydrogen analyses. Simultaneous thermogravimetric (TG) and derivative thermogravimetric (DTG) curves of these complexes were recorded in air. The decrease in mass observed indicates conversion of the complexes to oxides. The thermal decomposition of the halogen and nitrate complexes occurred in a number of steps; the thiocyanate complex decomposed in a single step. © 1994.

Thermal analysis of coordination compounds. Part 3. Thermal decomposition of platinum complexes containing triphenylphosphine, triphenylarsine and triphenylstibine

Studies by thermogravimetric analysis (TG) and differential thermal analysis (DTA) of the complexes [PtCl2L2] (L is PPh3, AsPh3, SbPh3), [PtLn] (n = 3, L is SbPh3; n = 4, L is PPh3, AsPh3); [(PtL3)2N2]; [(PtL3)2C2] and [Pt(CO)2L2] (L is SbPh3) are described. Analysis of the TG and DTA curves showed that Pt(II) complexes of the type [PtCl2L2] have a higher thermal stability than the corresponding Pt(0) complexes of the type [PtLn], with the exception of [Pt(SbPh3)3], which is more stable than [PtCl2(SbPh3)2]. Thermal stabilities of each of the complexes are compared with those of the others in the series. Mechanisms of thermal decomposition of complexes of the types [PtCl2L2] and [PtLn] are proposed. Residues of the samples were characterized by chemical tests and IR spectroscopy. The residue from the thermal decomposition of [PtCl2L2] (L is PPh3, AsPh3) and [Pt(PPh3)4] is metallic platinum. For [Pt(AsPh3)4] the residue is a mixture of Pt and As, whereas for the complexes containing SbPh3 the residues are mixtures of Pt and Sb. In these cases, the proportional contents of Pt and As or Pt and Sb correspond to the stoichiometry of these elements in the respective complexes. The complexes {[Pt(SbPh3)3]2N2}, {[Pt(SbPh3)3]2C2} lose N2 or the ethynediyl group at 130-150°C and are transformed into [Pt(SbPh3)3]. © 1995.

Comparative physical-chemical characterization of encapsulated lipid-based isotretinoin products assessed by particle size distribution and thermal behavior analyses

Isotretinoin is the drug of choice for the management of severe recalcitrant nodular acne. Nevertheless, some of its physical-chemical properties are still poorly known. Hence, the aim of our study consisted to comparatively evaluate the particle size distribution (PSD) and characterize the thermal behavior of the three encapsulated isotretinoin products in oil suspension (one reference and two generics) commercialized in Brazil. Here, we show that the PSD, estimated by laser diffraction and by polarized light microscopy, differed between the generics and the reference product. However, the thermal behavior of the three products, determined by thermogravimetry (TGA), differential thermal (DTA) analyses and differential scanning calorimetry (DSC), displayed no significant changes and were more thermostable than the isotretinoin standard used as internal control. Thus, our study suggests that PSD analyses in isotretinoin lipid-based formulations should be routinely performed in order to improve their quality and bioavailability. (C) 2010 Elsevier B.V. All rights reserved.

Citrate and Phosphate Influence on Green Fluorescent Protein Thermal Stability

Protein structure and function can be regulated by no specific interactions, such as ionic interactions in the presence of salts. Green fluorescent protein (GFP) shows remarkable structural stability and high fluorescence; its stability can be directly related to its fluorescence output, among other characteristics. GFP is stable under increasing temperatures, and its thermal denaturation is highly reproducible. The aim of this study was to evaluate the thermal stability of GFP in the presence of different salts at several concentrations and exposed to constant temperatures, in a range of 70-95 degrees C. Thermal stability was expressed in decimal reduction time. It was observed that the D-values obtained were higher in the presence of citrate and phosphate, when compared with that obtained in their absence, indicating that these salts stabilized the protein against thermal denaturation. (C) 2010 American Institute of Chemical Engineers Biotechnol. Prog., 27: 269-272, 2011

Effect of Polyethylene Glycol on the Thermal Stability of Green Fluorescent Protein

Green fluorescent protein (GFP) shows remarkable structural stability and high fluorescence; its stability can be directly related to its fluorescence output, among other characteristics. GFP is stable under increasing temperatures, and its thermal denaturation is highly reproducible. Some polymers, such as polyethylene glycol, are often used as modifiers of characteristics of biological macromolecules, to improve the biochemical activity and stability of proteins or drug bioavailability. The aim of this study was to evaluate the thermal stability of GFP in the presence of different PEG molar weights at several concentrations and exposed to constant temperatures, in a range of 70-95 degrees C. Thermal stability was expressed in decimal reduction time. It was observed that the D-values obtained were almost constant for temperatures of 85, 90, and 95 degrees C, despite the PEG concentration or molar weight studied. Even though PEG can stabilize proteins, only at 75 degrees C, PEG 600 and 4,000 g/mol stabilized GFP. (C) 2009 American Institute of Chemical Engineers Biotechnol. Prog., 26: 252-256, 2010

Investigation of charged polymer influence on green fluorescent protein thermal stability

Methods of stabilization and formulation of proteins are important in both biopharmaceutical and biocatalysis industries. Polymers are often used as modifiers of characteristics of biological macromolecules to improve the biochemical activity and stability of proteins or drug bioavailability. Green fluorescent protein (GFP) shows remarkable structural stability and high fluorescence; its stability can be directly related to its fluorescence output, among other characteristics. GFP is stable under increasing temperatures, and its thermal denaturation is highly reproducible. Relative thermal stability was undertaken by incubation of GFP at varying temperatures and GFP fluorescence was used as a reporter for unfolding. At 80 degrees C, DEAE-dextran did not have any effect on GFP fluorescence, indicating that it does not confer stability.

Analysis of the wind field and heat budget in an alpine lake basin during summertime fair weather conditions

Observational data collected in the Lake Tekapo hydro catchment of the Southern Alps in New Zealand are used to analyse the wind and temperature fields in the alpine lake basin during summertime fair weather conditions. Measurements from surface stations, pilot balloon and tethersonde soundings, Doppler sodar and an instrumented light aircraft provide evidence of multi-scale interacting wind systems, ranging from microscale slope winds to mesoscale coast-to-basin flows. Thermal forcing of the winds occurred due to differential heating as a consequence of orography and heterogeneous surface features, which is quantified by heat budget and pressure field analysis. The daytime vertical temperature structure was characterised by distinct layering. Features of particular interest are the formation of thermal internal boundary layers due to the lake-land discontinuity and the development of elevated mixed layers. The latter were generated by advective heating from the basin and valley sidewalls by slope winds and by a superimposed valley wind blowing from the basin over Lake Tekapo and up the tributary Godley Valley. Daytime heating in the basin and its tributary valleys caused the development of a strong horizontal temperature gradient between the basin atmosphere and that over the surrounding landscape, and hence the development of a mesoscale heat low over the basin. After noon, air from outside the basin started flowing over mountain saddles into the basin causing cooling in the lowest layers, whereas at ridge top height the horizontal air temperature gradient between inside and outside the basin continued to increase. In the early evening, a more massive intrusion of cold air caused rapid cooling and a transition to a rather uniform slightly stable stratification up to about 2000 m agl. The onset time of this rapid cooling varied about 1-2 h between observation sites and was probably triggered by the decay of up-slope winds inside the basin, which previously countered the intrusion of air over the surrounding ridges. The intrusion of air from outside the basin continued until about mid-night, when a northerly mountain wind from the Godley Valley became dominant. The results illustrate the extreme complexity that can be caused by the operation of thermal forcing processes at a wide range of spatial scales.

Numerical simulations of wind and temperature structure within an Alpine lake basin, Lake Tekapo, New Zealand

High-resolution numerical model simulations have been used to study the local and mesoscale thermal circulations in an Alpine lake basin. The lake (87 km(2)) is situated in the Southern Alps, New Zealand and is located in a glacially excavated rock basin surrounded by mountain ranges that reach 3000 m in height. The mesoscale model used (RAMS) is a three-dimensional non-hydrostatic model with a level 2.5 turbulence closure scheme. The model demonstrates that thermal forcing at local (within the basin) and regional (coast-to-basin inflow) scales drive the observed boundary-layer airflow in the lake basin during clear anticyclonic summertime conditions. The results show that the lake can modify (perturb) both the local and regional wind systems. Following sunrise, local thermal circulations dominate, including a lake breeze component that becomes embedded within the background valley wind system. This results in a more divergent flow in the basin extending across the lake shoreline. However, a closed lake breeze circulation is neither observed nor modelled. Modelling results indicate that in the latter part of the day when the mesoscale (coast-to-basin) inflow occurs, the relatively cold pool of lake air in the basin can cause the intrusion to decouple from the surface. Measured data provide qualitative and quantitative support for the model results.

Distributed MPC for Thermal Comfort and Load Allocation with Energy Auction

This paper presents a distributed predictive control methodology for indoor thermal comfort that optimizes the consumption of a limited shared energy resource using an integrated demand-side management approach that involves a power price auction and an appliance loads allocation scheme. The control objective for each subsystem (house or building) aims to minimize the energy cost while maintaining the indoor temperature inside comfort limits. In a distributed coordinated multi-agent ecosystem, each house or building control agent achieves its objectives while sharing, among them, the available energy through the introduction of particular coupling constraints in their underlying optimization problem. Coordination is maintained by a daily green energy auction bring in a demand-side management approach. Also the implemented distributed MPC algorithm is described and validated with simulation studies.

Climatology of the Iberia coastal low-level wind jet: weather research forecasting model high-resolution results

Coastal low-level jets (CLLJ) are a low-tropospheric wind feature driven by the pressure gradient produced by a sharp contrast between high temperatures over land and lower temperatures over the sea. This contrast between the cold ocean and the warm land in the summer is intensified by the impact of the coastal parallel winds on the ocean generating upwelling currents, sharpening the temperature gradient close to the coast and giving rise to strong baroclinic structures at the coast. During summertime, the Iberian Peninsula is often under the effect of the Azores High and of a thermal low pressure system inland, leading to a seasonal wind, in the west coast, called the Nortada (northerly wind). This study presents a regional climatology of the CLLJ off the west coast of the Iberian Peninsula, based on a 9km resolution downscaling dataset, produced using the Weather Research and Forecasting (WRF) mesoscale model, forced by 19 years of ERA-Interim reanalysis (1989-2007). The simulation results show that the jet hourly frequency of occurrence in the summer is above 30% and decreases to about 10% during spring and autumn. The monthly frequencies of occurrence can reach higher values, around 40% in summer months, and reveal large inter-annual variability in all three seasons. In the summer, at a daily base, the CLLJ is present in almost 70% of the days. The CLLJ wind direction is mostly from north-northeasterly and occurs more persistently in three areas where the interaction of the jet flow with local capes and headlands is more pronounced. The coastal jets in this area occur at heights between 300 and 400 m, and its speed has a mean around 15 m/s, reaching maximum speeds of 25 m/s.

Is the electric vehicle a solution for the wind power integration in the portuguese power system?

The integration of Plug-in electric vehicles in the transportation sector has a great potential to reduce oil dependency, the GHG emissions and to contribute for the integration of renewable sources into the electricity generation mix. Portugal has a high share of wind energy, and curtailment may occur, especially during the off-peak hours with high levels of hydro generation. In this context, the electric vehicles, seen as a distributed storage system, can help to reduce the potential wind curtailments and, therefore, increase the integration of wind power into the power system. In order to assess the energy and environmental benefits of this integration, a methodology based on a unit commitment and economic dispatch is adapted and implemented. From this methodology, the thermal generation costs, the CO2 emissions and the potential wind generation curtailment are computed. Simulation results show that a 10% penetration of electric vehicles in the Portuguese fleet would increase electrical load by 3% and reduce wind curtailment by only 26%. This results from the fact that the additional generation required to supply the electric vehicles is mostly thermal. The computed CO2 emissions of the EV are 92 g CO2/kWh which become closer to those of some new ICE engines.

Silver coordination polymers with tri- and hexacyanoethyl-functionalized macrocyclic ligands

Tri-and hexa-cyanoethyl functionalized 17-(L-1) and 42-membered (L-2) macrocyclic compounds were obtained by [1 + 1] (for L-1) or [2 + 2] (for L-2) cyclocondensation of the corresponding dialdehyde and diethylenetriamine, followed by hydrogenation by KBH4 and subsequent cyano-functionalization with acrylonitrile. They react with silver nitrate, leading to the formation of [AgL1](NO3) (1) and of the metalorganic coordination polymers [Ag-2(NO3)(2)L-1](n) (2) and {[Ag2L2](NO3)(2)}(n) (3). The complexes were characterized by elemental analysis, H-1 NMR, C-13 NMR, IR spectroscopies, and ESI-MS; moreover, L-2, 1, 2 and 3 were also characterized by single crystal X-ray diffraction. The metal cation in 1 is pentacoordinated with a N3O2 coordination environment; in 2, the metal cations display N4O2 octahedral and N2O3 square-pyramid coordination and in 3 they are in square-planar N-4 sites. In 1, the ligand acts as a pentadentate chelator, and in the other two cases, the ligands behave as octadentate chelators in a 1 kappa N-3:kappa O-2,2 kappa N,3 kappa N,4 kappa N (in 2) or 1 kappa N-3,2 kappa N-3,3 kappa N,4 kappa N fashion (in 3). The cyanoethyl strands of the ligands are directly involved in the formation of the 2D frameworks of 2 and 3, which in the former polymer can be viewed as a net composed of hexametallic 36-membered macrocyclic rings and in the latter generates extra hexametallic 58-membered cyclic sets that form zig-zag layers. The thermal analytical and electrochemical properties of these silver complexes were also studied.

Novel coordination polymers with (Pyrazolato)-based tectons: catalytic activity in the peroxidative oxidation of alcohols and cyclohexane

Coupling five rigid or flexible bis(pyrazolato)based tectons with late transition metal ions allowed us to isolate 18 coordination polymers (CPs). As assessed by thermal analysis, all of them possess a remarkable thermal stability, their decomposition temperatures lying in the range of 340-500 degrees C. As demonstrated by N-2 adsorption measurements at 77 K, their Langmuir specific surface areas span the rather vast range of 135-1758 m(2)/g, in agreement with the porous or dense polymeric architectures retrieved by powder X-ray diffraction structure solution methods. Two representative families of CPs, built up with either rigid or flexible spacers, were tested as catalysts in (0 the microwave-assisted solvent-free peroxidative oxidation of alcohols by t-BuOOH, and (ii) the peroxidative oxidation of cydohexane to cydohexanol and cydohexanone by H2O2 in acetonitrile. Those CPs bearing the rigid spacer, concurrently possessing higher specific surface areas, are more active than the corresponding ones with the flexible spacer. Moreover, the two copper(I)-containing CPs investigated exhibit the highest efficiency in both reactions, leading selectively to a maximum product yield of 92% (and TON up to 1.5 x 10(3)) in the oxidation of 1-phenylethanol and of 11% in the oxidation of cydohexane, the latter value being higher than that granted by the current industrial process.