Chromatographic characterization of thermally upgraded products from alternative fuels

An overview is presented of the analytical approaches developed by our research group over the last ten years for analysis of alternative fuel, both biomass and fossil. The alternative fuels are analyzed successively by PLC-8 (preparative liquid chromatography–group-type) fractionation and high resolution gas chromatography. Some of the possibilities for fractionation and characterization of alternative fuels are herein exemplified with sugar cane bagasse pyrolysis products.     

Towards understanding the increase in strength of thermotropic polyesters with heat treatment

Thermotropic copolyester fibers of oxynaphthoate and oxybenzoate have been subjected to conditions that promote solid-state polymerization as well as annealing. The annealing process causes the crystals to perfect with a simultaneous increase in heat of fusion and melting temperature. Solid-state polymerization, a reaction rate-controlled process, causes the polymer viscosity average molecular weight to increase by chain extension from about 14,000 g/mole to more than 87,000 g/mole with a simultaneous impressive increase in tenacity from about 10 g/d (1.2 GPa) to almost 30 g/d (3.7 GPa). To understand the changes in mechanical properties, we have modeled the fiber structure as short rod-like molecules poorly bonded to a continuous matrix of parallel molecules. Lengthening of the reinforcing molecules facilitates better transfer of load from matrix to molecules, resulting in higher tenacity fibers. © 1994 John Wiley & Sons, Inc.     

On interrelation between the internal pressure and the cohesion energy density

The question about the definition of the “internal pressure” concept is being discussed. It is shown that the previously found differential relation between the cohesion energy density and the internal pressure is one of the examples of an absolutely general interrelation between definitely connected differential functions. It is ascertained that the ratio (the internal pressure divided by the cohesion energy density) is a structuresensitive parameter inherent to the calorific (thermal) equation of a liquid state.     

Influence of Relative Permeability on the Stability Characteristics of Immiscible Flow in Porous Media

Relative permeability functions for immiscible displacements in porous media show a wide range of profiles. Although, this behavior is well known, its impact on the stability of the displacement process is unexplored. Our analysis clearly demonstrates for the first time that the viscous instability characteristics of two-phase flows are governed not only by their end point values, but are strongly dependent on the actual profile of relative permeability functions. Linear stability analysis predicts the capacity of the flow to develop large scale fingers which can result in substantial bypassing of the resident fluid. It is observed that relative permeability functions attributed to drainage processes yield a more unstable displacement as compared to functions related to imbibition processes. Moreover, instability is observed to increase for those relative permeability functions which result from increased wettability of the wetting fluid. High accuracy numerical simulations show agreement with these predictions and demonstrate how large amplitude viscous fingers result in significant bypassing for certain relative permeability functions. In the nonlinear regime, the finger amplitude grows at a rate ∝ t^1/2 initially, drops to t^1/4 at a later time and finally grows ∝ t. The basic mechanisms of finger interaction, however, are not substantially influenced by relative permeability functions.     

Separation of Monovinyl and Divinyl Protochlorophyllides Using C30 Reverse Phase High Performance Liquid Chromatography Column: Analytical and Preparative Applications

A new, high performance liquid chromatography method has been developed for the separation of monovinyl- and divinyl-protochlorophyllides, using commercially available, C₃₀ reverse phase column and isocratic elution. This method can be used both for analytical applications and preparative scale purification of monovinyl- and divinyl-protochlorophyllides using the same column where submilimolar concentrations of the crude protochlorophyllide extract can be separated in one run. The purity of the obtained protochlorophyllides was demonstrated by spectroscopic methods, as well by the formation of aggregates in toluene.     

Thermal transformations of selected transition metals oxyhydroxides

We investigated the features of the glass transition relaxation of two room temperature ionic liquids using DSC. An important observation was that the heat capacity jump, that is the signature of the glass transition relaxation, shows a particularly strong value in this type of new and promising materials, candidates for a range of applications. This suggests a high degree of molecular mobility in the supercooled liquid state. The study of the influence of the heating rate on the temperature location of the glass transition signal, allowed the determination of the activation energy at the glass transition temperature, and the calculation of the fragility index of these two ionic glass-formers. It was concluded that this kind of materials belong to the class of relatively strong glass-forming systems. This revised version was published online in July 2006 with corrections to the Cover Date.     

A novel greener glycosidation using an acid-ionic liquid containing a protic acid

The glycosidations of glucopyranosyl diethyl phosphite and alcohols using an ionic liquid, 1-n-hexyl-3-methylimidazolium trifluoromethanesulfonimidide (C₆mim[NTf₂]) containing a protic acid, trifluoromethanesulfonimide (HNTf₂), as a novel solvent-catalyst system, effectively proceeded under mild conditions to give the corresponding glycosides in good to high yields. Furthermore, this acid-ionic liquid combination could be reused many times for the glycosidations without any loss in efficiency.     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Liquid Chromatography-Mass Spectrometry Determination of Six 5-Nitroimidazoles in Animal Feedstuff

A liquid chromatography-mass spectrometry method for the determination of the coccidiostats metronidazole, ronidazole, dimetridazole, secnidazole, tinidazole and ipronidazole in feedstuff was developed. The 5-nitroimidazoles were extracted from animal feed with a pH 2 phosphate buffer solution followed by a solid phase extraction procedure based on HLB cartridges. The liquid chromatographic separation of the extracts was performed on a C₁₈ bonded silica column applying a gradient of elution with pH 4.3 ammonium acetate buffer solution and acetonitrile. Quantification for each 5-nitroimidazole was carried out monitoring its molecular ion [M + H]⁺ obtained by positive electrospray ionisation mode. A pool of feedstuffs was used to optimise and validate the method. Linearity, quantification limit, intra-day and inter-day reproducibility and accuracy were estimated using this pool of feedstuffs spiked with the drugs. For the confirmatory assay, several fragment ions from each 5-nitroimidazole were obtained and monitored. The method was applied successfully to determine 5-nitroimidazoles in feedstuff at level of 0.05 mg kg⁻¹.