Impact of injection solvents on supercritical fluid chromatography.

Even though there has been a rapid development in instrumentation and applications of supercritical fluid chromatography (SFC), relatively little is known about retention mechanisms compared to high-performance liquid chromatography (HPLC). Much effort has been made to characterize the influence of injection solvents on chromatographic efficiency in HPLC, however has been left rather uninvestigated in the domain of SFC. In this study properties of different injection solvents have been studied and correlated with properties of seven various analytes on three different columns, a C18, a 2-ethylpyridine and a bare-silica column. Aided by calculations of correlation coefficients and principal component analysis (PCA), the physical properties of injection solvents and the interactions between injection solvent, solute and stationary phase were investigated. The findings of this work shows that interactions capable of masking accessible silanol groups on a C18 column are of importance in order to maximize the plate number. While solvents with dipolar and hydrogen bond interaction properties are associated negatively with chromatographic efficiency using polar columns. Properties such as molar density, vapor pressure and boiling point were related to sharper peaks, mostly likely because of solubility issues of the injection solvent into the methanol-modified carbon dioxide. However, no additional solubility due to hydrogen interactions between the injection solvent and the carbon dioxide in SFC was observed. Surface tension and viscosity was not particularly associated with a decrease in plate numbers. By increasing the injection volume a stronger correlation between solubility related properties and plate numbers were obtained. Additional experiments showed that the resistance in solubility became an issue when performing partial-loop injection where additional washing solvent entered the system, thus providing broadened peaks

Method development in inverse modeling applied to supercritical fluid extraction of lipids

Modeling of the supercritical fluid extraction of solid materials is an important aspect in order to understand and predict the process. A comparison of two empirical models, two semi-empirical models and two mechanistic models is performed using calibration of single experiments. It is concluded that the best fit is obtained using a simple empirical expression. Furthermore, single calibrations did not generate reliable parameters with physical meaning and a methodology is proposed for inverse modeling with complete calibration using several experiments. The experimental dataset contained 29 extractions of lipids from crushed linseeds with varying temperatures, pressures and flow rates. A general rate model and a proposed extension of the hot ball model were evaluated for this purpose. The methodology includes data acquisition, model structure estimation, model calibration and a cross-validation. In general, it was found that the solubility model of Sovová outperformed the other evaluated correlations, and for the general rate model the Toth partition isotherm was also found in the top model structures. However, no generalization could be made regarding the correlations describing the Nernst diffusion layer and diffusivity

Photophysical characterization of the 9,10-disubstituted anthracene chromophore and its applications in triplet-triplet annihilation photon upconversion

Molecules based on anthracene are commonly used in applications such as OLEDs and triplet-triplet annihilation upconversion. In future design of blue emitting materials it is useful to know which part of the molecule can be altered in order to obtain new physical properties without losing the inherent optical properties. We have studied the effect of substitution of 9,10-substituted anthracenes. Eight anthracenes with aromatic phenyl and thiophene substituents were synthesised, containing both electron donating and accepting groups. The substitutions were found to affect the UV/Vis absorption only to a small extent, however the fluorescence properties were more affected with the thiophene substituents that decreased the fluorescence quantum yield from unity to <10%. DFT calculations confirm the minor change in absorption and indicate that the first and second triplet state energies are also unaffected. Finally the three most fluorescent derivatives 4-(10-phenylanthracene-9-yl) pyridine, 9-phenyl-10-(4-(trifluoromethyl)phenyl) anthracene and 4-(10-phenylanthracene-9-yl) benzonitrile were successfully utilized as annihilators in a triplet-triplet annihilation upconversion (TTA-UC) system employing platinum octaethylporphyrin as the sensitizer. The observed upconversion quantum yields, phi(UC), slightly exceeded that of the benchmark annihilator 9,10-diphenylanthracene (DPA)

Covalent incorporation of diphenylanthracene in oxotriphenylhexanoate organogels as a quasi-solid photon upconversion matrix

Triplet-triplet annihilation photon upconversion (TTA-UC) in solid state assemblies are desirable since they can be easily incorporated into devices such as solar cells, thus utilizing more of the solar spectrum. Realizing this is, however, a significant challenge that must circumvent the need for molecular diffusion, poor exciton migration, and detrimental back energy transfer among other hurdles. Here, we show that the above-mentioned issues can be overcome using the versatile and easily synthesized oxotriphenylhexanoate (OTHO) gelator that allows covalent incorporation of chromophores (or other functional units) at well-defined positions. To study the self-assembly properties as well as its use as a TTA-UC platform, we combine the benchmark couple platinum octaethylporphyrin as a sensitizer and 9,10-diphenylanthracene (DPA) as an annihilator, where DPA is covalently linked to the OTHO gelator at different positions. We show that TTA-UC can be achieved in the chromophore-decorated gels and that the position of attachment affects the photophysical properties as well as triplet energy transfer and triplet-triplet annihilation. This study not only provides proof-of-principle for the covalent approach but also highlights the need for a detailed mechanistic insight into the photophysical processes underpinning solid state TTA-UC

Singlet and triplet energy transfer dynamics in self-assembled axial porphyrin-anthracene complexes: Towards supra-molecular structures for photon upconversion

Energy and electron transfer reactions are central to many different processes and research fields, from photosynthesis and solar energy harvesting to biological and medical applications. Herein we report a comprehensive study of the singlet and triplet energy transfer dynamics in porphyrin-anthracene coordination complexes. Seven newly synthesized pyridine functionalized anthracene ligands, five with various bridge lengths and two dendrimer structures containing three and seven anthracene units, were prepared. We found that triplet energy transfer from ruthenium octaethylporphyrin to an axially coordinated anthracene is possible, and is in some cases followed by back triplet energy tra nsfer to the porphyrin. The triplet energy transfer follows an exponential distance dependence with an attenuation factor, β, of 0.64 \uc5 -1 . Further, singlet energy transfer from anthracene to the ruthenium porphyrin appears to follow a R 6 F\uf6rster distance dependence. Porphyrin-anthracene complexes are also used as triplet sensitizers for triplet-triplet annihilation (TTA) based photon upconversion, demonstrating their potential for photophysical and photochemical applications. The triplet lifetime of the complex is extended by the anthracene ligands, resulting in a threefold increase in the upconversion efficiency, Φ UC to 4.5%, compared to the corresponding ruthenium porphyrin-pyridine complex. Based on the results herein we discuss the future design of supra-molecular structures for TTA upconversion

Excitation of emission lines by fluorescence and recombination in IC 418

We predict intensities of lines of CII, NI, NII, OI and OII and compare them with a deep spectroscopic survey of IC 418 to test the effect of excitation of nebular emission lines by continuum fluorescence of starlight. Our calculations use a nebular model and a synthetic spectrum of its central star to take into account excitation of the lines by continuum fluorescence and recombination. The NII spectrum is mostly produced by fluorescence due to the low excitation conditions of the nebula, but many CII and OII lines have more excitation by fluorescence than recombination. In the neutral envelope, the NI permitted lines are excited by fluorescence, and almost all the OI lines are excited by recombination. Electron excitation produces the forbidden optical lines of OI, but continuum fluorescence excites most of the NI forbidden line intensities. Lines excited by fluorescence of light below the Lyman limit thus suggest a new diagnostic to explore the photodissociation region of a nebula.Comment: 2 pages, 4 figures, to appear in proceedings of the IAU Symposium 283: "Planetary Nebulae: An Eye to the Future", Eds.: A. Manchado, L. Stanghellini and D. Schoenberne