Development and Application of new C30-Modified TLC Plates

JPC – Journal of Planar Chromatography – Modern TLC - This paper reports the efficiency of the C30 phase for HPLC and TLC separation of a mixture of tocopherol homologs and...     

Splitless on-line coupling of capillary high-performance liquid chromatography,capillary electrochromatography and pressurized capillary electrochromatography with nuclear magnetic resonance spectroscopy

A mixture of unsaturated fatty acid methyl esters was separated with a new splitless capillary set-up. With the employed apparatus configuration different capillary separation techniques such as capillary high-performance liquid chromatography (cHPLC), capillary electrochromatography (CEC) and pressurized capillary electrochromatography (pCEC) could be applied. The detection and identification of the sample compounds were accomplished by hyphenating these capillary separation techniques with nuclear magnetic resonance (NMR) spectroscopy using a novel configuration of the detection capillary set-up. Using modified electrokinetically driven separation techniques, the electric field was applied solely across the separation column. With this improved interface for capillary liquid chromatography-NMR on-line coupling, the stereochemical assignment of the cis and trans configuration of unsaturated fatty acids could be easily accomplished. Finally, the results of cHPLC-NMR, CEC-NMR and pCEC-NMR coupling experiments were compared.Dedicated to Professor Günter Häfelinger on the occasion of his 65th birthday     

Possible reaction coordinates in the metastable states of sodiumnitroprusside Na2[Fe(CN)5NO]2H2O: a discussion based on neutron diffraction- and spectroscopic measurements

The metastable states of sodiumnitroprusside are extremely stable at temperatures below 200 K. It is possible to allocate structural changes measured by neutron diffraction to measured spectroscopic parameters, but the amount of the structural change is relatively small for a reaction co-ordinate as the metastable states have an extremely long lifetime. New hypotheses for related systems try to explain such a phenomena in two ways: The first way is a bending of the NO-bond in the metastable state, the second one an exchange of the oxygen and nitrogen atoms in the NO-bond (which can be regarded as an bending). As such changes would be possible also from our density functional calculations, we re-investigated our neutron diffraction data using the new models. However, our results are not compatible with one of these models. On the contrary, the neutron diffraction data show partially opposite tendencies. We compare both models with EXAFS measurements, with vibrational spectroscopic results and the data found by M?ssbauer spectroscopy. We propose a potential scheme for all three states (GS, and ) extracted from absorption and thermodynamic data to explain the electronic and energetic rearrangement, and the population dynamics. Received: 23 June 1997 / Accepted: 13 October 1997     

Error estimates for Rayleigh scattering density and temperature measurements in premixed flames

Rayleigh scattering has become an accepted technique for the determination of total number density during the combustion process. The interpretation of the ratio of total Rayleigh scattering signal as a ratio of densities or temperatures is hampered by the changing composition through a flame, since the average Rayleigh scattering cross-section depends on the gas composition. Typical correction factors as a function of degree of reaction, fuel and equivalence ratio were calculated. The fuels considered were H₂, CH₄, C₂H₄, C₂H₆ and C₃H₈. Factors as low as 0.7 and 0.56 were found for the heaviest hydrocarbon fuel at large equivalence ratio for interpreting the Rayleigh scattering intensity as gas density and inverse temperature, respectively. This is primarily due to the presence of CO and H₂ as intermediates. As CO and H₂ are subsequently oxidized to CO₂ and H₂O, these factors approach 1.0. Conversely, the worst case, when using H₂ as a fuel, occurs in the post flame zone. However, the correction factors for H₂ are near 1.0 and the errors involved will, in general, remain within the expected experimental accuracy of a typical Rayleigh scattering system. Linear correlations of correction factors with equivalene ratio and with the product of equivalence ratio and fuel molecular weight were found and presented. The interpretation of Rayleigh scattering as temperature was found to have larger errors than the interpretation as density. Corrections for changes in gas composition were applied to Rayleigh scattering temperature measurements in the post flame region of CH₄ and C₃H₈ flames with equivalence ratios of 0.75 and 1.0. The corrected temperatures were in excellent agreement with thermocouple measurements.List of symbols A ₁, A ₂ correlation coefficients - B ₁, B ₂ correlation coefficients - C ₁, C ₂ correlation coefficients - D ₁, D ₂ correlation coefficients - C calibration constant for Rayleigh scattering optics - H total enthalpy - Î I _R /I _RO - I _i incident laser intensity - I _R Rayleigh scattering intensity - I _R0 Rayleigh scattering intensity at reference condition - N total number density of gas - N ₀ total number density of gas at reference condition - n _i index of refraction of species i - – T/T _O - T temperature - T _a adiabatic flame temperature - T ₀ reference temperature - t time - W/W ₀ - W mean molecular weight - W ₀ mean molecular weight at reference condition - W _ij rate of production of species i by reaction j - X _i mole fraction of species i - degree of reaction (T – T ₀)/(T _a – T ₀) - laser wavelength - ₀ Loschmidt number - /₀ - density - ₀ density at reference condition - dimensionless mean Rayleigh scattering cross-section - _Ri Rayleigh scattering cross-section of species i - scattering angle measured from the electromagnetic field vector - equivalence ratio     

Application of high-performance liquid chromatography-nuclear magnetic resonance coupling to the identification of limonoids from mahogany tree (Switenia macrophylla, Meliaceae) by stopped-flow 1D and 2D NMR spectroscopy

Separation and characterization of limonoids from Switenia macrophylla (Meliaceae) by HPLC-NMR technique has been described. Analyses were carried out using reversed-phase gradient HPLC elution coupled to NMR (600 MHz) spectrometer in stopped-flow mode. Separated peaks were collected into an interface unit prior to NMR measurements, which were performed with suppression of solvent signals by shaped pulses sequences. Structure elucidation of the limonoids was attained by data obtained from 1H NMR, TOCSY, gHSQC and gHMBC spectra without conventional isolation that is usually applied in natural products studies.     

Synthesis and antidepressant evaluation of three para-benzoquinone mono-oximes and their oxy derivatives

A series of three para-benzoquinone mono-oximes and four oxy-derivatives were prepared and tested for their antidepressant properties. The (4E) oxime of 2-isopropyl-5-methyl-para-benzoquinone (4) and the corresponding 2-diethylamino-ethyl derivative (10) present antidepressant activities and were slightly more potent than the reference standard.     

Preparation of a new C18 stationary phase containing embedded urea groups for use in high-performance liquid chromatography

A new C18 urea stationary phase was prepared by a single-step modification process through the reaction of ProntoSil spherical silica (3 microm, Bischoff) with the trifunctional alkoxysilane (CH3CH2O)3-Si-(CH2)3-NH-C(O)-NH-(CH2)17-CH3, prepared in our laboratory. The phase was characterized by elemental analysis and solid-state 29Si and 13C nuclear mangnetic resonance spectrometry. Chromatographic evaluations of the new phase in 150 x 3.9 mm HPLC columns involving the separation of different test mixtures, indicate good performance for both polar and basic mixtures and also show promising results for further applications.     

Magnetic structure and magnetic excitations in the two-dimensional spin system of the Cu<Subscript>3</Subscript>B<Subscript>2</Subscript>O<Subscript>6</Subscript> compound

This paper reports on the results of measurements of the magnetic susceptibility, heat capacity, neutron scattering, muon spin relaxation, and electron paramagnetic resonance in Cu₃B₂O₆ for the study of the ground state of the spin system of this compound. The results obtained suggest that, at a temperature of 10 K, the spin subsystem of the crystal, which consists of single spins and clusters of pairs and fours of spins interacting with one another, undergoes a transition to a state representing a superposition of the singlet (for clusters) and magnetically ordered (for single spins) states.     

Neutron scattering study of the field-dependent ground state and the spin dynamics in spin-one-half NH4CuCl3

Elastic and inelastic neutron scattering experiments have been performed on the dimer spin system NH4CuCl3, which shows plateaus in the magnetization curve at m=1/4 and m=3/4 of the saturation value. Two structural phase transitions at T1 approximately 156 K and at T(2)=70 K lead to a doubling of the crystallographic unit cell along the b direction and as a consequence a segregation into different dimer subsystems. Long-range magnetic ordering is reported below T(N)=1.3 K. The magnetic field dependence of the excitation spectrum identifies successive quantum phase transitions of the dimer subsystems as the driving mechanism for the unconventional magnetization process in agreement with a recent theoretical model.     

Nonpremixed bluff-body burner flow and flame imaging study

A nonpremixed bluff-body burner flow and flame have been studied using planar flow visualization and species concentration imaging techniques. The burner consists of a central jet of CH ₄ in a cylindrical bluff-body and an outer coflowing-air stream. Planar flow visualization, using Mie scattering from seed particles added to the fuel jet, Raman scattering from CH ₄ and laser-induced fluorescence of CH combined with Raman scattering of CH ₄ provided information on turbulent flow, mixing and combustion. The CH ₄ imaging system utilized two cameras, which enhanced the dynamic range of the diagnostic system by a factor of 10 over a single-camera system. It was observed that the fuel jet stagnated on the axis due to interaction with the high velocity air flow. The flow and mixing were found to have significant coherent and noncoherent, large-scale, time-varying structures. The detailed CH ₄ Raman and CH fluorescence measurements of an air-dominated bluff-body flame revealed that the stagnation zone governs mixing and flame stability. Through large-scale mixing, the stagnated jet feeds the recirculation zone and also creates a favorable condition to stabilize the flame detached from the bluff-body. The instantaneous flame zone, as defined by CH, was found to be narrow and concentrated in an envelope around the stagnation zone. This narrow flame characteristic is consistent with that observed for jet flames. Although the internal structure of the flame envelops have not yet been defined, these results suggest that this bluff-body flame can be modeled by a flame sheet type approach, where the reaction front is captured by the large-scale structures. This should simplify the development of modeling approaches for these flows since molecular mixing and chemical reaction, which occur within the flame sheet, can be separated from the large-scale mixing process.