Co-eluent effect in partition chromatography. Rhamnose-xylose separation with strong and weak cation-exchangers in aqueous ethanol

The effect of ethanol in aqueous eluent on the chromatographic separation was studied at 298 K. Two sugars, L-rhamnose and D-xylose, were separated by using strong and weak cation-exchangers as a stationary phase. The ionic form of the resins was Na+ or Ca2+. The separations were carried out with sugar feed concentrations up to 35 wt% and with both low (about 1%) and high (about 10%) feed volume to bed volume ratios. The separation of the sugars was improved by adding ethanol into the eluent. The separation was also significantly enhanced when the weak cation-exchangers with the greatest affinity for water were used instead of strong cation-exchangers as a separation medium for the sugars having different hydrophilicities. The experimental data were successfully explained with a rate-based column model, which accounted for the volume changes of the stationary phase. A thermodynamic sorption model was utilized in column calculations.     

Narrowband bulk Bragg grating optical parametric oscillator

A narrowband, pulsed optical parametric oscillator (OPO) whose output coupler is a bulk glass Bragg grating is demonstrated. The OPO is based on periodically poled KTiOPO4 and is pumped by a pulsed, frequency-doubled Nd:YAG laser at 532 nm, generating a signal at 975 nm with a total efficiency of 35%. This novel and compact device shows a spectral bandwidth of 0.16 nm (50 GHz), a decrease by a factor of 20 compared with that when a conventional mirror is used. By using a folded cavity, we demonstrate tunable radiation with a tuning range of 60 nm and maintained spectral bandwidth.     

Simultaneous determination of polyether ionophores, macrolides and lincosamides in hen eggs by liquid chromatography-electrospray ionization tandem mass spectrometry using a simple solvent extraction

A liquid chromatography-electrospray ionization tandem mass spectrometric (LC-ESI-MS/MS) method was developed and validated for the determination of residues of 6 polyether ionophores (lasalocid, maduramicin, monensin, narasin, salinomycin, semduramicin), 3 macrolides (erythromycin, tylosin, clarithromycin) and 1 lincosamide (lincomycin) in eggs. Nigericin was used as qualitative internal standard. Samples were deproteinizated/extracted with acetonitrile without pH adjustments. Aliquots of the extracts were evaporated and reconstituted for injection in the instrument operated in positive multiple reaction monitoring (MRM) mode. The stability of the antibiotics and the intensity of the formed ions were considered in order to select a suitable solvent for the reconstitution of the obtained dry extracts. No clean-up steps were required and matrix effects were controlled by sample dilution, selection of appropriate chromatographic conditions and reduced injection volume. Good within-laboratory reproducibility was obtained, with relative standard deviations (RSD(R)) from 4.0 (semduramicin at 5 μgkg(-1)) to 18.6 (erythromycin at 25 μgkg(-1)) for the ionophores and macrolides. Lincomycin showed the least precise results, with a maximum RSD(R) of 20.2% at 75 μgkg(-1)). Satisfactory decision limits (CCα) and detection capabilities (CCβ) were also attained. Method limits of detection (LODs) from 0.04 (salinomycin) to 1.6 μgkg(-1) (lincomycin) were achieved. Method limits of quantification (LOQs) were from 0.14 to 5.3 μgkg(-1) for the same drugs, respectively. All the LOQs, except that obtained for maduramicin were remarkably below the lowest validation level. The proposed method is suitable for routine application in commercial egg samples.     

Mid-infrared ZGP OPO pumped by near-degenerate narrowband type-I PPKTP parametric oscillator

The total pulse energy of the signal and idler in a near-degenerate type-I periodically poled KTiOPO₄ (PPKTP) optical parametrical oscillator (OPO) was spectrally confined within a 2 nm spectral bandwidth at 2.13 μm. This was achieved by using a volume Bragg grating as the output coupler. Both the signal and the idler from the PPKTP OPO were then simultaneously used to pump a mid-infrared ZnGeP₂ (ZGP) OPO. The 2 nm bandwidth was narrower than the ZGP crystal acceptance bandwidth and, thus, made efficient conversion in the second OPO possible. A total slope efficiency of 10% from 1.06 μm to the 3.5–5 μm region was demonstrated, generating 250 μJ in the mid-IR with only 3.6 mJ of 1.06 μm pump energy. This corresponds to a Nd:YAG pump to mid-IR conversion efficiency of 7%. PACS 42.65.Yj; 42.72.Ai; 42.40.Eq     

A quartic force field coordinate substitution scheme using hyperbolic sine coordinates

Quartic force fields (QFF) are currently the most cost‐effective method for the approximation of potential energy surfaces for the calculation of anharmonic vibrational energies. It is known, although, that its performance can be less than satisfactory due to limitations related to slow convergence of the series. In this article, we present a coordinate substitution scheme using a combination of Morse and sinh coordinates, well adapted for its use with cartesian normal coordinates. We derive expressions for analytical integrals for use in VSCF and VCI calculations and show that the simultaneous substitution of symmetric and antisymmetric normal coordinates by Morse and sinh coordinates, respectively, significantly improves the vibrational transition frequencies for these modes in a well‐balanced fashion. The accuracy of this substitution scheme is demonstrated by comparing one and two‐dimensional sections of substituted and unsubstituted QFF with ab initio potential energy grids, as well as with vibrational energy calculations using as test cases two well‐studied benchmark molecules: water and formaldehyde. We conclude that the coordinate substitution scheme presented constitutes a very attractive alternative to simple QFFs in the context of cartesian normal coordinates.     

Stefan–Boltzmann Radiation on Non-convex Surfaces

We consider the stationary heat equation for a non-convex body with Stefan–Boltzmann radiation condition on the surface. The main virtue of the resulting problem is non-locality of the boundary condition. Moreover, the problem is non-linear and in the general case also non-coercive and non-monotone. We show that the boundary value problem has a maximum principle. Hence, we can prove the existence of a weak solution assuming the existence of upper and lower solutions. In the two dimensional case or when a part of the radiation can escape the system we obtain coercivity and stronger existence result. © 1997 by B.G. Teubner Stuttgart-John Wiley & Sons, Ltd.     

Integro-differential equation modelling heat transfer in conducting,radiating and semitransparent materials

In this work we analyse a model for radiative heat transfer in materials that are conductive, grey and semitransparent. Such materials are for example glass, silicon, water and several gases. The most important feature of the model is the non-local interaction due to exchange of radiation. This, together with non-linearity arising from the well-known Stefan–Boltzmann law, makes the resulting heat equation non-monotone. By analysing the terms related to heat radiation we prove that the operator defining the problem is pseudomonotone. Hence, we can prove the existence of weak solution in the cases where coercivity can be obtained. In the general case, we prove the solvability of the system using the technique of sub and supersolutions. © 1998 B. G. Teubner Stuttgart–John Wiley & Sons Ltd.     

Two-dimensional quasi-phase-matched multiple-cascaded four-wave mixing in periodically poled KTiOPO(4)

A two-dimensional quasi-phase-matched structure is realized in a noncollinear, nondegenerate periodically poled KTiOPO(4) parametric oscillator by utilizing the mutual coherence of two noncollinear pump beams. The mutually coherent pump beams form an interference pattern inside the crystal that is directed perpendicular to the existing quasi-phase-matched grating vector and acts as a parametric gain grating. The cavity itself supports two signal wavelengths around 1550 nm with tunable separation, while the gain grating reduces the operational threshold of the oscillator. Furthermore, with this two-dimensional quasi-phase-matched structure, we can demonstrate the generation of new spectral components through multiple chi((2)):chi((2))-cascaded four-wave mixing processes.     

Preparation of in-house reference material of benzylpenicillin in milk and results of a Brazilian proficiency testing scheme

Two milk test materials containing benzylpenicillin and a benzylpenicillin-free material were prepared and used for the operation of a Brazilian proficiency testing (PT) scheme according to the requirements of ISO/IEC 17043. The PT scheme was designed to include laboratories in charge of confirmatory analysis as well as screening analysis. Sets of sample vials, benzylpenicillin-free and spiked items containing 0.2 g of lyophilized milk, were distributed to each participant. Of 20 participants who reported screening data, 18 accomplished satisfying results, providing evidence of the capability of Brazilian laboratories to produce reliable qualitative information. The assigned value (robust average calculated from 6 results) and its uncertainty were (8.28 ± 0.52) μg/L. Participants’ performance was evaluated using z-scores. A small number of participants were able to report quantitative benzylpenicillin results, and consequently care should be taken in the interpretation of the laboratory’s performance, considering the statistical nature of z-scores. Long-term stability testing on remaining PT items showed that a stable benzylpenicillin quality control material was produced and can be used for internal quality control or validation purposes.