Thermal stability of glucose and other sugar aldoses in normal phase high performance liquid chromatography

Analysis of glucose and other simple sugars are often performed by use of normal phase HPLC methods with acetonitrile as major eluent. The present results clearly show that column temperature plays an important role with respect to chromatographic performance and detection limits of glucose when using a specific carbohydrate column. A change in column temperature from 25 to 45 degrees C reduced the detection of glucose (with ELSD) by more than 41%, whereas the detection of other sugar aldoses (galactose, xylose and rhamnose) were suppressed even more. By increase of column temperature to 70 degrees C the detector signal of glucose was found to be less than 2% compared to that obtained at 20 degrees C. Neither fructose nor sucrose showed similar correlation between column temperature and detection. The rate of decreased response is not dependent on sample concentration or the ELSD settings. The results express the importance of accurate temperature control in the analysis of sugar aldoses, and also values low column temperatures for samples with low concentrations of sugar aldoses in order to improve detection.     

Simultaneous quantification of reduced and oxidized glutathione in plasma using a two-dimensional chromatographic system with parallel porous graphitized carbon columns coupled with fluorescence and coulometric electrochemical detection

A method for the simultaneous quantification of reduced and oxidized glutathione in human plasma employing a two-dimensional chromatographic system with parallel porous graphitized carbon (PGC) columns coupled with fluorescence (FLD) and coulometric electrochemical detection (ED) has been developed. Post-sampling oxidation of reduced glutathione (GSH) was prevented by derivatizing the -SH group with monobromobimane (MBB) and the glutathione-bimane adduct (GSMB) was detected by FLD. Oxidized glutathione (GSSG) was detected by ED optimized to give lowest possible limits of detection (LOD). The method is fully validated and is currently used for determination of GSH, GSSG and its redox potential in different clinical studies.     

Nonlinear propagation acoustics of dual-frequency wide-band excitation pulses in a focused ultrasound system

In this article, acoustic propagation effects of dual-frequency wide-band excitation pulses in a focused ultrasound system are demonstrated in vitro. A designed and manufactured dual-frequency band annular array capable of transmitting 0.9/7.5 MHz center frequency wide-band pulses was used for this purpose. The dual-frequency band annular array, has been designed using a bi-layer piezo-electric stack. Water tank measurements demonstrate the function of the array by activating the low- and high-frequency layers individually and simultaneously. The results show that the array works as intended. Activating the low- and high-frequency layers individually, results in less than -50 dB signal level from the high- and low-frequency layers respectively. Activating both layers simultaneously, produce a well defined dual-frequency pulse. The presence of the low-frequency pulse leads to compression, expansion, and a time delay of the high-frequency pulse. There is a phase shift between the low- and high-frequency pulse as it propagates from the array to the focus. This makes the latter described effects also dependent on the array configuration. By varying the low-frequency pressure, a shift of up to 0.5 MHz in center frequency of a 8.0 MHz transmitted high-frequency pulse is observed at the array focus. The results demonstrate the high propagation complexity of dual-frequency pulses.     

Automated and temperature-controlled micro-PIV measurements enabling long-term-stable microchannel acoustophoresis characterization

We present a platform for micro particle image velocimetry (μPIV), capable of carrying out full-channel, temperature-controlled, long-term-stable, and automated μPIV-measurement of microchannel acoustophoresis with uncertainties below 5% and a spatial resolution in the order of 20 μm. A method to determine optimal μPIV-settings for obtaining high-quality results of the spatially inhomogeneous acoustophoretic velocity fields of large dynamical range is presented. In particular we study the dependence of the results on the μPIV interrogation window size and the number of repeated experiments. The μPIV-method was further verified by comparing it with our previously published particle tracking method. Using the μPIV platform we present a series of high-resolution measurements of the acoustophoretic velocity field as a function of the driving frequency, the driving voltage, and the resonator temperature. Finally, we establish a direct and consistent connection between the obtained acoustophoretic velocity fields, and continuous flow mode acoustophoresis, commonly used in applications.     

High turnover catalysis of water oxidation by Mn(II) complexes of monoanionic pentadentate ligands

Capillary electrophoresis (CE) and electrospray ionisation (ESI) mass spectra of aqueous solutions of manganese(II) complexes of the monoanions of the pentadentate ligands N-methyl-N'-carboxymethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine (mcbpen(-)) and N-benzyl-N'-carboxymethyl-N,N'-bis(2-pyridylmethyl)ethane-1,2-diamine (bcbpen(-)), show the presence of a mixture of closely related Mn(II) species, assigned to the mono, di-, tri- and poly-cationic complexes [Mn(II)(L)(H(2)O)](n)(n+), L = mcbpen(-) or bcbpen(-) with n = 1, 2, 3, etc. In solution, these complexes are reversibly oxidized by tert-butyl hydrogen peroxide (TBHP), (NH(4))(2)[Ce(NO(3))(6)], Ce(ClO(4))(4), oxone and [Ru(bipy)(3)](3+) to form metastable (t(?) = min to h) higher valent (hydr)oxide species, showing a collective maximum absorbance at 430 nm. The same species can be produced by [Ru(bipy)(3)](2+)-mediated photooxidization in the presence of an electron acceptor. TBHP oxidation of the complexes, in large excesses of the TBHP, is concurrent with an O(2) evolution with turnovers of up to 1.5 × 10(4) mol of O(2) per mol of [Mn] and calculated rate constants from two series of experiments of 0.039 and 0.026 mol[O(2)] s(-1) M(-2). A 1:1 reaction of TBHP with [Mn] is rate determining and the resultant species is proposed to be the mononuclear, catalytically competent, [Mn(IV)(O)(mcbpen)](+). At very close m/z values [Mn(III)(OH)(mcbpen)](+), [Mn(2)(III/IV)(O)(2)(mcbpen)(2)](+) and [Mn(IV)(2)(O)(2)(mcbpen)(2)](2+) are detected by ESI MS and CE when the concentration of TBHP is comparable to or lower than that of [Mn]. These are conditions that occur post catalysis and these species are derived from [Mn(IV)(O)(mcbpen)](+) through condensation reactions.     

Practical radical cyclizations with arylboronic acids and trifluoroborates

Practical radical cyclizations using organoboronic acids and trifluoroborates take place in water, open to air, and in a scalable fashion employing catalytic silver nitrate and stoichiometric potassium persulfate. Both Pschorr-type cyclizations and tandem radical cyclization/trap cascades are described, illustrating the utility of these mild conditions for the generation of polycyclic scaffolds.     

Nonlinear propagation delay and pulse distortion resulting from dual frequency band transmit pulse complexes

A method of acoustic imaging is discussed that potentially can improve the diagnostic capabilities of medical ultrasound. The method, given the name second order ultrasound field imaging, is achieved by the processing of the received signals from transmitted dual frequency band pulse complexes with at least partly overlapping high frequency (HF) and low frequency (LF) pulses. The transmitted HF pulses are used for image reconstruction whereas the transmitted LF pulses are used to manipulate the elastic properties of the medium observed by the HF imaging pulses. In the present paper, nonlinear propagation effects observed by a HF imaging pulse due to the presence of a LF manipulation pulse is discussed. When using dual frequency band transmit pulse complexes with a large separation in center frequency (e.g., 1:10), these nonlinear propagation effects are manifested as a nonlinear HF propagation delay and a HF pulse distortion different from conventional harmonic distortion. In addition, with different transmit foci for the HF and LF pulses, nonlinear aberration will occur.     

An acylation‐Finkelstein approach to radioiodination of bioactives: The role of amide group anchimeric assistance

Herein, we report a straightforward sequential acylation‐Finkelstein approach to achieve iodination of amine containing bioactives. The utility was demonstrated by successful radiolabelling with ¹²³I in high radiochemical yield. Moreover, microwave‐assisted Finkelstein reaction can be employed to enhance conversion and reaction rates to obtain the desired iodides. The method is of interest for radioiodination of amine‐containing bioactives. The mechanistic details of the iodination process were studied by kinetics and density functional theory calculations, which revealed the mechanistic complexity of the reaction involving amide group anchimeric assistance. We disclose a number of fundamental aspects of amide group anchimeric assistance in substitution reactions.     

Encapsulation and weighing of samples for analysis

Encapsulation and handling methods for hygroscopic, volatile, oily and other kinds of difficult samples for analysis are described. Hermetical encapsulation is achieved with an electrical spot welder.