Evaluation of a novel stationary phase for the separation of lactose and isomers in lactose-free products using high-performance anion-exchange chromatography coupled with pulsed amperometric detection (HPAEC-PAD).

Lactose intolerance is a widespread condition, which prevents a large number of people from consuming dairy products as a part of their daily diet. It is estimated that an average of 65% of the global population is suffering from lactose intolerance. The global market for 'lactose-free' dairy products is rapidly growing and the criteria for 'lactose-free' labelled products are becoming stricter. To check the lactose contents in these products there is a need for fast, sensitive, and selective analytical method. A method is presented for fast and sensitive determination of lactose and its isomers using High-Performance Anion Exchange Chromatography in combination with Pulsed Amperometric Detection (HPAEC-PAD). The use of a new anion-exchange column, SweetSep™ AEX200, which is a strong anion-exchange column with highly monodisperse 5 µm particles, allowed the separation of all compounds of interest in less than 8 min with high resolution. A variety of dairy products were analyzed to demonstrate the versatility of the method.

Cleaner and stronger: how 8-quinolinolate facilitates formation of Co(III)-thiolate from Co(II)-disulfide complexes.

The formation of Co(III)-thiolate complexes from Co(II)-disulfide complexes using the anionic ligand 8-quinolinolate (quin-) has been studied experimentally and quantum chemically. Two Co(II)-disulfide complexes [Co2(LxSSLx)(Cl)4] (x = 1 or 2; L1SSL1 = 2,2'-disulfanediylbis(N,N-bis(pyridin-2-ylmethyl)ethan-1-amine; L2SSL2 = 2,2'-disulfanedylbis (N-((6-methylpyridin-2-yl)methyl)-N-(pyridin-2-ylmethyl) ethan-1-amine) have been successfully converted with high yield to their corresponding Co(III)-thiolate complexes upon addition of the ligand 8-quinolinolate. Using density functional theory (DFT) computations the d-orbital splitting energies of the cobalt-thiolate compounds [Co(L1S)(quin)]+ and [Co(L2S)(quin)]+ were estimated to be 3.10 eV and 3.07 eV, indicating a slightly smaller ligand-field strength of ligand L2SSL2 than of L1SSL1. Furthermore, the orientation of the quin- ligand in the thiolate compounds determines the stability of the thiolate complex. DFT computations show that the thiolate structure benefits from more electrostatic attraction when the oxygen atom of the quin- ligand is positioned trans to the sulfur atom of the [Co(L1S)]2+ fragment. Quin- is the first auxiliary ligand with which it appeared possible to induce the redox-conversion reaction in cobalt(II) compounds of the relatively weak-field ligand L2SSL2.

Probing the redox-conversion of Co(II)-disulfide to Co(III)-thiolate complexes: the effect of ligand-field strength.

The redox-conversion reaction of cobalt(II)-disulfide to cobalt(III)-thiolate complexes triggered by addition of the bidentate ligand 2,2'-bipyridine has been investigated. Reaction of the cobalt(II)-disulfide complex [Co2(L1SSL1)(X)4] (L1SSL1 = di-2-(bis(2-pyridylmethyl)amino)-ethyldisulfide; X = Cl or Br) [1X] with 2,2'-bipyridine (bpy) resulted in the formation of two different products, namely the cobalt(III)-thiolate complex [Co(L1S)(bpy)]X2 and the unexpected side product [Co2(L1SSL1)(bpy)2(X)2]X2. Crystals of [Co2(L1SSL1)(bpy)2(Cl)2](BPh4)2 [2Cl](BPh4)2 obtained after anion exchange showed the cobalt(II) ions to be in octahedral geometries with the nitrogen donors of the disulfide ligand arranged in a facial conformation and the chloride ion trans to the tertiary amine nitrogen. Remarkably, this side product cannot be converted to the cobalt(III)-thiolate compound [Co(L1S)(bpy)](SbF6)2 [3](SbF6)2 by removal of the chloride ion with use of a silver salt, as this causes scrambling of the ligands, resulting in the formation of [Co(bpy)3]n+. [Co(L1S)(bpy)](SbF6)2 was obtained in a pure form by addition of bpy to a solution in acetonitrile of the compound [Co(L1S)(MeCN)2]2+ [4]2+. Addition of NEt4Cl to [3](SbF6)2 regenerates the cobalt(II)-disulfide complex [1Cl] as confirmed spectroscopically. DFT studies revealed that the conversion from [1Cl] to [3]2+ most likely occurs via the hypothetical intermediate species [2Cl]2+mer, in which the nitrogen atoms of the disulfide ligand are arranged in a meridional conformation. Interestingly, the estimated d-orbital splitting energy of [3]2+ is lower than that of [4]2+, indicating that the ligand-field strength of bpy is lower than anticipated, which hampers clean conversion in the redox-conversion reaction. This study shows that the redox-conversion reaction between cobalt(II)-disulfide and cobalt(III)-thiolate complexes is intricate rather than straightforward.