Structural elucidation of complex polyesters polyols from bio-lubricant using off-line liquid chromatography x supercritical fluid chromatography coupled with Orbitrap mass spectrometry.

Synthetic complex esters and polyol esters are incorporated as partially bio-based and biodegradable alternatives to petroleum base oils in lubricant formulations, to provide specific properties or performance and to help reducing their carbon footprint in certain cases. A sample can contain over 400 molecules of high chemical similarity including numerous isomers. To resolve such complexity, a separation technique with large peak capacity coupled to high-resolution mass spectrometry (HRMS) is essential. In this study, comprehensive off-line LCxSFC hyphenated with an Orbitrap analyzer was used for the structural elucidation of a synthetic bio-lubricant composed of a polyol reacted with fatty acids of varying length or with repetitive units of polyesters of ricinoleic acid. Retention in the LC first dimension was mostly due to the degree of oligomerization of ricinoleic acid within the polyester and to the chain length of the fatty acid. The SFC second dimension highlighted the esterification degree of the polyalcohol and the number and positions of fatty acids double bonds. The combination of both dimensions permitted the separation of isomers. The coupling of SFC with Orbitrap analyzer allowed an accurate assignment of molecular formulas. Finally, the fragmentation in the ionization source confirmed the attributed structures. By introducing a clear distribution of the chemical structures in the retention space, LCxSFC-HRMS provided a powerful analytical method for the comprehensive molecular characterization of the complex polyester polyols sample.

Reactive Desorption Electrospray Ionization Mass Spectrometry To Determine Intrinsic Degradability of Poly(lactic-co-glycolic acid) Chains.

Because of its speed, sensitivity, and ability to scrutinize individual species, mass spectrometry (MS) has become an essential tool in analytical strategies aimed at studying the degradation behavior of polyesters. MS analyses can be performed prior to the degradation event for structural characterization of initial substrates or after it has occurred to measure the decreasing size of products as a function of time. Here, we show that MS can also be usefully employed during the degradation process by online monitoring the chain solvolysis induced by reactive desorption electrospray ionization (DESI). Cleavage of ester bonds in random copolymers of lactic acid (LA) and glycolic acid (GA) was achieved by electrospraying methanol-containing NaOH onto the substrates. Experimental conditions were optimized to generate methanolysis products of high abundance so that mass spectra can be conveniently processed using Kendrick-based approaches. The same reactive-DESI performance was demonstrated for two sample preparations, solvent casting for soluble samples or pressed pellets for highly crystalline substrates, permitting to compare polymers with LA/GA ratios ranging from 100/0 to 5/95. Analysis of sample fractions collected by size exclusion chromatography showed that methanolysis occurs independently of the original chain size, so data recorded for poly(LA-co-GA) (PLAGA) copolymers with the average molecular weight ranging from 10 to 180 kDa could be safely compared. The average mass of methanolysis products was observed to decrease linearly (R2 = 0.9900) as the GA content increases in PLAGA substrates, consistent with the susceptibility of ester bonds toward solvolysis being higher in GA than in LA. Because DESI only explores the surface of solids, these data do not reflect bulk degradability of the copolymers but, instead, their relative degradability at the molecular level. Based on a "reactive-DESI degradability scale" such as that established here for PLAGA, the proposed method offers interesting perspectives to qualify intrinsic degradability of different polyesters and evaluate their erosion susceptibility or to determine the degradability of those polymers known to degrade via erosion only.

Mass Spectrometry-Based Analytical Strategy for Comprehensive Molecular Characterization of Biodegradable Poly(lactic-co-glycolic Acid) Copolymers.

An analytical methodology with mass spectrometry as the core technique was developed for precise characterization of end groups, size, and co-monomeric composition of poly(lactic-co-glycolic acid) (PLGA) copolymers, as a preliminary step to qualify their biodegradability. Four PLGA samples were studied, with GA molar content varying from 0 to 50% and Mw ranging from 18 to 75 kg mol-1 according to the supplier. Size exclusion chromatography (SEC) and liquid state nuclear magnetic resonance (NMR) were used as either complementary or validation techniques. As confirmed by tandem mass spectrometry (MS/MS) experiments, macrocycles were most prominent in the low mass range. Nevertheless, elemental compositions derived from high resolution (HR) mass measurements of linear species were consistent with chain terminations revealed by NMR. Off-line coupling of SEC with matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) permitted calibration curves to be built based on absolute molecular weights and, although slightly overestimated, so-obtained Mn and Mw values compared well with SEC and NMR results. Homogeneity of the co-monomeric content of all chains within each PLGA sample was demonstrated using surface-assisted laser desorption/ionization in a reactive mode (reactive-SALDI), a newly developed technique that takes advantage of residual acid on desorption ionization using through-hole alumina membrane (DIUTHAME) chips to induce dissociation of high-molecular-weight polymers containing cleavable C-O bonds. All HRMS data were best handled with Kendrick analysis, which helped reveal minor species and allowed automated computation of congested mass spectra.

Iridium(I)/N-Heterocyclic Carbene Hybrid Materials: Surface Stabilization of Low-Valent Iridium Species for High Catalytic Hydrogenation Performance.

An Ir(I) (NHC)-based hybrid material was prepared using a methodology which allowed the precise positioning and isolation of the Ir centers along the pore channels of a silica framework. The full characterization of the material by solid-state NMR spectroscopy showed that the supported Ir sites were stabilized by the silica surface, as low-coordinated single-site complexes. The material is extremely efficient for the hydrogenation of functional alkenes. The catalytic performance (TOF and TON) is one to two orders of magnitude higher than those of their molecular Ir analogues, and could be related to the prevention of the bimolecular deactivation of Ir complexes observed under homogeneous conditions.

Interplay between cationic and neutral species in the rhodium-catalyzed hydroaminomethylation reaction.

The reactivity of [Rh(CO)(2){(R,R)-Ph-BPE}]BF(4) (2) toward amine, CO and/or H(2) was examined by high-pressure NMR and IR spectroscopy. The two cationic pentacoordinated species [Rh(CO)(3) {(R,R)-Ph-BPE}]BF(4) (4) and [Rh(CO)(2)(NHC(5)H(10)){(R,R)-Ph-BPE}]BF(4) (8) were identified. The transformation of 2 into the neutral complex [RhH(CO)(2){(R,R)-Ph-BPE}] (3) under hydroaminomethylation conditions (CO/H(2), amine) was investigated. The full mechanisms related to the formation of 3, 4 and 8 starting from 2 are supported by DFT calculations. In particular, the pathway from 2 to 3 revealed the deprotonation by the amine of the dihydride species [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}]BF(4) (6), resulting from the oxidative addition of H(2) on 2.

Interception of a Rh(I)-Rh(III) dinuclear trihydride complex revealing the dihydrogen activation by [Rh(CO)2{(R,R)-Ph-BPE}].

Reaction of [Rh(CO)(2){(R,R)-Ph-BPE}][BF(4)] 1 under 7 bar H(2) provides the dihydride [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}][BF(4)] 3, which reacts with the neutral hydride [Rh(H)(CO){(R,R)-Ph-BPE}] 2 arising from 3 in THF. The resulting complex is the dimeric monocationic Rh((I))-Rh((III)) complex [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}][BF(4)] 4.

Acyl-CoA thioesterase activity in human placental choriocarcinoma (BeWo), cells: effects of fatty acids.

The effects of fatty acids on acyl-CoA thioesterase activity and peroxisome proliferator-activated receptor gamma (PPARgamma), a regulator of lipid metabolism, were investigated in placental choriocarcinoma (BeWo) cells. Substrate preference for acyl-CoA thioesterase was in the following order; gamma-linolenoyol-CoA>/=arachidonoyol-CoAz.Gt;palmitoyl-CoA>/=linoleyol-CoA. However, when these cells were incubated with fatty acids, acyl-CoA thioesterase activity was increased by both conjugated linoleic and gamma linolenic acids, but not by docosahexaenoic and eicosapentaenoic acids. In addition, these fatty acids also increased expression of PPARgamma in these cells, suggesting a putative relationship between free fatty acid generated by acyl-CoA thioesterase and expression of PPARgamma. Since expression of PPARgamma is critical for feto-placental growth, these fatty acids may be important during pregnancy.