Comprehensive analysis of umami compounds by ion-pair liquid chromatography coupled to mass spectrometry

An ion-pair LC-ESI-MS method was developed capable of analyzing various reported umami or umami-enhancing compounds, including glutamic acid and 5'-ribonucleotides. The method was validated using tomato and potato samples and showed overall good analytical performance with respect to selectivity, detection limit, linearity, and repeatability. The method was applied to various tomato samples resulting in concentrations of glutamic acid and 5'-ribonucleotides that were in good comparison with literature. The methodology might also be used for the discovery of new umami (enhancing) compounds in an untargeted mode. This was to a certain extent demonstrated for tomato samples by correlating all peaks observed with the ion-pair liquid chromatography-mass spectrometry (LC-MS) method to sensory properties using multivariate statistics. PRACTICAL APPLICATION: This study describes the development and application of a LC-MS method, which can be used to quantify several known umami (enhancing) compounds in various foods. Furthermore, the method might be useful for the discovery of new umami (enhancing) compounds.     

Formation of metal-arsenate precipitates at the goethite-water interface

Little information is available concerning cosorbing oxyanion and metal contaminants in the environment, yet in most metal-contaminated areas, cocontamination by arsenate [AsO4, As(V)] is common. This study investigated the cosorption of As(V) and Zn on goethite at pH 4 and 7 as a function of final solution concentration. Complimentary extended X-ray absorption fine structure (EXAFS) spectroscopic data were collected at the As and Zn K-edges in order to glean information about the coordination environment of As and Zn at the goethite-water interface. Macroscopic sorption studies revealed that As(V) and Zn sorption on goethite increased in cosorption experiments beyond that suggested by single sorption isotherms. At pH 4 and 7, As(V) surface saturation was 3.2 and 2.2 micromol m(-2), respectively, and Zn surface saturation was absent at pH 4 and approximately 1.0 micromol m(-2) at pH 7. Arsenate sorption on goethite increased in the presence of Zn by 29% and by more than 500% at pH 4 and 7, respectively. In the presence of As(V), Zn sorption on goethite increased by 800 and 1300% at pH 4 and 7, respectively. More As(V) than Zn sorbed on goethite below surface saturation at pH 7. Above surface saturation, the Zn:As surface density ratio (SDR) remained constant at 0.91 +/- 0.03. At pH 4, the Zn:As SDR was less than 1 throughout the concentration range. Below As(V) surface saturation on goethite, As(V) formed bidentate binuclear bridging complexes on Fe and/or Zn octahedra, while Zn mainly formed edge-sharing complexes with Fe at the goethite surface. Above surface saturation, Zn was increasingly complexed by AsO4, gradually forming an adamite-like [Zn2(AsO4)OH] surface precipitate on goethite. Precipitated contaminants are more stable due to the limited dissolution kinetics of their solid phase. This study may therefore prove useful in remediation strategies of sites knowingly contaminated with oxyanions and metals.     

Receptive Field Sizes of Nyxnob Mouse Retinal Ganglion Cells

Patients with congenital nystagmus, involuntary eye movements, often have a reduced visual acuity. Some of these patients have a retinal-specific mutation in the protein nyctalopin, which is also present in the Nyx^nob mouse. In these mice, retinal ganglion cells (RGCs) have oscillatory activity, which leads to expanded axonal projections towards the dLGN and consequently to a desegregation of retinal projections to the brain. In this study, we investigate whether the receptive fields of Nyx^nob RGCs have also expanded by measuring the size of their receptive fields using MEA recordings. Contrary to our expectation, relative to wild-type (WT) mice we found receptive field sizes in the Nyx^nob retina had not increased but instead had decreased for green-light preferring RGCs. Additionally, we also found the receptive fields of UV-light preferring RGCs are larger than green-light preferring RGCs in both WT and Nyx^nob mice.     

Metal Nanocatalyst Sintering Interrogated at Complementary Length Scales

Metal nanoparticle (NP) sintering is a prime cause of catalyst degradation, limiting its economic lifetime and viability. To date, sintering phenomena are interrogated either at the bulk scale to probe averaged NP properties or at the level of individual NPs to visualize atomic motion. Yet, “mesoscale” strategies which bridge these worlds can chart NP populations at intermediate length scales but remain elusive due to characterization challenges. Here, a multi-pronged approach is developed to provide complementary information on Pt NP sintering covering multiple length scales. High-resolution scanning electron microscopy (HRSEM) and Monte Carlo simulation show that the size evolution of individual NPs depends on the number of coalescence events they undergo during their lifetime. In its turn, the probability of coalescence is strongly dependent on the NP's mesoscale environment, where local population heterogeneities generate NP-rich “hotspots” and NP-free zones during sintering. Surprisingly, advanced in situ synchrotron X-ray diffraction shows that not all NPs within the small NP sub-population are equally prone to sintering, depending on their crystallographic orientation on the support surface. The demonstrated approach shows that mesoscale heterogeneities in the NP population drive sintering and mitigation strategies demand their maximal elimination via advanced catalyst synthesis strategies.     

First principles prediction of NRTL binary interaction parameters for furfural derivatives

Biobased molecules constitute sustainable alternatives for fossil-based chemicals. However, to allow further valorization, the complex product mixtures resulting from biomass processing typically require downstream separation. Although many (semi)empirical thermodynamic models, like NRTL, are available for separation process design, their application for biobased molecules is hampered due to the lack of the necessary data to determine the binary interaction parameters used in these models. Therefore, in this work a case study comprising a set of furfural derivates has been used to showcase a methodology to efficiently determine these parameters. Based on first principles, COSMO-RS is used to generate a dataset of thermodynamic activities, which is subsequently used to regress the NRTL model against. Comparison of NRTL-HOC simulated vapor–liquid equilibria (VLE's) with experimental VLE's showed excellent agreement, confirming that COSMO-RS can be used to extend the use of (semi)-empirical models toward applications involving biobased molecules of which limited experimental data is available.     

Magneto-hydrodynamic mixing: A new technique for preparing carbomer hydrogels

Magnetohydrodynamic mixing was evaluated as an alternative to conventional high shear mixing (HSM) in the preparation of carbomer hydrogels containing 1.22 wt% Carbopol® 980 NF. Neutralization of the carbomer dispersion (pH = 2.74) with triethanolamine (TEA) enabled to adjust the pH of the mixture and tune the viscosity of the hydrogel. Using HSM, this approach was limited to 0.2 wt% TEA (pH = 3.83) as the gel became too viscous and the recirculation flow dropped from 12 to 0.3 m³/h. Magnetohydrodynamic mixing enabled to reach TEA concentrations up to 1.0 wt% (pH = 5.31). Apparent viscosity measurements on samples having 0.2 wt% TEA revealed lower viscosities for carbomer hydrogels prepared with HSM, that is, 6800 mPa s versus 8800 mPa for magneto-hydrodynamic mixing. Based on ¹H NMR evidence, this decrease in apparent viscosity was attributed to structural damage to the carbomer backbone in combination with mechanochemical degradation of the added TEA.     

Nocturnal tidal barrier management improves glass eel migration in times of drought and salinization risk

Adjusted tidal barrier management (ATBM, setting tidal doors ajar during tidal rise) is currently applied in Belgium to improve glass eel passage through tidal gates. However, salt intrusion in the receiving waters due to upwelling and accumulation of saline groundwater as a result of intensive drought put severe pressure on the unrestrained use of this cost-efficient mitigation measure. We evaluated the efficacy of a very restricted ATBM at a tidal barrier on a small canalized waterway, located 3.5 km from the sea: one out of seven gate doors was left 20 cm ajar for ca. 30 min when the water levels on both sides of the tidal barrier were approximately equal. During 20 inflow events differing in tidal flow (i.e., flood or ebb tide) and daytime (i.e., day or night) in March/April 2019, migrating glass eels were caught with a fyke net fixed on the temporally opened gate. In total, 12,853 glass eels were captured, almost all during flood tides at night (96%), with a maximum catch of 3,827 individuals per inflow event. These results show that even small windows of opportunity can help glass eels pass tidal barriers.