Structure and composition of natural ferrihydrite nano-colloids in anoxic groundwater.

Fe-rich mobile colloids play vital yet poorly understood roles in the biogeochemical cycling of Fe in groundwater by influencing organic matter (OM) preservation and fluxes of Fe, OM, and other essential (micro-)nutrients. Yet, few studies have provided molecular detail on the structures and compositions of Fe-rich mobile colloids and factors controlling their persistence in natural groundwater. Here, we provide comprehensive new information on the sizes, molecular structures, and compositions of Fe-rich mobile colloids that accounted for up to 72% of aqueous Fe in anoxic groundwater from a redox-active floodplain. The mobile colloids are multi-phase assemblages consisting of Si-coated ferrihydrite nanoparticles and Fe(II)-OM complexes. Ferrihydrite nanoparticles persisted under both oxic and anoxic conditions, which we attribute to passivation by Si and OM. These findings suggest that mobile Fe-rich colloids generated in floodplains can persist during transport through redox-variable soils and could be discharged to surface waters. These results shed new light on their potential to transport Fe, OM, and nutrients across terrestrial-aquatic interfaces.

LCMS Measurement of Steroid Biomarkers Collected from Palmar Sweat.

Human eccrine sweat contains numerous biomarkers which can provide information on health, performance, and aging. Non-invasive collection and measurement of biomarkers has become especially important in recent times given viral outbreaks like SARS-CoV-2. In the current study we describe a method of sweat collection from palmar surfaces in participants via surface capture using glass beads and the resulting analysis of biomarkers from very low volumes of sweat using liquid chromatography mass spectrometry with selected ion monitoring. Study participants underwent a cognitive and physical stress task with easy and hard conditions with sweat being collected after each task. Resulting analysis found a signal for 22 steroid biomarkers and we report detailed information on selected biomarkers, given their applicability to timely real-world exemplars, including cortisol, dehydroepiandrosterone, allopregnanolone, estrone, aldosterone, and 20α/ß-dihydrocortisone.

Characterizing changes in levan physicochemical properties in different pH environments using asymmetric flow field-flow fractionation.

The purpose of this study was to assess the stability of the polyfructan levan under different pH solution conditions by monitoring changes in the levan physicochemical properties, such as molar mass (M), root mean square radius (r(rms)), hydrodynamic radius (r(h)), structure factor (r(rms)/r(h)), and aggregation state with respect to solution pH and hydrolysis time. A commercial levan produced from Z. Mobilis was characterized using asymmetric flow field-flow fractionation (AF4) in combination with online multiangle light scattering (MALS) and differential refractive index (dRI) detection. Under neutral pH solution conditions the levan was found to have a M ranging from 10(5) to 5 × 10(7) g/mol, a r(rms) ranging from ~25 to 100 nm and a r(h) from ~3 to 151 nm. Two populations were observed in the sample. One population with a M less than 106 g/mol which represented ~60 % of the sample and a second population with an ultrahigh M up to 5 × 10(7) g/mol, which comprised ~40 % of the sample. The measured r(rms)/r(h) structure factor decreased from 1.8 to 0.65 across the AF4 fractogram indicating that early eluting low M levan species had a random coil configuration and late eluting high M species had more homogeneous spherical structures. The measured apparent density values decreased from 80 to 10 kg/m(3) across the elution profile and suggest that the observed second population also contains aggregates. The stability of levan in different pH conditions ranging from 1.3 to 8.5 was assessed by tracking changes in the average M and r(h), and monitoring the formation of fructose over 1 week. The onset of levan acid hydrolysis was observed to occur sooner at lower pH conditions and no hydrolysis was observed for pH 5.5 and higher.

Characterization of oat proteins and aggregates using asymmetric flow field-flow fractionation.

The soluble proteins and protein aggregates in Belinda oats were characterized using asymmetric flow field-flow fractionation (AF4) coupled with online UV-vis spectroscopy and multiangle light-scattering detection (MALS). Fractions from the AF4 separation were collected and further characterized by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The AF4 fractogram of the oat extracts revealed three peaks which were determined to be monomeric forms of soluble proteins, globulin aggregates, and ß-glucan, respectively. The early eluting monomeric proteins ranged in molar mass (MM) between 5 and 90 kg/mol and in hydrodynamic diameter (D h) from 1.6 to 13 nm. The MM at peak maximum of the globulin aggregate peak was found to be ∼300 kg/mol and the D h was measured to be ∼20 nm. SDS-PAGE of the collected fraction across this peak revealed two bands with MM of 37 and 27 kg/mol which correspond to the α and ß subunits of globulin indicating the elution of globulin aggregates. A third peak at long retention time was determined to be ß-glucan through treatment of the oat extract with ß-glucanase and by injection of ß-glucan standards. The amount of soluble protein was measured to be 83.1 ± 2.3 wt.%, and the amount of albumin proteins was measured to be 17.6 ± 5.7 wt.% of the total protein in the oats. The results for Belinda oat extracts show that the AF4-MALS/UV platform is capable of characterizing the physicochemical properties such as MM and hydrodynamic size distribution of proteins and protein aggregates within a complicated food matrix environment and without the need to generate protein isolates.

Preparation of narrow dispersity gold nanorods by asymmetrical flow field-flow fractionation and investigation of surface plasmon resonance.

The development of an asymmetrical field-flow fractionation (AsFlFFF) method for separating gold nanorods (GNR) is reported. Collected fractions containing GNR subpopulations with aspect ratios, sizes, and shapes which are more narrowly dispersed than the original population were further characterized by UV-vis spectroscopy and transmission electron microscopy. This ability to obtain different sizes and shapes of nanoparticles enabled the evaluation of a new approach to estimating the retention time and hydrodynamic size of nanorods and the investigation of GNR optical properties at a previously unattainable level of detail. Experimental results demonstrate that the longitudinal surface plasmon absorption maximum of GNRs is correlated with the effective particle radius in addition to the aspect ratio. This may account for some of the variabilities reported in published empirical data from different research groups and supports reports of simulated absorption spectra of GNRs of different physical dimensions. The use of AsFlFFF with dual UV-vis detection to rapidly assess relative changes in GNR subpopulations was demonstrated for irregularly shaped gold nanoparticles formed at different synthesis temperatures.

A theory-based approach to thermal field-flow fractionation of polyacrylates.

A theory-based approach is presented for the development of thermal field-flow fractionation (ThFFF) of polyacrylates. The use of ThFFF for polymer analysis has been limited by an incomplete understanding of the thermal diffusion which plays an important role in retention and separation. Hence, a tedious trial-and-error approach to method development has been the normal practice when analyzing new materials. In this work, thermal diffusion theories based on temperature dependent osmotic pressure gradient and polymer-solvent interaction parameters were used to estimate thermal diffusion coefficients (D(T)) and retention times (t(r)) for different polymer-solvent pairs. These calculations identified methyl ethyl ketone as a solvent that would cause significant retention of poly(n-butyl acrylate) (PBA) and poly(methyl acrylate) (PMA). Experiments confirmed retention of these two polymers that have not been previously analyzed by ThFFF. Theoretical and experimental D(T)s and t(r)s for PBA, PMA, and polystyrene in different solvents agreed to within 20% and demonstrate the feasibility of this theory-based approach.

Composition and molecular weight analysis of styrene-acrylic copolymers using thermal field-flow fractionation.

Thermal field-flow fractionation coupled with online multiangle light scattering, differential refractive index and quasielastic light scattering (ThFFF-MALS/dRI/QELS) was used to simultaneously determine the molecular weight (MW) and composition of polystyrene-poly(n-butyl acrylate) (PS-PBA) and polystyrene-poly(methyl acrylate) (PS-PMA) copolymers. The online measurement of the normal diffusion coefficient (D) by QELS allowed calculation of the copolymer thermal diffusion coefficient (D(T)) of sample components as they eluted from the ThFFF channel. DT was found to be independent of MW for copolymers with similar compositions and dependent on composition for copolymers with similar MW in a non-selective solvent. By using a solvent that is non-selective to both blocks of the copolymer, it was possible to establish a universal calibration plot of DT versus mole fraction of one of the monomer chemistries comprising the copolymer. PS-PBA and PS-PMA linear diblock polymers were determined to vary in composition from 100/0 to 20/80 wt% PS/acrylate and ranged in MWs between 30 and 360 kDa. The analysis of a PS-PBA miktoarm star copolymer revealed a polydisperse material with a weight percent PBA of 50-75% and MW ranging from 100 to 900 kDa. The presented ThFFF-MALS/dRI/QELS method allowed rapid characterization of polymers with MW and chemical distributions in a single analysis.

Field-flow fractionation: addressing the nano challenge.

Field-flow fractionation is coming of age as a family of analytical methods for separating and characterizing macromolecules, nanoparticles, and particulates. The capabilities and versatility of these techniques are discussed in light of the challenges that are being addressed in analyzing nanometer-sized sample components and the insights gained through their use in applications ranging from materials science to biology. (To listen to a podcast about this feature, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html .).