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.

The Genus Enlinia Aldrich in Chile (Diptera: Dolichopodidae), with the Description of Four New Species.

Four new species of Enlinia Aldrich are described from Chile: Enlinia biobio n. sp., Enlinia chilensis n. sp., Enlinia enormis n. sp., and Enlinia isoloba n. sp. These specimens were collected during a 2013 invertebrate survey in sclerophyll and Valdivian temperate rain forest habitats of the central and southern Chilean Andes. The only other species of Enlinia recorded from Chile is E. atrata (Van Duzee). Photos of holotypes and type localities and a key to the five species known to occur in Chile are provided.

Volatile and Within-Needle Terpene Changes to Douglas-fir Trees Associated With Douglas-fir Beetle (Coleoptera: Curculionidae) Attack.

Mass attack by tree-killing bark beetles (Curculionidae: Scolytinae) brings about large chemical changes in host trees that can have important ecological consequences. For example, mountain pine beetle (Dendroctonus ponderosae Hopkins) attack increases emission of terpenes by lodgepole pine (Pinus contorta Dougl. ex Loud.), affecting foliage flammability with consequences for wildfires. In this study, we measured chemical changes to Douglas-fir (Pseudotsuga menziesii var. glauca (Mirb.) Franco) foliage in response to attack by Douglas-fir beetles (Dendroctonus pseudotsugae Hopkins) as trees die and crowns transitioned from green/healthy, to green-infested (year of attack), to yellow (year after attack), and red (2 yr after attack). We found large differences in volatile and within-needle terpene concentrations among crown classes and variation across a growing season. In general, emissions and concentrations of total and individual terpenes were greater for yellow and red needles than green needles. Douglas-fir beetle attack increased emissions and concentrations of terpene compounds linked to increased tree flammability in other conifer species and compounds known to attract beetles (e.g., [Formula: see text]-pinene, camphene, and D-limonene). There was little relationship between air temperature or within-needle concentrations of terpenes and emission of terpenes, suggesting that passive emission of terpenes (e.g., from dead foliage) does not fully explain changes in volatile emissions. The potential physiological causes and ecological consequences of these bark beetle-associated chemical changes are discussed.

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.

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.

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.

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 .).

Parasitism of the wheat stem sawfly (Hymenoptera: Cephidae) by Bracon cephi and B. lissogaster (Hymenoptera: Braconidae) in wheat fields bordering tilled and untilled fallow in Montana.

We evaluated wheat stem sawfly, Cephus cinctus Norton, parasitism, infestation, and sawfly-cut stems in wheat fields bordering intensely tilled (no visible stubble residue), minimally tilled (>75% stubble residue visible), and untilled (chemical fallow, herbicide fallow management) summer fallow fields in north-central and south-central Montana. No difference in sawfly parasitism or sawfly-cut stems was found between fields bordering minimally tilled and fields bordering untilled summer fallow. Sawfly parasitism in fields bordering untilled summer fallow was greater than in fields bordering intensely tilled summer fallow at six of the eight sites examined. Sawfly-cut stems were greater in the field bordering intensely tilled fallow at four sites, with no difference in sawfly-cut stems between the intensely tilled and untilled field at the other four sites. Although it has never been reported, we have observed that many sawfly stubs are completely buried. Therefore, we measured the depth of sawfly stubs in four untilled fields in Broadwater County, MT. Two-thirds of the stubs were completely buried (206 of 300) with an average depth of 6 mm. Intensive tillage, which results in soil-covered stubble, is not an effective sawfly control practice, because sawflies typically overwinter below ground and upon emergence must dig to reach the soil surface. However, Bracon cephi (Gahan) and Bracon lissogaster Muesebeck overwinter above ground in stems and might be unable to dig to the soil surface if buried. The elimination of intensive tillage in favor of chemical fallow should result in greater sawfly parasitism over time. Producers replacing minimal tillage with chemical fallow should see no effect on sawfly parasitism.

Pharmacodynamics and pharmacokinetics of higher-dose, double-bolus eptifibatide in percutaneous coronary intervention.

BACKGROUND: Pharmacodynamics of eptifibatide, a cyclic heptapeptide antagonist of platelet glycoprotein IIb/IIIa, are substantially altered by anticoagulants that chelate calcium, resulting in overestimation ex vivo of the in vivo effects of this agent. We conducted a dose-ranging study to characterize the pharmacodynamics and pharmacokinetics of eptifibatide under physiological conditions. METHODS AND RESULTS: Patients (n=39) undergoing elective percutaneous coronary intervention were randomly assigned to an eptifibatide bolus followed by an infusion (180-microgram/kg bolus followed by 2 microgram/kg per minute or 250-microgram/kg bolus followed by 3 microgram/kg per minute) for 18 to 24 hours. In a 2:1 ratio, these patients received either a second bolus of eptifibatide (90 microgram/kg or 125 microgram/kg for the initial 180-microgram/kg or 250-microgram/kg groups, respectively) or placebo 30 minutes after the initial bolus. Bleeding times, ex vivo platelet aggregation, receptor occupancy, and plasma eptifibatide levels at baseline and at 1, 2, 3, 4, 6, and 8 hours were evaluated. Platelet inhibition was dose dependent and >80% in all groups by steady state. The single-bolus regimens had a transient loss of inhibition at 1 hour, consistent with rapid distribution and drug elimination. Pharmacokinetic modeling suggested that optimal dosing of eptifibatide would be obtained with a 180-microgram/kg bolus and a 2-microgram/kg per minute infusion followed by a second 180-microgram/kg bolus 10 minutes later. CONCLUSIONS: A novel higher-dose, double-bolus regimen of eptifibatide in coronary intervention attains and maintains >90% inhibition of platelet aggregation in >90% of patients, providing the pharmacodynamic construct for the design of the Enhanced Suppression of the Platelet IIb/IIIa Receptor with Integrilin Therapy (ESPRIT) trial of adjunctive eptifibatide in coronary stent implantation.

Coronary perforation during percutaneous coronary intervention in the era of abciximab platelet glycoprotein IIb/IIIa blockade: an algorithm for percutaneous management.

Coronary perforation is an uncommon but potentially life-threatening complication of percutaneous coronary intervention. The use of both atheroablative technologies for coronary intervention and adjunctive platelet glycoprotein blockade pharmacology may increase the incidence of or risk for life-threatening bleeding complications following the occurrence of coronary artery perforation. The interventional database for 6,214 percutaneous coronary interventions performed between January 1995 and June 1999 was analyzed. Hospital charts and cine angiograms for all patients identified in the database as having had coronary perforation were reviewed. Coronary perforation complicated 0.58% of all procedures and was more commonly observed in patients with a history of congestive heart failure and following use of atheroablative interventional technologies (2.8%). There was no association of abciximab therapy with either the incidence of or classification for coronary perforation. Adverse clinical outcomes (death, emergency surgical exploration) were related to the angiographic classification of perforation and were more frequently observed in patients who experienced a class 3 coronary perforation. These data suggest that specific clinical and procedural demographic factors are associated with the occurrence and severity of angiographic coronary perforation. An angiographic perforation class-specific algorithm for treatment of coronary perforation is proposed.

Abciximab provides cost-effective survival advantage in high-volume interventional practice.

BACKGROUND: Placebo-controlled randomized trials of platelet glycoprotein (GP) IIb/IIIa blockade during percutaneous coronary intervention have demonstrated efficacy of these agents for reducing the risk of periprocedural ischemic events. However, cost-effectiveness of this adjunctive pharmacotherapy has been scrutinized. Extrapolation of cost-efficacy observations from clinical trials to "real world" interventional practice is problematic. METHODS: Consecutive percutaneous coronary interventions (n = 1472) performed by Ohio Heart Health Center operators at The Christ Hospital, Cincinnati, Ohio, in 1997 were analyzed for procedural and long-term (6-month) outcomes and charges. Observations on cost and efficacy (survival) were adjusted for nonrandomized abciximab allocation by means of "propensity scoring" methods. RESULTS: Abciximab therapy was associated with a survival advantage to 6 months after percutaneous coronary intervention. The average reduction in mortality rate at 6 months was 3.4% (unadjusted) and 4.9% when adjusted for nonrandomization. The average charge increment to 6 months was $1512 (unadjusted) and $950 when adjusted for nonrandomization. Patients deriving the greatest reduction in mortality rates also had a reduction in total cardiovascular charges to 6 months. Distinguishing demographics of this population included multivessel coronary intervention, coronary stent deployment, intervention within 1 week of myocardial infarction, and lower left ventricular ejection fraction. The average cost per life-year gained in this study was $2875 for all patients (unadjusted) and $1243 when adjusted for nonrandomization. CONCLUSIONS: Abciximab provides a cost-effective survival advantage in high-volume interventional practice that compares favorably with currently accepted standards. Clinical and procedural demographics associated with increased cost-effectiveness included multivessel coronary intervention, stent deployment, recent (<1 week) myocardial infarction, and impaired left ventricular function.

IIb's are not IIb's.

Platelet glycoprotein (GP) IIb/IIIa receptor blockade improves clinical outcomes after percutaneous coronary intervention (PCI) and for patients who present with non-ST-segment elevation acute coronary syndromes. Although this class of therapeutic agents has been defined by a common affinity for the platelet GP IIb/IIIa receptor, the 3 currently available agents differ markedly in pharmacodynamic and pharmacokinetic profile as well as receptor affinity. Differential (separate) binding sites on the GP IIb/IIIa receptor explain the observation that abciximab binding to platelets is not influenced by either tirofiban or eptifibatide. Abciximab (ReoPro, chimeric 7E3 Fab) is a low K(d) (high affinity) agent with a very short plasma t(1/2) and a prolonged duration of action at the platelet target receptor. Eptifibatide and tirofiban are high K(d) (low affinity) agents with a relatively long plasma t(1/2) and short duration of action at the platelet target receptor. These pharmacodynamic differences underlie the phenomena of gradual redistribution in abciximab binding and smooth tapering of abciximab antiplatelet effect after discontinuation of therapy. Furthermore, abciximab demonstrates affinity for both the CD11b/18 (alpha(m)beta(2) or MAC 1) and alpha(V)beta(3) (vitronectin) receptors. Although a survival advantage in favor of abciximab has been observed after PCI in both randomized controlled trials and high-volume clinical practice, no survival benefit has been observed to date after eptifibatide or tirofiban therapy for PCI. The mechanism of survival advantage after abciximab therapy has not been defined but may be distinct from the degree of platelet GP IIb/IIIa receptor inhibition during the duration of intravenous treatment. Although this important new "class" of therapeutic agent was simplistically defined by a common affinity for the GP IIb/IIIa receptor, this solitary unifying attribute may not define agent-specific benefit.

Time course, magnitude, and consistency of platelet inhibition by abciximab, tirofiban, or eptifibatide in patients with unstable angina pectoris undergoing percutaneous coronary intervention.

Adjunctive platelet glycoprotein IIb/IIIa blockade during percutaneous coronary intervention (PCI) reduces platelet-mediated adverse ischemic outcomes. Although abciximab, eptifibatide, and tirofiban have received U.S. Food and Drug Administration approval for use, these agents differ in their pharmacodynamic profiles. Each of these agents has been compared in randomized trials with placebo for patients undergoing PCI, but no randomized comparative studies of these agents have been performed. We compared ex vivo platelet function by both standard light transmission aggregometry and rapid platelet function assay during and after administration of abciximab, eptifibatide, or tirofiban in approved dose regimens on a randomized basis at the time of PCI in patients with unstable angina pectoris. A reduced intensity of platelet inhibition by light transmission aggregometry was observed for tirofiban compared with either eptifibatide or abciximab. In addition, the 30-minute bolus strategy used for tirofiban was associated with delayed onset of maximal platelet inhibition relative to the initiation of bolus infusion. Whether the trends in platelet function observed in this study will be translated into differences in clinical outcomes awaits definition by larger scale randomized clinical trials comparing these platelet glycoprotein IIb/IIIa inhibitors.