Apparent Partition Research Articles

Pharmacokinetics of lipophilically different 3-substituted 2,2,5,5-tetramethylpyrrolidine-N-oxyl radicals frequently used as redox probes in in vivo magnetic resonance studies

3-Carboxy-, 3-carbamoyl-, 3-hydroxymethyl, and 3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-N-oxyl radicals (CxP, CmP, HMP, and MCP, respectively) have been widely used as redox probes in in vivo magnetic resonance studies. Knowledge of the pharmacokinetics of these probes is essential for redox analyses. The apparent partition coefficient (Kp) of these probes at neutral pH was in the order of MCP>HMP>CmP>CxP. After these probes had been injected intravenously, their blood levels decayed in a bi-phasic manner, namely, fast decay followed by slow decay. The order of the area under the curve (AUC) was CxP»HMP>MCP≥CmP, which roughly coincided with that of Kp in the opposite direction, except for CmP. Decay in the slow phase largely affected the AUC of these probes. The reduction of these probes contributed to their decay in the slow phase. A two-compartment model analysis of blood levels, cyclic voltammetry, and magnetic resonance imaging provided the following pharmacokinetic information. The distribution of the probes between the central and peripheral compartments rapidly reached an equilibrium. In addition to lipophilicity, reduction potential may also be involved in the rate of in vivo reduction of the probes. Hydrophilic probes, such as CxP and CmP, were predominantly excreted in the urine. MCP was distributed to the peripheral tissues and then rapidly reduced. HMP was unique due to its moderate lipophilicity and slower reduction. Among the probes examined, the liver and kidney appear to be included in the central compartment in the two-compartment model analysis. MCP and HMP were rapidly distributed to the brain.

Reply to the comment by Wu et al. (2016) on “Behavior of Re and Os during contact between an aqueous solution and oil: Consequences for the application of the Re–Os geochronometer to petroleum” [Geochim. Cosmochim. Acta 158 (2015) 1–21

We reply here to the questions raised by Wu et al. concerning the results published by Mahdaoui et al. (2015). This paper describes experiments in which aqueous solutions containing ReO4− and OsCl62− were brought in contact with natural oils at various ranges of concentration, time and temperature. The main observation is that the transfer of Re and Os to oils is very efficient under all experimental conditions. Wu et al. argue that thermodynamic equilibrium was not achieved in these experiments as apparent partition coefficients are inconsistent. They conclude that the experiments were flawed by possible leaking of reactors and that the conclusions by Mahdaoui et al. (2015) were not justified. In the following reply we explain that Mahdaoui et al. (2015) never claimed that thermodynamic equilibrium was achieved. Any calculations or considerations in this context are therefore meaningless. We recall the objectives of our publication, which were to experimentally test the behavior of ReO4− and OsCl6− (two plausible chemical forms of Re and Os in deep aquifers of petroleum systems) in aqueous solution-oil systems. To our knowledge these are the first experiments of their kind. The parameters that could influence the precision and reproducibility of our results were discussed in detail in Mahdaoui et al. (2015). The essential point is that all 60 of the experiments provide evidence of substantial transfer of Re and Os from water to oil. In contrast to what was mistakenly understood by Wu et al., the paper does not challenge the use of Re–Os to date geological events affecting petroleum. Instead, by providing a mechanism that might allow Os isotopic homogenization on a basin-wide scale, a critical step missing from most current models, it offers a possible explanation of how Re–Os geochronology in oils could potentially work. More generally, our study suggests that transfer of Re and Os from waters to oil may be an important phenomenon that should not be overlooked.

Phosphorus-controlled trace element distribution in zircon revealed by NanoSIMS

To better understand the origin of oscillatory zoning in zircons, distributions of REEs (represented by Ce, Sm, Dy and Lu), Y, Ti, Li and P in the igneous zircons (QH) from a felsic syenite in the Qinghu alkaline complex and metamorphic zircons (DMP06-14) from a banded granulite xenolith from Hannuoba basalts have been investigated with NanoSIMS. The NanoSIMS analyses reveal well correlation between the trace element distributions and the cathodoluminescence dark–bright zonings of zircons. The QH zircons with oscillatory zonings display large trace element variations within single grains by a factor up to 13.5, with Y and P ranging from 574 and 227 ppm in the bright zones to 7754 and 2464 ppm in the dark zones, respectively. By contrast, the DMP06-14 zircons without oscillatory zonings show much smaller trace element variations by a factor of 1.4, with Y ranging from 477 to 636 ppm and P from 331 to 467 ppm. Such large trace element variations in oscillatory zonings cannot be produced by compositional fluctuation in the magma chambers. The correlations between P and Y, REEs (Ce, Sm, Dy and Lu) (R 2 > 0.97) indicate xenotime substitution in zircons. The oscillatory distribution of P in zircon could be formed by the fluctuation of P in the melt adjacent to the mineral-melt boundary, either because P diffuses slower than Zr in the melt or due to surfacial interaction of melt with crystals. Such a zoned distribution of P in turn controls the substitution types of phosphates in zircon, developing oscillatory distributions of Y and REEs. Our results indicate that apparent partition coefficients of Y and REEs between zircon and melt are controlled by P contents, which may result in the large discrepancy in zircon partitioning data.

Delivery of fluorescent-labeled cyclodextrin by liposomes: role of transferrin modification and phosphatidylcholine composition

Drug-in-CD-in-liposome (DCL) systems which encapsulate the drug/CD inclusion complexes into inner aqueous phase of liposomes have been applied as a novel strategy to improve efficacy of lipophilic antitumor drugs. The aim of this work was to assess the role of transferrin (Tf) modification and phosphatidylcholine (PC) composition on the properties of liposomes containing hydroxypropyl-β-cyclodextrin (HP-β-CD). Fluorescence dye, FITC, was conjugated with HP-β-CD to facilitate the analysis. The resulting FITC-HP-β-CD was further encapsulated into liposomes and then the liposomes were modified with Tf. The FITC-HP-β-CD-loaded liposomes with different PC compositions were compared in terms of particle size, zeta potential, FITC content, FITC-HP-β-CD leakage, phase transition temperature (Tm) and cellular uptake. The apparent partition coefficient values of different PCs were also determined. Compared to PEGylated liposomes, FITC-HP-β-CD-loaded liposomes modified with Tf had been proved to significantly increase vesicle stability and specific cellular uptake. Moreover, PC composition affected the properties of liposomes. Soybean phosphatidylcholine (SPC) liposomes modified with Tf were found to be more easily internalized into tumor cells than 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) and hydrogenated soybean phosphatidylcholine (HSPC) while Tf density on the liposomal surface was similar. And the lipophilicity of SPC was found to be much higher than DPPC and HSPC. Collectively, by the optimization of PC composition, the development of DCL modified with Tf might represent a potential strategy for the antitumor application of lipophilic drugs.

Mussel shells of <i>Mytilus edulis</i> as bioarchives of the distribution of rare earth elements and yttrium in seawater and the potential impact of pH and temperature on their partitioning behavior

Abstract. Mussel shells are potential bioarchives of proxies for changes in the physicochemical conditions in the bivalve's habitat. One such proxy is the distribution of rare earths and yttrium (REY) in seawater, as REY speciation in seawater is sensitive to pH and temperature variations, due to the impact of these parameters on the activity of CO32− in seawater. We present a new protocol for sample preparation and determination of ultratrace concentrations of REY in bulk bivalve shells (comprised of calcite and aragonite) that includes sample treatment with NaOCl followed by REY separation and preconcentration. The data obtained were used to calculate REY partition coefficients between bulk bimineralic shells of Mytilus edulis (calcite aragonite mix) and ambient seawater, and the results acquired were then used to investigate the potential effects of pH and temperature on REY partitioning.Shells of Mytilus edulis mussels from the North Sea show consistent shale-normalized (SN) REY patterns that increase from the light REY to the middle REY and decrease from the middle REY to the heavy REY. Despite being different from the general seawater REYSN pattern, the shells still display distinct REY features of seawater, such as a negative CeSN anomaly and small positive YSN and GdSN anomalies. Apparent REY partition coefficients between shells and seawater (appDTot.REYshell/seawater) are low and decrease strongly from the light REY (4.04 for La) to the heavy REY (0.34 for Lu). However, assuming that only the free REY3+ are incorporated into the shell, modDFreeREY3+shell/seawater values are higher and comparatively similar for all REY (102.46 for La; 113.44 for Lu) but show a slight maximum at Tb (199.18). Although the impact of vital effects, such as REY speciation in a mussel's extrapallial fluid from which the carbonate minerals precipitate, cannot be quantified yet, it appears that M. edulis shells are bioarchives of some REY features of seawater.We modeled the REYSN patterns of a hypothetical mussel shell at pH 8.2 and 7.6 and at temperatures of 25 and 5 °C, assuming that only free REY3+ are incorporated into the carbonate's crystal lattice and that vital effects do not obliterate the REY signal of the shells. The results suggest that with lower pH, REY concentrations in shells increase, but with little effect on the shape of the REYSN patterns, while a temperature change has an impact on the REYSN pattern but only minor effects on REY concentrations. Hence, after additional calibration studies, the REY systematics in mussel shells may become a valuable proxy for paleo-pH and ocean acidification.

Concentration-dependent apparent partition coefficients of ionic liquids possessing ethyl- and bi-sulphate anions.

This study deals with the concentration dependent apparent partition coefficients log P of the ethyl and bisulfate-based ionic liquids. It is observed that the bisulfate-based ionic liquids show different behaviour with respect to concentration as compared to ethyl sulphate-based ionic liquids. It is significant and useful analysis for the further implementation of alkyl sulfate based ionic liquids as solvents in extraction processes. The log P values of the ethyl sulphate-based ionic liquids were noted to vary linearly with the concentration of the ionic liquid, whereas a flip-flop trend with the concentration for the log P values of the bisulphate-based ionic liquids was observed due to the difference in hydrogen bond accepting basicity and possibility of aggregate formation of these anions. The π-π interactions between the imidazolium and pyridinium rings were seen to affect the log P values. The alkyl chain length of anions was also observed to influence the log P values. The hydrophobicity of ionic liquid changes with the alkyl chain in the anion in the order; [HSO4](-) < [EtSO4](-) < [BuSO4](-).

Characterizing informative sequence descriptors and predicting binding affinities of heterodimeric protein complexes.

BackgroundProtein-protein interactions (PPIs) are involved in various biological processes, and underlying mechanism of the interactions plays a crucial role in therapeutics and protein engineering. Most machine learning approaches have been developed for predicting the binding affinity of protein-protein complexes based on structure and functional information. This work aims to predict the binding affinity of heterodimeric protein complexes from sequences only.ResultsThis work proposes a support vector machine (SVM) based binding affinity classifier, called SVM-BAC, to classify heterodimeric protein complexes based on the prediction of their binding affinity. SVM-BAC identified 14 of 580 sequence descriptors (physicochemical, energetic and conformational properties of the 20 amino acids) to classify 216 heterodimeric protein complexes into low and high binding affinity. SVM-BAC yielded the training accuracy, sensitivity, specificity, AUC and test accuracy of 85.80%, 0.89, 0.83, 0.86 and 83.33%, respectively, better than existing machine learning algorithms. The 14 features and support vector regression were further used to estimate the binding affinities (Pkd) of 200 heterodimeric protein complexes. Prediction performance of a Jackknife test was the correlation coefficient of 0.34 and mean absolute error of 1.4. We further analyze three informative physicochemical properties according to their contribution to prediction performance. Results reveal that the following properties are effective in predicting the binding affinity of heterodimeric protein complexes: apparent partition energy based on buried molar fractions, relations between chemical structure and biological activity in principal component analysis IV, and normalized frequency of beta turn.ConclusionsThe proposed sequence-based prediction method SVM-BAC uses an optimal feature selection method to identify 14 informative features to classify and predict binding affinity of heterodimeric protein complexes. The characterization analysis revealed that the average numbers of beta turns and hydrogen bonds at protein-protein interfaces in high binding affinity complexes are more than those in low binding affinity complexes.

Sorption and desorption kinetics and isotherms of volatile methylsiloxanes with atmospheric aerosols.

This study investigated sorption and desorption behaviors of airborne volatile methylsiloxanes (VMS) such as octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) on nine major primary and secondary atmospheric aerosols at a relative humidity (RH) of 30%. It was found that sorption and desorption of VMS took place via a two-phase process, which included an initial rapid step, followed by slower subsequent step. The initial rapid step was favored especially at low concentrations. Equilibrium sorption isotherms were slightly better fitted to Polanyi-Manes sorption model than Langmuir model except D4 on black carbon and D5 on sea salt. Values of apparent aerosol-air partition coefficients ranged 0.09-50.4 L/m(2) for D4 and 2.1-284 L/m(2) for D5 with carbon black having the largest values. Some of aerosols such as carbon black and sea salts reversibly interacted with D4 and D5 whereas other aerosols such as kaolinite and sulfates showed highly irreversible sorption for the VMS, especially at low concentrations. As sorption density of D4 and D5 on kaolinite was decreased from 1100 to 250 µg/m(2), the irreversible fraction was increased from 27% to 80%.The mechanism responsible for these differences is essential for a better understanding and prediction of atmospheric chemistry of VMS as affected by the presence of atmospheric aerosols.

Tryptophan probes reveal residue-specific phospholipid interactions of apolipoprotein C-III

Apolipoproteins are essential human proteins for lipid metabolism. Together with phospholipids, they constitute lipoproteins, nm to μm sized particles responsible for transporting cholesterol and triglycerides throughout the body. To investigate specific protein–lipid interactions, we produced and characterized three single-Trp containing apolipoprotein C-III (ApoCIII) variants (W42 (W54F/W65F), W54 (W42F/W65F), W65 (W42F/W54F)). Upon binding to phospholipid vesicles, wild-type ApoCIII adopts an α-helical conformation (50% helicity) as determined by circular dichroism spectroscopy with an approximate apparent partition constant of 3×104M−1. Steady-state and time-resolved fluorescence measurements reveal distinct residue-specific behaviors with W54 experiencing the most hydrophobic environment followed by W42 and W65. Interestingly, time-resolved anisotropy measurements show a converse trend for relative Trp mobility with position 54 being the least immobile. To determine the relative insertion depths of W42, W54, and W65 in the bilayer, fluorescence quenching experiments were performed using three different brominated lipids. W65 had a clear preference for residing near the headgroup while W54 and W42 sample the range of depths ~8–11Å from the bilayer center. On average, W54 is slightly more embedded than W42. Based on Trp spectral differences between ApoCIII binding to phospholipid vesicles and sodium dodecyl sulfate micelles, we suggest that ApoCIII adopts an alternate helical conformation on the bilayer which could have functional implications.

Enhancement of the 1-Octanol/Water Partition Coefficient of the Anti-Inflammatory Indomethacin in the Presence of Lidocaine and Other Local Anesthetics.

Side effects and excessive potentiation of drug efficacy caused by polypharmacy are becoming important social issues. The apparent partition coefficient of indomethacin (log P'IND) increases in the presence of lidocaine, and this is used as a physicochemical model for investigating polypharmacy. We examined the changes in log P'IND caused by clinically used local anesthetics-lidocaine, tetracaine, mepivacaine, bupivacaine, and dibucaine-and by structurally similar basic drugs-procainamide, imipramine, and diltiazem. The quantitative structure-activity relationship study of log P'IND showed that the partition coefficient values (log PLA) and the structural entropic terms (ΔSobs, log f) of the additives affect log P'IND. These results indicate that the local anesthetics and structurally similar drugs function as phase-transfer catalysts, increasing the membrane permeability of indomethacin via heterogeneous intermolecular association. Therefore, we expect that the potency of indomethacin, an acidic nonsteroidal anti-inflammatory drug, will be increased by concurrent administration of the other drugs.

GC×GC Quantification of Priority and Emerging Nonpolar Halogenated Micropollutants in All Types of Wastewater Matrices: Analysis Methodology, Chemical Occurrence, and Partitioning.

We report the development and validation of a method to detect and quantify diverse nonpolar halogenated micropollutants in wastewater treatment plant (WWTP) influent, effluent, primary sludge, and secondary sludge matrices (including both the liquid and particle phases) by comprehensive two-dimensional gas chromatography (GC×GC) coupled to micro- electron capture detector (μECD). The 59 target analytes included toxaphenes, polychlorinated naphthalenes, organochlorine pesticides, polychlorinated biphenyls, polybrominated diphenyl ethers, and emerging persistent and bioaccumulative chemicals. The method is robust for a wide range of nonpolar halogenated micropollutants in all matrices. For most analytes, recoveries fell between 70% and 130% in all matrix types. GC×GC-μECD detections of several target analytes were confirmed qualitatively by further analysis with GC×GC coupled to electron capture negative chemical ionization-time-of-flight mass spectrometry (ENCI-TOFMS). We then quantified the concentrations and apparent organic solid-water partition coefficients (Kp) of target micropollutants in samples from a municipal WWTP in Switzerland. Several analyzed pollutants exhibited a high frequency of occurrence in WWTP stream samples, including octachloronaphthalene, PCB-44, PCB-52, PCB-153, PCB-180, several organochlorine pesticides, PBDE-10, PBDE-28, PBDE-116, musk tibetene, and pentachloronitrobenzene. Our results suggest that sorption to dissolved organic carbon (DOC) can contribute substantially to the apparent solids-liquid distribution of hydrophobic micropollutants in WWTP streams.

Abundances of Ag and Cu in mantle peridotites and the implications for the behavior of chalcophile elements in the mantle

Silver abundances in mantle peridotites and the behavior of Ag during high temperature mantle processes have received little attention and, as a consequence, the abundance of Ag in the bulk silicate Earth (BSE) has been poorly constrained. In order to better understand the processes that fractionate Ag and other chalcophile elements in the mantle, abundances of Ag and Cu in mantle peridotites from different geological settings (n=68) have been obtained by isotope dilution ICP-MS methods. In peridotite tectonites and in a few suites of peridotite xenoliths which display evidence for variable extents of melt depletion and refertilization by silicate melts, Ag and Cu abundances show positive correlations with moderately incompatible elements such as S, Se, Te and Au. The mean Cu/Ag in fertile peridotites (3500±1200, 1s, n=38) is indistinguishable from the mean Cu/Ag of mid ocean ridge basalts (MORB, 3600±400, 1s, n=338) and MORB sulfide droplets. The constant mean Cu/Ag ratios indicate similar behavior of Ag and Cu during partial melting of the mantle, refertilization and magmatic fractionation, and thus should be representative of the Earth’s upper mantle. The systematic fractionation of Cu, Ag, Au, S, Se and Te in peridotites and basalts is consistent with sulfide melt–silicate melt partitioning with apparent partition coefficients of platinum group elements (PGE)>Au⩾Te>Cu≈Ag>Se⩾S.Because of the effects of secondary processes, the abundances of chalcophile elements, notably S, Se, but also Cu and the PGE in many peridotite xenoliths are variable and lower than in peridotite massifs. Refertilization of peridotite may change abundances of chalcophile and lithophile elements in peridotite massifs, however, this seems to mostly occur in a systematic way. Correlations with lithophile and chalcophile elements and the overlapping mean Cu/Ag ratios of peridotites and ocean ridge basalts are used to constrain abundances of Ag and Cu in the BSE at 9±3(1s)ng/g and 30±6μg/g(1s), respectively. The very different extent of depletion of Ag and Cu in the BSE cannot be explained by low pressure–temperature core formation if currently available metal–silicate partitioning data are applied.

Effects of hydrodynamic conditions on the sorption behaviors of aniline on sediment with coexistence of nitrobenzene.

The sorption behaviors of pollutants affected by hydrodynamic conditions were confirmed in natural water environment. The effects of hydrodynamic conditions on the sorption behaviors of aniline on sediment with coexistence of nitrobenzene were investigated. The particle entrainment simulator (PES) was used to simulate varied bottom shear stresses. The batch equilibrium method was applied to the experiments with the stress levels and the action time controlled at 0.2-0.5 N/m(2) and 24 h, respectively. The findings indicated that apparent partition coefficient of aniline on sediment increased with the shear stress significantly, while decreased with nitrobenzene concentration. On the contrary, both the sorption amount of aniline on suspended particulate matter (Q s) and the effect of nitrobenzene concentration on Q s declined as the shear stress increased. The sorption kinetic results showed that the sorption process followed the pseudo-second-order kinetics equation, and the process included two stages: fast sorption stage and slow sorption stage, among which the average sorption rate of fast stage was 7.5-9.5 times that of slow one. The effect of shear stress on the average sorption rate of aniline was enhanced with the increase of nitrobenzene concentration. And shear stress weakened the disturbance of cosolute on main solute sorption process. In addition, experiment results of sorption kinetic show that only the initial sorption rate was affected by shear stress and cosolute concentration. In the first 5 min, shear stress had positive effects on the sorption rate. After that, the sorption rate barely changed with shear stress and cosolute concentration.

Fixed-bed study and modeling of selective phenanthrene removal from surfactant solutions

Abstract Recovering and then recycling surfactant solution is required in the surfactant-enhanced remediation (SER) of contaminated sites and groundwater to reduce operating costs and prevent secondary contamination. In this study, fixed-beds with activated carbon were employed to selectively remove phenanthrene from Triton X-100 (TX100) aqueous solution as a potential model system for the recovery of surfactant solution in SER. The effects of various operating conditions such as flow rate, bed height, and influent phenanthrene concentration on the performance of the fixed beds were investigated. The sorption of TX100 in the fixed-bed can rapidly reach saturation, but the effluent concentrations of phenanthrene are much lower than its influent concentrations, even with a great volume of solution flowing through the columns. The total removal percentage of phenanthrene from effluent solution was greater than the sorption loss of TX100 under all experimental conditions. The corresponding selectivity parameters for phenanthrene removal versus surfactant sorption were all greater than 4.0, a selectivity value representing 80% phenanthrene removal and 80% surfactant retention. Moreover, better selectivity was obtained at a higher bed height and lower flow rate, but had little dependence on the influent phenanthrene concentration. The constant-pattern model and the apparent partition coefficient were applied successfully to describe and predict the breakthrough curves of TX100 and phenanthrene in fixed-bed columns. The results suggested that fixed-beds could be effectively used to recover surfactant solutions from the washing effluents in SER.

Preclinical studies of the potent and selective nicotinic α4β2 receptor ligand VMY-2-95.

The discovery and development of small molecules that antagonize neuronal nicotinic acetylcholine receptors may provide new ligands for evaluation in models of depression or addiction. We discovered a small molecule, VMY-2-95, a nAChR ligand with picomolar affinity and high selectivity for α4β2 receptors. In this study, we investigated its preclinical profile in regards to solubility, lipophilicity, metabolic stability, intestinal permeability, bioavailability, and drug delivery to the rat brain. Metabolic stability of VMY-2-95·2HCl was monitored on human liver microsomes, and specific activity of VMY-2-95·2HCl on substrate metabolism by CYP1A2, 2C9, 2C19, 2D6, and 3A4 was tested in a high-throughput manner. The intestinal transport of VMY-2-95·2HCl was studied through Caco-2 cell monolayer permeability. VMY-2-95·2HCl was soluble in water and chemically stable, and the apparent partition coefficient was 0.682. VMY-2-95·2HCl showed significant inhibition of CYP2C9 and 2C19, but weak or no effect on 1A2, 2D6, and 3A4. The Caco-2 cell model studies revealed that VMY-2-95·2HCl was highly permeable with efflux ratio of 1.11. VMY-2-95·2HCl achieved a maximum serum concentration of 0.56 mg/mL at 0.9 h and was orally available with a half-life of ∼9 h. Furthermore, VMY-2-95·2HCl was detected in the rat brain after 3 mg/kg oral administration and achieved a maximal brain tissue concentration of 2.3 μg/g within 60 min. Overall, the results demonstrate that VMY-2-95·2HCl has good drug like properties and can penetrate the blood–brain barrier with oral administration.

The effect of natural organic matter on the adsorption of mercury to bacterial cells

We investigated the ability of non-metabolizing Bacillus subtilis, Shewanella oneidensis MR-1, and Geobacter sulfurreducens bacterial species to adsorb mercury in the absence and presence of Suwanee River fulvic acid (FA). Bulk adsorption and X-ray absorption spectroscopy (XAS) experiments were conducted at three pH conditions, and the results indicate that the presence of FA decreases the extent of Hg adsorption to biomass under all of the pH conditions studied. Hg XAS results show that the presence of FA does not alter the binding environment of Hg adsorbed onto the biomass regardless of pH or FA concentration, indicating that ternary bacteria–Hg–FA complexes do not form to an appreciable extent under the experimental conditions, and that Hg binding on the bacteria is dominated by sulfhydryl binding. We used the experimental results to calculate apparent partition coefficients, Kd, for Hg under each experimental condition. The calculations yield similar coefficients for Hg onto each of the bacterial species studies, suggesting there is no significant difference in Hg partitioning between the three bacterial species. The calculations also indicate similar coefficients for Hg–bacteria and Hg–FA complexes. S XAS measurements confirm the presence of sulfhydryl sites on both the FA and bacterial cells, and demonstrate the presence of a wide range of S moieties on the FA in contrast to the bacterial biomass, whose S sites are dominated by thiols. Our results suggest that although FA can compete with bacterial binding sites for aqueous Hg, because of the relatively similar partition coefficients for the types of sorbents, the competition is not dominated by either bacteria or FA unless the concentration of one type of site greatly exceeds that of the other.

Boron isotopic fractionation and trace element incorporation in various species of modern corals in Sanya Bay, South China Sea

The boron isotope paleo-pH proxy has been extensively studied due to its potential for understanding past climate change, and further calibrations were considered for accurate applications of the proxy because of significant variability related to biocarbonate microstructure. In this work, we studied the boron isotopic fractionation between modern marine corals and their coexisting seawater collected along shallow area in Sanya Bay, South China Sea. The apparent partition coefficient of boron (KD) ranged from 0.83×10−3 to 1.69×10−3, which are in good agreement with previous studies. As the analyzed coral skeleton (∼5 g) spanned the growth time period of 1–2 years, we discussed the boron isotopic fractionation between pristine corals and modern seawater using the annual mean seawater pH of 8.12 in this sea area. Without taking the vital effect into account, (11B/10B)coral values of all living corals spread over the curves of (11B/10B)borate vs. (11B/10B)sw with the α4−3 values ranging from 0.974 to 0.982. After calibrating the biological effect on the calcifying fluid pH, the field-based calcification on calcifying fluid pH (i.e., Δ(pHbiol-pHsw)) for coral species of Acropora, Pavona, Pocillopora, Faviidae, and others including Proites are 0.42, 0.33, 0.36, 0.19, respectively, and it is necessary to be validated by coral culturing experiment in the future. Correlations in B/Ca vs. Sr/Ca and B/Ca vs. pHbiol approve temperature and calcifying fluid pH influence on skeletal B/Ca. Fundamental understanding of the thermodynamic basis of the boron isotopes in marine carbonates and seawater will strengthen the confidence in the use of paleo-pH proxy as a powerful tool to monitor atmospheric CO2 variations in the past.

Determination of pore size distributions in capillary-channeled polymer fiber stationary phases by inverse size-exclusion chromatography and implications for fast protein separations

Capillary-channeled polymer (C-CP) fibers have been utilized as liquid chromatography stationary phases, primarily for biomacromolecule separations on the analytical and preparative scales. The collinear packing of the eight-channeled C-CP fibers provides for very efficient flow, allowing operation at high linear velocity (u>100mm s−1) and low backpressure (<2000psi) in analytical-scale separations. To take advantage of these fluid transport properties, there must not be mass transfer limitations as would be imposed by having an appreciably porous phase, wherein solute diffusion limits the overall mass transport rates. To better understand the physical nano-/micro- structure of C-CP fibers, inverse size exclusion chromatography (iSEC) has been employed to determine the pore size distribution (PSD) within C-CP fibers. A diversity of test species (from metal ions to large proteins) was used as probes under non-retaining conditions to obtain a response curve reflecting the apparent partition coefficient (Kd) versus hydrodynamic radii (rm). A mean pore radius (rp) of 4.2nm with standard deviation (sp) of ±1.1nm was calculated by fitting the Kd versus rm data to model equations with a Gaussian pore size distribution, and a pore radius of 4.0±0.1nm was calculated based on a log-normal distribution. The derived mean pore radius is much smaller than traditional support materials, with the standard deviation showing a relatively uniform pore distribution. van Deemter plots were analyzed to provide practical confirmation of the structural implications. Large molecules (e.g., proteins) that are fully excluded from pores have no significant C-terms in the van Deemter plots whereas small molecules that can access the pore volumes display appreciable C-terms, as expected. Fitting of retention data to the Knox equation suggests that the columns operate with a characteristic particle diameter (dp) of ∼53μm.

Migration of conventional and new plasticizers from PVC films into food simulants: A comparative study

Abstract PVC is one of the resins with the higher quantity of additives and the possibility of migration is always a concern when its intended use is food packaging. In this study, the migration of several plasticizers was investigated with the aim of finding out a relationship between migration and conformance with legislation in force, and tensile properties as well. Therefore, six PVC cling films intended to come into contact with foodstuffs have been formulated in order to have same hardness and thickness. The reference film was produced with DEHA and ESBO, while the other films were produced with conventional plasticizers (ATBC and Polyadipate), new plasticizers from renewable resources (Mixture of glycerin acetates – MGA and Acetic acid esters of mono- and diglycerides of fatty acids – AGM) or a plasticizer employed in toy and childcare applications (DEHT). The films were evaluated as to the overall and specific migration to food simulants and the effect of the formulation was studied. The results have shown that the coefficient of apparent partition of DEHT is similar to that of DEHA, whereas MGA and AGM plasticizers displayed higher coefficients of apparent partition than the other plasticizers under study. This difference in migration has been attributed to the different molecular structures of plasticizers. In addition, commercial films have been evaluated as to plasticizers concentration and specific migration into food simulants. It was found that 25% of the samples comply with the specific migration limits for fatty foods contact while 50% might be used for contact with fatty foods with FRF 2–5. On the other hand, all commercial samples showed no restriction for aqueous acidic food contact. Thus, it has been demonstrated that a contact for prolonged time up to 40 °C did not promote the migration of plasticizers into acidic foodstuffs, but the migration of plasticizers to fatty foods can be high (75%–90% loss of plasticizers) and limit the use of PVC films as fatty food packaging.

Utilizing zeta potential measurements to study the effective charge, membrane partitioning, and membrane permeation of the lipopeptide surfactin

The effective charge of membrane-active molecules such as the fungicidal lipopeptide surfactin (SF) is a crucial property governing solubility, membrane partitioning, and membrane permeability. We present zeta potential measurements of liposomes to measure the effective charge as well as membrane partitioning of SF by utilizing what we call an equi-activity analysis of several series of samples with different lipid concentrations. We observe an effective charge of −1.0 for SF at pH8.5 and insignificantly lower at pH7.4, illustrating that the effective charge may deviate strongly from the nominal value (−2 for 1 Asp, 1 Glu). The apparent partition coefficient decreases from roughly 100 to 20/mM with increasing membrane content of SF in agreement with the literature. Finally, by comparing zeta potentials measured soon after the addition of peptide to liposomes with those measured after a heat treatment to induce transmembrane equilibration of SF, we quantified the asymmetry of partitioning between the outer and inner leaflets. At very low concentration, SF binds exclusively to the outer leaflet. The onset of partial translocation to the inner leaflet occurs at about 5mol-% SF in the membrane. This article is part of a Special Issue entitled: Interfacially Active Peptides and Proteins. Guest Editors: William C. Wimley and Kalina Hristova.