Coupling Ion Research Articles

Suspect screening of halogenated carboxylic acids in drinking water using ion exchange chromatography – high resolution (Orbitrap) mass spectrometry (IC-HRMS)

Retrospective in silico screening of analytical data for the identification of new or emerging disinfection by-products in drinking waters could be useful to assess quality and potential hazards, as well as help implement mitigation procedures more rapidly. Herein, the first study coupling ion exchange chromatography (IC) with high resolution mass spectrometry (HRMS) for the determination of halogenated carboxylic acid disinfectant by-products is reported. Separation was achieved using a Metrohm A Supp 5 column and a Na2CO3/NaHCO3 gradient eluent from 1/0.31 to 10/3.1mM. A variety of solid phase extraction (SPE) sorbents were tested for added selectivity to organic ions and Isolute ENV+ cartridges were selected because of their best overall extraction performance. Method LODs were in the μgL−1 concentration range, with R2 ≥ 0.99 for all the analytes, and isobaric ions could be easily discriminated using HRMS. The method was applied to municipal drinking water. Targeted quantitative analysis revealed the presence of 10 haloacetic acids at levels not exceeding the limits set by WHO and USEPA. Furthermore, suspect screening for additional halogenated carboxylic acids via retrospective HRMS data analysis also indicated the presence of other iodinated HAAs and chlorinated propionic acids, of which one (i.e. monochloropropionic acid) is discussed here for the first time. Most importantly, several potential suspects could be eliminated from further consideration through HRMS data analysis alone. To our knowledge, this represents the first time that a retrospective IC-HRMS screen of halogenated carboxylic acids in drinking water has been reported.

Daytime zonal drifts in the ionospheric 150 km and E regions estimated using EAR observations

AbstractMultibeam observations of the 150 km echoes made using the Equatorial Atmosphere Radar (EAR), located at Kototabang, Indonesia, provide unique opportunity to study both vertical and zonal E × B plasma drifts in the equatorial ionosphere. In this paper, we focus on estimating daytime zonal drifts at the 150 km (140–160 km) and E (100–110 km) regions using multibeam observations of 150 km and E region echoes made using the EAR and study the daytime zonal drifts covering all seasons not studied before from Kototabang. Zonal drifts in the 150 km and E regions are found to be westward and mostly below −80 m s−1 and −60 m s−1, respectively. While the zonal drifts in the 150 km and E regions do not go hand in hand on a case‐by‐case basis, the seasonal mean drifts in the two height regions are found to be in good agreement with each other. Zonal drifts at the 150 km region show seasonal variations with three maxima peaking around May, September, and January. The zonal drifts at the 150 km region are found to be smaller than the F region drifts obtained from Coupled Ion Neutral Dynamics Investigation (CINDI) onboard Communication and Navigation Outage Forecasting System (C/NOFS) by about 25 m s−1 consistent with the height variations of F region zonal drifts observed by the Jicamarca radar. These results constitute the first comprehensive study of zonal drifts at the 150 km and E regions from Kototabang, Indonesia, and the results are discussed in the light of current understanding on the low‐latitude electrodynamics and coupling.

Infrared spectrum and structure of the homochiral serine octamer-dichloride complex.

The amino acid serine is known to form a very stable octamer that has properties that set it apart from serine complexes of different sizes or from complexes composed of other amino acids. For example, both singly protonated serine octamers and anionic octamers complexed with two halogen ions strongly prefer homochirality, even when assembled from racemic D,L mixtures. Consequently, the structures of these complexes are of great interest, but no acceptable candidates have so far been identified. Here, we investigate anionic serine octamers coordinated with two chloride ions using a novel technique coupling ion mobility spectrometry-mass spectrometry with infrared spectroscopy, in combination with theoretical calculations. The results allow the identification of a unique structure for (Ser8Cl2)2- that is highly symmetric, very stable and homochiral and whose calculated properties match those observed in experiments.

Iodine Vacancy Redistribution in Organic-Inorganic Halide Perovskite Films and Resistive Switching Effects.

Organic-inorganic halide perovskite (OHP) materials, for example, CH3 NH3 PbI3 (MAPbI3 ), have attracted significant interest for applications such as solar cells, photodectors, light-emitting diodes, and lasers. Previous studies have shown that charged defects can migrate in perovskites under an electric field and/or light illumination, potentially preventing these devices from practical applications. Understanding and control of the defect generation and movement will not only lead to more stable devices but also new device concepts. Here, it is shown that the formation/annihilation of iodine vacancies (VI 's) in MAPbI3 films, driven by electric fields and light illumination, can induce pronounced resistive switching effects. Due to a low diffusion energy barrier (≈0.17 eV), the VI 's can readily drift under an electric field, and spontaneously diffuse with a concentration gradient. It is shown that the VI diffusion process can be suppressed by controlling the affinity of the contact electrode material to I- ions, or by light illumination. An electrical-write and optical-erase memory element is further demonstrated by coupling ion migration with electric fields and light illumination. These results provide guidance toward improved stability and performance of perovskite-based optoelectronic systems, and can lead to the development of solid-state devices that couple ionics, electronics, and optics.

Equatorial plasma bubbles: Variations of occurrence and spatial scale in local time, longitude, season, and solar activity

AbstractWe examine the location and structure of equatorial topside depletions referred to here as equatorial plasma bubbles (EPBs). The Coupled Ion Neutral Dynamics Investigation Ion Velocity Meter instrument on board the Communication/Navigation Outage Forecasting System is used to measure the ion density from August 2008 to December 2014, a time period in which solar activity transitioned from solar minimum conditions to more moderate solar activity conditions. EPB data are divided into four longitude sectors to determine seasonal and solar cycle variability. In the early phase of the mission, during solar minimum, EPBs occur late in local time, primarily after midnight in all longitude sectors. In the later phase of the mission EPB occurrence after midnight diminishes in all seasons and longitude sectors with the exception of the sector extending from −15° to 60°. An examination of the widths of bubbles indicates that all longitudes show similar distributions between 115 km and 460 km with a prominent peak near 200 km. Among these widths is a distinct width that belongs to discrete individual bubbles with no substructure. We suggest that many bubbles are actually combinations of these individual bubbles; however, in the later phase of the mission there is a population of bubbles that do not conform to this description, perhaps due to the influence of large‐scale plasma motions affecting the background density in which they are embedded.

Determination of antimony compounds in waters and juices using ion chromatography-inductively coupled plasma mass spectrometry.

A method was developed by coupling ion chromatography (IC) and inductively coupled plasma mass spectrometry (ICP-MS) for the speciation of antimony. In this study, antimony species such as antimonite [Sb(III)], antimonate [Sb(V)] and trimethyl antimony(V) (TMeSb) were separated in less than 8min using anion exchange chromatography with a Hamilton PRP-X100 column as the stationary phase. Mobile phase A was 20mmolL-1 ethylenediaminetetraacetic acid (EDTA), 2mmolL-1 potassium hydrogen phthalate (KHP) in 1% v/v methanol (pH 5.5) and 20mmolL-1 EDTA, 2mmolL-1 KHP, 40mmolL-1 (NH4)2CO3 in 1% v/v methanol (pH 9.0) formed mobile phase B. Detection limits and relative standard deviations (RSD) were 0.012-0.032ngmL-1 and 2.2-2.8% respectively. This method was applied to bottled waters and fruit juices purchased in Kaohsiung, Taiwan. In water samples, Sb(V) was the major species where as in juices organometallic Sb species were also present.

Metabolic Profiling as a Screening Tool for Cytotoxic Compounds: Identification of 3-Alkyl Pyridine Alkaloids from Sponges Collected at a Shallow Water Hydrothermal Vent Site North of Iceland.

Twenty-eight sponge specimens were collected at a shallow water hydrothermal vent site north of Iceland. Extracts were prepared and tested in vitro for cytotoxic activity, and eight of them were shown to be cytotoxic. A mass spectrometry (MS)-based metabolomics approach was used to determine the chemical composition of the extracts. This analysis highlighted clear differences in the metabolomes of three sponge specimens, and all of them were identified as Haliclona (Rhizoniera) rosea (Bowerbank, 1866). Therefore, these specimens were selected for further investigation. Haliclona rosea metabolomes contained a class of potential key compounds, the 3-alkyl pyridine alkaloids (3-APA) responsible for the cytotoxic activity of the fractions. Several 3-APA compounds were tentatively identified including haliclamines, cyclostellettamines, viscosalines and viscosamines. Among these compounds, cyclostellettamine P was tentatively identified for the first time by using ion mobility MS in time-aligned parallel (TAP) fragmentation mode. In this work, we show the potential of applying metabolomics strategies and in particular the utility of coupling ion mobility with MS for the molecular characterization of sponge specimens.

Study on the mechanism of deoxidization and purification for Li2BeF4 molten salt via graphite nanoparticles

Graphite nanoparticles originated from high purity graphite crucible were used for deoxidization and purification of Li2BeF4 molten salt containing a bit of (NH4)2BeF4 under high temperature vacuum condition. And the mechanism of deoxidization and purification via graphite nanoparticles was put forward based on analysis of sample characterization and chemical reaction Gibbs free energy calculation. The morphology, particle size, chemical composition and crystal structure of graphite nanoparticles in Li2BeF4 molten salt were characterized by High Resolution Transmission Electron Microscopy (HRTEM, SAED and EDS). Phase analysis, total oxygen content, full elemental and anion concentration for as-prepared Li2BeF4 products were studied by X-Ray Diffraction (XRD), LECO nitrogen-oxygen analyzer, Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and Ion Chromatography (IC), respectively. The results of sample characterization showed that graphite nanoparticles in Li2BeF4 molten salt were the poly-crystal round sheet shape with an average diameter of <100 nm. The concentration of total oxygen, sulfur and nickel in as-prepared Li2BeF4 molten salt after treatment were 548 ppm, <0.6 ppm and <0.4 ppm, respectively. Experiment and calculation all showed that SO42− and NO3− could react with carbon at 700 °C. And vacuum degassing play an excellent role in deoxidization and purification for Li2BeF4 molten salt via graphite nanoparticles.

Analysis of haloacetic acids, bromate, and dalapon in natural waters by ion chromatography–tandem mass spectrometry

The addition of oxidants for disinfecting water can lead to the formation of potentially carcinogenic compounds referred to as disinfection byproducts (DBPs). Haloacetic acids (HAAs) are one of the most widely detected DBPs in US water utilities and some of them are regulated by the US Environmental Protection Agency (USEPA). The present study developed a method to analyze all the compounds in the USEPA method 557 (nine HAAs, bromate and dalapon) plus four potentially more toxic iodinated HAAs in water by coupling ion chromatography with tandem mass spectrometry (IC–MS/MS). This aqueous direct injection method has significant advantages over traditional GC methods, which require a derivatization and sample extraction that are laborious, time-consuming, and can negatively impact reproducibility. The method developed in this study requires half the time of the current USEPA method 557 on IC–MS/MS while including more compounds and achieving sub-μg/L level method detection limits (MDLs) for all 15 target analytes. The single laboratory lowest concentration minimum reporting level (LCMRL) has also been determined in reagent water, which ranged from 0.011 to 0.62μg/L for the analytes. The mean recoveries of the analytes during matrix spike recovery tests were 77–125% in finished drinking water and 81–112% in surface water. This method was then applied to untreated, chlorinated, and chloraminated groundwater and surface water samples. Bromate and 9 HAAs were detected at different levels in some of these samples.

Complementation and joint contribution of appropriate intramolecular coupling and local ion symmetry to improve magnetic relaxation in a series of dinuclear Dy2 single-molecule magnets

The joint contribution of appropriate intramolecular coupling and local ion symmetry to improve magnetic relaxation in a series of dinuclear Dy2 SMMs.

Ion Selectivity of the Flagellar Motors Derived from the Alkaliphilic Bacillus and Paenibacillus Species.

Many bacteria can swim using their flagella, which are filamentous organelles that extend from the cell surface. The flagellar motor is energized by either a proton (H+) or sodium ion (Na+) as the motive force. MotAB-type stators use protons, whereas MotPS- and PomAB-type stators use Na+ as the coupling ions. Recently, alkaliphilic Bacillus alcalophilus was shown to use potassium ions (K+) and rubidium ions (Rb+) for flagellar rotation, and the flagellar motor from Paenibacillus sp. TCA-20 uses divalent cations such as magnesium ions (Mg2+), calcium ions (Ca2+), and strontium ions (Sr2+) for coupling. In this chapter, we focus on how to identify the coupling ions for flagellar rotation of alkaliphilic Bacillus and Paenibacillus species.

Source Apportionment of PM2.5 Particles: Influence of Outdoor Particles on Indoor Environment of Schools Using Chemical Mass Balance

ABSTRACTChildren have higher lung function than adults and they spend most of their day time in schools. Also, children studying at schools located in the vicinity of busy roadways are vulnerable to childhood asthma and respiratory disorders. The present study is focused on estimating the sources of PM2.5 particles present in the indoor air quality in schools which are located adjacent to urban and suburban roadways. The indoor PM2.5 samples from all the four schools were collected using fine dust sampler from 8 a.m. to 4 p.m. The sampling was carried out for one complete week during various seasons including both working and non-working days. The chemical compositions of the PM2.5 samples were analyzed for certain elements like Ba, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sr, Ti, V and Zn using Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) and ions like F–, Cl–, NO3–, PO43–, SO42–, K+, Ca2+, Mg2+, NH4+, Na+ using Ion Chromatography (IC). Source apportionment study using Chemical Mass Balance was carried out using the species concentration of the collected samples. The major sources were found to be Paved Road Dust, Soil Dust, Gasoline Vehicle Emissions, Diesel Vehicle Emissions and Marine Source Emissions. Among these, vehicular emissions contribution was found to be higher for the schools located close to roadways rather than the school located at a considerable distance from highway. The difference in source type contribution at each school clearly depicts the difference in nature of location and type of activities in the vicinity of the sampling sites.

Dynamics in the Dual Fuel Flagellar Motor of Shewanella oneidensis MR-1.

The stator is an eminent component of the flagellar motor and determines a number of the motor's properties, such as the rotation-energizing coupling ion (H+ or Na+) or the torque that can be generated. The stator consists of several units located in the cytoplasmic membrane surrounding the flagellar drive shaft. Studies on flagellar motors of several bacterial species have provided evidence that the number as well as the retention time of stators coupled to the motor is highly dynamic and depends on the environmental conditions. Notably, numerous species possess more than a single distinct set of stators. It is likely that the presence of different stator units enables these bacteria to adjust the flagellar motor properties and function to meet the environmental requirements. One of these species is Shewanella oneidensis MR-1 that is equipped with a single polar flagellum and two stator units, the Na+-dependent PomAB and the H+-dependent MotAB. Here, we describe a method to determine stator dynamics by fluorescence microscopy, demonstrating how bacteria can change the composition of an intricate molecular machine according to environmental conditions.

Nonconventional cation-coupled flagellar motors derived from the alkaliphilic Bacillus and Paenibacillus species.

Prior to 2008, all previously studied conventional bacterial flagellar motors appeared to utilize either H+ or Na+ as coupling ions. Membrane-embedded stator complexes support conversion of energy using transmembrane electrochemical ion gradients. The main H+-coupled stators, known as MotAB, differ from Na+-coupled stators, PomAB of marine bacteria, and MotPS of alkaliphilic Bacillus. However, in 2008, a MotAB-type flagellar motor of alkaliphilic Bacillus clausii KSM-K16 was revealed as an exception with the first dual-function motor. This bacterium was identified as the first bacterium with a single stator-rotor that can utilize both H+ and Na+ for ion-coupling at different pH ranges. Subsequently, another exception, a MotPS-type flagellar motor of alkaliphilic Bacillus alcalophilus AV1934, was reported to utilize Na+ plus K+ and Rb+ as coupling ions for flagellar rotation. In addition, the alkaline-tolerant bacterium Paenibacillus sp. TCA20, which can utilize divalent cations such as Ca2+, Mg2+, and Sr2+, was recently isolated from a hot spring in Japan, which contains a high Ca2+ concentration. These findings show that bacterial flagellar motors isolated from unique environments utilize unexpected coupling ions. This suggests that bacteria that grow in different extreme environments adapt to local conditions and evolve their motility machinery.

The Effect of Next-Nearest Neighbour Hopping in the One, Two, and Three Dimensional Holstein Model.

Allowing a single electron to hop to next-nearest neighbours (NNN) in addition to the closest atomic sites in the Holstein model, a modified Trugman method is applied to exactly calculate the effect on the polaronic effective mass in one, two, and three dimensions, building on the previous study of the one-dimensional NNN Holstein model. We also present perturbative calculations and a heuristic scaling factor for the coupling strength and ion frequency to nearly map the NNN Holstein model back onto the original Holstein model. When account is taken of the modified electronic bandwidth near the electron energy, we find that including NNN hopping effectively increases the polaron effective mass.

Retention of Native Protein Structures in the Absence of Solvent: A Coupled Ion Mobility and Spectroscopic Study.

Can the structures of small to medium‐sized proteins be conserved after transfer from the solution phase to the gas phase? A large number of studies have been devoted to this topic, however the answer has not been unambiguously determined to date. A clarification of this problem is important since it would allow very sensitive native mass spectrometry techniques to be used to address problems relevant to structural biology. A combination of ion‐mobility mass spectrometry with infrared spectroscopy was used to investigate the secondary and tertiary structure of proteins carefully transferred from solution to the gas phase. The two proteins investigated are myoglobin and β‐lactoglobulin, which are prototypical examples of helical and β‐sheet proteins, respectively. The results show that for low charge states under gentle conditions, aspects of the native secondary and tertiary structure can be conserved.

Fast Detection of Carbonate and Bicarbonate in Groundwater and Lake Water by Coupled Ion Selective Electrode

Abstract The content of carbonate (HCO3−) and bicarbonate (CO32−) in the freshwater is an important characteristic of the geochemical environment. However, the environmental factors affect the concentration of two ions easily during the process of sampling, transportation and storage. It is a worldwide problem to determine the real content of carbonate and bicarbonate ions in the freshwater. To solve this problem, a new approach was proposed for the rapid determination of carbonate and bicarbonate ions in groundwater and lake water through a pH electrode combined with a CO2 electrode. The results showed that the liner range of bicarbonate was 0.027–570 mg L−1 and that of carbonate was 1.25 × 10−8−39.7 mg L−1. In the most case, the coexisting cation, anion and weak acid (K+, Na+, Mg2+, Cl−, SO42−

The mechanism of inward rectification in Kir channels: A novel kinetic model with non-equilibrium thermodynamics approach

The mechanisms of the strong inward rectification in inward rectifier K+ (Kir) channels are controversial because the drop in electrical potential due to the movement of the blocker and coupling ions is insufficient to explain the steep voltage-dependent block near the equilibrium potential. Here, we study the “driving force”-dependent block in Kir channels with a novel approach incorporating concepts from the non-equilibrium thermodynamics of small systems, and computer kinetic simulations based on the experimental data of internal Ba2+ block on Kir2.1 channels. The steep exponential increase in the apparent binding rate near the equilibrium potential is explained, when the encounter frequency is construed as the likelihood of transfer events down or against the electrochemical potential gradient. The exponent of flux ratio, nf=2.62, implies that the blockage of the internal blocker may be coupled with the outward transport of 2 to 3K+ ions. The flux-coupled block in the single-file multi-ion pore can be demonstrated by the concentration gradient alone, as well as when the driving force is the electrochemical potential difference across the membrane.

A novel type bacterial flagellar motor that can use divalent cations as a coupling ion.

The bacterial flagellar motor is a sophisticated nanomachine embedded in the cell envelope and powered by an electrochemical gradient of H+, Na+, or K+across the cytoplasmic membrane. Here we describe a new member of the bacterial flagellar stator channel family (MotAB1 of Paenibacillus sp. TCA20 (TCA-MotAB1)) that is coupled to divalent cations (Ca2+and Mg2+). In the absence of divalent cations of alkaline earth metals, no swimming was observed in Paenibacillus sp. TCA20, which grows optimally in Ca2+-rich environments. This pattern was confirmed by swimming assays of a stator-free Bacillus subtilis mutant expressing TCA-MotAB1. Both a stator-free and major Mg2+uptake system-deleted B. subtilis mutant expressing TCA-MotAB1 complemented both growth and motility deficiency under low Mg2+conditions and exhibited [Mg2+]in identical to that of the wild-type. This is the first report of a flagellar motor that can use Ca2+and Mg2+as coupling ions. These findings will promote the understanding of the operating principles of flagellar motors and molecular mechanisms of ion selectivity.

Microwave-Induced Combustion of Coal for Further Sulfur Determination by Inductively Coupled Plasma Optical Emission Spectrometry or Ion Chromatography

In this work, a method using microwave-induced combustion (MIC) was optimized in order to obtain a fast, simple, efficient and greener sample preparation method for coal digestion and further determination of sulfur by inductively coupled plasma optical emission spectrometry (ICP OES). Accuracy was evaluated by comparison of the results with those obtained using elemental analysis by UV-fluorescence, microwave-assisted acid digestion with determination by ICP OES and by analysis of certified reference materials of coal. Some parameters that influence MIC method, such as the type and concentration of absorbing solution, the necessity of using a reflux step as well as the cooling time were carefully optimized. No statistical difference was observed for combustion without reflux followed by 5 min of cooling, in comparison to the reference values obtained by elemental analysis. Complete digestion was obtained with this fast and simple method (total digestion program required only 6 min) and using a diluted acid solution for quantitative recovery. The feasibility of digests for sulfur determination as sulfate by ion chromatography (IC) with conductivity detection was also demonstrated. The possibility of determining other elements, commonly monitored in coals, is another advantage of this high-efficiency digestion method (MIC) combined with the multielemental capacity of ICP OES or IC instruments.