Injection of reagent ions into the selvedge region in fast-atom bombardment mass spectrometry

A divided probe that incorporates a potassium aluminosilicate glass target and an analyte/glycerol matrix target, spatially separated, was used to inject potassium ions (K⁺) into the high-pressure “selvedge” region formed above the analyte/glycerol matrix target during fast-atom bombardment (FAB); [M+K]⁺ adduct ions that represent the types of gas-phase neutral molecules present in the selvedge region are observed. Computer modeling assisted in designing the divided target and an additional ion optical element for the FAB ion source to optimize interactions between K⁺ ions and the desorbed neutral molecules. The capability of injecting K⁺ ions into the FAB experiment has utility in both mechanistic studies and analyses. Experimental results here are consistent with a model for the desorption/ionization processes in FAB in which some types of neutral analyte molecules are desorbed intact and are subsequently protonated by glycerol chemical ionization. Unstable protonated molecules undergo unimolecular decomposition to yield observed fragment ions. The use of K⁺ cationization of analytes for molecular weight confirmation is demonstrated, as well as its utility in FAB experiments in which mixtures are encountered.     

Metal‐Cation Recognition in Water by a Tetrapyrazinoporphyrazine‐Based Tweezer Receptor

A series of zinc azaphthalocyanines with two azacrowns in a rigid tweezer arrangement were prepared and the fluorescence sensing properties were investigated. The size‐driven recognition of alkali and alkaline earth metal cations was significantly enhanced by the close cooperation of the two azacrown units, in which both donor nitrogen atoms need to be involved in analyte binding to switch the sensor on. The mono‐ or biphasic character of the binding isotherms, together with the binding stoichiometry and magnitude of association constants (K_A), indicated specific complexation of particular analytes. Water solvation was shown to play an important role and resulted in a strong quenching of sensor fluorescence in the ON state. The lead compound was embedded into silica nanoparticles and advantageous sensing properties towards K⁺ were demonstrated in water (λ_F=671 nm, apparent K_A=82 m ^?1, increase of 17×), even in the presence of (supra)physiological concentrations of Na⁺ and Ca²⁺.     

Application of a multifunctional microelectrode to the in vivo analysis of the K+ response to CO2 stress

The K⁺ concentration in the vacuole in leaf cells of Tradescantia virginiana L. decreased abruptly in response to CO₂ stress. This K⁺ response was analysed with a multifunctional microelectrode system. When valinomycin was introduced into the vacuole before exposure to CO₂, the K⁺ concentration increased from 60 to 68 mM. After reaching a steady state, CO₂ was applied again to the leaf. The abrupt decrease in K⁺ concentration observed before did not occur. When valinomycin was introduced during CO₂ exposure, the K⁺ concentration sharply increased reaching 67 mM. Therefore, the K⁺ response was caused by the K⁺ transport from the vacuole to the exterior against its concentration gradient. This phenomenon, however, preceded the H⁺ movement. This does not support the direct involvement of the H⁺ pump system. The blocking of the H⁺ pump system in the vacuolar membrane, however, caused the K⁺ response to disappear. Therefore, it is essential for the K⁺ response that the H⁺ pump system is in the active state, although they are not directly coupled.     

Use of zwitterionic micelles in the eluent II: a new approach to ion chromatographic analysis of inorganic cations in biological fluids with direct sample injection

A new ion chromatographic (IC) technique has been developed for the determination of inorganic cations in biological fluids with direct sample injection. This involved the use of a mixed zwitterionic-micelle/electrolyte solution as an eluent. The proteins in the sample became bound to the zwitterionic micelles in the eluent and were thus eliminated from the column. The cations were separated by cation exchange. This method is ideal for the on-line, simultaneous determination of common inorganic cations (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺) in urine and serum samples. Such an application was demonstrated experimentally. Non-suppressed conductivity was used for analyte detection. The detection limits obtained using this IC system were 2.94, 5.22, 34.9, 32.6, and 56.7 μg/L for Na⁺, NH₄ ⁺, K⁺, Mg²⁺, and Ca²⁺, respectively.     

Ultrastructural and Intracellular Chemical Changes of a Novel Halophilic Strain V430 of <Emphasis Type="Italic">Staphylococcus saprophyticus</Emphasis> under CaCl<Subscript>2</Subscript> Stress

Observation of the ultrastructural and intracellular chemical changes of CaCl₂-tolerant strains is important both for understanding their adaptation mechanism under high salt stress and for providing theoretical basis of their application in treating high-CaCl₂ wastewaters. A novel strain V 430 isolated by us has been successfully used to decrease the chemical oxygen demand (COD) concentration of diosgenin wastewater from 20 g l⁻¹ to less than 0.5 g l⁻¹. For this study, strain V430 was incubated in culture media of different CaCl₂ concentrations (up to 9.0%). Strain V430 cells incubated in media of high CaCl₂ concentration excreted extracellular substances and accumulated intracellular Ca²⁺ and K⁺ and free amino acids. The levels of intracellular cations and free amino acids increased with increase in CaCl₂ concentration of the medium. The increase in total free amino acids was mostly due to accumulation of glutamic acid. The strain cells under 9.0% CaCl₂ stress took up K⁺ in a short time, while accumulation of Ca²⁺ proceeded over the whole growth process.     

Transport of Ca2+, Sr2+, Ba2+, Na+, K+ and Cs+ through hollow fiber supported liquid membrane

The transport of metal ions (Ca²⁺, Sr²⁺, Ba²⁺, Na⁺, K⁺, Cs⁺) through hollow fiber supported dichlorobenzene liquid membrane has been studied. The transport of cations using 8-crown-6 ether as a carrier and picrate as co-counter ion as well as a pertraction device and capillary isotachophoresis (ITP) measurement of the cation concentration is described.     

Determination of sodium,potassium, calcium and magnesium cations in biodiesel by ion chromatography

This work reports an ion chromatographic (IC) method for the quantitative determination of inorganic cations (Na⁺, K⁺, Mg²⁺ and Ca²⁺) in biodiesel samples that were synthesized from different vegetable oils and fat. The proposed method uses water extraction, heating and ultrasound. The limits of detection (LOD) for each ion, in milligrams of the analyte per kilogram of biodiesel (mg kg⁻¹), were respectively: 0.11 (Na⁺); 0.42 (K⁺); 0.23 (Ca²⁺); and 0.36 (Mg²⁺). The accuracy of the method was studied through recovery tests. For comparison, two samples were also analyzed using an Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) procedure. The paired Student t test and the Snedecor F test showed that both methods offer equivalent results in terms of accuracy and precision. The operational simplicity, accuracy and precision of the proposed method suggest that it can be a good alternative for the determination of inorganic cations in biodiesel samples.     

Development and validation of a qualitative screening method for the detection of exogenous anabolic steroids in urine by liquid chromatography-tandem mass spectrometry

A screening method for the urinary detection of 34 exogenous anabolic steroids has been developed. The method involves an enzymatic hydrolysis, liquid-liquid extraction and detection by liquid chromatography-tandem mass spectrometry. The use of some adducts such as [M+NH₄]⁺, [M+CH₃COO]⁻ and [M+H+MeOH]⁺ was necessary in order to detect some analytes at the required level (lower than 10 ng/ml). Two transitions were selected for each analyte. Different concentration factors have been studied in order to increase the sensitivity. A concentration factor of 50 was selected for the screening method although the high ion suppression observed under these conditions can hamper its application as a quantitative method. The method was validated and limits of detection were obtained by spiking ten different blank urine samples at five different concentration levels. Up to 29 analytes were detected in all spiked urines at the required level. Limits of detection between 1 and 10 ng/ml were obtained for most analytes which fulfil current requirements. The applicability of the method was shown by analysing positive samples.     

ATPases as Multi-Response Sensing System for Various Organic and Inorganic Analytes

Summary. The possibility of using synaptic plasma membrane (SPM) enzymes Na⁺/K⁺-ATPase and Mg²⁺-ATPase, isolated from rat brain, as a biological component of multi-response sensing system for detection of different compounds (alkaline and heavy metal salts, organic compounds) was studied. The method is based on the spectrophotometric determination of inorganic ortho-phosphate (P_i) that serves as a measure of the enzymatic activity in the presence of various analytes. The concentration of P_i, liberated by enzyme catalysed hydrolysis of adenosinetriphosphate (ATP), was followed spectrophotometrically, by single exposure to analytes or in the mixture. P_i was dose dependent on the analyte concentration. Alkaline elements (Na, K, Mg), heavy metals (Pb, Cd, Hg, Cu, Fe, Co, Zn), toxic organic compounds (pyridine, urea, chlorpyrifos), and some drugs (digoxin, gitoxin) showed diverse effects, inducing the inhibition or stimulation of the enzymes activity. Development of simple test method for simultaneous detection of the investigated analytes based on the variation of medium assay composition was discussed.     

A steady-state approach to evaluation of proposed excitation mechanisms in the analytical ICP

A method is described for the evaluation of proposed analyte ionization and excitation mechanisms in the analytical ICP. In the method, a steady-state kinetic expression is derived for each proposed mechanism; the resulting expression predicts a linear relationship between analyte emission and the concentrations or concentration products of species important in the excitation and deactivation processes. The application of this approach to Ca ionization and excitation is described for the region 15 mm above the load coil and 0–5 mm from the center of the plasma. Importantly, the concentration of ground-state Ca seems not to be important in the production of either excited Ca atoms or ions. Rather, Ca atom excitation appears to occur by means of three-body or radiative Ca⁺-electron recombination. In contrast, Ca⁺ seems to be excited directly by electron impact. Among the mechanisms evaluated here, depopulation of excited-state calcium species by collisional deactivation appears to be less significant than radiative decay to the ground state.     

The cell model of the electrolyte transport mechanisms for cultured human colonocytes. Electromotive forces of the cellular pathways

The purpose of this work was to explain the chloride secretory model of the human colonocytes in terms of the equivalent electromotive forces and the relative apical ionic permeabilities using a conventional micro-electrode technique and different ion-substitution experiments. Both equivalent electromotive forces (for apical and basolateral membranes: E_a=−47.7±5.1 mV and E_b=−65.2±2.9 mV, respectively) depend strongly on the external K⁺ concentration. The most important conclusion is that both cell membrane potentials are largely dominated by a K⁺ permeability. The apical membrane has low Na⁺ and Cl⁻ permeabilities in non-stimulated conditions (P_Na/P_K=0.06±0.01 and P_Cl/P_K=0.23±0.09). An interesting response was found for the basolateral Na⁺ substitutions. Lowering the basolateral Na⁺ concentration at 1 mM we have seen a slow, but large depolarisation of the cell membrane potential of about 30 mV. We think that this is mostly caused by the presence of the basolateral Na⁺/H⁺ exchanger mechanism for the intracellular pH regulation. The Na⁺/K⁺ pump has a significant contribution to the basolateral electromotive force. The basolateral membrane has also a Cl⁻ permeability in non-stimulated conditions, but the basolateral Na⁺ permeability is undetectable.     

Enhancing the detection sensitivity of trace analysis of pharmaceutical genotoxic impurities by chemical derivatization and coordination ion spray-mass spectrometry

Many pharmaceutical genotoxic impurities are neutral molecules. Trace level analysis of these neutral analytes is hampered by their poor ionization efficiency in mass spectrometry (MS). Two analytical approaches including chemical derivatization and coordination ion spray-MS were developed to enhance neutral analyte detection sensitivity. The chemical derivatization approach converts analytes into highly ionizable or permanently charged derivatives, which become readily detectable by MS. The coordination ion spray-MS method, on the other hand, improves ionization by forming neutral-ion adducts with metal ions such as Na⁺, K⁺, or NH₄⁺ which are introduced into the electrospray ionization source. Both approaches have been proven to be able to enhance the detection sensitivity of neutral pharmaceuticals dramatically. This article demonstrates the successful applications of the two approaches in the analysis of four pharmaceutical genotoxic impurities identified in a single drug development program, of which two are non-volatile alkyl chlorides and the other two are epoxides.     

Preparation of a hybrid monolithic stationary phase with allylsulfonate for the rapid and simultaneous separation of cations in capillary ion chromatography

A hybrid monolithic column with sulfonate functionality was successfully prepared for the simultaneous separation of common inorganic cations in ion‐exchange chromatographic mode through a simple and easy single‐step preparation method. The strong cation‐exchange moieties were provided directly from allylsulfonate, which worked as an organic monomer in the single‐step reaction. Inorganic cations (Li⁺, Na⁺, K⁺, NH₄⁺, Cs⁺, Rb⁺, Mg²⁺, Ca²⁺, and Sr²⁺) were separated satisfactorily by using CuSO₄ as the eluent with indirect UV detection. The allysulfonate hybrid monolith showed a better performance in terms of speed and pressure drop than the capillary packed column. The number of theoretical plates achieved was 19 017 plates/m (in the case of NH₄⁺ as the analyte). The relative standard deviations (n = 6) of both retention time and peak height were less than 1.96% for all the analyte cations. The allysulfonate hybrid monolithic column was successfully applied for the rapid and simultaneous separation of inorganic cations in groundwater and the effluent of onsite domestic wastewater treatment system.     

Active transport of Na + and K + through animal cell membranes

The transport of Na⁺ out of the cell and K⁺ into the cell against a concentration gradient is catalyzed by a (Na⁺ + K⁺)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na⁺-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K⁺-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na⁺ pump.     

Transport of Na+, K+ ions in a bubbling pseudo-emulsion liquid membrane system with p-tert-butylcalixarenes as carriers

The liquid membrane transport of Na⁺ ions by p-tert-butylcalix[6]arene and that of K⁺ ions by p-tert-butylcalix[8]arene were investigated by means of a bubbling pseudo-emulsion liquid membrane system. This system represents a proton-coupled transport with a flow of protons in the opposite direction. The driving force for the transport is the pH gradient between the source and receiving phases. When the pH difference between the two phases is sufficient, the carriers calix[6]arene(or calix[8]arene) can successfully transport Na⁺ (or K⁺) ions from the source phase with a lower Na⁺ (or K⁺) concentration into the receiving phase with a higher Na⁺ (or K⁺) concentration, like a Na⁺ (or K⁺) ion pump.     

501—An electrochemical study of energy-dependent potassium accumulation in E. coli: Part IX. Reversal of the mechanism exchanging 2 H+ for K+ with the coupled synthesis of ATP

E. coli is able to exchange 2 H⁺ from the external medium for one K⁺ of a cell with the concurrent synthesis of ATP. The 2 H⁺/K⁺ exchange and the coupled ATP synthesis are in need of both the essential Δ$\text{}\text{?}$gm_H+ (around 24 kJ) and the high K⁺ gradient (10³) directed from a cell to the medium. The reverse pump cycle is actuated as well as the direct one [3] merely through an increase of osmolarity in the environmental medium. The reverse process can be blocked by the insignificant ncrease in external pH or in K⁺ concentration, as well as by DCCD or by protonophore. The stoichiometry of the entire pump cycle is ATP: 2 H⁺ :K⁺. These observations, as well as the previous findings [8,9] that 2 H⁺ from a cell and one external K⁺ are transported through F₁·F₀ and TrkA respectively, suggest that F₁·F₀ and TrkA form the structural association in bacterial membrane for the joint employment of phosphate bond energy, the supercomplex (F₁ ·F₀TrkA operating as an electrogenic proton-potassium pump with stable stoichiometry ATP:2 H⁺ :K⁺.     

关于在钾与负氢混合物中钾钙嬗变的检测

报道了在室温下钾与负氢混合物中钾钙发生嬗变的现象，负氢是由NaBH₄、LiBH₄和NH₃BH₃提供的.实验中的钾和钙的浓度分别用诱导耦合等离子发射光谱法（ICP-OES）和诱导耦合等离子质谱法（ICP-MS）进行检测.ICP-OES结果表明随着混合物中钾浓度的降低伴随着钙的浓度增加.此外ICP-MS结果还表明⁴⁰Ca浓度的增加伴随着⁴¹K浓度的增加，可能表明在负氢存在的条件下混合物中⁴⁰Ca的生成与⁴¹K物种有关.     

Nonmonotonic Transient Potential Signals with an 18‐Crown‐6 based Ion‐Selective Electrode in a Flow‐Injection System

The dynamic potential response of an 18‐crown‐6 based ion‐selective electrode towards Li⁺, Na⁺, K⁺ and Ca²⁺, in a flow‐injection system is studied. Different double nonmonotonic transient signals are obtained for the different ions. The influence of the flow‐injection variables and of ion concentration on the signals is studied. Two signal parameters, the relative return rates, are found to be characteristic for each ion and are constant for a concentration range of 1–3 decades. The nonmomotonic transient signals obtained are explained by reference to the theoretical models reported.     

Complexation Properties of a Carbon-Bridged Cryptand with Metal Ions in Aqueous Solution at 25°C

Abstract

Thermodynamic quantities (log K, ΔH, and ΔS) for the interactions of a carbon-bridged cryptand with Li⁺, Na⁺, K⁺, Ca²⁺, Sr²⁺, Ba²⁺, and Pb²⁺ were determined at 25° C by calorimetric titration in aqueous solution. The cryptand forms complexes with Na⁺, Sr²⁺, Ba²⁺, and Pb²⁺ with log K ≤ 2. Complexation was not detected for Li⁺, K⁺, and Ca²⁺. Weak interactions with Li⁺ and K⁺ and a log K value of 2.4 for Na⁺ suggest that the cavity size of the cryptand is close to that of Na⁺ but too small for K⁺ and too large for Li⁺. The carbon-bridged cryptand selectively binds Sr²⁺ (log K = 3.2) over Ca²⁺ and Ba²⁺ by more than one order of magnitude.     

Chiral recognition and enantiomer assays of N-(3,5-dinitrobenzoyl)amino acid derivatives using electrospray ionization–mass spectrometry

A pair of pseudoenantiomers, anilide derivatives of N-pivaloylproline were prepared and used as chiral selectors for enantiomer discrimination of amides or esters of N-(3,5-dinitrobenzoyl)amino acids in single-stage electrospray ionization/mass spectrometric experiments. Addition of a chiral analyte to a solution of the two pseudoenantiomeric chiral selectors affords selector–analyte complexes in the electrospray ionization mass spectrum where the ratio of these complexes is dependent on the enantiomeric composition of the analyte. The relationship between the ratio of the selector–analyte complexes in the electrospray ionization mass spectrum and the enantiomeric composition of the analyte can be used to relate the extent of the measured enantioselectivity and for quantitative enantiomeric composition determinations. Effects of the added cationic ions (H⁺, Li⁺, Na⁺ and K⁺) and instrument conditions on the selector–analyte ion intensity and the enantioselectivity (α_MS) were investigated. The percent ratio of the sum of the selector–analyte ion counts and the total ion counts decreases accordingly with the increase of the desolvation temperature for H⁺, Na⁺ and K⁺. The ratio for Li⁺ kept almost constant. The best α_MS was observed at a desolvation temperature of 200 °C with the added H⁺. The cone voltage has little effects on the α_MS values though the intensities of selector–analyte complexes are decreased at higher cone voltages. The observed MS enantioselectivities are comparable to the HPLC enantioselectivities and the sense of chiral recognition by MS is consistent with what is observed chromatographically. Quantitative enantiomeric composition determinations for five different samples of N-(3,5-dinitrobenzoyl)leucinyl butylamide at four different concentrations were performed. The average % difference between the HPLC and MS enantiomer determinations is 6.8% and 3.7% for the calibration lines constructed at a concentration of the analyte of 125 μM and 12.5 μM, respectively.