Isomeric Distinction of Small Oligosaccharides: A Bottom-Up Approach Using the Kinetic Method

Isomeric distinction of di- and tri-saccharides could be efficiently achieved by using data previously obtained while performing experiments aimed at discriminating monosaccharides using trimeric ion dissociation with data analysis by the kinetic method. This study shows that effects observed for lower homologues when one of the partners is changed in the metal/reference system (typically a transition metal divalent cation associated to amino acids) can be extrapolated to upper homologues, at least for the tested analyte series. Systems allowing galactose, glucose, and fructose distinction were used as starting conditions to resolve cellobiose, lactose, maltose, and saccharose disaccharides. When a unique dissociation reaction was observed from the trimeric clusters, a new reference was selected based on its propensity to favor the analyte or the reference release, as revealed from monosaccharide experiments, depending on the desired effect. The same approach could be implemented from data obtained for disaccharides to select efficient metal/reference systems to distinguish cellotriose, isomaltotriose, maltotriose, and panose trisaccharides. As a result, method optimization is greatly improved due to an enhanced rationalization of the search for discriminant systems. While 40 systems had to be tested for monosaccharides, by screening five transition metals and eight amino acids, the proposed approach allowed efficient metal/reference systems to be found for disaccharides after testing 18 combinations; then, only four systems had to be scrutinized to achieve trisaccharide distinction. Accurate quantitative analyses could be performed in binary mixtures using three-point calibration curves to correct for competition effects between analytes for the formation of the trimeric clusters.     

Chiral and isomeric analysis by electrospray ionization and sonic spray ionization using the fixed-ligand kinetic method

The fixed-ligand version of the kinetic method has been used for chiral and for isomeric analysis by studying the dissociation kinetics of transition metal-bound trimeric cluster ions ([(M(II) + L(fixed)-H)(ref*)(An)](+), where M(II) is a transition metal, L fixed is a fixed (non-dissociating) ligand, ref* is a reference ligand and An is the analyte. The trimeric cluster ions are readily generated by electrospray ionization (ESI) or sonic spray ionization (SSI). The size of the fixed ligand, L- Phe-Gly-L-P he-Gly, is chosen based on previous results but with the inclusion of aromatic functionality to increase chiral recognition. Improved chiral/isomeric differentiation results from enhanced chiral/isomeric interactions (metal-ligand and ligand-ligand) due to the fixed ligand. As shown in the cases of chiral dipeptides (D-Ala-D-Ala/L-Ala-L-Ala), sugars (D/L-glucose, D/L-mannose) and isomeric tetrapeptides (L-Ala-Gly-Gly-Gly/Gly-Gly -Gly-L-Ala), improved chiral/isomeric discrimination by factors from three to six were obtained by the fixed ligand procedure. Chiral recognition is independent of the concentrations of the analyte, the reference ligand, the fixed ligand and the transition metal salt, a great advantage for practical applications. In addition to increased chiral distinction, the simplified dissociation kinetics also contribute to improved accuracy in chiral quantification, in comparison with data obtained by investigating the dissociation kinetics of simple trimeric cluster ions [M(II)(ref*)2(An) H](+). Accurate determination of enantiomeric excess (ee) is demonstrated by enantiomeric quantification of D-Ala-D-Ala/L-Ala-L-Ala down to 2% ee. Both ESI and SSI allow chiral quantification with similar accuracies. The performance of chiral analysis experiments is not limited to ion trapping devices such as quadrupole ion trap mass spectrometers by a hybrid quadrupole-time of flight (Q-ToF) mass spectrometer is shown to provide an alternative choice. The fixed-ligand kinetic method is not restricted to any particular kinds of isomers and, hence, represents a general procedure for improving molecular recognition and chiral analysis in the gas phase.     

Magnesium interference and different efficiencies of diastereoisomeric cluster formation in phenylalanine enantiomeric discrimination by the kinetic method

The kinetic method has been applied for determination of d-Phe/l-Phe enantiomeric ratio. Discrimination of enantiomers was inferred from product ion mass spectra of trimeric cluster ions containing the analyte (l,d-Phe), Cu²⁺ as a central metal and l-Trp as a chiral reference ligand. Unsatisfactory quantitative results achieved on an ion trap were rationalized by high-resolution mass spectrometry. The formation of Mg²⁺-containing cluster isobaric to trimeric cluster [Cu(l-Trp)₂Phe]⁺ was observed. Interference like this was identified as a possible reason for deterioration of quantitative low-resolution mass spectrometric analyses of real-world samples based on the kinetic method. Cation-exchanger was used for easy removal of magnesium from a sample and improvement of quantitation.Chiral dependence of formation of the Cu²⁺-containing trimeric cluster was also observed. Heterochiral diastereoisomeric ions were created less effectively.     

Isomeric discrimination and quantification of thyroid hormones, T3 and rT3, by the single ratio kinetic method using electrospray ionization mass spectrometry

The single ratio kinetic method is applied to the discrimination and quantification of the thyroid hormone isomers, 3,5,3′-triiodothyronine and 3,3′,5′-triiodothyronine, in the gas phase, based on the kinetics of the competitive unimolecular dissociations of singly charged transition-metal ion-bound trimeric complexes [M^II(A)(ref*)₂-H]⁺ (M^II = divalent transition-metal ion; A=T₃ or rT₃; ref* = reference ligand). The trimeric complex ions are generated using electrospray ionization mass spectrometry and the ions undergo collisional activation to realize isomeric discrimination from the branching ratio of the two fragment pathways that form the dimeric complexes [M^II(A)(ref*)-H]⁺ and [M^II(ref*)₂-H]⁺. The ratio of the individual branching ratios for the two isomers R_iso is found strongly dependent on the references and the metal ions. Various sets are tried by choosing the reference from amino acids, substituted amino acids, and dipeptides in combination with the central metal ion chosen from five transition-metal ions (Co^II, Cu^II, Mn^II, Ni^II, and Zn^II) for the complexes in this experiment. The results are compared in terms of the isomeric discrimination for the T₃/rT₃ pair. Calibration curves are constructed by relating the ratio of the branching ratios against the isomeric composition of their mixture to allow rapid quantitative isomer analysis of the sample pair. Furthermore, the instrument-dependence of this method is investigated by comparing the two sets of results, one obtained from a quadrupole ion trap mass spectrometer and the other from a quadrupole time-of-flight mass spectrometer.     

Selective Separation of Isomeric Dicarboxylic Acid by the Preferable Crystallization of Metal‐Organic Frameworks

Simple and effective separation of isomeric organic molecules is an important but challenging task. Herein, we successfully developed a selective crystallization strategy to separate the mixtures of isomeric dicarboxylic acids (DCAs) for the first time. The target DCAs could be preferably combined with crystallization inducer of Zr⁴⁺ ions to form a pre‐designed metal‐organic frameworks (MOFs) crystal structure whereas the entry of non‐target isomeric DACs into the MOFs lattice could be exclusively inhibited. Several isomeric pairs were exemplified to verify the extensibility and validity of the developed strategy.     

Differentiation and quantitation of isomeric dipeptides by low-energy dissociation of copper(II)-bound complexes

Application of the kinetic method based on the dissociation of transition metal centered cluster ions is extended from chiral analysis (Tao, W. A.; Zhang, D.; Nikolaev, E. N.; Cooks, R. G. J. Am. Chem. Soc. 2000, 122, 10598) to quantitative analysis of isomeric mixtures, including those with Leu/Ile substitutions. Copper(II)-bound complexes of pairs of peptide isomers are generated by electrospray ionization mass spectrometry and the trimeric complex [CuII(ref)2(A) - H]+ (analyte A, a mixture of isomeric peptides; reference compound ref, usually a peptide) is caused to undergo collisional dissociation. Competitive loss of the neutral reference compound or the neutral analyte yields two ionic products and the ratio of rates of the two competitive dissociations, viz. the product ion branching ratio R is shown to depend strongly on the regiochemistry of the analyte in the precursor [CuII(A)(ref)2 - H]+ complex ion. Calibration curves are constructed by relating the branching ratio measured by the kinetic method, to the isomeric composition of the mixture to allow rapid quantitative isomer analysis.     

Efficient ensemble and IDA system based on the metal binding motif for highly sensitive and selective detection and determination of carbonate and citrate ions

Herein, we have reported a novel naked eye detection method which is based on the analyte competing for a metal reporter with a chromogenic indicator. This assay is based on the highly specific interaction between the anions and the metal ions and murexide (Mure) probe in a competition assay format. The resulting high sensitivity and selectivity for citrate and carbonate were achieved by changing the metal ions. The indicator is set free due to its displacement from the Mure/Cu²⁺ complex by citrate (Cit³ˉ) and the change in absorbance may be due to the further complexation of carbonate (CO₃²ˉ) with the additional coordination sites present in the zinc atom of Mure/Zn²⁺ complex. The dye-based ensemble systems are expected to be a potential and practical way for the detection of nanomolar concentrations of analytes in 100% aqueous solutions. The chemosensor enabled sensitive and selective detection of Cit³ˉ and CO₃²ˉ with detection limits of 19.1 and 9.4 nmol L^?1, respectively. These systems are simple in design, fast in operation and are more promising than previous methods. This novel method eliminated the need for separation processes, chemical modifications, organic cosolvents, and sophisticated instrumentations. Chiefly, the protocol offers high selectivity for the determination of Cit³ˉ and CO₃²ˉ among anions found in human urine samples in the presence of some biological species, including K⁺, Mg²⁺, Fe³⁺, Ca²⁺, Zn²⁺, Na⁺, glucose, urea, uric acid and ascorbic acid. Further, NAND and INHIBIT molecular logic gates were obtained using chemical inputs and UV–Vis absorbance signal as the output.     

Binding heavy metal ions with polymerized onion skin

Red onion skin is highly effective for binding heavy metal ions from aqueous solutions. Color leaching can be prevented and the physical characteristics of the substrate can be improved by treatment with formaldehyde in an acidic medium. Batch and column experiments have been conducted with Cu²⁺, Cd²⁺, Zn²⁺, Ni²⁺, Hg²⁺, and Pb²⁺. Almost quantitative removal of the metal ions from solution can be achieved by using columns of the treated onion skin. Competition of the various metal ions for the substrate has been investigated. The capacity of the substrate in the majority of the metal ions studied is well above 1 meq/g. The use of polymerized onion skin to remove heavy metal ions from domestic and industrial wastewater to safe levels has been recommended as a cheap and effective alternative for commercial ion-exchange resins.     

Differential Pulse Polarography of the Zn2+ Complexation by Glutathione Fragments Cys‐Gly and gamma‐Glu‐Cys

The metal binding properties of glutathione (GSH) and their fragments γ‐Glu‐Cys and Cys‐Gly are of biological and environmental interest. In this work a differential pulse polarographic study of the Zn²⁺/γ‐Glu‐Cys and Zn²⁺/Cys‐Gly systems was carried out for a better understanding of the results obtained in previous studies on the Zn²⁺‐GSH system. In the case of γ‐Glu‐Cys, complexation with Zn²⁺ was not detected. In the case of Cys‐Gly, the parallel analysis, by multivariate curve resolution with alternating least squares, of data from the titration of peptide with metal and of metal with peptide suggested the presence of two types of bound Zn²⁺. This could be attributed to Zn²⁺ strongly bound to two sulfur atoms of two peptides, to form a complex of 1 : 2 stoichiometry, and to Zn²⁺ weakly bound to carboxylate and/or amino groups.     

1H NMR spectroscopic determination of the isomeric ratios of bisphenol-F diglycidyl ethers

¹H NMR spectroscopy was used as a rapid method of determining the amount of the three possible isomeric forms of bisphenol-F diglycidyl ether, one of the basic materials of epoxy resins for industrial applications. The complete spectral analysis of the glycidyl group, with respect to chemical shifts, coupling constants and magnetic anisotropy, made it possible to separate the overlapping signal regions by computational spectral simulation. Partial separation could also be obtained by application of the ‘Aromatic Solvent Induced Shift’ effect. A combination of both methods has been used successfully for the quantitative determination of the isomeric ratios of commercially available bisphenol-F diglycidyl ethers.     

Synthetic functionalized terpolymeric resin for the removal of hazardous metal ions: synthesis,characterization and batch separation analysis

An effectual functionalized synthetic resin involving anthranilic acid/4‐nitroaniline/formaldehyde was synthesized for the detoxification of hazardous metal ions. The resin was characterized by Fourier transform infrared, ¹H, and ¹³C nuclear magnetic resonance spectroscopy, and its morphology was established through scanning electron microscope and X‐ray diffraction. The resin was analyzed by thermogravimetric analysis to assess the thermal stability, in which the resin could be used in high temperature aqueous solutions for the elimination of harmful metal ions. The ion‐exchange property of the resin was evaluated by batch technique for specific metal ions viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. The study was extended to three variations such as effect of metal ion uptake in the presence of various electrolytes in different concentrations, effect of pH, and effect of contact time. The outcome proved that the resin can be used as a strong cation‐exchanger to remove various metal ions from the solutions. The resin could be regenerated and reused with quantitative recovery of metal ions for few cycles. On comparison with the earlier reported resins, the synthesized resin has found excellent capability of metal ion recovery. The resin possesses an utmost ion‐exchange capacity, which is in good harmony with isotherm models and kinetics. Copyright © 2015 John Wiley & Sons, Ltd.     

Ion-exchange behavior of stannic selenoiodate and stannic selenosilicate: analytical application of stannic selenoiodate

Two new inorganic ion exchangers, stannic selenoiodate and stannic selenosilicate have been synthesized. The ion-exchange capacity of stannic selenoiodate and stannic selenosilicate for K⁺ was found to be 1.84 and 1.23 meq g^–1, respectively. pH titration studies reveal monofunctional and bifunctional behavior for stannic selenosilicate and stannic selenoiodate, respectively. Distribution coefficients of metal ions in dimethylformamide–HCl and formamide–HCl systems have been determined. Some important and analytically difficult quantitative binary and ternary separations, and selective separations of Ag⁺, Sn⁴⁺, Zr⁴⁺, Co²⁺, and Ni²⁺ have been achieved on stannic selenoiodate columns. The practical utility of the material has been demonstrated by analyzing the metal ion content of electroplating waste.     

Qualitative and quantitative 1H NMR spectroscopy for determination of divalent metal cation concentration in model salt solutions,food supplements,and pharmaceutical products by using EDTA as chelating agent

This paper introduces an ¹H NMR method to identify individual divalent metal cations Be²⁺, Mg²⁺, Ca²⁺, Sr²⁺, Zn²⁺, Cd²⁺, Hg²⁺, Sn²⁺, and Pb²⁺ in aqueous salt solutions through their unique signal shift and coupling after complexation with the salt of ethylenediaminetetraacetic acid (EDTA). Furthermore, quantitative determination applied for the divalent metal cations Ca²⁺, Mg²⁺, Hg²⁺, Sn²⁺, Pb²⁺, and Zn²⁺ (limit of quantification: 5–22 μg/ml) can be achieved using an excess of EDTA with aqueous model salt solutions. An internal standard is not required because a known excess of EDTA is added and the remaining free EDTA can be used to recalculate the quantity of chelated metal cations. The utility of the method is demonstrated for the analysis of divalent cations in some food supplements and in pharmaceutical products.     

An approach by using near-infrared diffuse reflectance spectroscopy and resin adsorption for the determination of copper, cobalt and nickel ions in dilute solution

Near-infrared spectroscopy (NIRS) has been proved to be a powerful analytical tool and used in various fields, it is seldom, however, used in the analysis of metal ions in solutions. A method for quantitative determination of metal ions in solution is developed by using resin adsorption and near-infrared diffuse reflectance spectroscopy (NIRDRS). The method makes use of the resin adsorption for gathering the analytes from a dilute solution, and then NIRDRS of the adsorbate is measured. Because both the information of the metal ions and their interaction with the functional group of resin can be reflected in the spectrum, quantitative determination is achieved by using multivariate calibration technique. Taking copper (Cu²⁺), cobalt (Co²⁺) and nickel (Ni²⁺) as the analyzing targets and D401 resin as the adsorbent, partial least squares (PLS) model is built from the NIRDRS of the adsorbates. The results show that the concentrations that can be quantitatively detected are as low as 1.00, 1.98 and 1.00 mg L⁻¹ for Cu²⁺, Co²⁺ and Ni²⁺, respectively, and the coexistent ions do not influence the determination.     

ESI‐MS/MS analysis of protonated N‐methyl amino acids and their immonium ions

Methylation is one of the important posttranslational modifications of biological systems. At the metabolite level, the methylation process is expected to convert bioactive compounds such as amino acids, fatty acids, lipids, sugars, and other organic acids into their methylated forms. A few of the methylated amino acids are identified and have been proved as potential biomarkers for several metabolic disorders by using mass spectrometry–based metabolomics workstation. As it is possible to encounter all the N‐methyl forms of the proteinogenic amino acids in plant/biological systems, it is essential to have analytical data of all N‐methyl amino acids for their detection and identification. In earlier studies, we have reported the ESI‐MS/MS data of all methylated proteinogenic amino acids, except that of mono‐N‐methyl amino acids. In this study, the N‐methyl amino acids of all the amino acids ( 1 ‐ 21 ; including one isomeric pair) were synthesized and characterized by ESI‐MS/MS, LC/MS/MS, and HRMS. These data could be useful for detection and identification of N‐methyl amino acids in biological systems for future metabolomics studies. The MS/MS spectra of [M + H]⁺ ions of most N‐methyl amino acids showed respective immonium ions by the loss of (H₂O, CO). The other most common product ions detected were [MH‐(NH₂CH₃]⁺, [MH‐(RH)]⁺ (where R = side chain group) ions, and the selective structure indicative product ions due to side chain and N‐methyl group. The isomeric/isobaric N‐methyl amino acids could easily be differentiated by their distinct MS/MS spectra. Further, the MS/MS of immonium ions inferred side chain structure and methyl group on α‐nitrogen of the N‐methyl amino acids.     

Characterization of metal ion-exchange on modified surfaces of porous carbon

Two biologically based ligands, cysteine (Cys) and poly-l-cysteine (PLCys), were coupled with Carbopack-X, a commercially available porous carbon surface after acid activation, through simple cross-linking techniques. The resulting Cys-X and PLCys-X systems are effective for metal binding with capacities in the range of 1-25 μmol metal/g column, depending on the metal tested. Both columns demonstrate similar selectivity for the soft and moderately soft acid metals such as Cd²⁺, Cu⁺, and Pb²⁺, probably as a result of the soft basic character of the thiol ligand side chains, and exhibit minimal binding of the harder groups IA and IIA metals. Even though PLCys-X and Cys-X displayed similar strong and weak binding characteristics, the PLCys-X system contained stronger binding sites than those possessed by Cys-X. The strongest site displayed by Cys-X has a binding constant of 1×10⁹, with the ability to compete for metal with moderately strong ligands such as ethylenediamine. However, the strongest PLCys-X site possessed a binding constant of about 10¹³, with the ability to compete for metals bound by very strong ligands such as EDTA. Both systems gave quantitative release of bound metals upon exposure to acid. Exposing the thiol-rich ligands to chemical reducing or oxidizing environments altered the metal binding characteristics of both columns, with at least a 50% decrease in metal binding on the oxidized columns due to thiol binding sites because of disulfide bond formation.     

Circular Polarized Light Activated Chiral Satellite Nanoprobes for the Imaging and Analysis of Multiple Metal Ions in Living Cells

Here, we construct a handedness‐dependent circular polarized light (CPL)‐activated chiral satellite assemblies formed from DNAzymes and spiny platinum modified with gold nanorods and upconversion nanoparticles (UCNPs), enabling the simultaneous quantitative analysis of multiple divalent metal ions in living cells. The chiral nanoprobes, in coordination with their corresponding divalent metal ions under 980 nm left circular polarized (LCP) light illumination, served as an in situ confocal bioimaging platform for the quantitation of the given intracellular metal ions. The limit of detection (LOD) of the chiral probes in living cells is 1.1 nmol/10⁶ cells, 1.02 nmol/10⁶ cells and 0.45 nmol/10⁶ cells for Zn²⁺, Mg²⁺, and Cu²⁺, respectively.     

Electron spin resonance of Langmuir-Blodgett films fabricated with metal derivatives of polyazamacrocycles

This review analyses the results obtained through the Electron Spin Resonance (ESR) spectroscopy on multilayer Langmuir-Blodgett films fabricated with metal derivatives (mainly Cu²⁺, VO²⁺ and low-spin CO²⁺) of polyazamacrocycles (porphyrins, tetraazaannulenes, phthalocyanines). These metal ions are particularly suitable for an ESR analysis because of their relatively long electron spin relaxation times that render possible their observation even at room temperature and in all co-ordination symmetry. This allows us to obtain valuable data on both mobility and orientation of the metal-macrocycle systems adsorbed onto a solid support. The preliminary characterisation of the spreading monolayer obtained from the systems considered, as it is typically done by surface pressure/area isotherms, optical (UV-Vis) and ESR spectroscopies, is also reviewed.     

Diastereochemical differentiation of some cyclic and bicyclic β-amino acids, via the kinetic method

Stereochemical differentiation of five diastereomeric pairs of β-amino acids, di-endo- and di-exo-2,3-disubstituted norbornane and norbornene amino acids, cis- and trans-2-aminocyclohexane-, 2-amino-4-cyclohexene-, and 2-aminocyclopentanecarboxylic acids, was investigated via the kinetic method with metal-bound trimeric complexes. This is the first time that diastereomers (di-endo/di-exo and cis/trans) have been differentiated with metal-bound trimeric complexes and the kinetic method. Moreover, determination of diastereochemical excess by the kinetic method was applied to norbornane β-amino acids and cyclopentane β-amino acids. Experiments showed that a remarkable differentiation of the studied diastereomers was achieved. It was observed that better selectivity values correlated to more rigid structures. The reference compounds for the studied β-amino acids varied from α-amino acids to some β-amino acids. In addition, variation of the metal ion (Cu²⁺ and Ni²⁺) had some role in the selectivity values obtained. Ab initio and hybrid density functional theory calculations were performed to clarify the results obtained by mass spectrometry.     

Study on the Liquid‐Solid Flotation Separation of Cadmium by Ammonium Sulfate‐Potassium Iodide‐Cetylpyridine Chloride‐Water System

The liquid‐solid flotation separation behaviors of Cd²⁺ in ammonium sulfate‐potassium iodide‐cetylpyridine chloride‐water system and the conditions for the separation of Cd²⁺ from other metal ions were studied. The results showed that in the presence of 1.0 g (NH₄)₂SO₄ and when the dosage of 0.1 M potassium iodide was 2.0 mL and 0.01 M cetylpyridine chloride (CPC) solution was 1.0 mL respectively, the formed water‐insoluble ternary association complex of KI‐CPC‐Cd floated above water phase and liquid‐solid phases were formed with clear interface. In this condition, Zn²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺ and Al³⁺ could not be floated and Cd²⁺ was floated quantitatively at pH 5.0. Therefore, the quantitative separation of Cd²⁺ from the above metal ions could be achieved. The quantitative flotation separation determination of Cd²⁺ in the sample of synthetic water and industrial waster water was performed, and the results agreed well with those by AAS method. The recoveries were 97.2%～102.4%, and the RSD was 1.8%.