Affinity For Cations Research Articles

Structure and Surface Behavior of Rh Complexes in Ionic Liquids Studied Using Angle-Resolved X-ray Photoelectron Spectroscopy

We present an ARXPS study on the surface composition and interfacial behavior of commercial [Rh(COD)2][TfO] in [C2C1Im][TfO], [C4C1Im][TfO], [C8C1Im][TfO], and [C2C1Im][EtOSO3]. The complex was found to be non-intact in a solution of these ILs through the loss of COD ligands, accompanied by the depletion of the metal center from the IL/vacuum interface. Increasing the chain length of the aliphatic substituent on the imidazolium cation of the [TfO]−-based ILs led to a more pronounced depletion from the interface, due to the higher surface affinity of the solvent cations with the longer alkyl chains. The loss of COD ligands offered facile in situ ligand substitution with surface-active TPPTS to afford a moderate increase in the surface concentration of Rh. We propose the formation of a Schrock−Osborn-type catalyst [Rh(COD)(TPPTS)2][TfO]. Information on the surface composition and targeted design of the gas/IL interface is highly relevant for applications in IL-based catalytic systems, such as in supported ionic liquid phase (SILP) catalysis.

Periodicity of the Affinity of Lanmodulin for Trivalent Lanthanides and Actinides: Structural and Electronic Insights from Quantum Chemical Calculations.

Lanmodulin (LanM) is the first identified macrochelator that has naturally evolved to sequester ions of rare earth elements (REEs) such as Y and all lanthanides, reversibly. This natural protein showed a 106 times better affinity for lanthanide cations than for Ca, which is a naturally abundant and biologically relevant element. Recent experiments have shown that its metal ion binding activity can be further extended to some actinides, like Np, Pu, and Am. For this reason, it was thought that LanM could be adopted for the separation of REE ions and actinides, thus increasing the interest in its potential use for industry-oriented applications. In this work, a systematic study of the affinity of LanM for lanthanides and actinides has been carried out, taking into account all trivalent ions belonging to the 4f (from La to Lu) and 5f (from Ac to Lr) series, starting from their chemistry in solution. On the basis of a recently published nuclear magnetic resonance structure, a model of the LanM-binding site was built and a detailed structural and electronic description of initial aquo- and LanM-metal ion complexes was provided. The obtained binding energies are in agreement with the available experimental data. A possible reason that could explain the origin of the affinity of LanM for these metal ions is also discussed.

Control of the pore chemistry in metal-organic frameworks for efficient adsorption of benzene and separation of benzene/cyclohexane

Control of the pore chemistry in metal-organic frameworks for efficient adsorption of benzene and separation of benzene/cyclohexane

Cation affinity purification of histidine-tagged proteins.

Protein purification is a basic technology in both biological research and industrial production, and efficient, convenient, economical, and environmentally friendly purification methods have always been pursued. In this study, it was found that alkaline earth metal cations (Mg2+, Ca2+) and alkali metal cations (Li+, Na+, K+) and even nonmetal cations (e.g., NH4+, imidazole, guanidine, arginine, lysine) can precipitate multi-histidine-tagged proteins (at least two tags in a whole protein) at low salts concentrations that are 1-3 orders of magnitude lower than salting-out, and precipitated proteins could be dissolved at moderate concentration of corresponding cation. Based on this finding, a novel cation affinity purification method was developed, which requires only three centrifugal separations to obtain highly purified protein with purification fold similar to that of immobilized metal affinity chromatography. The study also provides a possible explanation for unexpected protein precipitation and reminds researchers to consider the influence of cations on the experimental results. The interaction between histidine-tagged proteins and cations may also have broad application prospects. KEY POINTS: • Histidine-tagged proteins can be precipitated by low-concentrations common cations • A novel nonchromatographic protein purification method was developed • Purified protein can be obtained in pellet form by only three centrifugations.

Design of TiO2-Surfactin Hybrid Systems with Multifunctional Properties.

In recent years, multifunctional inorganic-organic hybrid materials have been widely investigated in order to determine their potential synergetic, antagonist, or independent effects in terms of reactivity. The aim of this study was to design and characterize a new hybrid material by coupling well-known photocatalytic TiO2 nanoparticles with sodium surfactin (SS), a biosurfactant showing high binding affinity for metal cations as well as the ability to interact with and disrupt microorganisms' cell membranes. We used both chemical and colloidal synthesis methodologies and investigated how different TiO2:SS weight ratios affected colloidal, physicochemical, and functional properties. We discovered a clear breaking point between TiO2 and SS single-component trends and identified different ranges of applicability by considering different functional properties such as photocatalytic, heavy metal sorption capacity, and antibacterial properties. At low SS contents, the photocatalytic properties of TiO2 are preserved (conversion of organic dye = 99% after 40 min), and the hybrid system can be used in advanced oxidation processes, taking advantage of the additional antimicrobial SS properties. At high SS contents, the TiO2 photoactivity is inhibited, and the hybrid can be usefully exploited as a UV blocker in cosmetics, avoiding undesired oxidative effects (UV adsorption in the range between 300-400 nm). Around the breaking point (TiO2:SS 1:1), the hybrid material preserves the high surface area of TiO2 (specific surface area around 180 m2/g) and demonstrates NOx depletion of up to 100% in 80 min, together with improved adhesion of hybrid antibacterial coating. The last design demonstrated the best results for the concurrent removal of inorganic, organic, and biological pollutants in water/soil remediation applications.

Brown Algal Residue for the Recovery of Metal Ions—Application to La(III), Cd(II), and Ni(II) Sorption

AbstractRemoving hazardous metals and recovering valuable strategic metals from wastewater has become an important challenge for the industry. Herein, brown algal biomass residue (AR, after bio‐stimulant extraction, currently poorly valorized) is tested for the removal of Ni(II), Cd(II), and La(III) from aqueous solutions. This valorization of industrial waste makes profit of residual amounts of alginate‐based materials, which have a strong affinity for metal cations. Fourier transform infrared (FTIR) and X‐ray photoelectron spectroscopy (XPS) techniques are used for characterizing metal/biosorbent interactions. Uptake kinetics are relatively fast (equilibrium being reached in 180–240 min). The Sips equation fits the sorption isotherms; the maximum sorption capacities at pH ≈5 reach up to 0.84 mmol La g−1, 0.92 mmol Cd g−1, and 0.78 mmol Ni g−1. In binary solutions, AR shows marked preference for La(III) over divalent cations. This selectivity may be increased by complexing base metals with EDTA, opening the route for the selective recovery of rare earth elements. HCl solution reveals more efficient (>90% for La(III), ≈82% for Cd(II) and Ni(II)) than CaCl2 solution at pH 2 for metal desorption. This waste residue from biostimulant extraction (in brown algal biomass) can be valorized for the recovery of hazardous and strategic metal ions.

Vacancy Engineering for High-Efficiency Nanofluidic Osmotic Energy Generation.

Two-dimensional (2D) nanofluidic membranes have shown great promise in harvesting osmotic energy from the salinity difference between seawater and fresh water. However, the output power densities are strongly hampered by insufficient membrane permselectivity. Herein, we demonstrate that vacancy engineering is an effective strategy to enhance the permselectivity of 2D nanofluidic membranes to achieve high-efficiency osmotic energy generation. Phosphorus vacancies were facilely created on NbOPO4 (NbP) nanosheets, which remarkably enlarged their negative surface charge. As verified by both experimental and theoretical investigations, the vacancy-introduced NbP (V-NbP) exhibited fast transmembrane ion migration and high ionic selectivity originating from the improved electrostatic affinity of cations. When applied in a natural river water|seawater osmotic power generator, the macroscopic-scale V-NbP membrane delivered a record-high power density of 10.7 W m-2, far exceeding the commercial benchmark of 5.0 W m-2. This work endows the remarkable potential of vacancy engineering for 2D materials in nanofluidic energy devices.

Preorganized Polyaromatic Soft Terdentate Hosts for the Capture of [Ln(β-diketonate)3 ] Guests in Solution.

The concept of preorganization is famous in coordination chemistry for having transformed flexible bidentate 2,2'-bipyridine scaffolds into rigid 1,10-phenanthroline platforms. The resulting boosted affinities for d-block cations has successfully paved the way for the design of a wealth of functional complexes, devices and materials for analysis and optics. Its extension toward terdentate homologues adapted for the selective complexation of f-block cations with larger coordination numbers remains more overlooked. The resulting rigidification of 2,6-bis(1-methyl-1H-benzo[d]imidazol-2-yl)pyridine ligands (L1-L7) produces the highly preorganized and extended polyaromatic benzo[4',5']imidazo[1',2' : 1,2]pyrido[3,4-b]benzo[4,5]imidazo[1,2-h][1,7]naphthyridines (L8-L11) receptors, which offer some novel and rare opportunities for efficiently complexing trivalent lanthanides with polyaromatic soft terimine ligands. The crystal structures of the stable heteroleptic [LkLn(hfac)3 ] adducts (Lk=L1, L8, L9; Ln=La, Eu, Gd, Er, Yb, Y; H-hfac=1,1,1,5,5,5-hexafluoropentane-2,4-dione) show a drastic decrease in the Ln-N bond valences upon replacement of the flexible ligand L1 with its preorganized counterparts L8 and L9. This points to a limited match between the preorganized cavity and the entering [Ln(hfac)3 ] lanthanide containers. However, thermodynamic studies conducted in dichloromethane reach the opposite conclusion, with an improved affinity, by up to three orders of magnitude for catching Ln(hfac)3 when L1 is replaced by the preorganized L8-L9 receptors. The key to the enigma lies in the removal of the energy penalty which accompanies the formation of flexible [L1Ln(hfac)3 ] complexes in solution. This driving force overcomes the poor match between the preorganized terdentate N∩ N∩ N cavity in L8 and L9 and the size of trivalent lanthanides. As planned, the rigid, planar and extended π-conjugated system found in L8 and L9 shifts the ligand-centered absorption bands by about 5000 cm-1 toward lower energies, a crucial point if these stable [L8Ln(hfac)3 ] and [L9Ln(hfac)3 ] platforms have to be considered for the visible sensitization of luminescent lanthanides in metallopolymers.

Coordination effects on the binding of late 3d single metal species to cyanographene.

Anchoring single metal atoms on suitable substrates is a convenient route towards materials with unique electronic and magnetic properties exploitable in a wide range of applications including sensors, data storage, and single atom catalysis (SAC). Among a large portfolio of available substrates, carbon-based materials derived from graphene and its derivatives have received growing concern due to their high affinity to metals combined with biocompatibility, low toxicity, and accessibility. Cyanographene (GCN) as highly functionalized graphene containing homogeneously distributed nitrile groups perpendicular to the surface offers exceptionally favourable arrangement for anchoring metal atoms enabling efficient charge exchange between the metal and the substrate. However, the binding characteristics of metal species can be significantly affected by the coordination effects. Here we employed density functional theory (DFT) calculations to analyse the role of coordination in the binding of late 3d cations (Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Cu+, and Zn2+) to GCN in aqueous solutions. The inspection of several plausible coordination types revealed the most favourable arrangements. Among the studied species, copper cations were found to be the most tightly bonded to GCN, which was also confirmed by the X-ray photoelectron spectroscopy (XPS), atomic absorption spectroscopy (AAS), and isothermal titration calorimetry (ITC) measurements. In general, the inclusion of coordination effects significantly reduced the binding affinities predicted by implicit solvation models. Clearly, to build-up reliable models of SAC architectures in the environments enabling the formation of a coordination sphere, such effects need to be properly taken into account.

Understanding the cation exchange affinity in modified-MMT catalysts for the conversion of glucose to lactic acid.

This study investigated the exchange affinity of Fe3+, Cu2+, and Zn2+ cations in sulfuric acid-purified montmorillonite (S-MMT) to enhance Lewis acid sites and subsequently improve the catalytic conversion of glucose to lactic acid. XRD analysis suggested the successful cation exchange process, leading to structural expansion of the resultant cation exchanged-MMTs (CE-MMTs). XRF and TGA indicated that Zn2+ had the highest exchange affinity, followed by Cu2+ and then Fe3+. This finding was further supported by the results of TPD-NH3 analysis and pyridine-adsorption test, which demonstrated that Zn-MMT had the highest total acid sites (TAS) and the ratio of Lewis acid-to-Brønsted acid surface site (LA/BA). These results indicated dominant presence of Lewis acid sites in Zn-MMT due to the higher amount of exchanged Zn2+ cations. Consistently, time-dependent catalytic studies conducted at 170 °C showed that a 7 h-reaction generated the highest lactic acid yield, with the catalytic performance increasing in the order of Fe-MMT < Cu-MMT < Zn-MMT. The study also observed the impact of adding alcohols as co-solvents with water at various ratios on the conversion of glucose to lactic acid catalysed by Zn-MMT. The addition of ethanol enhanced lactic acid yield, while methanol and propanol inhibited lactic acid formation. Notably, a water-to-ethanol ratio of 30 : 70 v/v% emerged as the optimal solvent condition, resulting in ca. 35 wt% higher lactic acid yield compared to using water alone. Overall, this study provides valuable insights into the cation exchange affinity of different cations in MMT catalysts and their relevance to the conversion of glucose to lactic acid. Furthermore, the incorporation of alcohol co-solvent presents a promising way of enhancing the catalytic activity of CE-MMTs.

Vertically aligned carbon nanotubes for monovalent cation selective membranes designed by in silico experiments

Many membrane-based ion separation technologies require monovalent cations selectivity. However, available membranes usually show limited specific ion selectivity. In order to provide basic information on the membrane ion selectivity, the confinement effect on narrow pores disrupting the ion hydration is investigated in this work, with the aim to provide a new alternative to classical Cation Exchange Membranes (CEM). Starting from solvated cations structures used as templates and obtained by a quantum approach, Single-Wall Carbon Nanotubes (SWCNT) with ad-hoc designed diameters were chosen to perform in-silico experiments of single-cation permeation through CNT by means of Molecular Dynamics simulations, for which partial charges at nanotube inlets were parametrized through ab initio calculations. Cations' trajectories and energy decomposition analysis suggest that 100 % perm-selectivity towards Na+ with respect to Ca2+ and Mg2+ is virtually attainable with CNT of 1.33 nm diameter. Interestingly, the origin of this behaviour lays on thermodynamics rather than on size exclusion mechanisms. Opposite to polymeric homogeneous CEM, showing higher affinity for multivalent cations, an inverted trend was found for CNT in terms of hydration free energies, where Na+ shows more affinity up to 36 kJ/mol. Finally, total rejection of Cl− was observed in the range of CNT diameters investigated.

Basicity of five-membered cyclic allenes: Proton and cation affinity evaluation using density functional theory calculations

The proton affinity (PA) of stable five-membered cyclic allenes 1–13 in the gas phase was studied by DFT/B3LYP computational method in conjunction with the 6-311+G(d,p) basis set. The PAs of the title compounds are large. Their protonation at the central carbon introduces super- and hyperbases as evidenced by their enthalpies of protonation ΔH = 272–315 kcal/mol, which are above the threshold of superbasicity and in some cases close to the hyperbasicity. The trends of PA correlate quite well with the energy level of the HOMO orbitals and the molecular electrostatic potential maps of the studied allenes. The Wiberg bond order analysis gives a reasonable explanation of the exocyclic delocalization involving the π-donor substituents with the allenic unit of the studied compounds. Protonation of central carbon in the cyclic allenes leads to a change in the structural arrangement and an increment in the aromaticity of the pyrazole ring, which was evaluated by the HOMA index. Furthermore, the B3LYP/6-311+G(d,p) calculated cation affinities for the cyclic allene 6 increases as K+<Na+<Li+<Cu+<Mg2+<Fe2+<Cu2+. Cation affinity is strongly dependent on the charge-to-size ratio of the Mn+.

The distinctive role of nano-hydroxyapatite modified biochar for alleviation of cadmium and arsenic toxicity in aqueous system

The synergetic behavior of cadmium and arsenic in water is characterized by increased mobility and toxicity. The control of Cd and As toxicity is one of the greatest environmental challenges in the world. Biochar with a strong adsorption affinity for cations is considered to sequester Cd(II). However, little is known about whether biochar and its modified materials are efficient in the removal of cations and anions in a dual system. In this study, wheat straw and nanohydroxyapatite were used to prepare nanohydroxyapatite-modified biochar (HBC) and to control cationic Cd(II) and anionic As(III) in water. As the mass ratio of nHAP to wheat straw biochar was increased from 0.1 % to 1.0 %, the amount of nHAP particles loaded on the surface of BC increased, and the particles tended to aggregate. In the single and binary contaminant systems, the maximum Langmuir adsorption capacities of HBC for Cd(II) and As(III) were 55.95 and 14.84 and 14.24 and 12.44 mg/g, respectively. Cd and As adsorption by HBCs was influenced by physical adsorption, electrostatic interactions, hydroxyl groups, and surface complexation, accompanied by specific adsorption induced by HAP particles on HBCs. The findings of the current investigation showed that HBCs can be used as green and low-cost amendments, which would help in the treatment of wastewater contaminated by multiple heavy metals.

Heterotropic roles of divalent cations in the establishment of allostery and affinity maturation of integrin αXβ2.

SUMMARYAllosteric activation and silencing of leukocyte β2-integrins transpire through cation-dependent structural changes, which mediate integrin biosynthesis and recycling, and are essential to designing leukocyte-specific drugs. Stepwise addition of Mg2+ reveals two mutually coupled events for the αXβ2 ligand-binding domain—the αX I-domain—corresponding to allostery establishment and affinity maturation. Electrostatic alterations in the Mg2+-binding site establish long-range couplings, leading to both pH− and Mg2+-occupancy-dependent biphasic stability change in the αX I-domain fold. The ligand-binding sensorgrams show composite affinity events for the αX I-domain accounting for the multiplicity of the αX I-domain conformational states existing in the solution. On cell surfaces, increasing Mg2+ concentration enhanced adhesiveness of αXβ2. This work highlights how intrinsically flexible pH− and cation-sensitive architecture endows a unique dynamic continuum to the αI-domain structure on the intact integrin, thereby revealing the importance of allostery establishment and affinity maturation in both extracellular and intracellular integrin events.

A detailed density functional theory investigation on physicochemical properties of ciclopirox derivatives: A potential candidate for prevention of age-related macular degeneration

Structural, electronic and spectral data such as intramolecular hydrogen bonding interaction, HOMO, LUMO energies, reactivity indices, molecular electrostatic potential maps, aromaticity indices, 1HNMR and 13CNMR of ciclopirox derivatives 1-7 as antifungal agents and efficient compounds for treatment and prevention of age-related macular degeneration were calculated using B3LYP/6-311+G(d, p) method and interpreted in detail. Their antioxidant properties were also investigated by three mechanisms. The results show that the antioxidant activity of ciclopirox derivatives 1-7 is higher than phenol as the reference molecule. Finally, the interaction of ciclopirox 3 with metals cations Mn+ was investigated by DFT calculations. The calculated cation affinity for 3 increases as Cu+<Fe2+< Cu2+<Fe3+. Cation affinity is strongly dependent on the charge-to-size ratio of the Mn+.

Nano-bio effects: Interaction of ZnO and DNA-bases

In this study, we report on the complex formation and characterization of nano-bio conjugates synthesized by the sol–gel chemical method. The nano-bio conjugates, consisting of inorganic ZnO nanoparticles (NPs) and organic nitrogenous bases of DNA (Thymine and Cytosine), are investigated using electron microscopies, molecular vibrational analysis and X-ray spectroscopies. In this experimental investigation, we used two basic nitrogenous bases of DNA – Cytosine, and Thymine. The X-ray diffraction patterns of both ZnO NP and the nanoconjugate (NJ) reveal a highly phase pure ZnO structure with negligible changes in the unit cell dimensions. The Raman peaks due to the molecular vibration of C2=O7 and C4=O8 sites of Thymine and C=O and N-H sites in Cytosine are shifted due to the cation affinity after the interaction with ZnO NPs. The shifted XPS spectra towards higher binding energies of the NJ divulge the atomic level interaction between the DNA bases and ZnO NPs at the surface. Moreover, the formation of NJs reduces the surface defect states of the ZnO NPs and increases the fluorescence properties by quenching the oxygen vacancy concentration. Thus, the current study on the interfacial properties of organic–inorganic conjugate materials opens new frontiers for developing novel nano-bio conjugate materials and their integration for targeted drug delivery, biomolecular sensing and therapeutic tools medicine applications.

Lead (Pb) Biosorption by Intact Biomass and Alginate Extract of Sargassum crassifolium Originated from Gresik Regency Waters

The fisheries potential in Gresik Regency is in danger from industrial lead (Pb) pollution. One possible solution is using Sargassum crassifolium, which acts as an absorbent to eliminate Pb in waters. S. crassifolium is characterized by its great affinity for metal cations to bind heavy metal content. This study aimed at finding the effect of S. crassifolium in different forms (wet, dry, and alginate) to absorb Pb content in water. This research was conducted from July to September 2020. The water sample was taken from Gresik Regency and S. crassifolium was obtained from farmers in Talango Island, Sumenep District, Madura. The effectiveness test of the three treatments was conducted based on contact time and biomass factor. Based on the contact time, each treatment was compared with the contact time (1, 7, and 14 days) with 10 g mass per treatment. Meanwhile, for the biomass factor, each treatment was compared by weight (10, 20, and 30 g) for 7 days. The contact time showed that in 14 days, the alginate form of S. crassifolium had the highest absorbent power with 1.370±0.0034 mg.L-1 of lead absorbed and 100% absorbed value. Based on the absorbent mass treatment, 10 g alginate gave the best result with the absorbed lead of 1.364±0.0028 mg.L-1 and an absorption value of 99.71%. The water quality showed that parameters of Dissolved Oxygen (DO), salinity, and nitrates from Gresik Regency were not above standard due to heavy metal pollution. S. crassifolium treatment could decrease the nitrite and nitrate values while increasing DO although still below the standard. This study indicated that 10 g alginate of S. crassifolium in 14 days was effective as a bio-absorbent for Pb heavy metal.

Oxygen affinity of transition metal cations: A coherent descriptor elucidating catalytic oxygenate transformations

This work reports a complementary descriptor to acidity for metal cations - oxygen affinity, to scale the interaction strength of metal cations with oxygenate groups. A method for measuring oxygen affinity is developed in alkyl methylimidazolium chloride solvents using in-situ far infrared (FIR) spectroscopy. The relative oxygen affinity values of metal cations in metal chlorides with model compounds including cyclopentanol (for alcohols), cyclohexanone (for ketones), ethylene glycol diethyl ether (for ethers), and H2O are measured from the dissociation kinetics of the metal-oxygenate complexes. The concentrations of metal-chloride and metal-oxygenate complexes are determined during evaporative removal of oxygenate molecules according to the FIR absorbance of metal-Cl bonds. The oxygen affinity values are shown to reasonably account for the catalytic performances of metal cations in furfural-acetone condensation and glucose isomerization reactions. The oxygen affinity descriptor could be potentially exploited as an intrinsic property of metal cation broadly for metal chloride or metal oxide.

Upcycling of blending waste plastics as zwitterionic hydrogel for simultaneous removal of cationic and anionic heavy metals from aqueous system

Upcycling of waste plastics as functional materials is a new approach for synthesizing low-cost and durable adsorbents with zwitterionic property. Herein, a facile process for recycling blending waste plastics to fabricate zwitterionic plastic-g-hydrogel (ZPH) for simultaneous adsorbing cationic and anionic heavy metals was developed. ZPH possessed high affinities for cations and anions in both acid and alkaline conditions owing to its zwitterionic property, and the maximum adsorption capacities of Pb2+, Cd2+, Ba2+, and Cr(VI) (Cr2O72-) were 132.13, 85.58, 69.92 and 85.15 mg/g, respectively. Mechanism study indicated the incompatibility of blending plastics was skillfully overcome through the crosslinking between sodium alginate (SA)/chitosan (CTS) and plastics. Cations were adsorbed onto ZPH via electrostatic interaction, cation exchange and coordination interactions with Cl/N/O-containing groups. Furthermore, the reduction of Cr(VI) to Cr(III) was another important path for ZPH to capture anionic Cr2O72-, and subsequently Cr(III) was adsorbed via coordination interaction and cation exchange. Moreover, the regeneration experiment showed ZPH possessed excellent reusability and stable structure. Accordingly, this research provides a profitable approach for recycling blending plastics, and ZPH has potentials for industrial application in wastewater treatment or contaminated site remediation with complex heavy metals pollution.

Field-amplified sample injection and graphene quantum dot dual preconcentration in the analysis of melamine and dicyandiamide by capillary electrophoresis

通过热解法制备了硫掺杂的石墨烯量子点(S-GQDs),同石墨烯量子点(GQDs)相比,S原子的引入有效改善了GQDs的表面状态和化学特性、增强其对正电荷的捕获能力,使其更易与阳离子相互作用。以S-GQDs为载体,结合电堆积富集技术,发展了一种基于场放大进样(FASI)和S-GQDs放大的双重富集毛细管电泳(CE)分离检测三聚氰胺和双氰胺的方法。三聚氰胺和双氰胺在酸性介质中带正电荷,电动进样时快速迁移到毛细管入口端进行FASI预富集;同时带负电荷的S-GQDs向阳极端迁移,在样品与缓冲溶液的界面处通过静电作用吸附样品离子,S-GQDs作为载体使检测信号进一步放大。实验考察了缓冲溶液中S-GQDs的体积分数、缓冲溶液的组成及pH、进样时间等因素对富集分离效果的影响。当缓冲溶液的pH为4.6时,进样时间可延长至450 s。同常规电动进样(10 kV×10 s)相比,采用FASI与S-GQDs双重放大技术可使检测灵敏度提高1.6×105倍。该方法对三聚氰胺和双氰胺检测的线性范围是1.0×10-14~1.0×10-8mol/L,相关系数(r2)大于0.999,检出限分别为2.6×10-15和5.7×10-15mol/L。实现了对盐酸二甲双胍中三聚氰胺和双氰胺的高灵敏检测,回收率分别为95.9%~102.4%和92.0%~106.0%,相对标准偏差(RSD)小于5%。该方法操作简单,分离效果好,准确度高,重现性好,适用于分离检测不同盐酸二甲双胍制剂中的三聚氰胺和双氰胺。