Jun-qin Qiao

Room-temperature phosphorescence chemosensor and Rayleigh scattering chemodosimeter dual-recognition probe for 2,4,6-trinitrotoluene based on manganese-doped ZnS quantum dots.

Rayleigh scattering (RS) as an interference factor to detection sensitivity in ordinary fluorescence spectrometry is always avoided in spite of considerable efforts toward the development of RS-based resonance Rayleigh scattering (RRS) and hyper-Rayleigh scattering (HRS) techniques. Here, combining advantages of quantum dots (QDs) including chemical modification of functional groups and the installation of recognition receptors at their surfaces with those of phosphorescence such as the avoidance of autofluorescence and scattering light, l-cys-capped Mn-doped ZnS QDs have been synthesized and used for room-temperature phosphorescence (RTP) to sense and for RS chemodosimetry to image ultratrace 2,4,6-trinitrotoluene (TNT) in water. The l-cys-capped Mn-doped ZnS QDs interdots aggregate with TNT species induced by the formation of Meisenheimer complexes (MHCs) through acid-base pairing interaction between l-cys and TNT, hydrogen bonding, and electrostatic interaction between l-cys intermolecules. Although the resultant MHCs may quench the fluorescence at 430 nm, interdots aggregation can greatly influence the light scattering property of the aqueous QDs system, and therefore, dominant RS enhancement at defect-related emission wavelength was observed under the excitation of violet light of Mn-doped ZnS QDs, which was applied in chemodosimetry to image TNT in water. Meanwhile, Mn-doped ZnS QDs also exhibited a highly selective response to the quenching of the (4)T(1)-(6)A(1) transition emission (RTP) and showed a very good linearity in the range of 0.0025-0.45 μM TNT with detection limit down to 0.8 nM and RSD of 2.3% (n = 5). The proposed methods are well-suited for detecting the ultratrace TNT and distinguishing different nitro compounds.

Synthesis in aqueous solution and characterisation of a new cobalt-doped ZnS quantum dot as a hybrid ratiometric chemosensor

In this paper, cobalt (Co(2+))-doped (CoD) ZnS quantum dots (QDs) are synthesised in aqueous solution and characterised for the first time. L-Cysteine (L-Cys) ligands on the surface of CoD ZnS QDs can bind 2,4,6-trinitrotoluene (TNT) to form Meisenheimer complexes (MHCs) mainly through acid-base pairing interactions between TNT and L-Cys and the assistance of hydrogen bonding and electrostatic co-interactions among L-Cys intermolecules. The aggregation of inter-dots induced by MHCs greatly influenced the light scattering property of the QDs in aqueous solution, and Rayleigh scattering (RS) enhancement at the defect-related emission wavelengths as well as its left side was observed with the excitation of CoD ZnS QDs by violet light. RS enhancement, combining with the quenching of the orange transition emission induced by TNT anions, resulted in a change in the ratiometric visualisation of the system being investigated. A novel CoD ZnS QD-based hybrid ratiometric chemosensor has therefore been developed for simple and sensitive analysis of TNT in water. This ratiometric probe can assay down to 25 nM TNT in solution without interference from a matrix of real water sample and other nitroaromatic compounds. Because of the excellent electron-accepting ability and strong affinity of TNT to L-Cys on the surface of CoD ZnS QDs, the CoD photoluminescent nanomaterials reported here are well suited for detecting ultra-trace TNT and for distinguishing different nitro-compounds in aqueous solution.

Solid phase extraction of magnetic carbon doped Fe3O4 nanoparticles.

Carbon decorated Fe3O4 nanoparticles (Fe3O4/C) are promising magnetic solid-phase extraction (MSPE) sorbents in environmental and biological analysis. Fe3O4/C based MSPE method shows advantages of easy operation, rapidness, high sensitivity, and environmental friendliness. In this paper, the MSPE mechanism of Fe3O4/C nanoparticles has been comprehensively investigated, for the first time, through the following three efforts: (1) the comparison of extraction efficiency for polycyclic aromatic hydrocarbons (PAHs) between the Fe3O4/C sorbents and activated carbon; (2) the chromatographic retention behaviors of hydrophobic and hydrophilic compounds on Fe3O4/C nanoparticles as stationary phase; (3) related MSPE experiments for several typical compounds such as pyrene, naphthalene, benzene, phenol, resorcinol, anisole and thioanisole. It can be concluded that there are hybrid hydrophobic interaction and hydrogen bonding interaction or dipole-dipole attraction between Fe3O4/C sorbents and analytes. It is the existence of carbon and oxygen-containing functional groups coated on the surface of Fe3O4/C nanoparticles that is responsible for the effective extraction process.

A practical interface designed for on-line polymer monolith microextraction: synthesis and application of poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) monolith.

A simple and facile needle-adapter was designed for constructing manual on-line polymer monolith microextraction-high performance liquid chromatography (PMME-HPLC). A capillary poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) [poly(VP-co-EGDMA)] monolith was prepared by in situ polymerization, using 4-vinylpyridine (VP) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The synthesized monolith was used as the extraction medium for concentrating four EPA priority pollutants, 2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol, from water samples. The effect of the dosage of porogen polyethylene glycol 6000 (PEG) on back pressure and extraction performance of the capillary monolith was also investigated. Moreover, the influences of several parameters (such as extraction time, desorption time, content of MeOH in sample solution and sample pH) were examined to obtain the optimal PMME conditions. As a result, the established on-line PMME-HPLC protocol, with good extraction efficiency (80.6-91.7%), satisfactory recovery (94.7-106% and 76.8-86.3% for water and serum samples, respectively) and low detection limit (0.3-1.4 μg/L), exhibited potential applicability for the analysis of chlorophenols in environmental and biological samples.

Determination of n-octanol/water partition coefficients of weak ionizable solutes by RP-HPLC with neutral model compounds

The utilization of neutral compounds as model compounds is put forward for determination of the n-octanol/water partition coefficient (K(ow)) of highly hydrophobic, weak acidic compounds by reversed-phase high performance liquid chromatography (RP-HPLC). It is based on a linear relationship between the logarithm of apparent n-octanol/water partition coefficient (log K(ow)″), expressing hydrophobicity of acidic solutes more accurately, and the logarithm of RP-HPLC retention factor of the solutes corresponding to the neat aqueous fraction of mobile phase (log k(w)). The availability of neutral model compounds was theoretically tested for this novel protocol. Moreover, a high consistency of linear log K(ow)″-log k(w) correlations was demonstrated between a mixed training set of neutral and acidic model compounds, and a training set of neutral model compounds. It is proved in theory that for a certain set of compounds investigated, all derived linear relationships between log K(ow)″ and log k(w) have a unit slope and the same intercept, regardless of mobile phase pH. This model was applied to measure log K(ow) of lipophilic aristolochic acid I (AA I) and aristolochic acid II (AA II). Log K(ow) values for AA I and AA II are 4.45±0.07 and 3.99±0.06, respectively. To the best of our knowledge, this is the first report on experimental log K(ow) data for AAs. The proposed strategy solves the problem of lacking suitable acidic model compounds with reliable experimental K(ow) in determining K(ow) of lipophilic acidic solutes by RP-HPLC.

A novel evaluation method for extrapolated retention factor in determination of n-octanol/water partition coefficient of halogenated organic pollutants by reversed-phase high performance liquid chromatography.

The retention factor corresponding to pure water in reversed-phase high performance liquid chromatography (RP-HPLC), k(w), was commonly obtained by extrapolation of retention factor (k) in a mixture of organic modifier and water as mobile phase in tedious experiments. In this paper, a relationship between logk(w) and logk for directly determining k(w) has been proposed for the first time. With a satisfactory validation, the approach was confirmed to enable easy and accurate evaluation of k(w) for compounds in question with similar structure to model compounds. Eight PCB congeners with different degree of chlorination were selected as a training set for modeling the logk(w)-logk correlation on both silica-based C(8) and C(18) stationary phases to evaluate logk(w) of sample compounds including seven PCB, six PBB and eight PBDE congeners. These eight model PCBs were subsequently combined with seven structure-similar benzene derivatives possessing reliable experimental K(ow) values as a whole training set for logK(ow)-logk(w) regressions on the two stationary phases. Consequently, the evaluated logk(w) values of sample compounds were used to determine their logK(ow) by the derived logK(ow)-logk(w) models. The logK(ow) values obtained by these evaluated logk(w) were well comparable with those obtained by experimental-extrapolated logk(w), demonstrating that the proposed method for logk(w) evaluation in this present study could be an effective means in lipophilicity study of environmental contaminants with numerous congeners. As a result, logK(ow) data of many PCBs, PBBs and PBDEs could be offered. These contaminants are considered to widely exist in the environment, but there have been no reliable experimental K(ow) data available yet.

Mechanism and application of halogen bond induced fluorescence enhancement and iodine molecule cleavage in solution

In this paper, a strong halogen bond (XB) donor (iodine) and photoinduced electron transfer (PET) molecule (ciprofloxacin, Cip) were selected with the objective to investigate halogen bonding under weakly alkaline conditions. A series of experimental characterization techniques was employed to elucidate the interaction mechanism of the XB, in combination with theoretical calculations. It is found that new UV-Vis absorption peaks and the fluorescence enhancement with the mixing of Cip and iodine are attributed to the disruption of the PET charge separation process through the halogen bonding interaction. The 2 : 1 stoichiometry of the XB complex (I2 : Cip) was attested using a modified Benesi–Hildebrand method. 1H NMR spectra showed that the iodine molecule can interact with three nitrogen atoms of Cip to form three XBs. FT-IR spectra indicated that the nitrogen atom of the imino group is the preferential interaction site of the XB. Notably, direct analysis in real time-mass spectrometry (DART-MS) gave a distinct quasi-molecular ion of the supramolecular complex (Cip + I) in solution. Meanwhile, density functional theory (DFT), taking into account the dispersion energy, revealed that the formation of an I⋯N XB not only disrupts the PET charge separation process of Cip to enhance fluorescence but also induces the cleavage of an iodine molecule (I–I) to produce a triiodine anion (I3−) XB. This explained why I3− was observed in UV-Vis and DART-MS as well as in the crystal, and how the fourth iodine atom involved in the self-assembly of the XB existed stably. Moreover, a developed optosensor based on halogen bonding has been successfully used to analyze commercial Cip·HCl capsules, suggesting the potential applicability of halogen bonding in real pharmaceutical analyses.

Influence of variation in mobile phase pH and solute pKa with the change of organic modifier fraction on QSRRs of hydrophobicity and RP-HPLC retention of weakly acidic compounds

The variation in mobile phase pH and ionizable solute dissociation constant (pK(a)) with the change of organic modifier fraction in hydroorganic mobile phase has seemingly been a troublesome problem in studies and applications of reversed phase high performance liquid chromatography (RP-HPLC). Most of the early studies regarding the RP-HPLC of acid-base compounds have to measure the actual pH of the mixed mobile phase rigorously, sometimes bringing difficulties in the practices of liquid chromatographic separation. In this paper, the effect of this variation on the apparent n-octanol/water partition coefficient (K(ow)″) and the related quantitative structure-retention relationship (QSRR) of logK(ow)″ vs. logk(w), the logarithm of retention factor of analytes in neat aqueous mobile phases, was investigated for weakly acidic compounds. This QSRR is commonly used as a classical method for K(ow) measurement by RP-HPLC. The theoretical and experimental derivation revealed that the variation in mobile phase pH and solute pK(a) will not affect the QSRRs of acidic compounds. This conclusion is proved to be suitable for various types of ion-suppressors, i.e., strong acid (perchloric acid), weak acid (acetic acid) and buffer salt (potassium dihydrogen phosphate/phosphoric acid, PBS). The QSRRs of logK(ow)″ vs. logk(w) were modeled by 11 substituted benzoic acids using different types of ion-suppressors in a binary methanol-water mobile phase to confirm our deduction. Although different types of ion-suppressor all can be used as mobile phase pH modifiers, the QSRR model obtained by using perchloric acid as the ion-suppressor was found to have the best result, and the slightly inferior QSRRs were obtained by using acetic acid or PBS as the ion-suppressor.

Retention of nucleic acids in ion‐pair reversed‐phase high‐performance liquid chromatography depends not only on base composition but also on base sequence

The study on nucleic acid retention in ion-pair reversed-phase high-performance liquid chromatography mainly focuses on size-dependence, however, other factors influencing retention behaviors have not been comprehensively clarified up to date. In this present work, the retention behaviors of oligonucleotides and double-stranded DNAs were investigated on silica-based C18 stationary phase by ion-pair reversed-phase high-performance liquid chromatography. It is found that the retention of oligonucleotides was influenced by base composition and base sequence as well as size, and oligonucleotides prone to self-dimerization have weaker retention than those not prone to self-dimerization but with the same base composition. However, homo-oligonucleotides are suitable for the size-dependent separation as a special case of oligonucleotides. For double-stranded DNAs, the retention is also influenced by base composition and base sequence, as well as size. This may be attributed to the interaction of exposed bases in major or minor grooves with the hydrophobic alky chains of stationary phase. In addition, no specific influence of guanine and cytosine content was confirmed on retention of double-stranded DNAs. Notably, the space effect resulted from the stereostructure of nucleic acids also influences the retention behavior in ion-pair reversed-phase high-performance liquid chromatography.

Influence of n-octanol in mobile phase on QSRRs of lipophilicity and retention mechanism of acidic and basic compounds in RP-HPLC

The influence of n-octanol additive agent on the retention behavior, the uniformity of the retention mechanism, as well as the quantitative structure–retention relationships (QSRRs) of weak acidic and basic compounds on reversed-phase high performance liquid chromatography (RP-HPLC) was systematically discussed in this paper, especially for the QSRRs of logarithm of apparent n-octanol/water partition coefficient (log K′′ow) and logarithm of retention factor extrapolated to neat aqueous mobile phase (log kw(o)), which have not been discussed in other studies to date. For this purpose, the aqueous fraction of mobile phase was saturated with n-octanol and 0.25% (v/v) n-octanol was added into organic modifier. Eleven substituted benzoic acids, as well as fifteen anilines or pyridines were selected to establish QSRR models by using different types of ion-suppressors. The results indicated that the roles of n-octanol were different in various systems. For acids compounds, if perchloric acid (strong acid) acts as an ion-pair agent, the silanophilic interaction between solutes and residual silanol groups of alkyl-silica stationary phase can be ignored, and n-octanol/water partition and chromatographic process are homo-energetic. In this case, n-octanol acts only as organic modifier. However, if acetic acid (weak acid) or phosphoric acid/potassium dihydrogen phosphate (buffer salt) were used as the ion-suppressor, n-octanol is not only an organic modifier, but also a masking agent of free silanols. For weak bases, if ammonium chloride–ammonia was employed as the ion-suppressor, the addition of n-octanol will make QSRRs correlation significantly worse. Therefore, for studying on QSRRs of lipophilicity and retention behavior of acidic and basic compounds, n-octanol is only recommended for acidic system, and strong monoprotic acids, e.g., perchloric acid, are recommended as the ion-suppressors.