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Rapid qualitative and quantitative analysis of 4-methylimidazole (4-MEI) in caramel and beverage samples is demonstrated using the paper spray form of ambient ionization mass spectrometry. The minimum level of pure 4-MEI detectable using multiple reaction monitoring (MRM) in a triple quadrupole instrument was 3 pg μL⁻¹ in neat solvent and 5 pg μL⁻¹ in a matrix containing caramel. This method was used to analyze 11 caramel samples for 4-MEI. After implementing effective quality control protocols, average relative standard deviations for paper spray triple quadrupole MS were less than 15% and the linear dynamic range was three orders of magnitude. Results obtained on three different days by two different analyst groups agreed closely. An ion trap tandem MS method of approximate quantitative analysis is also described and it gave similar precision to the triple quadrupole experiment when fluctuations in ion currents were cancelled by simultaneously isolating the analyte and internal standard and fragmenting both in an ion trap simultaneous MRM experiment. As another alternative, a rapid qualitative screening method based on the use of high-resolution measurements instead of tandem mass spectrometry using an Orbitrap was also tested and found to give a detection limit of 100 pg μL⁻¹.

We report the design and characterization of a disposable light shielded paper–plastic microfluidic device that can detect nanomolar levels of H2O2 using a smartphone camera and a light sealed accessory. Chemiluminescence reaction of H2O2 with bis(2,4,6-trichlorophenyl)oxalate in the presence of rubrene and imidazole is confined to a paper reaction site where the individual reagents are delivered via plastic microfluidic channels. The net photon emission from the chemiluminescence reactions, detected by using a smartphone, is correlated with H2O2 concentrations. With a total reagent volume of 25 μL, the sensor system was able to detect H2O2 concentrations as low as 250 nM. The smartphone based chemiluminescence sensing system has great potential as a point of care diagnostic tool for monitoring nanomolar levels of H2O2 in biological samples. [ABSTRACT FROM AUTHOR]

In this study, a novel and highly efficient "turn-off" fluorescence imidazole-based sensor (BIB) with a symmetric structure was synthesized by a four-step reaction, from o-phenylenediamine, 6-bromo-2-pyridinecarboxaldehyde, and 1-bromohexane. The sensing mechanism was confirmed via fluorescence titration, HRMS, and 1HNMR techiniques. The results showed that the binding ratio of BIB and Ag+ was 1 : 1 in a DMF-HEPES (pH 7.4) solution (9 : 1, v/v). The fluorescence response of BIB exhibited a good linear response within the Ag+ concentration ranging from 2 × 10−7 to 8 × 10−6 mol L−1, and the limit of detection was calculated to be 4.591 × 10−8 mol L−1. BIB was successfully applied to the detection of Ag+ in water samples with recoveries of 97.25–109.50% and relative standard deviations (RSD) of 1.14–2.45%. In addition, BIB can successfully be applied to qualitatively and quantitatively identify Ag+ in water by test paper strips of BIB, which is fast and convenient. This provides a possible potential for the rapid monitoring of metal ions by sensors in environmental research. [ABSTRACT FROM AUTHOR]

The zeolitic imidazole framework with a leaf-shaped morphology (ZIF-L) has a wide range of promising applications in gas storage, battery materials, catalytic reactions, and optoelectronic devices due to its planar leaf-like structure and large surface area. However, the low conductivity, weak catalytic activity, and poor stability in the water dielectric medium of ZIF-L limit its further practical application. To solve these problems, we added the conductive polymer heterocyclic poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to ZIF-L for the sensitive detection of dopamine (DA). The synthesized composite ZIF-L/PEDOT:PSS (ZIF-L/PEDOT) not only retained the surface morphology of ZIF-L but also exhibited excellent electrochemical properties. The higher electrical conductivity of ZIF-L/PEDOT than that of ZIF-L was due to the enhanced electron transfer at the interface between ZIF-L and PEDOT:PSS. As a result, we developed an electrochemical biosensor based on the ZIF-L/PEDOT composite, which has a limit of detection of 7 nM for DA and a wide linear range from 25 nM to 500 μM. Furthermore, the current drop was negligible after 28 days, proving that the biosensor has excellent stability. Based on the above-mentioned outstanding performance, the ZIF-L/PEDOT-based biosensor was successfully used to detect DA in human serum samples. These results demonstrated that ZIF-L/PEDOT is expected to play an essential role in disease detection. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are composed of metal ions and organic ligands with high specific surface areas, controllable porous structures and abundant metal active sites, showing their extraordinary potential in electrochemical sensors. Here, a 3D conductive network structure (C–Co–N@MWCNTs) is designed by anchoring zeolite imidazole frameworks (ZIF-67) onto multi-walled carbon nanotubes (MWCNTs) and carbonizing them. The C–Co–N@MWCNTs exhibit excellent electron conductivity, a porous structure and considerable electrochemical active sites, which can effectively demonstrate high sensitivity and selectivity in the detection of adrenaline (Ad). The Ad sensor exhibited a low detection limit of 6.7 nmol L−1 (S/N = 3) and a wide linear range of 0.02 μmol L−1–1.0 mmol L−1. The developed sensor also displayed high selectivity, good reproducibility and repeatability. The C–Co–N@MWCNTs electrode was further employed in the detection of Ad in a real sample of human serum, suggesting that it is a promising candidate for electrochemical sensing of Ad. [ABSTRACT FROM AUTHOR]

Three novel imidazole-based two-photon absorption compounds bearing different organic cations (1PIPy, 2PIQu, and 3PIIm) were facilely synthesized and fully characterized by 1H NMR, 13C NMR, FT-IR, and HRMS. The linear and nonlinear photophysical properties of the target compounds were systematically investigated in various solvents, supplemented with the density functional theory calculations to shed light on their structure–property relationships. The maximum two-photon action cross-sections (Φ × δmax) were determined to be 22.4–98.2 (CH2Cl2), 9.6–41.3 (DMF), and 3.9–11.8 (H2O) GM. It is found that 3PIIm shows significant viscosity sensitivity with a sharp 27-fold increase in fluorescence intensity. Its fluorescence intensity also exhibits a linear relationship with the viscosity of the media in a logarithmic plot. The Φ × δmax value of 3PIIm in highly viscous glycerol was found to be 107.5 GM. Cytotoxicity tests indicate that these compounds have relatively low cytotoxicity. All the target compounds were successfully characterized by one- and two-photon fluorescence imaging in living cells. The colocalization experiments reveal that 1PIPy and 3PIIm are specially located in the endoplasmic reticulum (ER) with the Pearson's coefficients above 0.90. 3PIIm can also monitor the fluctuation of ER viscosity during etoposide-induced apoptosis. [ABSTRACT FROM AUTHOR]

Responsive photonic crystals have attracted extensive attention due to their features of transforming external stimuli into a variation of optical signals or structural colors. In recent years, the accumulation of heavy metal ions has become a serious threat to human health and the environment. Thus, a simple and rapid method for the accurate detection of metal ions is of great importance. Herein, an imidazole-based-silica inverse opal photonic crystal (IOPC) sensor is prepared. Three different particle sizes of SiO2 photonic crystals were used as templates for the preparation of an IOPC. The results show that the template presents a high specific surface area and interconnected nanopores. When the nanopores adsorb copper ions, the functional monomer imidazole will chelate with copper ions to form a flat quadrilateral structure. Then the nanopores of the IOPC shrink, which will result in the red shifting of the diffraction peak to complete the visual response sensing. When immersed in different concentrations of metal ions, the structural color of the IOPC changes, making it a visual sensor. In addition, it is proved that the imidazole-modified IOPC is specifically responsive to Cu2+, and the structural color of the sensor will shift from green to yellow after sensing. The detection limit is as low as 1 × 10−6 mol L−1, and the maximum offset of the diffraction peak can reach 50 nm. Therefore, the IOPC prepared here provides an ideal platform for the fast and high selective detection of Cu2+, and it has potential applications in the rapid detection of other heavy metal ions. [ABSTRACT FROM AUTHOR]

In this paper, a kind of aminopropyl imidazole-modified silica sorbent was synthesized and used as a solid-phase extraction (SPE) sorbent for the determination of carboxylic acid compounds and polycyclic aromatic hydrocarbons (PAHs). The resultant aminopropyl imidazole-modified silica sorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and elemental analysis (EA) to ensure the successful binding of aminopropyl imidazole on the surface of silica gel. Then the aminopropyl imidazole-modified silica sorbent served as a SPE sorbent for the enrichment of carboxylic acid compounds and PAHs. The new sorbent exhibited high extraction efficiency towards the tested compounds and the results show that such a sorbent can offer multiple intermolecular interactions: electrostatic, π–π, and hydrophobic interactions. Several parameters affecting the extraction recovery, such as the pH of sample solution, the pH of eluent, the solubility of eluent, the volume of eluent, and sample loading, were also investigated. Under the optimized conditions, the proposed method was applied to the analysis of four carboxylic acid compounds and four PAHs in environmental water samples. Good linearities were obtained for all the tested compounds with R2 larger than 0.9903. The limits of detection were found to be in the range of 0.0065–0.5 μg L−1. The recovery values of spiked river water samples were from 63.2% to 112.3% with relative standard deviations (RSDs) less than 10.1% (n = 4). [ABSTRACT FROM AUTHOR]

Creating more exposed active sites on the metal–organic framework (MOF) surface is crucial for enhancing the recognition ability of MOF artificial receptors. Here, a copper-based MOF Cu(im)2 (im = imidazole) was utilized to act as an artificial receptor, inhibiting the activity of α-chymotrypsin. The shortest diazole ligand reduced the distance between regenerative copper sites, creating as many active sites as possible on the MOF unit surface. The amount of copper(II) centers on the Cu(im)2 surface was calculated to be 4.96 × 106 μm−2. Thus, Cu(im)2 showed exceedingly higher inhibition performance than other copper-based MOFs. The ChT activity was almost inhibited (88.8%) after the incubation with only 20 μg mL−1 Cu(im)2 for 10 min. The binding between ChT and Cu(im)2 was very fast with high affinity. Further results proved that Cu(im)2 inhibited the activity of ChT through electrostatic interactions and coordination interactions via the mixed inhibition mode. This strategy to use short ligands to create more active sites on the MOF surface provides a new direction to enhance the inhibition efficiency. [ABSTRACT FROM AUTHOR]

In this paper, we described the electrogenerated chemiluminescence (ECL) processes of tris(2,2'-bipyridine) ruthenium(II) (Ru(bpy)(3)(2+)) in room-temperature ionic liquid (RTIL). The results showed that ECL signals in RTIL, 1-butyl-3-methylimidazolium tetrafluoroborate ([Bmim]BF(4)), were stronger than those obtained in aqueous solutions, which means that the RTIL could be used as a good solvent for ECL. The effect of tri-n-propylamine (TPrA) on the ECL process in [Bmim]BF(4) was also investigated and the results showed that the ECL peak occurred at 1.9 V, which is more positive than the previous reports in aqueous solutions, and the ECL intensity reached the maximum when the scan rate of CV is 200 mV s(-1). Moreover, the ECL signal can be quenched by oxygen due to the reaction of oxygen with TPrA* and Ru(bpy)(3)(+). Finally, the inhibition of Ru(bpy)(3)(2+) ECL by water-insoluble analyte, naphthol, was carried out and the results showed that the ECL signal can be quenched completely by naphthol at a very low concentration (1.0 x 10(-6) M).

Phenazine fluorophore based imidazole derivatives (S1 and S2) were synthesized and sensor studies were carried out with various cations. Aggregation induced emission (AIE) was observed selectively for Al3+ among other cations under study in case of both sensors. 1H NMR titration supported the aggregation induced emission of S2 with Al3+. ESI mass spectra successfully confirmed the aggregate formation. SEM images clearly showed the aggregation of receptor induced by Al3+ in a flower-like fashion. AIE probe was successfully applied for bio-imaging of RAW264.7 cells. [ABSTRACT FROM AUTHOR]

We synthesized novel ultra-low fouling ionic liquids and demonstrated their use with surface plasmon resonance (SPR) sensing for the analysis of HER2 in breast cancer cell lysates. Whilst biomarkers are commonly detected in serum, this remains challenging for cancer diagnosis due to their low concentrations in circulation and in some cases, there is a poor correlation between serum and tissue concentrations. Therefore, a cell lysate constitutes an interesting biosample for cancer diagnosis and typing, which has been largely unexploited for chemical biosensing of cancer biomarkers. However, high fouling of surfaces in contact with the cell lysate and the absence of effective surface chemistry to prevent fouling are currently limiting biomarker analysis in cell lysates. To address this challenge, we report the synthesis of 1-(carboxyalkyl)-3-(12-mercaptododecyl)-1H-imidazolium ionic liquids with different anions (Br−, BF4−, PF6−, ClO4−, and NTf2−) and ethyl and pentyl chains to form monolayers and analyse specific proteins from cell lysates. The most efficient ionic liquid monolayer, 1-(carboxyethyl)-3-(12-mercaptododecyl)-1H-imidazolium bromide, was able to eliminate the nonspecific adsorption (surface coverage of 2 ± 2 ng cm−2) of a concentrated cell lysate (protein concentration of ∼3.5 mg mL−1), which was significantly better than carboxy–PEG (surface coverage of 14 ± 7 ng cm−2), a benchmark monolayer commonly used to reduce nonspecific adsorption. These ionic liquid monolayers were modified with anti-HER2 and the detection of the HER2 breast cancer biomarker was carried out in crude breast cancer cell lysates, as shown with HER2-negative MCF-7 cells spiked with HER2 and with HER2 positive SK-BR-3 cells. [ABSTRACT FROM AUTHOR]

A new solid-phase microextraction (SPME) fiber coating material, a zeolitic imidazole framework-67 (ZIF-67) templated nanoporous carbon, Co-NPC, was fabricated by one-step direct carbonization of ZIF-67 without using any other carbon precursors. The prepared Co-NPC was then coated onto a functionalized stainless steel wire by a simple physical coating method to prepare SPME fibers. By coupling the Co-NPC coated fiber based SPME with gas chromatography/micro-electron capture detection (GC/μECD), the developed method exhibited low limits of detection (0.07–0.45 ng g−1) and a wide linearity (0.30–50 ng g−1) for the determination of five organochlorine pesticides (OCPs) in vegetable samples. The method was applied to the analysis of cabbage, cucumber and celery cabbage samples, and the recoveries of the analytes were in the range of 87.9–103.9% with the relative standard deviations (RSDs) ranging from 5.1% to 10.4% (n = 5). Single fiber repeatability and fiber-to-fiber reproducibility values expressed as RSDs were in the range of 4.9–9.6% and 5.8–11.0%, respectively. The method was simple, convenient and feasible for the determination of OCPs in real samples. [ABSTRACT FROM AUTHOR]

In the current study, a novel ionic liquid-based zwitterionic organic polymer monolithic column was developed by copolymerizing 1-vinyl-3-(butyl-4-sulfonate) imidazolium, acrylamide and N,N′-methylenebisacrylamide in a quaternary porogenic solvent consisting of formamide, dimethyl sulphoxide, polyethylene glycol 8000 and polyethylene glycol 10 000 for capillary hydrophilic interaction chromatography. The monolithic stationary phase was optimized by adjusting the amount of monomer in the polymerization solution along with the composition of porogenic solvent. The optimized monolith exhibited excellent selectivity and favorable retention for nucleosides and benzoic acid derivatives. The primary factors affecting the separation efficiency of the monolithic column (including acetonitrile content, pH, and buffer salt concentration in the mobile phase) have been thoroughly evaluated. Excellent reproducibility of the retention times for five nucleosides was achieved, with relative standard deviations of run-to-run (n = 3), column-to-column (n = 3) and batch-to-batch (n = 3) in the range of 0.18–0.48%, 2.33–4.20% and 3.07–6.50%, respectively. [ABSTRACT FROM AUTHOR]

The unique properties of metal–organic frameworks, such as diversity in structures and pore sizes, high surface area, shape selectivity and available to functionality make them as potential materials of the stationary phase for gas chromatography. Here we show an in situ growth approach to the fabrication of zeolite imidazolate framework-90 (ZIF-90) bonded capillary column for gas chromatography separation. ZIF-90 was directly grown onto the inner wall of the carboxyl modified capillary via the coordination between Zn(ii) and carboxyl group. The fabricated ZIF-90 bonded capillary column acted as a weak polar stationary phase. It not only exhibits high capacity in the separation of linear molecules, but also offers excellent features for the separation of 2- and 3-substituted ketones. [ABSTRACT FROM AUTHOR]

A simple strategy to fabricate a fluorescent SiO2@zeolitic imidazolate framework-8 (ZIF-8) core-shell nanosensor for Cu2+ detection was demonstrated in this work. The nanosensor was synthesized using carboxyl-functionalized SiO2 nanoparticles (SiO2 NPs) as a template to induce the growth of ZIF-8 on its surface. The porous SiO2@ZIF-8 exhibited extremely good adsorption properties and a large specific surface area to accumulate Cu2+, and the pyridyl nitrogen sites in imidazole played vital roles in the recognition of Cu2+. The fluorescent intensity decreased linearly with the increasing of Cu2+ concentration in the range of 10-500 nM and the detection limit was estimated to be 3.8 nM. The SiO2@ZIF-8 nanosensor could be further used to determine trace amounts of Cu2+ in real water samples, while some previous sensors had to be dispersed in organic solution for use, such as DMSO and MeCN. The core-shell nanostructures of SiO2@ZIF-8 made it possible for it to be dispersed directly in aqueous solution and prevented ZIF-8 from aggregation, which enhanced the sensing performance of the SiO2@ZIF-8 nanosensor. [ABSTRACT FROM AUTHOR]

The detection of creatinine via an enzymeless electrochemical method is reported through an indirect electrochemical system in which the picrate anion consumed upon the reaction with creatinine is electrochemically measured. After careful optimisation it is found that in pH 13 two linear analytical ranges are possible utilising an Edge Plane Pyrolytic Graphite (EPPG) electrode: 0–6 mM and 7.5–11.5 mM, with a limit of detection (3σ) corresponding to 0.27 mM; all measurements were taken after a five minute reaction time. Furthermore, screen printed carbon electrodes were applied to the same system and yielded remarkably similar linear ranges to the case of the EPPG electrode: 0–6 mM and 6–11 mM, with a limit of detection (3σ) of 0.72 mM. These results are critically analysed and contrasted with the previous literature. This electrochemical protocol is applied to the detection of urinary creatinine where we find creatinine content of three samples falling well within our reported linear ranges and more importantly indicating correct kidney function. Additionally our electrochemical results are ‘benchmarked’ against UV/Vis spectrometry. The devised electroanalytical protocols have the potential to serve as a more solid foundation for electrochemical creatinine testing and have potential to be applied as a point-of-care diagnostics system through the use of screen printing technology, especially considering urinary creatinine concentrations fall within our reported linear ranges for both healthy adults and adults with deficient glomerular filtration. [ABSTRACT FROM AUTHOR]

Accurate fabrication of fluorescence probes to efficiently monitor and detect H2S levels in the fields of foodstuffs and physiology is crucial. Herein, we report two isomeric phenanthro[9,10-d]imidazole benzene sulfonamide-derived fluorescence probes (PI-2-SA and PI-4-SA), both of which display remarkable responses toward H2S over other analytes. The spectral characteristics of the two probes were investigated and are discussed in detail. By comparison, PI-2-SA was specific, sensitive (the limit of detection was ca. 12.3 nM), rapid (within ≤3 min) and dynamic (the rate constant was 0.02 s−1). Significantly, PI-2-SA was proved to be effective in monitoring the shelf-time progress of egg samples in real time as well as in the imaging of exogenous and endogenous H2S in HeLa cells. [ABSTRACT FROM AUTHOR]

Reduced graphene oxide has been rationally functionalized with histamine for the highly sensitive and selective electrochemical determination of bisphenol A (BPA). Histamine is covalently attached to graphene oxide by amide coupling and the oxygen functionalities of graphene oxide are partially reduced electrochemically. The facilitated electrochemical oxidation of BPA was achieved in neutral pH with functionalized reduced graphene oxide. The pH of the reaction controls the oxidation of BPA. Electrochemical oxidation is not favourable at pH less than the pKa of histamine due to the protonation of the imidazole nitrogen. The electrode is highly sensitive (1727.29 ± 12.48 nA μM−1 cm−2) towards BPA and shows a linear response up to 30 μM of BPA. It could detect as low as 0.03 nM of BPA (S/N = 5). The other coexisting analytes do not interfere with the voltammetric measurement of BPA. [ABSTRACT FROM AUTHOR]

A family of imidazolium and pyridinium salts was synthesized for the purpose of labeling amines and 1,2-diols for highly sensitivite analysis by mass spectrometry. The chosen mass labels are shown to serve as effective reporters when bound to particles functionalized with amines or 1,2-diols and the binding is reversible. The straightforward synthetic route allows analogous internal standards to be generated quickly. Solvents amenable to electrospray ionization facilitate the rapid liberation of imidazolium and pyridinium mass labels from particles by hydrolysis in aqueous acid, while the acetal bond remains stable in anhydrous or buffered aqueous solution. Detection of the labels is demonstrated at 1 nM and quantitation of mass labels released from particles is also demonstrated. [ABSTRACT FROM AUTHOR]

A novel method for the detection of histamine (HIM) via the formation of a self-assembled magic number cluster with thymine (T) by electrospray ionization tandem mass spectrometry (ESI-MS/MS) is described. The formation of the magic number cluster [T17 + HIM + 2H]2+ shifts the MS signal of histamine to the interference-free higher mass range and the signal intensity is increased by four orders of magnitude. In addition, the formation of [T17 + HIM + 2H]2+ is highly specific to histamine compared with its metabolite and other similar biogenic amines, which may be attributed to both of its amino and imidazole groups. The linear dynamic range of the method is in the range of 1 nM–20 μM, and the limit of detection can be as low as 0.1 nM. The feasibility of this method is further demonstrated by the quantitative analysis of histamine in a red wine sample. Since little sample preparation or separation is required before the analysis, this method provides a rapid new way for the sensitive and specific detection of histamine by MS. [ABSTRACT FROM AUTHOR]

Knowledge about electrochemical and electrical properties of nanopore structures and the influence of pore dimensions on these properties is important for the development of nanopore biosensing devices. The aim of this study was to explore the influence of nanopore dimensions (diameter and length) on biosensing performance using non-faradic electrochemical impedance spectroscopy (EIS). Nanoporous alumina membranes (NPAMs) prepared by self-ordered electrochemical anodization of aluminium were used as model nanopore sensing platforms. NPAMs with different pore diameters (25–65 nm) and lengths (4–18 μm) were prepared and the internal pore surface chemistry was modified by covalently attaching streptavidin and biotin. The performance of this antibody nanopore biosensing platform was evaluated using various concentrations of biotin as a model analyte. EIS measurements of pore resistivity and conductivity were carried out for pores with different diameters and lengths. The results showed that smaller pore dimensions of 25 nm and pore lengths up to 10 μm provide better biosensing performance. [ABSTRACT FROM AUTHOR]

Responsive photonic crystals have attracted extensive attention due to their features of transforming external stimuli into a variation of optical signals or structural colors. In recent years, the accumulation of heavy metal ions has become a serious threat to human health and the environment. Thus, a simple and rapid method for the accurate detection of metal ions is of great importance. Herein, an imidazole-based-silica inverse opal photonic crystal (IOPC) sensor is prepared. Three different particle sizes of SiO2 photonic crystals were used as templates for the preparation of an IOPC. The results show that the template presents a high specific surface area and interconnected nanopores. When the nanopores adsorb copper ions, the functional monomer imidazole will chelate with copper ions to form a flat quadrilateral structure. Then the nanopores of the IOPC shrink, which will result in the red shifting of the diffraction peak to complete the visual response sensing. When immersed in different concentrations of metal ions, the structural color of the IOPC changes, making it a visual sensor. In addition, it is proved that the imidazole-modified IOPC is specifically responsive to Cu2+, and the structural color of the sensor will shift from green to yellow after sensing. The detection limit is as low as 1 × 10−6 mol L−1, and the maximum offset of the diffraction peak can reach 50 nm. Therefore, the IOPC prepared here provides an ideal platform for the fast and high selective detection of Cu2+, and it has potential applications in the rapid detection of other heavy metal ions. [ABSTRACT FROM AUTHOR]