Analytica Chimica Acta (v.860, #C)

Zone fluidics for measurement of octanol–water partition coefficient of drugs by Panwadee Wattanasin; Phoonthawee Saetear; Prapin Wilairat; Duangjai Nacapricha; Saowapak Teerasong (1-7).
Display OmittedA novel zone fluidics (ZF) system for the determination of the octanol–water partition coefficient (P ow) of drugs was developed. The ZF system consisted of a syringe pump with a selection valve, a holding column, a silica capillary flow-cell and an in-line spectrophotometer. Exact microliter volumes of solvents (octanol and phosphate buffer saline) and a solution of the drug, sandwiched between air segments, were sequentially loaded into the vertically aligned holding column. Distribution of the drug between the aqueous and octanol phases occurred by the oscillation movement of the syringe pump piston. Phase separation occurred due to the difference in densities. The liquid zones were then pushed into the detection flow cell. In this method, absorbance measurements in only one of the phase (octanol or aqueous) were employed, which together with the volumes of the solvents and pure drug sample, allowed the calculation of the P ow. The developed system was applied to the determination of the P ow of some common drugs. The log (P ow) values agreed well with a batch method (R 2  = 0.999) and literature (R 2  = 0.997). Standard deviations for intra- and inter-day analyses were both less than 0.1log unit. This ZF system provides a robust and automated method for screening of P ow values in the drug discovery process.
Keywords: Zone fluidics; Octanol–water partition coefficient; Drug discovery;

Display OmittedA slurry sampling inductively coupled plasma mass spectrometry (ICP-MS) method has been developed for the determination of Ge, As, Cd, Sb, Hg and Bi in cosmetic lotions using flow injection (FI) vapor generation (VG) as the sample introduction system. A slurry containing 2% m/v lotion, 2% m/v thiourea, 0.05% m/v l-cysteine, 0.5 μg mL−1 Co(II), 0.1% m/v Triton X-100 and 1.2% v/v HCl was injected into a VG-ICP-MS system for the determination of Ge, As, Cd, Sb, Hg and Bi without dissolution and mineralization. Because the sensitivities of the analytes in the slurry and that of aqueous solution were quite different, an isotope dilution method and a standard addition method were used for the determination. This method has been validated by the determination of Ge, As, Cd, Sb, Hg and Bi in GBW09305 Cosmetic (Cream) reference material. The method was also applied for the determination of Ge, As, Cd, Sb, Hg and Bi in three cosmetic lotion samples obtained locally. The analysis results of the reference material agreed with the certified value and/or ETV-ICP-MS results. The detection limit estimated from the standard addition curve was 0.025, 0.1, 0.2, 0.1, 0.15, and 0.03 ng  g−1 for Ge, As, Cd, Sb, Hg and Bi, respectively, in original cosmetic lotion sample.
Keywords: Inductively coupled plasma mass spectrometry; Flow injection; Slurry sampling; Vapor generation; Lotions; Multi-elemental analysis;

Detection of explosives on the surface of banknotes by Raman hyperspectral imaging and independent component analysis by Mariana R. Almeida; Deleon N. Correa; Jorge J. Zacca; Lucio Paulo Lima Logrado; Ronei J. Poppi (15-22).
Display OmittedThe aim of this study was to develop a methodology using Raman hyperspectral imaging and chemometric methods for identification of pre- and post-blast explosive residues on banknote surfaces. The explosives studied were of military, commercial and propellant uses. After the acquisition of the hyperspectral imaging, independent component analysis (ICA) was applied to extract the pure spectra and the distribution of the corresponding image constituents. The performance of the methodology was evaluated by the explained variance and the lack of fit of the models, by comparing the ICA recovered spectra with the reference spectra using correlation coefficients and by the presence of rotational ambiguity in the ICA solutions. The methodology was applied to forensic samples to solve an automated teller machine explosion case. Independent component analysis proved to be a suitable method of resolving curves, achieving equivalent performance with the multivariate curve resolution with alternating least squares (MCR-ALS) method. At low concentrations, MCR-ALS presents some limitations, as it did not provide the correct solution. The detection limit of the methodology presented in this study was 50 μg cm−2.
Keywords: Explosives; Banknotes; Raman hyperspectral imaging; Independent component analysis; Detection limit;

Display OmittedIn this paper, we report an improved electrochemical aptasensor based on exonuclease III and double-stranded DNA (dsDNA)-templated copper nanoparticles (CuNPs) assisted signal amplification. In this sensor, duplex DNA from the hybridization of ligated thrombin-binding aptamer (TBA) subunits and probe DNA can act as an effective template for the formation of CuNPs on the electrode surface, so copper ions released from acid-dissolution of CuNPs may catalyze the oxidation of ο-phenylenediamine to produce an amplified electrochemical response. In the presence of thrombin, a short duplex domain with four complementary base pairs can be stabilized by the binding of TBA subunits with thrombin, in which TBA subunit 2 can be partially digested from 3′ terminal with the cycle of exonuclease III, so the ligation of TBA subunits and the subsequent formation of CuNPs can be inhibited. By electrochemical characterization of dsDNA-templated CuNPs on the electrode surface, our aptasensor can display excellent performances for the detection of thrombin in a broad linear range from 100 fM to 1 nM with a low detection limit of 20.3 fM, which can also specially distinguish thrombin in both PBS and serum samples. Therefore, our aptasensor might have great potential for clinical diagnosis of biomarkers in the future.
Keywords: Electrochemical aptasensor; Thrombin; Exonuclease III; Double-stranded DNA-templated copper nanoparticles; Signal amplification;

Display OmittedIn present study, a convenient, sensitive and environmentally friendly method for the determination of five benzoylurea insecticides (BUs) in water and juice samples was developed. To extract trace benzoylurea insecticides effectively, poly(methacrylic acid-co-ethylene dimethacrylate) monolith was prepared and used as the sorbent of multiple monolithic fiber solid-phase microextraction (MMF-SPME). The influences of preparation conditions of monolith and extraction parameters of MMF-SPME on BUs were studied thoroughly. Under the optimized conditions, the combination of MMF-SPME with high performance liquid chromatography-diode array detection (MMF-SPME-HPLC-DAD) showed expected analytical performance for target analytes. The limits of detection (S/N = 3) of the developed method were 0.026–0.075 μg L−1 in water and 0.053–0.29 μg L−1 in juice samples. Good linearity was obtained for analytes with the correlation coefficients (R 2) above 0.99. Satisfactory repeatability and reproducibility was achieved, with relative standard deviations (RSD) of both less than 10%. Finally, the established MMF-SPME-HPLC-DAD method was successfully applied for the determination of BUs residues in juice and environmental water samples. Recoveries obtained for the determination of BUs in spiking samples ranged from 65.1% to 118%, with RSD below 10% in all cases.
Keywords: Multiple monolithic fiber solid-phase microextraction (MMF-SPME); Monolith; Sorbent; Benzoylurea insecticide; High performance liquid chromatography;

Biogenic aldehyde determination by reactive paper spray ionization mass spectrometry by Soumabha Bag; P.I. Hendricks; J.C. Reynolds; R.G. Cooks (37-42).
Display OmittedIonization of aliphatic and aromatic aldehydes is improved by performing simultaneous chemical derivatization using 4-aminophenol to produce charged iminium ions during paper spray ionization. Accelerated reactions occur in the microdroplets generated during the paper spray ionization event for the tested aldehydes (formaldehyde, n-pentanaldehyde, n-nonanaldehyde, n-decanaldehyde, n-dodecanaldehyde, benzaldehyde, m-anisaldehyde, and p-hydroxybenzaldehyde). Tandem mass spectrometric analysis of the iminium ions using collision-induced dissociation demonstrated that straight chain aldehydes give a characteristic fragment at m/z 122 (shown to correspond to protonated 4-(methyleneamino)phenol), while the aromatic aldehyde iminium ions fragment to give a characteristic product ion at m/z 120. These features allow straightforward identification of linear and aromatic aldehydes. Quantitative analysis of n-nonaldehyde using a benchtop mass spectrometer demonstrated a linear response over 3 orders of magnitude from 2.5 ng to 5 μg of aldehyde loaded on the filter paper emitter. The limit of detection was determined to be 2.2 ng for this aldehyde. The method had a precision of 22%, relative standard deviation. The experiment was also implemented using a portable ion trap mass spectrometer.
Keywords: Ambient mass spectrometry; Reactive ionization; Chemical derivatization; Mannich reaction; In-situ analysis; Trace analysis; Amines;

Towards SERS based applications in food analytics: Lipophilic sensor layers for the detection of Sudan III in food matrices by Martin Jahn; Sophie Patze; Thomas Bocklitz; Karina Weber; Dana Cialla-May; Jürgen Popp (43-50).
Display OmittedFood safety is a topic of great importance for our society which places high demands on analytical methods. Surface enhanced Raman spectroscopy (SERS) meets the requirements for a rapid, sensitive and specific detection technique. The fact that metallic colloids, one of the most often used SERS substrates, are usually prepared in aqueous solution makes the detection of water-insoluble substances challenging. In this paper we present a SERS based approach for the detection of water-insoluble molecules by applying a hydrophobic surface modification onto the surface of enzymatic generated silver nanoparticles. By this approach the detection of the illegal water-insoluble food dyes, such as Sudan III in presence of riboflavin, as water-soluble competitor, is possible. Moreover, we demonstrate the usability of this kind of SERS substrates for determination of Sudan III out of spiked paprika extracts.
Keywords: Surface enhanced Raman spectroscopy; Sensor layers; Food safety; Sudan dye detection;

Potentiometric characteristic plots showing variation of membrane potential with the concentration of Cd2+ ions based on macrocyclic ionophore (M1) with different plasticizers.Display OmittedNovel 5-amino-1,3,4-thiadiazole-2-thiol unit based macrocyclic ionophore 5,11,17-trithia-1,3,7,9,13,15,19,20,21-nonaazatetracyclo[14.2.1.14,7.110,13]henicosa-4(20),10(21),16(19)-triene-6,12,18-trithione (M1), was synthesized and characterized. Preliminary studies on M1 have showed that it has more the affinity toward Cd2+ ion. Thus, the macrocyclic ionophore (M1) was used as electroactive material in the fabrication of PVC-membrane electrodes such as polymeric membrane electrode (PME), coated graphite electrode (CGE) and coated pyrolytic graphite electrode (CPGE) were prepared and its performance characteristic were compared with. The electroanalytical studies performed on PME, CGE and CPGE revealed that CPGE having membrane composition M1:PVC:1-CN:NaTPB in the ratio of 7:37:54:2 exhibits the best potentiometric characteristics in terms of detection limit of 7.58 × 10−9  mol L−1, Nernstian slope of 29.6 mV decade−1 of activity. The sensor was found to be independent of pH in the range 2.5–8.5. The sensor showed a fast response time of 10 s and could be used over a period of 4 months without any significant divergence in its potentiometric characteristics. The sensor has been employed for monitoring of the Cd2+ ion in real samples and also used as an indicator electrode in the potentiometric titration of Cd2+ ion with EDTA.
Keywords: Macrocycle; Single crystal X-ray diffraction; Coated pyrolytic graphite electrode; Cd(II) ion-selective sensor; Potentiometry;

Paper-based assay of antioxidant activity using analyte-mediated on-paper nucleation of gold nanoparticles as colorimetric probes by Tatiana G. Choleva; Foteini A. Kappi; Dimosthenis L. Giokas; Athanasios G. Vlessidis (61-69).
Display OmittedWith the increasing interest in the health benefits arising from the consumption of dietary products rich in antioxidants, there exists a clear demand for easy-to-use and cost-effective tests that can be used for the identification of the antioxidant power of food products. Paper-based analytical devices constitute a remarkable platform for such expedient and low-cost assays with minimal external resources but efforts in this direction are still scarce. In this work we introduce a new paper-based device in the form of a sensor patch that enables the determination of antioxidant activity through analyte-driven on-paper formation of gold nanoparticles. The principle of detection capitalizes, for the first time, on the on-paper nucleation of gold ions to its respective nanoparticles, upon reduction by antioxidant compounds present in an aqueous sample. The ensuing chromatic transitions, induced on the paper surface, are used as an optical “signature” of the antioxidant strength of the solution. The response of the paper-based sensor was evaluated against a large variety of antioxidant species and the respective dose response curves were constructed. On the basis of these data, the contribution of each species according to its chemical structure was elucidated. For the analysis of real samples, a concentration-dependent colorimetric response was established against Gallic acid equivalents over a linear range of 10 μM–1.0 mM, with detection limits at the low and ultra-low μM levels (i.e. <1.0 μM) and satisfactory precision (RSD = 3.6–12.6%). The sensor has been tested for the assessment of antioxidant activity in real samples (teas and wines) and the results correlated well with commonly used antioxidant detection methods. Importantly, the sensor performed favorably for long periods of time when stored at moisture-free and low temperature conditions without losing its activity thus posing as an attractive alternative to the assessment of antioxidant activity without specialized equipment. The use of the sensor by non-experts for a rapid assessment of natural products in field testing is envisioned. Importantly, we demonstrate for the first time that analyte-mediated growth of nanomaterials directly on the paper surface could open new opportunities in paper-based analytical devices.
Keywords: Paper-based sensor; Gold nanoparticles; Antioxidant activity; Instrumental-free detection;

Display OmittedIn this work, a dual-signaling electrochemical aptasensor based on exonuclease-catalyzed target recycling was developed for thrombin detection. The proposed aptasensor coupled “signal-on” and “signal-off” strategies. As to the construction of the aptasensor, ferrocene (Fc) labeled thrombin binding aptamer (TBA) could perfectly hybridize with the methylene blue (MB) modified thiolated capture DNA to form double-stranded structure, hence emerged two different electrochemical signals. In the presence of thrombin, TBA could form a G-quadruplex structure with thrombin, leading to the dissociation of TBA from the duplex DNA and capture DNA formed hairpin structure. Exonuclease could selectively digest single-stranded TBA in G-quadruplex structure and released thrombin to realize target recycling. As a consequence, the electrochemical signal of MB enhanced significantly, which realized “signal on” strategy, meanwhile, the deoxidization peak current of Fc decreased distinctly, which realized “signal off” strategy. The employment of exonuclease and superposition of two signals significantly improved the sensitivity of the aptasensor. In this way, an aptasensor with high sensitivity, good stability and selectivity for quantitative detection of thrombin was constructed, which exhibited a good linear range from 5 pM to 50 nM with a detection limit of 0.9 pM (defined as S/N = 3). In addition, this design strategy could be applied to the detection of other proteins and small molecules.
Keywords: Electrochemical aptasensor; Dual-signaling; Exonuclease; Target recycling; Thrombin;

Ultrasensitive electrochemical detection for thrombin using hybridization chain reaction with enzyme-amplification by Weiling Song; Xuxu Xie; Wenbo Sun; Ningbo Zhang; Chunxiang Li (77-82).
Display OmittedIn this work, a new electrochemical aptasensor using hybridization chain reaction (HCR) for signal amplification was developed for highly sensitive detection of thrombin. The sandwich system of aptamer/thrombin/aptamer–primer complex was fabricated as the sensing platform. As the initiator strands, aptamer–primer complex could propagate a chain reaction of hybridization events between the two hairpin probes, and whether long nicked DNA polymers could be formed on the modified electrode. Then the biotin-labeled dsDNA polymers could introduce numerous avidin-labeled horseradish peroxidase (HRP), resulting in significantly amplified electrochemical signal through the electrocatalysis of HRP. On the basis of the enzymatic oxidization of Fe2+ by H2O2 to yield Fe3+, the imaging of thrombin was detected by the reduction current of Fe3+ with the scanning electrochemical microscopic tip. The electrochemical signals had a good linear with logarithm of thrombin concentration in the range from 1.0 fM to 100 fM, reaching a detection limit of thrombin as low as 0.04 fM. In addition, the proposed strategy exhibited excellent specificity and was successfully applied in real sample assay which demonstrated the potential application in clinical diagnostics.
Keywords: Aptasensor; Thrombin; Hybridization chain reaction; Topographic imaging;

Display OmittedThe combination of high selectivity of aptamer with the peroxidase-mimicking property of DNAzyme has presented considerable opportunities for designing colorimetric aptasensor for detection of ochratoxin A (OTA). The activities of both aptamer (as biorecognition element) and DNAzyme (as signal amplification element) are blocked via base pairing in the hairpin structure. Hybridization chain reaction (HCR) between two hairpin DNAs was employed to further improve the sensitivity of this method. The presence of OTA triggers the opening of the hairpin structure and the beginning of HCR, which results in the release of many DNAzyme, and generates enhanced colorimetric signals, which is correlated to the amounts of OTA with linear range between 0.01 to 0.32 nM, and the limit of detection is 0.01 nM under optimal conditions. OTA in yellow rice wine and wheat flour samples was also detected using this method. We demonstrate that a new colorimetric method for the detection of OTA has been established, which is simple, easy to conduct, label-free, sensitive, high throughput, and cost-saving.
Keywords: Ochratoxin A; Hybridization chain reaction; Aptamer; Colorimetric method;