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Reviewing the mode of interaction between this kind of active pharmaceutical ingredients and DNA has received much more attention in current years. Anthracycline drugs such as Epirubicin are frequently used in cancer treatment for breast cancer treatment. In the present study, the Epirubicin -calf thymus DNA interaction was investigated by using spectroscopic, fluorimetric and molecular docking methods. Water-soluble quantum dots (QDs) with nanometric particle size fabricated and characterized by transmission electron microscope and photon correlation spectroscopy. The binding constant value and the free energy change for this interaction were obtained to be 3.00×106 M-1 and -42.26 kJ mol-1, using the spectroscopic method and docking investigations, respectively. Additionally, fluorescent thioglycolic acid-capped CdTe QDs were used for investigation of EPI and DNA interaction. Epirubicin as a quencher quenched the fluorescence of CdTe QDs after electrostatic adsorption on the surface of QDs. With the addition of DNA, EPI will be desorbed from the surface of CdTe QDs, inserted into the DNA. Subsequently, fluorescence changes of QDs were used for calculation of binding constant value, which was in good agreement with that obtained by the spectroscopic method. By the comparison of the achieved results, the intercalation mode of interaction between Epirubicin and DNA proved.

This review (with 340 refs) focuses on methods for specific and sensitive detection of metabolites for diagnostic purposes, with particular emphasis on electrochemical nanomaterial-based sensors. It also covers novel candidate metabolites as potential biomarkers for diseases such as neurodegenerative diseases, autism spectrum disorder and hepatitis. Following an introduction into the field of metabolic biomarkers, a first major section classifies electrochemical biosensors according to the bioreceptor type (enzymatic, immuno, apta and peptide based sensors). A next section covers applications of nanomaterials in electrochemical biosensing (with subsections on the classification of nanomaterials, electrochemical approaches for signal generation and amplification using nanomaterials, and on nanomaterials as tags). A next large sections treats candidate metabolic biomarkers for diagnosis of diseases (in the context with metabolomics), with subsections on biomarkers for neurodegenerative diseases, autism spectrum disorder and hepatitis. The Conclusion addresses current challenges and future perspectives. Graphical abstract This review focuses on the recent developments in electrochemical biosensors based on the use of nanomaterials for the detection of metabolic biomarkers. It covers the critical metabolites for some diseases such as neurodegenerative diseases, autism spectrum disorder and hepatitis.

In this study, a novel electrochemical sensor for the determination of methanol based on palladium nanoparticles supported on Santa barbara amorphous-15- PrNHEtNH 2 (PdNPs@SBA-15-PrEn) as nanocatalysis platform is presented. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and electrochemical methods are employed to characterize the PdNPs@SBA-15-PrEn nanocomposite. The Nafion-Pd@SBA-15-PrEn modified glassy carbon electrode (Nafion-PdNPs@SBA-15-PrEn/GCE) displayed the high electrochemical activity and excellent catalytic characteristic for electro-oxidation of methanol in an alkaline solution. The electro-oxidation performance of the proposed sensor was investigated using cyclic voltammetry (CV) and amperometry. The sensor exhibits a good sensitivity of 0.0905 Amol -1 Lcm -2 , linear range of 20-1000 μM and the corresponding detection limit of 12 μM (3σ). The results demonstrate that the Nafion-PdNPs@SBA-15-PrEn/GCE has potential as an efficient and integrated sensor for methanol detection., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The sensitive quantification of Human Epidermal growth factor Receptor 2 (HER2), as a key prognostic tumor marker, plays a critical role in screening, early diagnosis and management of breast cancer. This paper describes a sandwich-type immunoassay with silver signal enhancement strategy for highly sensitive detection of HER2. For this purpose, the target capturing step was designed by functionalization of 3-aminopropyltrimethoxysilane coated magnetite nanoparticles with antibody (antiHER2/APTMS-Fe 3 O 4 ), as a platform bioconjugate (PB), and immobilized at a bare GCE. Then, in the presence of label-free immunosensor, the PB was covered by magnetic gold nanoparticles self-assembled with thiolated antibodies (antiHER2/Hyd@AuNPs-APTMS-Fe 3 O 4 ) containing chemically reduced silver ions, as a label bioconjugate (LB). Under optimum conditions, a linear relationship between the differential pulse voltammetric (DPV) stripping signal of silver and the logarithm of HER2 concentrations was obtained in the range of 5.0 × 10 -4 -50.0ngmL -1 (R 2 = 0.9906) with a detection limit of 2.0 × 10 -5 ngmL -1 . The effectiveness of this protocol was evaluated experimentally through employing of designed immunosensor for detection of the serum level of tumor marker. The good consistency of the results with those obtained by the enzyme-linked immunosorbent assay (ELISA) conventional method (p-value of < 0.05) showed that this immunosensor can be applied for the testing of HER2 in clinical samples of breast cancer patients., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The balance between water-metal interactions and water-water hydrogen bonding (HBs) controls the process of water adsorption on metallic surfaces. In other hand, the yield of oxygen evolution reaction (OER) is dependent on the binding energy of H 2 O at electrode surface. Therefore, on a specific metal substrate, attenuation of HBs may be a promising route for improving OER. In this study, the computational and experimental evidences indicate that the performance of ultrasonically irradiated deionized water (USI-DW), participated in water oxidation reaction (WOR), is different from its in the intact bulk water. To date, establishing of new electrocatalysts with lower overpotentials (η) and higher current densities (J) in OER have been mostly considered based on metals and oxide materials. Here, we ultrasonically agitated the water clusters formed by strong HBs, and as a sustainable improvement route explored its particular effects on the efficiency of OER. The molecular modeling (MM) of the (H 2 O) n clusters (n = 1-100 molecules), the corresponding IR spectra, the molecular orbitals energy levels and the adsorption of free and cluster confined H 2 O molecules on the Pt surface were studied by the appropriate quantum mechanical (QM) methods. The result of deconvolution of FTIR spectra recorded for USI-DW in the -OH stretching region (∼2600-3900 cm -1 ) properly confirmed the expected increase of the single water molecules. The reduction in overpotentials was 82 ± 8 mV and 158 ± 12 mV, to reach the J of 1 mA cm -1 at the typical pHs 12.2 and 13.1, respectively., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Nucleolin is a multifunctional protein that is markedly overexpressed on the surface of most cancer cells. By taking advantage of the high affinity and specificity of the AS1411 aptamer for nucleolin, a signalling probe displacement electrochemical aptasensor was developed. The thiolated AS1411 aptamer was conjugated to hydroxyapatite nanorods (HApNRs) decorated with gold nanoparticles (AuNPs). To further increase the electrical conductivity of the interface, the ionic liquid 1-ethyl-3-methylimidazolium alanine with its high ion conductivity was placed on the electrode surface. Then, the aptamer was immobilized on the modified electrode and conjugated to signalling c-DNA tagged with AgNPs (c-DNA@AgNPs). In the presence of the MCF7 target cells, the signalling probe is displaced and released from the electrode surface. This leads to a decrease in the current that is proportional to the concentration of cancer cells in the range from 10 to 10 6 cells mL -1 , with a detection limit as low as 8 ± 2 cells mL -1 (n = 3) (based as 3σ/m, where σ is the standard deviation of the blank and m is the slope of the calibration plot). This method presents a promising tool for highly sensitive and selective detection of surface nucleolin on MCF7 cancer cells. Graphical abstract HApNR-AuNP-AS1411 aptamer nanocomposite as an electrochemical sensing interface was immobilized on the gold electrode surface and conjugated to signaling c-DNA tagged with AgNPs for determination of surface nucleolin on MCF7 cancer cells.

The main advances in control and early diagnosis of cancer is greatly aided by low level detection of tumor markers in biological samples. Extensive efforts have been devoted to developing some ultrasensitive electrochemical biosensors for detection of cancer markers with high selectivity. These efforts include the development of the bioreceptors with high specificity and affinity, synthesis of novel signal amplifiers based on nanomaterials and the exploration of appropriate design strategies. Electrochemical measurement protocols are suitable for mass fabrication of miniaturized devices. They have a major role in the move towards rapid and simplified testing for point-of-care usage. This review discusses the remarkable advances of the last 6 years in the electrochemical affinity biosensors for determination of protein and glycoprotein tumor markers, with a particular focus on antibodies and aptamers as biorecognition probes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The authors describe an electrochemical method for aptamer-based determination of insulin at femtomolar concentrations. The surface of a screen printed electrode was modified with ordered mesoporous carbon that was chemically modified with 1,3,6,8-pyrenetetrasulfonate (TPS). The amino-terminated aptamer was then covalently linked to TPS via reactive sulfonyl chloride groups. Subsequently, the redox probe Methylene Blue (MB) was interacted into the aptamer. The MB-modified binds to insulin and this results in the release of MB and a decreased signal as obtained by differential pulse voltammetry, best at a working voltage of -0.3 V (versus silver pseudo-reference electrode). Insulin can be quantified by this method in the 1.0 fM to 10.0 pM concentration range, with a 0.18 fM limit of detection (at 3σ/slope). The assay was applied to the determination of insulin in spiked human serum samples. The method is highly sensitive, selective, stable, and has a wide analytical range. Graphical abstract The surface of a screen printed electrode was modified with ordered mesoporous carbon-1,3,6,8-pyrenetetrasulfonate. The amino-terminated aptamer was then linked to the 1,3,6,8-pyrenetetrasulfonate. Then, the Methylene Blue was interacted into the aptamer. The modified electrode was applied to the determination of insulin.

Herein, for the first time a visible-light-driven photoelectrochemical (PEC) aptasensor for shrimp tropomyosin determination was fabricated by using graphitic carbon nitride (g-C 3 N 4 ) and titanium dioxide (TiO 2 ) as photoactive nanomaterials, ascorbic acid (AA) as electron donor and ruthenium (III) hexaammine (Ru(NH 3 ) 6 3+ ) as signal enhancer. The surface of an ITO electrode was first modified with g-C 3 N 4 , TiO 2 , and polyethyleneimine (PEI) and then the amine terminal aptamer TROP probe was attached to PEI by the use of glutaraldehyde (GA) as cross-linker. After that, Ru(NH 3 ) 6 3+ was adsorbed on aptamer to enhance the photocurrent signal. The principle of proposed PEC aptasensor is based on the formation of a selective complex between tropomyosin and immobilized aptamer TROP probe on the surface of ITO/g-C 3 N 4 -TiO 2 /PEI/aptamer TROP -Ru(NH3) 6 +3 . After the incubation of tropomyosin with TROP aptamer probe, the photocurrent signal decreased due to releasing adsorbed Ru(NH 3 ) 6 3+ on aptamer and preventing AA from scavenging photogenerated holes to the photoactive modified electrode. Under the optimized conditions, the fabricated PEC aptasensor was used for the determination of shrimp tropomyosin in the concentration range of 1-400ngmL -1 with a limit of detection of 0.23ngmL -1 . The proposed PEC aptasensor exhibited high selectivity, sensitivity, and good stability., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Recent developments in biotechnology offer the new methods for the sensitive detection of heavy metals based on the affinity and specificity of aptamers, as nucleic acid ligands selected from random sequence pools in vitro. Heavy metals have received considerable importance as the most toxic metallic pollutants which may cause serious environmental damages. They are classified as trace elements because of their presence in trace concentrations in various environmental matrices. Thus, the precise and sensitive methods to detect heavy metals are important to ensure human and environment safety. Aptamers as the biological probes, show high binding affinity which can often be directly translated into high detection sensitivity. On the other hand, high selectivity and stability make them possible to detect a wide range of targets, especially metallic ions. This review provides current progress of aptamers for environmental and biological monitoring of heavy metals using the nanomaterials mainly in two groups: (i) aptamer based biosensors (aptasensors) and (ii) aptamer based biosorbents (aptasorbents). The introduction of nanomaterials can efficiently increase the immobilization quantity of aptamers. Furthermore, they play an important role in the orientation and assembly density controlling of aptamers for the optimized recognition ability., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In this research, we demonstrated a flow injection amperometric sandwich-type aptasensor for the determination of human leukemic lymphoblasts (CCRF-CEM) based on poly(3,4-ethylenedioxythiophene) decorated with gold nanoparticles (PEDOT-Au nano ) as a nano platform to immobilize thiolated sgc8c aptamer and multiwall carbon nanotubes decorated with palladium nanoparticles/3,4,9,10-perylene tetracarboxylic acid (MWCNTs-Pd nano /PTCA) to fabricate catalytic labeled aptamer. In the proposed sensing strategy, the CCRF-CEM cancer cells were sandwiched between immobilized sgc8c aptamer on PEDOT-Au nano modified surface electrode and catalytic labeled sgc8c aptamer (MWCNTs-Pd nano /PTCA/aptamer). After that, the concentration of CCRF-CEM cancer cells was determined in presence of 0.1 mM hydrogen peroxide (H 2 O 2 ) as an electroactive component. The attached MWCNTs-Pd nano nanocomposites to CCRF-CEM cancer cells amplified the electrocatalytic reduction of H 2 O 2 and improved the sensitivity of the sensor to CCRF-CEM cancer cells. The MWCNT-Pd nano nanocomposite was characterized with transmission electron microscopy (TEM) and energy dispersive X-ray (EDX). The electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to confirm the stepwise changes in the electrochemical surface properties of the electrode. The proposed sandwich-type electrochemical aptasensor exhibited an excellent analytical performance for the detection of CCRF-CEM cancer cells ranging from 1.0 × 10 1 to 5.0 × 10 5  cells mL -1 . The limit of detection was 8 cells mL -1 . The proposed aptasensor showed high selectivity toward CCRF-CEM cancer cells. The proposed aptasensor was also applied to the determination of CCRF-CEM cancer cells in human serum samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The exploration of novel adsorption properties of conductive polymers based on hybridization with biocompatible nanomaterials receives an increasing interest. In this regard, hydroxyapatite (HA) bioceramic is of critical importance mainly owing to its facile synthesis, high surface area, economic and low toxicity in biological environments. In this work, we first prepared and characterized a magnetite/hydroxyapatite (Fe 3 O 4 /HA) nanocomposite using the bio-waste chicken eggshell via an attractive green way that involved low cost and irrespective of toxicity. Then, polythionine as a novel class of conductive polymers was in situ coated on the synthesized magnetic bioceramic for the separation and preconcentration of riboflavin (vitamin B 2 ) in human plasma before its fluorimetric determination. Considering the putative role of riboflavin in protecting against cancer and cardiovascular diseases, it is essential to evaluate this vitamin in biological fluids. The described method possesses a linear range of 0.75-262.5μgL -1 (R 2 =0.9985) and a detection limit of 0.20μgL -1 (signal-to-noise ratio of 3). The relative standard deviations (RSDs) for single-sorbent repeatability and sorbent-to-sorbent reproducibility were less than 4.0% and 7.6% (n=5), respectively. The respective enrichment factor and extraction recovery of the method found to be 35.7 and 98.4%. The analytical performance of method for riboflavin was characterized by good consistency of the results with those obtained by the enzyme-linked immunosorbent assay (ELISA) conventional method (p-value of <0.05). The optimized protocol intended for control determinations of riboflavin in human subjects and is addressed to clinical laboratories., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Lead (Pb) as a topically poisonous metal represents a serious threat to the ecological environment and especially to human beings. Therefore, it is urgent to develop a rapid and reliable monitoring technique for this heavy metal in the environmental samples. In the present study, we have designed a selective and sensitive method for the determination of ultratrace contents of Pb 2+ in biological samples, based on the guanine (G)-quadruplex formed by the aptamer with hairpin structure and Pb 2+ . For this purpose, Pb 2+ specific aptamer serving as affinity probe to capture and separate trace amounts of the analyte, was covalently linked to Fe 3 O 4 /graphene oxide (GO) surface by using a suitable cross-linking agent. Then, the G-quadruplex complex was formed by the opening of the "neck- ring" of the hairpin structure of aptamer in the presence of Pb 2+ . Inductively coupled plasma mass spectrometry (ICP-MS) was used for determination of Pb 2+ in biological matrices. The analysis conditions were optimized and the performance of the proposed method was investigated. Under optimum conditions, the calibration curve was linear over the range of 0.3-867.5μgL -1 and an enrichment factor (EF) of 50 was obtained. The limit of detection (LOD) was 0.05μgL -1 and the relative standard deviation (RSD) for single-sorbent repeatability and sorbent-to-sorbent reproducibility were <4.7% and 8.8% (n=5), respectively. The accuracy of aptamer-based affinity purification method was confirmed by the analysis of quality control materials (QCMs, Seronorm™ Blood REF NO 201505 and Urine REF NO 2525)., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Two chiral stationary phases (CSPs) based on crystalline degradation products (CDPs) of vancomycin by using different synthetic methods were prepared and compared. Crystalline degradation products of vancomycin were produced by hydrolytic loss of ammonia from vancomycin molecules. Performances of two chiral columns prepared with these degradation products were investigated using several acidic and basic drugs as model analytes. Retention and resolution of these analytes on the prepared columns, as two main parameters, in enantioseparation were studied. The results demonstrated that the stationary phase preparation procedure has a significant effect on the column performance. The resolving powers of prepared columns for enantiomers resolution were changed with the variation in vancomycin-CDP coverage on the silica support. Elemental analysis was used to monitor the surface coverage of silica support by vancomycin-CDP. The results showed that both columns can be successfully applied to chiral separation studies.

The synthesis of a novel nanocomposite comprised of SiO 2 -coated magnetic graphene oxide modified with a pyrrole-thiophene (mGO/SiO 2 @coPPy-Th) copolymer is reported in the present work. The nanocomposite was applied for the fast magnetic solid phase extraction (MSPE) of trace levels of copper, lead, chromium, zinc and cadmium from water and agricultural samples. The nanocomposite was prepared in three steps: (1) decoration of graphene oxide sheets with magnetite nanoparticles thorough a facile one-step chemical reaction strategy; (2) chemical grafting by a silica layer to obtain high stability in acidic solutions; and (3) surface modification by coPPy-Th via simultaneous oxidation polymerization of pyrrole and thiophene in the presence of mGO/SiO 2 composite. The nanocomposite was subsequently characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD) and vibrating sample magnetometry (VSM) techniques. Several important experimental variables that could affect MSPE performance, including the pH of the sample, sorption time, sorbent dosage, eluent type and its concentration, eluent volume and elution time, were investigated and optimized. Under optimal conditions, the limits of detection for the target heavy metals ranged from 0.15 to 0.65μgL -1 . The maximum sorption capacity of the mGO/SiO 2 @coPPy-Th nanocomposite was 201, 230, 125, 98 and 80mgg -1 for Cu(II), Pb(II), Zn(II), Cr(III) and Cd(II), respectively. Finally, the feasibility of the proposed method was investigated for the extraction and determination of the target metals from real matrices., (Copyright © 2017 Elsevier B.V. All rights reserved.)

In the present study, we developed a sensitive method based on fluorescence resonance energy transfer (FRET) for the determination of the BCR/ABL fusion gene, which is used as a biomarker to confirm the clinical diagnosis of both chronic myelogenous leukemia (CML) and acute lymphocytic leukemia (ALL). For this purpose, CdTe quantum dots (QDs) were conjugated to amino-modified 18-mer oligonucleotide ((N)DNA) to form the QDs-(N)DNA nanosensor. In the presence of methylene blue (MB) as an intercalator, the hybridization of QDs-(N)DNA with the target BCR/ABL fusion gene (complementary DNA), brings the MB (acceptor) at close proximity of the QDs (donor), leading to FRET upon photoexcitation of the QDs. The enhancement in the emission intensity of MB was used to follow up the hybridization, which was linearly proportional to concentration of the target complementary DNA in a range from 1.0 × 10 -9 to 1.25 × 10 -7  M. The detection limit of the proposed method was obtained to be 1.5 × 10 -10  M. Finally, the feasibility and selectivity of the proposed nanosensor was evaluated by the analysis of derived nucleotides from both mismatched sequences and clinical samples of patients with leukemia as real samples., (Copyright © 2017 Elsevier B.V. All rights reserved.)

It is well known that cytochrome c (Cyt c) is a crucial death regulator that triggers programmed cell death, apoptosis. Here, we report on the successful application of an aptamer bioconjugated nanoclusters for the detection of apoptosis based on release of cytochrome c from mitochondria in lysates human embryonic kidney cells HEK293T. The aptamer-conjugated silver nanoclusters (Apt@AgNCs) were synthesized and immobilized on gold electrode for impedimetric detection of Cyt c over the range of 0.15-375nM. It was found that the presence of Ag(I) ions shell at the surface of prepared NCs could increase their affinity to the donor groups (COO - and some amine groups in its deprotonated form, NH 2 ) of cysteine attached on the gold electrode surface. The use of NCs, which play the role of conductive holders, established a simple immobilization procedure based on a low cost non-functionalized DNA sequence. To diminish the probable nonspecific impedance changes and decrease time of measurement, a rapid single frequency measurements (SFM) was assessed based on recording total impedance |Z| in different individual frequencies., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A very sensitive and convenient nanobiosensor based on fluorescence resonance energy transfer (FRET) was developed for the detection of a 22-mer oligonucleotides sequence in Human Papillomavirus 18 virus (HPV18) gene. For this purpose, water-soluble CdTe quantum dots (QDs) were synthesized and, subsequently, amino-modified 11-mer oligonucleotide as one of the two necessary probes was attached to QDs surface to form functional QDs-DNA conjugates. Right after addition of the QDs-DNA and a second Cyanine5 (Cy5)-labeled 11-mer oligonucleotide probe to the DNA target solution, the sandwiched hybrids were formed. The resulting hybridization brings the Cy5 fluorophore as the acceptor to close proximity of the QDs as donor, so that an effective transfer of energy from the excited QDs to the Cy5 probe would occur via FRET processing. The fluorescence intensity of Cy5 found to linearly enhance by increasing the DNA target concentration from 1.0 to 50.0nM, with a detection limit of 0.2nM. This homogeneous DNA detection method does not require excessive washing and separation steps of un-hybridized DNA, due to the fact that no FRET can be observed when the probes are not ligated. Finally, feasibility and selectivity of the proposed one-spot DNA detection nanobiosensor were investigated by analysis of derived nucleotides from HPV18 and mismatched sequences., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A "signal off" voltammetric aptasensor was developed for the sensitive and selective detection of ultra-low levels of adenosine triphosphate (ATP). For this purpose, a new strategy based on the principle of recognition-induced switching of aptamers from DNA/DNA duplex to DNA/target complex was designed using thioglycolic acid (TGA)-capped CdTe quantum dots (QDs) as the signal amplifying nano-platforms. Owing to the small size, high surface-to-volume ratio and good conductivity, quantum dots were immobilized on the electrode surface for signal amplification. In this work, methylene blue (MB) adsorbed to DNA was used as a sensitive redox reporter. The intensity of voltammetric signal of MB was found to decrease linearly upon ATP addition over a concentration range of 0.1nM to 1.6μM with a correlation coefficient of 0.9924. Under optimized conditions, the aptasensor was able to selectively detect ATP with a limit of detection of 45pM at 3σ. The results also demonstrated that the QDs-based amplification strategy could be feasible for ATP assay and presented a potential universal method for other small biomolecular aptasensors., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A new method for the selective extraction of p-aminosalicylic acid from aqueous and urine samples has been developed using magnetic molecularly imprinted polymer nanoparticles before determination by high-performance liquid chromatography. The Fe 3 O 4 nanoparticles were first prepared through the chemical coprecipitation of Fe 2+ and Fe 3+ and then coated with a vinyl shell. Subsequently, a layer of molecularly imprinted polymers was grafted onto the vinyl-modified magnetic nanoparticles by precipitation polymerization. FTIR spectroscopy, scanning electron microscopy, vibrating sample magnetometry, and thermogravimetric analysis were applied to characterize the sorbent properties. Moreover, the predominant parameters affecting the magnetic solid phase extraction such as sample pH, sorption and elution times, the amount of sorbent, and composition and volume of eluent were investigated thoroughly. The maximum sorption capacity of the imprinted polymer toward p-aminosalicylic acid was 70.9 mg/g, which is 4.5 times higher than that of the magnetic nonimprinted polymer. The magnetic molecularly imprinted polymer nanoparticles were applied for the selective extraction of p-aminosalicylic acid from aqueous and urine samples and satisfactory results were achieved. The results illustrate that magnetic molecularly imprinted polymer nanoparticles have a great potential in the extraction of p-aminosalicylic acid from environmental and biological matrices., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A liquid-phase microextraction based on application of supramolecular solvent as a carrier for ferrofluid has been developed for the extraction and determination of three organophosphorus pesticides (OPPs). The ferrofluid was produced from combination of oleic acid coated magnetic particles and supramolecular solvent as the extractant solvent. Ferrofluid can be attracted by a magnet, and no centrifugation step was needed for phase separation. A response surface methodology (RSM) based on central composite design (CCD) was used for efficient optimization of the main variables in the extraction procedure. Under the optimum experimental conditions, the calibration curves found to be linear in the range of 0.5-400µgL(-1) with correlation coefficients ranging from 0.9967 to 0.9984. The intra-day and inter-day precision (RSD %) for 100 and 200µgL(-1) of each pesticides were in the range of 2.0-5.3% and 2.6-5.7%, respectively. The limit of detection (S/N=3), ranged from 0.1 to 0.35μgL(-1). The proposed method was successfully applied to the extraction and determination of organophosphorus pesticide residues in water and fruit juice samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Electrospinning technique was used to convert polydimethyl siloxane (PDMS) sol-gel solution to a new nanostructure on a stainless steel wire. The surface morphology of the fiber was observed by scanning electron microscopy (SEM). It showed a diameter range of 30-60nm for PDMS nanoparticles with a homogeneous and porous surface structure. The applicability of this coating was assessed for the headspace SPME (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water samples followed by gas chromatography-mass spectrometry. The important parameters affecting extraction efficiency such as extraction time and temperature, desorption conditions, agitation rate and ionic strength were investigated and optimized. Under the optimized conditions, LODs and LOQs of 0.3-5μgL(-1) and 1-10μgL(-1) were obtained, respectively. The method showed linearity in the broad range of 1-5000μgL(-1) with correlation coefficient of >0.99. Inter-day and intra-day precisions of the developed method ranged from 2.43% to 6.54% and from 5.24% to 13.73%, respectively. The thermal stability of the fiber was investigated on stainless steel wire. It was found to be durable at 260°C for more than 360min. Furthermore, the proposed method was successfully applied for quantification of BTEX in real water samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A pH-responsive drug carrier based on chitosan coated iron oxide nanoparticles (CS-Fe3O4) for prolonged antibiotic release in a controlled manner is reported. As an antibiotic drug model, ciprofloxacin was loaded onto the nanocarrier via H-bonding interactions. The nanoparticles were characterized using scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, photon correlation spectroscopy and Fourier transform infrared spectroscopy. The particle size of CS-Fe3O4 nanoparticles were found to lie in the range of 30-80nm. The analytical characteristics of the designed system were thoroughly investigated. The in vitro drug loading at pH 4.8 and release kinetics at pH 7.4 studies revealed that the drug delivery system can take 99% of ciprofloxacin load and quantitatively release the drug over a sustained period of 5 days. The release kinetics study indicated that the system follows a zero order kinetics via a diffusion-controlled mechanism. These results indicated that CS-Fe3O4 nanoparticles have the potential for use as controlled antibiotic delivery systems through oral administration by avoiding the drug release in the highly acidic gastric fluid region of the stomach. Furthermore, the ability of low-frequency ultrasound in fast release of the encapsulated drug in less than 60min from the CS-Fe3O4 nanoparticles in a controlled manner was confirmed., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this study, preparation of novel pH-sensitive N-doped carbon dots (NCDs) using glucose and urea is reported. The prepared NCDs present strong excitation-dependent fluorescence changes towards the pH that is a new behavior from these nanomaterials. By taking advantage of this unique behavior, two separated ratiometric pH sensors using emission spectra of the NCDs for both acidic (pH 2.0 to 8.0) and basic (pH 7.0 to 14.0) ranges of pH are constructed. Additionally, by considering the entire Excitation-Emission Matrix (EEM) of NCDs as analytical signal and using a suitable multivariate calibration method, a broad range of pH from 2.0 to 14.0 was well calibrated. The multivariate calibration method was independent from the concentration of NCDs and resulted in a very low average prediction error of 0.067 pH units. No changes in the predicted pH under UV irradiation (for 3 h) and at high ionic strength (up to 2 M NaCl) indicated the high stability of this pH nanosensor. The practicality of this pH nanosensor for pH determination in real water samples was validated with good accuracy and repeatability., (Copyright © 2016 Elsevier B.V. All rights reserved.)

In this work, an effective preconcentration method for the extraction and determination of traces of multi-residue pesticides was developed using solid-phase extraction (SPE) coupled with dispersive liquid-liquid microextraction and gas chromatography-mass spectrometry (GC-MS). Variables affecting the performance of both extraction steps such as type and volume of elution and extraction solvents, breakthrough volume, salt addition, extraction time were thoroughly investigated. The proposed method resulted in good linearities (R(2)>0.9915) over the ranges of 1-10,000ngkg(-1), limits of detection (LODs) in the range of 0.5-1.0ngkg(-1) at S/N=3, and precision of RSD% of ⩽11.8. Under optimal conditions, the preconcentration factors were obtained in the range of 2362-10,593 for 100mL sample solutions. Comparison of the proposed method with other ones demonstrated that SPE-DLLME method provides higher extraction efficiency and larger preconcentration factor for determination of pesticides residues. Further, it is simple, inexpensive, highly sensitive, and can be successfully applied to separation, preconcentration and determination of the pesticides (and other noxious materials) in different real food samples., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A new ratiometric fluorescent sensor was developed for the sensitive and selective detection of cyanide ion (CN(-)) in aqueous media. The ratiometric sensing system is based on CN(-) modulated recovery of copper(II) phthalocyanine (Cu(PcTs)) fluorescence signal at the expense of diminished fluorescence intensity of gold nanoclusters (AuNCs). Preliminary experiments revealed that the AuNCs and Cu(PcTs) possess a turn-off effect on each other, the interaction of which being verified through studying their interactions by principle component analysis (PCA) and multivariate cure resolution-alternating least-squares (MCR-ALS) methods. In the presence of CN(-) anion, the AuNCs and Cu(PcTs) interaction was perturbed, so that the fluorescence of Cu (PcTs), already quenched by AuNCs, was found to be efficiently recovered, while the fluorescence intensity of AuNCs was quenched via the formation of a stable [Au(CN)2](-) species. The ratiometric variation of AuNCs and Cu(PcTs) fluorescence intensities leads to designing a highly sensitive probe for CN(-) ion detection. Under the optimal conditions, CN(-) anion was detected without needing any etching time, over the concentration range of 100 nM-220 μM, with a detection limit of 75 nM, which is much lower than the allowable level of CN(-) in water permitted by the World Health Organization (WHO). Moreover, the detection of CN(-) was developed based on the CN(-) effects on the blue and red florescent colors of Cu(PcTs) and AuNCs, respectively. The designed probe displays a continuous color change from red to blue by addition of CN(-), which can be clearly observed by the naked eye in the range of 7-350 μM, under UV lamp. The prepared AuNCs/Cu(PcTs) probe was successfully utilized for the selective and sensitive determination of CN(-) anion in two different types of natural water (Rodbal dam and rainwater) and also in blood serum as a biological sample.

Delocalized electrons are free to move throughout a graphite sheet. Based on the interruption of this flux, a new strategy has been developed to establish a highly sensitive impedimetric sensing device for K(+) ions. Here, we report on the successful application of a simple graphite paste incorporated into dibenzo-18-crown-6 (DB18C6), which effectively impedes the electron flux on the graphite sheet. Most importantly, this interruption can be selectively obviated in the presence of potassium ion. Our quantum mechanics-density functional theory (QM-DFT) calculations revealed that, among the possible surface-configurations of the ligand on the graphite surface, the "distorted concave" form is a more energy-favorable configuration and existed in a higher probability. This form is capable of impeding the passage of delocalized electrons over the graphite sheets. From modeling of the detecting processes, the surface configuration of DB18C6 in treating with K(+) was intensely changed to "convex", which facilitates the passage of electrons along the graphite sheet. Optimizations of the structures of DB18C6 and its 1 : 1 and 2 : 1 complexes with potassium ion were also performed using QM-DFT calculations. On the other hand, the modeling of the graphene sheet was performed using the molecular mechanics MMFF94 method, which was used to model the detecting process. The proposed sensor was found to quantify the potassium ion by faradaic impedance spectroscopy in the range of 50 to 1500 pM with a detection limit of 35 pM.

An analytical method is reported for the preparation of K(+) -imprinted nanoparticles using cryptand 222 as the complexing agent, methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the crosslinker and 2,2'-azobisisobutyronitrile as the radical initiator. The prepared particles have a diameter of 200-250 nm. The maximum adsorption capacity of potassium ion-imprinted polymer particles was 120 μmol/g. The optimum pH for quantitative extraction was 9.0. The nature of the eluent, eluent concentration, adsorption and desorption times, weight of the polymer material, aqueous phase, and desorption volumes were also studied. The relative selectivity coefficients of K(+) /Li(+) , K(+) /Na(+) , K(+) /Rb(+) and K(+) /Cs(+) were 48.10, 4.80, 29.70, and 43.4, respectively. The relative standard deviation and limit of detection of the method were obtained 1.61% and 4.62 ng/L, respectively. Finally, the method was applied for the determination of potassium ions from different samples using flame photometry., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In the present paper, a new bisphosphoramidate derivative compound, 1, 4-bis(N-methyl)-benzene-bis(N-phenyl, N-benzoylphosphoramidate) (BMBPBP), was synthesized and used as a mediator for the electrocatalytic oxidation of olanzapine. The electro-oxidation of olanzapine at the surface of the BMBPBP/CdS-quantum dots/multi-walled carbon nanotubes (BMBPBP/CdS-QDs/MWCNTs) modified gold electrode was studied using cyclic voltammetry, chronoamperometry and electrochemical impedance spectroscopy. This sensor showed an excellent electrocatalytic oxidation activity toward olanzapine at less positive potential, pronounced current response, and good sensitivity. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) were determined for olanzapine oxidation, using the electrochemical approaches. Surface morphology and electrochemical properties of the prepared modified electrode were investigated by scanning electron microscopy (SEM), cyclic voltammetry and electrochemical impedance spectroscopy techniques. The hydrodynamic amperometry at rotating modified electrode at constant potential versus reference electrode was used for detection of olanzapine. Under optimized conditions, the calibration plot was linear in the concentration range of 20 nM to 100 μM and detection limit was found to be 6 nM. The proposed method was successfully applied to the determination of olanzapine in pharmaceuticals and human serum samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Cytochrome c (Cyt c) is an important biomarker in cell lysates for the early stage of apoptosis or anticancer agents. Here, two novel label-free fluorescence assays based on hemoglobin-stabilized gold nanoclusters (Hb/AuNCs) and aptamer-stabilized silver nanoclusters (DNA/AgNCs) for analysis of Cyt c are presented. The heme group of the protein induces sensitive sensing platforms accompanied by the decreased fluorescence of both metal nanoclusters. The quenching processes observed found to be based on the fluorescence resonance energy transfer mechanism from Hb/AuNCs to Cyt c and photoinduced electron transfer from DNA/AgNCs to the aptamer-Cyt c complex. The linear range for Cyt c was found to be 0-10 μM for Hb/AuNCs and from 0 to 1 μM for DNA/AgNCs, with limits of detection of ∼15 nM. On the basis of strong binding affinity of DNA aptamers for their target proteins, the DNA/AgNCs probe was successfully applied to the quantitative determination of Cyt c in cell lysates, which opens a new avenue to early diagnostics and drug screening with high sensitivity. Compared to the conventional Western blot method, the presented assays are low cost, easy to prepare the fluorescent probes, and sensitive, while overall time for the detection and quantitation of Cyt c from isolated mitochondria is only 20 min. The proposed method for Cyt c detection may also be useful for the study of those materials that cause mitochondrial dysfunction and apoptotic cell death.

Interactions between efavirenz (EFZ) with calf thymus DNA (CT-DNA) were investigated in vitro under stimulated physiological conditions using multispectroscopic techniques, cyclic voltammetry viscosity measurement, and gel electrophoresis. Methylene blue and acridine orange dyes were used as spectral probes by fluorescence spectroscopy. Hypochromicity was observed in ultra-violet (UV) absorption band of EFZ. Considerable fluorescence enhancement of EFZ was observed in the presence of increasing amounts of DNA solution and the binding constants (Kf ) and corresponding numbers of binding sites (n) were calculated at different temperatures. Thermodynamic parameters including enthalpy change (ΔH) and entropy change (ΔS) were calculated to be -304.78 kJ mol(-1) and -924.52 J mol(-1)  K(-1) according to the van 't Hoff equation, which indicated that reaction is predominantly enthalpically driven. In addition, UV/vis absorption titration of DNA bases confirmed that EFZ interacted with guanine and cytosine preferentially. Gel electrophoresis of DNA with EFZ demonstrated that EFZ also has the ability to cleave supercoiled plasmid DNA. Circular dichroism study showed stabilization of the right-handed B form of CT-DNA. All results suggest that EFZ interacts with CT-DNA via an intercalative mode of binding., (Copyright © 2015 John Wiley & Sons, Ltd.)

Herein, an electrochemical human immunoglobulin G (HIgG) immunosensor was fabricated using overoxidized polypyrrole decorated with gold nanoparticle (OPPy-Aunano) modified screen printed electrode (OPPy-Aunano/SPE). The results clearly demonstrate that OPPy-Aunano film is very permeable to [Fe(CN)6](3-/4-). Therefore, the fabrication of immunosensor based on permeability of OPPy-Aunano film to [Fe(CN)6](3-/4-) probe is a novel strategy for the fabrication of label free electrochemical immunosensor. The electrochemical impedance spectroscopy (EIS) techniques are used for the determination of HIgG in the concentration range 0.5 to 125.0ngmL(-1) and with a limit of detection of 0.02ngmL(-1), respectively., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A simple and sensitive method for the detection of DNA hybridization in a homogeneous format was developed, using bis(8-hydroxyquinoline-5-solphonate)cerium(III) chloride (Ce(QS)2Cl) as a novel fluorescent probe. The method is based on fluorescence quenching by gold nanoparticles used as both nanoscafolds for the immobilization of the probe DNA sequence, which is related to Alicyclobacillus acidophilus strain TA-67 16S ribosomal RNA, and nanoquenchers of the Ce(QS)2Cl probe. The probe DNA-functionalized GNPs were synthesized by derivatizing the colloidal gold nanoparticles solution with 3-thiolated 16-base oligonucleotides. Addition of sequence-specific target DNAs (16 bases) into the mixture containing probe DNA-functionalized GNPs and fluorescent probe lead to the quenching of Ce(QS)2Cl fluorescence at 360 nm (λex=270 nm), due to DNA hybridization, the resulting quenched intensity being proportional to the concentration of target DNA. Under optimal conditions of pH 7.4 and Ce(QS)2Cl concentration of 1.0 × 10(-7) M, the linear dynamic range found to be 1.0 × 10(-10)-3.0 × 10(-8) M DNA, with a limit of detection of 7.0 × 10(-11) M. The interaction mechanism for the binding of Ce(QS)2Cl to DNA was studied in detail, and results proved that the interaction mode between Ce(QS)2Cl and DNA is groove binding, with a binding constant of 1.0 × 10(5) M(-1)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Nanospheres of Ag-coated Fe3 O4 were successfully synthesized and characterized. Photocatalytic properties of Fe3 O4 @Ag composites have been investigated using steady-state studies and laser pulse excitations. Accumulation of the electrons in the Ag shell was detected from the shift in the surface plasmon band from 430 to 405 nm, which was discharged when an electron acceptor such as O2 , Thionine (TH) or C60 was introduced into the system. Charge equilibration with redox couple such as C60 (●-) /C60 indicated the ability of these core-shell structures to carry out photocatalytic reduction reactions. As well, outer Ag layer could boost charge separation in magnetic core through dual effects of Schottky junction and localized surface plasmonic resonance (LSPR)-powered band gap breaking effect under sunlight irradiation; resulted in higher photocatalytic degradation of diphenylamine (DPA). The maximum photocatalytic degradation rate was achieved at optimum amount of Ag-NP loading to products. Adsorption studies confirmed that degradation of DPA dominantly occurred in solution. Moderately renewability of the nanocatalysts under sunlight was due to oxidation and dissolution of the outer Ag layer., (© 2015 The American Society of Photobiology.)

A simple and sensitive sensor based on carbon paste electrode (CPE) modified by chitosan-coated magnetic nanoparticle (CMNP) was developed for the electrochemical determination of morphine (MO). The proposed sensor was characterized with scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The electrooxidation of MO was studied on modified carbon paste electrode using cyclic voltammetry, chronoamperometry and differential pulse voltammetry as diagnostic techniques. The oxidation peak potential of morphine on the CMNP/CPE appeared at 380 mV which was accompanied with smaller overpotential and increase in oxidation peak current compared to that obtained on the bare carbon paste electrode (CPE). Under optimum conditions the sensor provides two linear DPV responses in the range of 10-2000 nM and 2-720 μM for MO with a detection limit of 3 nM. The proposed sensor was successfully applied for monitoring of MO in serum and urine samples and satisfactory results were obtained., (Copyright © 2015. Published by Elsevier B.V.)

In this work, a label free electrochemical aptasensor for the detection of ultra-traces of vascular endothelial growth factor (VEGF165) based on "signal off" and "signal on" mechanisms of response was developed. The BSA-gold nanoclusters/ionic liquid (BSA-AuNCs/IL) was used as a suitable nanocomposite platform for immobilization of the aptamer on a glassy carbon electrode. In "signal off" mechanism, the interaction of VEGF165 with its anti-VEGF165 aptamers, resulted in desorption of methylene blue (MB) probe from aptamer and its release into solution. Consequently, the decrease in current intensity of the differential pulse voltammogram of adsorbed MB was monitored and found to be linearly proportional with increasing concentration of VEGF165 in sample solution in the range of 1-120 pM with a limit of detection of 0.32p M. While, in "signal on" mechanism, the interaction of immobilized anti-VEGF165 aptamers on the electrode surface with VEGF165, led to more mass-transfer limiting of the [Fe(CN)6](3-/4-) probe to the electrode surface. Therefore, the charge transfer resistance (Rct) of the probe was increased linearly with increasing concentration of VEGF165 in the range of 2.5-250 pM with a limit of detection of 0.48 pM. The experimental results demonstrated that both of these mechanisms are suitable for determination of low levels of the VEGF165 tumor marker in serum samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Herein, a label free electrochemical aptasensor based on ordered mesoporous carbon-gold nanocomposite modified screen printed electrode has been fabricated for the detection of vascular endothelial growth factor (VEGF165) as a tumor marker. The electrochemical behavior of prepared biosensor was investigated by cyclic voltammetry and electrochemical impedance spectroscopy. The principle of operation of the proposed aptasensor is based on the changes in the interfacial properties of the electrode due to interaction of the immobilized antiVEGF165 aptamer at the electrode surface with VEGF165 tumor marker in the sample solution, which results in a change in the interfacial charge transfer resistance as detected by electrochemical impedance spectroscopy. The calibration curve for VEGF165 determination was linear over 10.0-300.0 pg mL(-1) with a limit of detection (3σ/S) of 1.0 pg mL(-1). The prepared aptasensor exhibited high sensitivity and good selectivity and reproducibility. The aptasensor was successfully applied to the determination of VEGF165 in serum sample of a lung cancer patient., (Copyright © 2015 Elsevier B.V. All rights reserved.)

In this work, we report the first application of ion-imprinted technology via precipitation polymerization for simple and practical determination of rubidium ions. The rubidium-ion-imprinted polymer nanoparticles were prepared using dibenzo-21-crown-7 as a selective ligand, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as cross linker, and 2,2'-azobisisobutyronitrile as radical initiator. The resulting powder material was characterized using scanning electron microscopy, which showed colloidal nanoparticles of 100-200 nm in diameter and slightly irregular in shape. The maximum adsorption capacity of the ion imprinted particles was 63.36 μmol/g. The experimental conditions such as nature and concentration of eluent, pH, adsorption and desorption times, weight of the polymer material, aqueous phase and desorption agent volumes were also studied. Finally, selectivity of the prepared IIP particles toward rubidium ion was investigated in the presence of some foreign metal ions., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new, simple, and rapid chiral HPLC method was developed for enantioselective analysis of levetiracetam and its enantiomer [(R)-α-ethyl-2- oxo-pyrrolidine acetamide] in a pharmaceutical formulation and bulk material. Enantiomeric separation was achieved on a chiral-α1-acid glycoprotein (AGP) column (150×4.0 mm, 5 μm) using an isocratic mobile phase of phosphate buffer (pH=7) at a flow rate of 0.7 mL/min. The UV detector was set at 210 nm. Calibration curves were linear in the range of 1-100 μg/mL and 0.4-20 μg/mL for levetiracetam and the (R)-enantiomer, respectively. LOD and LOQ for the (R)-enantiomer were 0.1 and 0.4 μg/mL, respectively. The run time of analysis was less than 5.0 min.

Herein, the poly(o-phenylenediamine) decorated with gold-silver nanoparticle (Ag-Au NPs) nanocomposite modified glassy carbon was used for the determination of hydrogen peroxide. Electrochemical experiments indicated that the proposed sensor possesses an excellent sensitivity toward the reduction of hydrogen peroxide. The resulting sensor exhibited a good response to hydrogen peroxide over linear range from 0.2 to 60.0μM with a limit of detection of 0.08μM, good reproducibility, long-term stability and negligible interference from ascorbic acid, uric acid and dopamine. The proposed sensor was successfully applied to the determination of hydrogen peroxide in human serum sample., (Copyright © 2015 Elsevier B.V. All rights reserved.)

For the first time, electrospun polystyrene nanostructure was used as coating material on a stainless steel wire for solid-phase microextraction. Surface morphology of the coating was studied by scanning electron microscopy which showed the formation of nanofibers on the wire. The coating was stable after conditioning at 250°C for 2h. The efficiency of the polystyrene coating was approved by extracting a mixture of seven pesticides (polar and apolar) from head space of honey samples followed by gas chromatography-mass spectrometry. The important parameters affecting extraction efficiency such as, extraction time and temperature, desorption conditions, agitation rate and ionic strength were investigated. Under optimized experimental conditions, detection limits for the investigated pesticides ranged from 0.1-2μgL(-1). The intra- and inter-day precisions of the developed method were 3.5-17.6% and 10.0-25.0%, respectively. Finally, all the investigated pesticides were spiked to honey samples and extracted by the proposed method. The accuracies of determination of all the species were found to be in the range of 81-125%., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Herein, we have described the application of high fluorescent carbon dots (CDs) without any surface modification as a simple and fast responding fluorescence probe for sensitive and selective determination of hemoglobin (Hb) in the presence of H2O2. Although Hb itself was able to quench the fluorescence of CDs, based on the inner filter effect (IFE) of the protein that affects both excitation and emission spectra of CDs, the presence of H2O2 resulted in further improvement of the sensitivity of Hb detection. The assay is based on the reaction of Hb with H2O2 that generates reactive oxygen species including hydroxyl (OH•) and superoxide (O2(•-)) radicals under heme degradation and/or iron release from Hb and the subsequent reaction of hydroxyl radicals, as strong oxidizing agents, with CDs resulting in high fluorescence quenching. The proposed probe was used for determination of Hb in concentration range of 1-100 nM with a detection limit of 0.4 nM. The method was successfully applied to the determination of Hb in human blood samples., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A dispersive liquid-liquid microextraction based on solidification of floating organic drop method combined with solid-phase extraction (500-mg C18 sorbent) was developed for preconcentration and determination of some parabens. The experimental parameters influencing the extraction efficiency such as the type of extraction and disperser solvents, as well as their volumes, breakthrough volume, flow rate and salt addition were studied and optimized. The optimum experimental conditions found included: sample volume, 100 mL; KCl concentration, 1% (w/v); extraction solvent (1-undecanol) volume, 20 µL and disperser solvent (acetone) volume, 250 µL. Under the optimum experimental conditions, calibration graphs were linear in the range of 1-200 µg L(-1) with limits of detection ranged from 0.3 to 1.7 µg L(-1). The relative standard deviations were in the range of 1.2-3.1% (n = 5). The enrichment factors and absolute recoveries of parabens in different matrices were 245-1886 and 9.0-69.8%, respectively. The method was applied to the simultaneous determination of parabens in different matrices. The relative recoveries from water, shampoo and mouth rinse samples, which have been spiked at different levels of parabens, were 87.83-112.25%, 82.80-108.40% and 90.10-97.60%, respectively., (© The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Herein, an easy and cost-effective approach to the immobilization of probe was performed. The amino modified salmonella ssDNA probe sequence was covalently linked with carboxylic group on the surface of nanoporous glassy carbon electrode to prepare the DNA biosensor. The differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) techniques were used for the determination of salmonella DNA in the concentration ranges of 10-400pM and 1-400pM with limits of detection of 2.1pM and 0.15pM, respectively., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A highly sensitive impedimetric immunosensor based on a gold nanoparticles/multiwall carbon nanotube-ionic liquid electrode (AuNPs/MW-CILE) was developed for the determination of human epidermal growth factor receptor 2 (HER2). Gold nanoparticles were used to enhance the extent of immobilization and to retain the immunoactivity of the antibody Herceptin on the electrode. Cyclic voltammetry and electrochemical impedance spectroscopy were employed for characterization of various layers coated onto the AuNPs/MW-CILE. The impedance measurements at different steps were based on the charge transfer kinetics of the [Fe(CN)6](3-/4-) redox pair. The immobilization of antibody and the corresponding antigen-antibody interaction at the electrode surface altered the interfacial electron transfer. The interactions of antibody with various concentrations of antigen were also monitored via the change of impedance response. The results showed that the charge transfer resistance increases linearly with increasing concentrations of HER2 antigen. The linear range and limit of detection were found as 10-110 ng mL(-1) and 7.4 ng mL(-1), respectively. The sensitivity and specificity of the immunosensor were validated. The results showed that the prepared immunosensor is a useful tool for screening of trace amounts of HER2 in serum samples of breast cancer patients., (Copyright © 2015 Elsevier B.V. All rights reserved.)

This work reports the preparation of a voltammetric sensor for selective recognition and sensitive determination of mercury ions using a carbon ionic liquid paste electrode (CILE) impregnated with novel Hg(2+)-ion imprinted polymeric nanobeads (IIP) based on dithizone, as a suitable ligand for complex formation with Hg(2+) ions. The differential pulse anodic stripping voltammetric technique was employed to investigate the performance of the prepared IIP-CILE for determination of hazardous mercury ions. The designed modified electrode revealed linear responses in the ranges of 0.5nM-10nM and 0.08μM-2μM with a limit of detection of 0.1nM (S/N=3). It was found that the peak currents of the modified electrode for Hg(2+) ions were at a maximum value in phosphate buffer of pH4.5. The optimized preconcentration potential and accumulation time were to be -0.9V and 35s, respectively. The applicability of the proposed sensor to mercury determination in waste water samples is reported., (Copyright © 2014. Published by Elsevier B.V.)

The fluorescence spectra and response characteristics of two porphyrin compounds meso-tetrakis(2-hydroxynaphthyl) porphyrin and meso-tetra (2-thiophene) porphyrin (MTHNP) to Hg(2+) were investigated. MTHNP showed preferable fluorescence response to Hg(2+). Thereby, an efficient and selective fluorimetric optode membrane based on the fluorescence quenching of MTHNP for Hg(2+) ion determination at low concentration levels has been developed. The sensing membrane containing MTHNP reversibly responded to Hg(2+) with a working concentration range covering from 5.0×10(-9) to 1.25×10(-5)M with a relatively fast response time less than 3min. In addition to high stability, reversibility and reproducibility, the sensor showed extremely high selectivity toward Hg(2+) ion with respect to some alkali, alkaline earth and heavy metal ions. The limit of detection for Hg(2+) was 5.0×10(-9)M. The proposed fluorescent sensor was successfully applied to the direct determination of mercury content of biofenac eye drop, hair and different water samples., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Herein, a facile hydrothermal treatment of lime juice to prepare biocompatible nitrogen-doped carbon quantum dots (N-CQDs) in the presence of ammonium bicarbonate as a nitrogen source has been presented. The resulting N-CQDs exhibited excitation and pH independent emission behavior; with the quantum yield (QY) up to 40%, which was several times greater than the corresponding value for CQDs with no added nitrogen source. The N-CQDs were applied as a fluorescent probe for the sensitive and selective detection of Hg(2+) ions with a detection limit of 14 nM. Moreover, the cellular uptake and cytotoxicity of N-CQDs at different concentration ranges from 0.0 to 0.8 mg/ml were investigated by using PC12 cells as a model system. Response surface methodology was used for optimization and systematic investigation of the main variables that influence the QY, including reaction time, reaction temperature, and ammonium bicarbonate weight., (Copyright © 2014. Published by Elsevier B.V.)

A new nano-sized silver(I) ion-imprinted polymer (IIP) was prepared via precipitation copolymerization using ethyleneglycol dimethacrylate, as a cross-linking agent in the presence of Ag(+) and an aza-thioether crown containing a 1,10-phenanthroline subunit as a highly selective complexing agent. The imprint silver(I) ion was removed from the polymeric matrix using a 1.0M HNO3 solution. The resulting powder material was characterized using IR spectroscopy and scanning electron microscopy. The SEM micrographs showed colloidal nanoparticles of about 52 nm and 75 nm in diameter and slightly irregular in shape for leached and unleached IIPs, respectively. The optimal pH for quantitative enrichment was 6.0 and maximum sorbent capacity of the prepared IIP for Ag(+) was 18.08 μmol g(-1). The relative standard deviation and limit of detection (LOD=3Sb/m) for flame atomic absorption spectrometric determination of silver(I) ion, after its selective extraction by the prepared IIP nanobeads, were evaluated as 2.42% and 2.2×10(-8) M, respectively. The new Ag(+)-IIP was also applied as a suitable sensing element to the preparation of highly selective and sensitive voltammetric and potentiometric sensors for ultra trace detection of silver(I) ion in water samples, with limits of detection of 9.0×10(-10) and 1.2×10(-9) M, respectively., (Copyright © 2014. Published by Elsevier B.V.)

A solid phase extraction (SPE) coupled with dispersive liquid-liquid microextraction based on the solidification of floating organic drop (DLLME-SFO) method, using diethyldithiphosphate (DDTP) as a proper chelating agent, has been developed as an ultra preconcentration technique for the determination of inorganic arsenic in water samples prior to graphite furnace atomic absorption spectrometry (GFAAS). Variables affecting the performance of both steps were thoroughly investigated. Under optimized conditions, 100mL of As(ΙΙΙ) solution was first concentrated using a solid phase sorbent. The extract was collected in 2.0 mL of acetone and 60.0 µL of 1-undecanol was added into the collecting solvent. The mixture was then injected rapidly into 5.0 mL of pure water for further DLLME-SFO. Total inorganic As(III, V) was extracted similarly after reduction of As(V) to As(III) with potassium iodide and sodium thiosulfate and As(V) concentration was calculated by difference. A mixture of Pd(NO3)2 and Mg(NO3)2 was used as a chemical modifier in GFAAS. The analytical characteristics of the method were determined. The calibration graph was linear in the rage of 10-100 ng L(-1) with detection limit of 2.5 ng L(-1). Repeatability (intra-day) and reproducibility (inter-day) of method based on seven replicate measurements of 80 ng L(-1) of As(ΙΙΙ) were 6.8% and 7.5%, respectively. The method was successfully applied to speciation of As(III), As(V) and determination of the total amount of As in water samples and in a certified reference material (NIST RSM 1643e)., (Copyright © 2014 Elsevier B.V. All rights reserved.)