A novel aptasensor platform for the detection of carcinoembryonic antigen using quartz crystal microbalance.

In this study, a quartz crystal microbalance (QCM) aptasensor for carcinoembryonic antigen (CEA), a well-known biomarker for various cancer types, was reported, utilizing two different aptamers. To achieve this, a nanofilm of 4-mercaptophenyl was electrochemically attached to gold-coated QCM crystal surfaces via the reduction of 4-mercaptobenzenediazonium salt (4 MB-DAT) using cyclic voltammetry. Subsequently, gold nanoparticles (AuNP) were affixed to this structure, and then aptamers (antiCEA1 and antiCEA2) modified with SH-functional ends bound to AuNPs completed the modification. The analytical performance of the CEA sensor was evaluated through simultaneous QCM measurements employing CEA solutions ranging from 0.1 ng/mL to 25 ng/mL. The detection limit (LOD) for CEA was determined to be 102 pg/mL for antiCEA1 and 108 pg/mL for antiCEA2 aptamers. Interday and intraday precision and accuracy tests yielded maximum results of 4.3 and + 3.8, respectively, for both aptasensors, as measured by relative standard deviation (RSD%) and relative error (RE%). The kinetic data of the aptasensors resulted in affinity values (KD) of 0.43 ± 0.14 nM for antiCEA1 and 0.75 ± 0.42 nM for antiCEA2. These values were lower than the reported values of 3.9 nM and 37.8 nM for both aptamers, respectively. The selectivity of the aptasensor was evaluated by measuring the signal changes caused by alpha-fetoprotein (AFP), cancer antigen (CA-125), and vascular endothelial growth factor (VEGF-165) individually and together at a concentration of 500 ng/mL, resulting in a maximum 4.1 % change, which was comparable to precision and accuracy values reported in the literature. After confirming the selectivity of the aptamers, recovery experiments were conducted using spiked commercial serum samples to simulate real samples, and the lowest recovery value obtained was 95.4 %. It was determined that two different aptasensors could be successfully used for the QCM-based detection of CEA in this study.

A novel molecularly imprinted electrochemical sensor for the ultrasensitive detection of tert-butylhydroquinone in edible oils.

Tert-butylhydroquinone (TBHQ) is widely used to increase the stability of food products; however, it is considered to be a highly unsafe preservative ingredient that has caused serious damage to human health. Thus, in this paper, a novel molecularly imprinted electrochemical sensor was designed for ultrasensitive, and selective detection of TBHQ in edible oils. The sensor was based on the molecularly imprinted polymer (MIP) synthesized with multiwalled carbon nanotube (MWCNT), and gold nanoparticle (GNP), as the coating materials, o-phenylenediamine (o-PDA) as the functional monomer, and TBHQ as the template molecule. The electrochemical behavior of MIP/GNP/MWCNT/GCE was studied using several electrochemical methods, which showed a low detection limit of 5 nM. Furthermore the sensor demostrated excellent stability, selectivity, repeatability, and reproducibility. It was successfully used to detect TBHQ in edible oils, with recoveries ranging from 98.44% to 102.09% and relative standard deviations (RSDs) of less than 2.16%, indicating that TBHQ detection in actual samples is both possible and accurate.

An Overview of Aptamer-Based Sensor Platforms for the Detection of Bisphenol-A.

Endocrine disruptive compounds are natural or anthropogenic environmental micropollutants that alter the function of the endocrine system ultimately damaging the metabolism. Bisphenol A (BPA) is the most common of these pollutants and it is often used in epoxy coatings and polycarbonates as a plasticizer. Therefore, monitoring BPA levels in different environments is very important and challenging. In recent years, an increasing number of BPA detection methods have been proposed. This article presents a critical review of aptamer-based electrochemical, fluorescence-based, colorimetric, and several other BPA detection platforms published in the last decade. Furthermore, a statistical evaluation has been made using principle component analysis showing analytical performance parameters do not create very different clusters. Comparisons to other BPA detection methods are also presented so that the reader has an overall literature overview.

Detection Strategies of Zearalenone for Food Safety: A Review.

Zearalenone (ZEN) is a toxic compound produced by the metabolism of fungi (genus Fusarium) that threaten the food and agricultural industry belonging to the in foods and feeds. ZEN has toxic effects on human and animal health due to its mutagenicity, teratogenicity, carcinogenicity, nephrotoxicity, immunotoxicity, and genotoxicity. To ensure food safety, rapid, precise, and reliable analytical methods can be developed for the detection of toxins such as ZEN. Different selective molecular diagnostic elements are used in conjunction with different detection strategies to achieve this goal. In this review, the use of electrochemical, colorimetric, fluorometric, refractometric as well as other strategies were discussed for ZEN detection. The success of the sensors in analytical performance depends on the development of receptors with increased affinity to the target. This requirement has been met with different immunoassays, aptamer-assays, and molecular imprinting techniques. The immobilization techniques and analysis strategies developed with the combination of nanomaterials provided high precision, reliability, and convenience in ZEN detection, in which electrochemical strategies perform the best.

Spectroscopic ellipsometry methods for brevetoxin detection.

The spectroscopic ellipsometry (SE), and attenuated internal reflection spectroscopic ellipsometry (TIRE) are promising methods in label-free biosensing applications. An ellipsometer running under surface plasmon resonance (SPR) conditions has unique advantages over other SPR-based methods in terms of sensitivity and real-time/label-free measurement capability. In this study, both SE and TIRE-based brevetoxin B (BTX) sensors were developed using two anti-BTX aptamers reported before. A new aptamer sequence was also derived from these two antiBTX aptamers using predictive modeling tools and an exclusion method. All three antiBTX aptamers' analytical performances were quite competitive in terms of both detecting range and detection limits. However, the selectivity of the previously reported aptamers against analogs of BTX was poor at low detection ranges, especially for okadaic acid. Furthermore, the selectivity of the derived aptamer was lower than its predecessors. The sensors were capable of detecting BTX in the range of 0.05 nM-1600 nM in the TIRE and 0.5 nM-2000 nM in the SE configuration. The detection limits of the sensors were 1.48 nM (1.32 ng/mL) and 0.80 nM (0.72 ng/mL) for SE and TIRE configurations, respectively. Both configurations have been used successfully to detect BTX standards spiked into real fish and shrimp samples.

A sensitive spectrophotometric ellipsometry based Aptasensor for the vascular endothelial growth factor detection.

A sensitive and selective, aptamer and spectroscopic ellipsometry based sensor is reported here for the early diagnosis of breast cancer, which is a common type of cancer following lung cancer. It was aimed to develop a single-step and label-free assay for the sensitive and selective detection of VEGF165. To this end, two different aptamers and spectroscopic ellipsometry were used. In the presented study, by determining the appropriate aptamer immobilization conditions, the spectroscopic ellipsometry technique was successfully applied for the detection of VEGF165 at the range of 1 pM-1000 pM in the buffer. Aptasensors have a detection limit of 5.81 pM and 4.29 pM, respectively.

An electrochemical label-free DNA impedimetric sensor with AuNP-modified glass fiber/carbonaceous electrode for the detection of HIV-1 DNA.

In this study, a highly sensitive, electrochemical, and label-free DNA impedimetric sensor was developed using carbonized glass fiber-coal tar pitch (GF-CTP) electrodes supported with gold nanoparticles (AuNPs) for the detection of HIV-1 gene. Thiol-modified GF-CTP electrodes were prepared using amine crosslinking chemistry and AuNPs were self-assembled obtaining highly conductive nanoelectrodes, GF-CTP-ATP-Au. All steps of electrode modifications were characterized using electrochemical, spectroscopic, and microscopic methods. GF-CTP-ATP-Au electrode was then modified with a capture DNA probe (C-ssDNA) and optimized with a target DNA probe in terms of hybridization time and temperature between 30 and 180 min and 20-50 °C, respectively. Finally, the analytic performance of the developed ssDNA biosensor was evaluated using electrochemical impedance spectroscopy. The calibration of the sensor was obtained between 0.1 pM and 10 nM analyte working range. The limit of detection was calculated using signal to noise ratio of 3 (S/N = 3) as 13 fM. Moreover, interference results for two noncomplementary DNA probes were also tested to demonstrate non-specific ssDNA interactions. An electrochemical label-free DNA impedimetric sensor was successfully developed using a novel GF-CTP-ATP-Au electrode. This study suggests that highly sensitive DNA-based biosensors can be developed using relatively low-cost carbonaceous materials.

Saxitoxin aptasensor based on attenuated internal reflection ellipsometry for seafood.

In this study, we proposed label-free saxitoxin (STX) sensor using STX specific aptamer in combination with spectroscopic ellipsometry (SE) and attenuated internal reflection (AIR) spectroscopic ellipsometry method which is operated under surface plasmon resonance (SPR) conditions. Besides the other surface plasmon resonance-based applications, AIR-SE applications have unique advantages in terms of sensitivity and it was used herein for real-time detection of STX in real samples. Another method, SE, was also used and compared with AIR-SE. Analytical performances were satisfactory with low detection limits and a wide detection range. Limit of detection was 0.01 ng/mL for AIR-SE and 0.11 ng/mL for SE. Both proposed sensors were operable in 0.01 nM-1000 nM STX range. These methods were also used for the accurate, selective, and sensitive detection of STX from fish and shrimp samples.

Recent advances in aptamer-based sensors for breast cancer diagnosis: special cases for nanomaterial-based VEGF, HER2, and MUC1 aptasensors.

Cancer is one of the most common and important diseases with a high mortality rate. Breast cancer is among the three most common types of cancer in women, and the mortality rate has reached 0.024% in some countries. For early-stage preclinical diagnosis of breast cancer, sensitive and reliable tools are needed. Today, there are many types of biomarkers that have been identified for cancer diagnosis. A wide variety of detection strategies have also been developed for the detection of these biomarkers from serum or other body fluids at physiological concentrations. Aptamers are single-stranded DNA or RNA oligonucleotides and promising in the production of more sensitive and reliable biosensor platforms in combination with a wide range of nanomaterials. Conformational changes triggered by the target analyte have been successfully applied in fluorometric, colorimetric, plasmonic, and electrochemical-based detection strategies. This review article presents aptasensor approaches used in the detection of vascular endothelial growth factor (VEGF), human epidermal growth factor receptor 2 (HER2), and mucin-1 glycoprotein (MUC1) biomarkers, which are frequently studied in the diagnosis of breast cancer. The focus of this review article is on developments of the last decade for detecting these biomarkers using various sensitivity enhancement techniques and nanomaterials.

A review on nanostructure-based mercury (II) detection and monitoring focusing on aptamer and oligonucleotide biosensors.

Heavy metal ion pollution is a severe problem in environmental protection and especially in human health due to their bioaccumulation in organisms. Mercury (II) (Hg2+), even at low concentrations, can lead to DNA damage and give permanent harm to the central nervous system by easily passing through biological membranes. Therefore, sensitive detection and monitoring of Hg2+ is of particular interest with significant specificity. In this review, aptamer-based strategies in combination with nanostructures as well as several other strategies to solve addressed problems in sensor development for Hg2+ are discussed in detail. In particular, the analytical performance of different aptamer and oligonucleotide-based strategies using different signal improvement approaches based on nanoparticles were compared within each strategy and in between. Although quite a number of the suggested methodologies analyzed in this review fulfills the standard requirements, further development is still needed on real sample analysis and analytical performance parameters.

Spectrophotometric ellipsometry based Tat-protein RNA-aptasensor for HIV-1 diagnosis.

Rapid and reliable diagnosis of Human Immunodeficiency Virus (HIV) Type I that causes autoimmune deficiency syndrome (AIDS) is still important today. In this study, the HIV-I Tat (trans-activator of transcription) protein-specific RNA-aptamer (antiTat) and spectroscopic ellipsometer were preferred to increase specificity and sensitivity in the diagnosis. The ellipsometry is a well-known characterization tool for the ultra-thin films, where polarization state changes show surface deposition in terms of the ellipsometric angles, psi (Ψ) and delta (Δ). Here, we reported the HIV-Tat protein detection performance of antiTat aptamers both for the spectroscopic ellipsometry (SE) and for the surface plasmon resonance enhanced total internal reflection ellipsometry (SPReTIRE), first time. Detection limits for antiTat aptamers with various configurations were in the range of nM-pM protein in the buffer solution. For instance, SPRe-TIRE configuration revealed a detection limit of 1 pM (or about 1.5 pg/mL) for HIV-Tat protein in the range of 1.0-500 nM.

Detection of zearalenone in an aptamer assay using attenuated internal reflection ellipsometry and it's cereal sample applications.

Mycotoxins are toxic compounds produced by the metabolism of certain fungi that threaten the food and agricultural industry. Over hundreds of mycotoxins, one of the most common toxins, zearalenone (ZEN), has toxic effects on human and animal health due to its mutagenicity, treatogenicity, carcinogenicity, nephrotoxicity, immunotoxicity, and genotoxicity. In this work, attenuated internal reflection spectroscopic ellipsometry (AIR-SE) combined with the signal amplification via surface plasmon resonance conditions that were proved to be a highly sensitive analytical tool in bio-sensing was developed for the sensitive and selective ZEN detection in cereal products such as corn, wheat, rice, and oat. Combined with the oligonucleotide aptamer for ZEN recognition, our proposed method showed good performance with yielding 0.08 ng/mL LOD and 0.01-1000 ng/mL detection range. A mini-review was also introduced in, to compare various methods for ZEN detection.

Methods for the Determination of Endocrine-Disrupting Phthalate Esters.

Phthalates are endocrine disruptors frequently occurring in the general and industrial environment and in many industrial products. Moreover, they are also suspected of being carcinogenic, teratogenic, and mutagenic, and they show diverse toxicity profiles depending on their structures. The European Union and the United States Environmental Protection Agency (US EPA) have included many phthalates in the list of priority substances with potential endocrine-disrupting action. They are: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), butylbenzyl phthalate (BBP), diethylhexyl phthalate (DEHP), di-iso-nonyl phthalate (DINP), di-iso-decyl phthalate (DIDP), di-n-decyl phthalate (DnDP), and dioctyl phthalate (DOP). There is an ever-increasing demand for new analytical methods suitable for monitoring different phthalates in various environmental, biological, and other matrices. Separation and spectrometric methods are most frequently used. However, modern electroanalytical methods can also play a useful role in this field because of their high sensitivity, reasonable selectivity, easy automation, and miniaturization, and especially low investment and running costs, which makes them suitable for large-scale monitoring. Therefore, this review outlines possibilities and limitations of various analytical methods for determination of endocrine-disruptor phthalate esters in various matrices, including somewhat neglected electroanalytical methods.

Manganese Dioxide/Reduced Graphene Oxide with Poly(3,4-ethylenedioxythiophene) for Improved Electrocatalytic Oxygen Reduction Reaction.

Poly(3,4-ethylenedioxythiophene)-(PEDOT)-functionalized reduced graphene oxide (rGO) with MnO2 nanoparticles (MnO2/PEDOT/rGO) was prepared using electrochemical methods. The MnO2/ PEDOT/rGO was obtained through the electrochemical reduction of PEDOT/GO and under electrochemical treatment in KMnO4. The PEDOT/rGO and MnO2/PEDOT/rGO were characterized by several instrumental and electrochemical methods. The electrocatalytic 02 reduction for both electrodes was investigated via cyclic and hydrodynamic voltammetry in 0.1 M KOH aqueous solutions. The kinetic analysis in comparison to PEDOT/rGO a significant enhancement was found for the MnO2/PEDOT/rGO. The proposed main path in the oxygen reduction reaction (ORR) mechanism on the MnO2/PEDOT/rGO was the direct four-electron transfer process with faster transfer kinetic rate. The better ORR kinetics were obtained due to the excellent composite formation and well attachment of MnO2 NPs within oxide form. The PEDOT/rGO was less stable for long term use than MnO2/PEDOT/rGO.

High catalytic activity of electrochemically reduced graphene composite toward electrochemical sensing of Orange II.

Orange II, an azo dye, is sometimes illegally used as a red dye in food products despite its adverse health effects if consumed. Therefore, the determination of low concentrations of Orange II is an important target. An Orange II sensor was prepared using electrochemically reduced graphene oxide grafted with 5-amino-1,3,4-thiadiazole-2-thiol-Pt nanoparticles (denoted as ERGO-ATDT-Pt) onto a glassy carbon electrode (GCE) and investigated for Orange II detection in 0.1M acetate buffer solution (ABS at pH 4.5) with prominent reversible redox peaks. A wide linear range of 1×10(-)(8)-6×10(-)(7)M with a low detection limit of 3.4×10(-)(10)M (s/n=3) was found for Orange II detection. This developed ERGO-ATDT-Pt/GCE sensor showed good selectivity, excellent stability and better response to the real sample analysis with excellent recovery.

Phosphorus-nitrogen compounds. Part 29. Syntheses, crystal structures, spectroscopic and stereogenic properties, electrochemical investigations, antituberculosis, antimicrobial and cytotoxic activities and DNA interactions of ansa-spiro-ansa cyclotetraphosphazenes.

A number of novel ansa-spiro-ansa (asa) cyclotetraphosphazenes (1a-5b) was prepared in the range of 63-90 % yields. The structures of the compounds were verified by MS, FTIR, (1)H, (13)C{(1)H} and (31)P{(1)H} NMR, heteronuclear single quantum coherence (HSQC), and heteronuclear multiple-bond correlation (HMBC) techniques. The crystal structures of 1b, 2c and 5a were determined by X-ray crystallography. The compound 2c was analyzed by the changes in the (31)P{(1)H}NMR spectrum in addition of the chiral solvating agent; (R)-(+)-2,2,2-trifluoro-1-(9'-anthryl)-ethanol (CSA), to investigate its stereogenic properties. The result supports that compound 2c was found to be in the racemic mixture. Cyclic voltammetric and chronoamperometric data of the mono-ferrocenyl-spiro-asa-cyclotetraphosphazenes exhibited electrochemically reversible one-electron oxidation of Fe redox centres. The mono-ferrocenyl-spiro-asa compounds (3a-5b) were evaluated for antituberculosis activity against reference strain Mycobacterium tuberculosis H37Rv and M. tuberculosis clinical strain, which is resistant to rifampicin and isoniazid. These compounds appear not to be good candidates for being antituberculosis agents to clinical strains. All of the compounds were screened for antibacterial activities against G(+) and G(-) bacteria, and for antifungal activities against yeast strains. They seem to be more active against Gram positive bacteria than Gram negative. The interactions of the phosphazenes with plasmid DNA and the evaluations for cytotoxic activity against MCF-7 breast cancer cell lines were investigated. The compounds 1b, 2b, 3a and 4a were found to be more effective than Cisplatin against MCF-7 breast cancer cell lines at lower concentrations.

A novel magnetic Fe@Au core-shell nanoparticles anchored graphene oxide recyclable nanocatalyst for the reduction of nitrophenol compounds.

In this study, a novel catalyst based on Fe@Au bimetallic nanoparticles involved graphene oxide was prepared and characterized by transmission electron microscope (TEM), and x-ray photoelectron spectroscopy (XPS). The nanomaterial was used in catalytic reductions of 4-nitrophenol and 2-nitrophenol in the presence of sodium borohydride. The experimental parameters such as temperature, the dosage of catalyst and the concentration of sodium borohydride were studied. The rates of catalytic reduction of the nitrophenol compounds have been found as the sequence: 4-nitrophenol>2-nitrophenol. The kinetic and thermodynamic parameters of nitrophenol compounds were determined. Activation energies were found as 2.33 kcal mol(-1) and 3.16 kcal mol(-1) for 4-nitrophenol and 2-nitrophenol, respectively. The nanomaterial was separated from the product by using a magnet and recycled after the reduction of nitrophenol compounds. The recyclable of the nanocatalyst is economically significant in industry.

A novel glucose biosensor platform based on Ag@AuNPs modified graphene oxide nanocomposite and SERS application.

This study represents a novel template demonstration of a glucose biosensor based on mercaptophenyl boronic acid (MBA) terminated Ag@AuNPs/graphene oxide (Ag@AuNPs-GO) nanomaterials. The nanocomposites were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) method. The TEM image shows that Ag@AuNPs in the nanocomposite is in the range of diameters of 10-20 nm. The nanocomposite was used for the determination of glucose through the complexation between boronic acid and diol groups of glucose. Thus, a novel glucose biosensor was further fabricated by immobilizing glucose oxidase (GOD) into MBA terminated Ag@AuNPs-GO nanocomposite film (MBA-Ag@AuNPs-GO). The linearity range of glucose was obtained as 2-6mM with detection limit of 0.33 mM. The developed biosensor was also applied successfully for the determination of glucose in blood samples. The concentration value of glucose in blood samples was calculated to be 1.97±0.002 mM from measurements repeated for six times.

A novel Surface Plasmon Resonance enhanced Total Internal Reflection Ellipsometric application: electrochemically grafted isophthalic acid nanofilm on gold surface.

The scope of this study is to modify a Surface Plasmon Resonance (SPR) sensor slide with isophthalic acid to evaluate the possible application on the detection of copper(II) ions in aqueous media by total internal reflection ellipsometry. A gold sensor surface was modified by an electrochemical diazonium reduction modification method. The modified surfaces are characterized with cyclic voltammetry (CV) and ellipsometry. Isophthalic acid monolayer modified gold slides were used for in situ detection of aqueous Cu(2+) solution with the SPR enhanced total internal reflection ellipsometry (SPRe-TIRE) technique. Layer formation, pH dependency of adsorption, sensor response of the SPRe-TIRE and isothermal kinetic parameters were examined. A high dependency on the number of CV cycles in the monolayer-multiple layer transition was observed. The suggested sensor gave a linear response over a wide range of Cu(2+) concentrations. It was also reported that adsorption on the SPRe-TIRE sensor gave Langmuir adsorption model behavior.

Effect of Au and Au@Ag core-shell nanoparticles on the SERS of bridging organic molecules.

Gold nanoparticles (AuNPs) with about 6 nm size were produced and stabilized with mercaptopropionic acid (MPA) film to produce a monolayer protected cluster (MPC) of AuS(CH(2))(2)COOH. 4-Aminothiophenol (ATP) molecules were introduced to the activated carboxylic acid ends of the film surrounding the AuNPs to produce AuS(CH(2))(2)CONHPhSH MPC. These modified AuNPs were again self-assembled with Au@Ag core-shell bimetallic nanoparticles via the -SH groups to produce an organic bridge between Au and Au@Ag metallic nanoparticles. An unusually strong enhancement of the Raman signals was observed and assigned to the plasmon coupling between the AuNPs and Au@Ag NPs bridged assembly. Formation of AuS(CH(2))(2)COOH and AuS(CH(2))(2)CONHPhSH clusters and AuS(CH(2))(2)CONHPhS(Au@Ag) assembly is confirmed by UV-Vis, reflection-absorption IR spectroscopy (RAIRS) and X-ray photoelectron spectroscopy (XPS), as well as by TEM analysis. The SERS activity of the AuNPs and Au@Ag NPs was tested using the HS(CH(2))(2)CONHPhSH molecule as a probe to compare the effectiveness of monometallic and bimetallic systems. SERS spectra show that Au@Ag bimetallic nanoparticles are very effective SERS-active substrates.