Selective and Rapid Optical Detection of Citalopram Using a Fluorescent Probe Based on Carbon Quantum Dots Embedded in Silica Molecularly Imprinted Polymer.

In this study, a citalopram optical nano-sensor was developed. Citalopram is a well-known antidepressant drug that reduces the reuptake of serotonin in neurons as a result, serotonin neurotransmission, the primary response to antidepressant treatments, increases in many parts of the brain. This study introduces a carbon quantum dots (CQDs)-based optical nanosensor for rapid detection of citalopram. This fluorescent nanosensor was made through the polymerization of tetraethyl orthosilicate in the presence of CQDs as the fluorescent materials and citalopram as the template molecule. Following the polymerization, the templated molecules were washed and removed from the structure, and the matrix of the polymer was left with some cavities that resembled citalopram in terms of size and shape. The final structure which is used as a chemical nanosensor, is named carbon quantum dots embedded silica molecularly imprinted polymer (CQDs-SMIP). The materials used in designing nano-sensors were characterized using FTIR, UV/Vis, and fluorescence spectroscopy, as well as high-resolution transmission electron microscopy (HR-TEM), and field emission scanning electron microscopy (FESEM). CQDs-SMIP showed a strong fluorescence emission at 420 nm in the absence of the template molecule. The fluorescence intensity of the nanosensor decreased in the presence of citalopram. The correlation between the extent of the fluorescence quenching and the concentration of citalopram provided the nano-sensor signal. The nano-sensor was used to measure citalopram in complex matrices such as human plasma and urine samples with remarkable selectivity and sensitivity. The detection limit of 10.3 µg.L-1 over a linear range of 100 to 700 µg.L-1, and RSD of 3.15% was obtained. This nano-sensor was applied to analyze of citalopram in plasma and human urine samples with remarkable results.

Effective PDT/PTT dual-modal phototherapeutic killing of bacteria by using poly(N-phenylglycine) nanoparticles.

This study investigated, for the first time, the antimicrobial properties of polyethylene glycol-functionalized poly(N-phenylglycine) nanoparticles (PNPG-PEG NPs). PNPG-PEG NPs exhibit high extinction coefficient in the near-infrared (NIR) region; they can convert light energy into heat energy with high thermal transformation efficiency. Additionally, they can generate cytotoxic reactive oxygen species (ROS) upon light irradiation. Also, PNPG-PEG NPs are not cytotoxic. All these properties make them appropriate for combined dual-modal photothermal and photodynamic therapies. The antibacterial activity of PNPG-PEG NPs was assessed using Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) pathogenic strains. The results revealed that NIR light (810 nm) irradiation for 10 min could kill effectively the planktonic bacteria and destroy Escherichia coli and Staphylococcus aureus biofilms. The results demonstrated that PNPG-PEG NPs represent a very effective nanoplatform for killing of pathogenic bacteria.

A Novel Fluorescence Nanobiosensor based on Modified Graphene Quantum dots-HTAB for Early Detection of Fetal Sexuality with Cell Free Fetal DNA.

Recently, prenatal diagnosis with non-invasive insight is a progressive approach in clinical medicine to prevent the birth of infants with genetic abnormalities. Cell free fetal DNA (cffDNA) makes up approximately 3-6% of the bare DNA in the mother's bloodstream which is produced during pregnancy and can be used to detect fetal sex and disease in the early stages. SRY is a gene located on the chromosome Y which determines the sex of male infants. In this work, a new nanobiosensor based on the fluorescence property of r-GQD@HTAB (reduced graphene quantum dots modified with hexadecyl trimethyl ammonium bromide) was fabricated that can identify the SRY gene in cffDNA with high sensitivity and specificity. A detection limit of 0.082 nM and the linear response range of 0.16-1.5 nM was obtained for the method. It was able to discriminate the target sequence with high specificity from the non-target sequences. This biosensor includes a new graphene quantum dot modified with a surfactant, HTAB which leads to high fluorescence emission of it and then more precise differentiation between ssDNA and DsDNA in a solution. In conclusion, it provides a novel analytical tool for detection of small amount of DNA and fetal sex and genetic diseases in early stage with prenatal and noninvasive tests and applicable for clinical use.

Serotonin level as a potent diabetes biomarker based on electrochemical sensing: a new approach in a zebra fish model.

Serotonin (5-HT) levels have been associated with several exclusively metabolic disorders. Herein, a new approach for 5-HT level as a novel biomarker of diabetes mellitus is considered using a simple nanocomposite and HPLC method. Reduced graphene oxide (rGO) comprising gold nanoparticles (AuNPs) was decorated with 18-crown-6 (18.Cr.6) to fabricate a simple nanocomposite (rGO-AuNPs-18.Cr.6). The nanocomposite was positioned on a glassy carbon electrode (GCE) to form an electrochemical sensor for the biomarker 5-HT in the presence of L-tryptophan (L-Trp), dopamine (DA), ascorbic acid (AA), urea, and glucose. The nanocomposite exhibited efficient catalytic activity for 5-HT detection by square-wave voltammetry (SWV). The proposed sensor displayed high selectivity, excellent reproducibility, notable anti-interference ability, and long-term stability even after 2 months. SWV defined a linear range of 5-HT concentration from 0.4 to 10 µg L-1. A diabetic animal model (diabetic zebrafish model) was then applied to investigate 5-HT as a novel biomarker of diabetes. A limit of detection (LOD) of about 0.33 µg L-1 was found for the diabetic group and 0.15 µg L-1 for the control group. The average levels of 5-HT obtained were 9 and 2 µg L-1 for control and diabetic groups, respectively. The recovery, relative standard deviation (RSD), and relative error (RE) were found to be about 97%, less than 2%, and around 3%, respectively. The significant reduction in 5-HT level in the diabetic group compared to the control group proved that the biomarker 5-HT can be applied for the early diagnosis of diabetes mellitus.

Determination of the biomarker L-tryptophan level in diabetic and normal human serum based on an electrochemical sensing method using reduced graphene oxide/gold nanoparticles/18-crown-6.

A novel nanocomposite-modified electrode based on reduced graphene oxide (rGO) decorated with 18-crown-6 (Cr.6) and gold nanoparticles (GNPs) on the surface of a glassy carbon electrode (GCE) was successfully fabricated to investigate the electrochemical sensing of the biomarker L-tryptophan (L-Trp) in the presence of dopamine (DA), ascorbic acid (AA), urea, and glucose. The rGO-GNPs-Cr.6/GCE displayed high electrochemical catalytic activity for L-Trp determination using square-wave voltammetry (SWV). The electrochemical behavior of L-Trp at the rGO-GNPs-Cr.6/GCE displayed higher oxidation current and potential (oxidation peak current of 40 µA at 0.85 V) than rGO-GNPs/GCE, Cr.6/GCE, GNPs/GCE, rGO/GCE, and bare GCE. The SWV demonstrated a linear range of L-Trp concentration from 0.1 to 2.5 µM. A low limit of detection (LOD) was found for L-Trp, with LOD of about 0.48 µM and 0.61 µM in diabetic and normal serum, respectively. The fabricated sensor demonstrated high selectivity and sensitivity, and good stability and reproducibility for L-Trp sensing. Finally, the nanocomposite (rGO-GNPs-Cr.6)-modified GCE was applied for the determination of L-Trp in normal and diabetic human serum samples, and displayed excellent LOD and recoveries higher than 91.8%. Graphical Abstract.

Entacapone detection by a GOQDs-molecularly imprinted silica fluorescent chemical nanosensor.

A sensitive fluorescent chemical nanosensor for the detection of entacapone (EN) in pharmaceutical samples is introduced. EN is a nitrocatechol drug that functions as a selective and reversible inhibitor of catechol-O-methyl transferase and is widely prescribed in the treatment of Parkinson disease. Molecularly imprinting technology and graphene oxide quantum dots (GOQDs) were employed in designing the EN fluorescent nanosensor. GOQDs were embedded into an inorganic polymer while the imprinting process occurred. The synthesized GOQDs-embedded silica molecularly imprinting polymer (SMIP) showed strong fluorescent emission at 450 nm by exciting at 360 nm. The fluorescence intensity of GOQDs-embedded SMIP was quenched effectively by adsorption of EN as a template molecule. The quenching corresponded to EN concentration in a linear range of at least 0.40-6.00 µM with a limit of detection of 0.31 µM. The designed chemical nanosensor was successfully applied to the analysis of entacapone in some pharmaceutical tablets also containing carbidopa and levodopa (RSD 3.8%).

Nanomaterial based electrochemical sensing of the biomarker serotonin: a comprehensive review.

This review (with 131 references) summarizes the progress made in the past years in the field of nanomaterial based sensing of serotonin (5-HT). An introduction summarizes the significant role of 5-HT as a biomarker for several major diseases, methods for its determination and the various kinds of nanomaterials for use in electrochemical sensing process relies principally on a precise choice of electrodes. The next main section covers nanomaterial based methods for sensing 5-HT, with subsections on electrodes modified with carbon nanotubes, graphene related materials, gold nanomaterials, and by other nanomaterials. A concluding section discusses future perspectives and current challenges of 5-HT determination. Graphical abstract Conceptual design of electrochemical sensing process of the biomarker serotonin by using nanomaterials and the role of 5-HTas biomarker in the body from preclinical to clincal.

Voltammetric Electronic Tongue for the Simultaneous Determination of Three Benzodiazepines.

The presented manuscript reports the simultaneous detection of a ternary mixture of the benzodiazepines diazepam, lorazepam, and flunitrazepam using an array of voltammetric sensors and the electronic tongue principle. The electrodes used in the array were selected from a set of differently modified graphite epoxy composite electrodes; specifically, six electrodes were used incorporating metallic nanoparticles of Cu and Pt, oxide nanoparticles of CuO and WO3, plus pristine electrodes of epoxy-graphite and metallic Pt disk. Cyclic voltammetry was the technique used to obtain the voltammetric responses. Multivariate examination using Principal Component Analysis (PCA) justified the choice of sensors in order to get the proper discrimination of the benzodiazepines. Next, a quantitative model to predict the concentrations of mixtures of the three benzodiazepines was built employing the set of voltammograms, and was first processed with the Discrete Wavelet Transform, which fed an artificial neural network response model. The developed model successfully predicted the concentration of the three compounds with a normalized root mean square error (NRMSE) of 0.034 and 0.106 for the training and test subsets, respectively, and coefficient of correlation R ≥ 0.938 in the predicted vs. expected concentrations comparison graph.

Ligand-Capped CdTe Quantum Dots as a Fluorescent Nanosensor for Detection of Copper Ions in Environmental Water Sample.

In this work, as a novel fluorescent nano-sensor, a ligand-capped CdTe QDs (CdTe-L QDs) was designed for the detection and quantification of Cu2+ ions in environmental water samples. The synthesized QDs were characterized by transmission electron microscopy (TEM), thermo-gravimetric (TG) analysis, Fourier transform infrared (FTIR), UV-Vis spectrophotometry and fluorescence spectroscopy. Optical properties of the produced nanosensor were monitored by UV-Vis and fluorescence spectrophotometry. It was observed that fluorescence intensity of the produced nano-sensor selectively quenched by adding Cu2+ ions in comparison to other metal ions tested. Using CdTe-L QDs, a rapid and facile analytical method was developed to determine Cu2+ ions in the concentration range of 5.16 ± 0.07 × 10- 8 mol L- 1-1.50 ± 0.03 × 10- 5 mol L- 1 with a detection limit of 1.55 ± 0.05 × 10- 8 mol L- 1. The nanosensor was successfully applied for the determination of Cu2+ ions in various water samples, and the results were compared with the standard method. Graphical Abstract.

Cerium(III) Ion Sensing Based on Graphene Quantum Dots Fluorescent Turn-Off.

In this work, graphene quantum dots (GQDs) was synthesized through hydrothermal method and used as a photoluminescent bulk nano-chemosensor for detection of Ce3+ ion in the aqueous solution. The synthesized GQD was characterized by transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), UV-Visible absorption and fluorescence emission spectroscopy. The sheet diameters of the synthesized GQDs were mainly distributed in the range of 15-20 nm. The interactions of GQDs with common cations and lanthanide ions were studied by fluorescence spectroscopy. Among the tested cations, Ce3+ ions was able to quench the fluorescence emission intensity of the GQD selectively. This quenching can be attributed to a redox mechanism between Ce3+ ion on the GQDs surface.

Isatin functionalized nanoporous SBA-15 as a selective fluorescent probe for the detection of Hg(II) in water.

A highly ordered mesoporous silica material functionalized with isatin (SBA-Pr-IS) was designed and synthesized. Characterization techniques including XRD, TGA, BET, SEM, and FT-IR were employed to characterize the pore structure, textural properties, microscopic morphology, and molecular composition of grafted organic moieties of SBA-Pr-IS. The successful attachment of the organic moiety (0.34 mmol g-1) without the SBA-15 structure collapsing after the modification steps was confirmed. Fluorescence characterization of SBA-Pr-IS was examined upon addition of a wide variety of cations in aqueous medium and it showed high sensitivity toward Hg2+ ions. During testing in an ion competition experiment, it was observed that the fluorescence changes of the probe were remarkably specific for Hg2+ ions. Furthermore, a good linearity between the fluorescence intensity of this material and the concentration of Hg2+ ions was constructed with a suitable detection limit of 3.7 × 10-6 M. Finally, the applicability of the proposed method was successfully evaluated for the determination of Hg2+ ions in real samples. Therefore, SBA-Pr-IS can be used as an efficient fluorescence probe for Hg2+ ions. Graphical Abstract A novel organic-inorganic hybrid material was designed and synthesized by functionalization of SBA-15 mesoporous silica material with isatin. The evaluation of the sensing ability of SBA-Pr-IS using fluorescence spectroscopy revealed that the SBA-Pr-IS was a selective fluorescent probe for Hg2+ ion in water in the presence of a wide range of metal cations.

Synthesis and Assessment of DNA/Silver Nanoclusters Probes for Optimal and Selective Detection of Tristeza Virus Mild Strains.

Citrus Tristeza virus (CTV) is one of the most destructive pathogens worldwide that exist as a mixture of malicious (Sever) and tolerable (Mild) strains. Mild strains of CTV can be used to immunize healthy plants from more Severe strains damage. Recently, innovative methods based on the fluorescent properties of DNA/silver nanoclusters have been developed for molecular detection purposes. In this study, a simple procedure was followed to create more active DNA/AgNCs probe for accurate and selective detection of Tristeza Mild-RNA. To this end, four distinct DNA emitter scaffolds (C12, Red, Green, Yellow) were tethered to the Mild capture sequence and investigated in various buffers in order to find highly emissive combinations. Then, to achieve specific and reliable results, several chemical additives, including organic solvents, PEG and organo-soluble salts were used to enhance control fluorescence signals and optimize the hybridization solution. The data showed that, under adjusted conditions, the target sensitivity is enhanced by a factor of five and the high discrimination between Mild and Severe RNAs were obtained. The emission ratio of the DNA/AgNCs was dropped in the presence of target RNAs and I0/I intensity linearly ranged from 1.5 × 10(-8) M to 1.8 × 10(-6) M with the detection limit of 4.3 × 10(-9) M.

A novel solid-state electrochemiluminescence sensor for detection of cytochrome c based on ceria nanoparticles decorated with reduced graphene oxide nanocomposite.

A novel ultrasensitive sensing system for the rapid detection of cytochrome c (Cyt C) was developed on the basis of an electrochemiluminescence (ECL) method. A nanocomposite biosensor was made of reduced graphene oxide decorated with cerium oxide/tris(2,2-bipyridyl)ruthenium(II)/chitosan (CeO2NPs-RGO/ Ru(bpy)3 (2+)/CHIT) and used for this purpose. The ECL signal was produced by an electrochemical interaction between Ru(bpy)3 (2+) and tripropyl amine (TPA) on the surface of the electrode. Addition of Cyt C to the solution decreases the ECL signal due to its affinity for TPA and inhibition of its reaction with Ru(bpy)3 (2+). The effects of the amount of CeO2NPs-RGO, Ru(bpy)3 (2+), TPA concentration as a co-reactant, and the pH of the electrolyte solution on the ECL signal intensity were studied and optimized. The results showed that the method was fast, reproducible, sensitive, and stable for the detection of Cyt C. The method has a linear range from 2.5 nM to 2 µM (R (2) = 0.995) with a detection limit of 0.7 nM. Finally, the proposed biosensor was used for the determination of Cyt C in human serum samples with RSDs of 1.8-3.6 %. The results demonstrate that this solid-state ECL quenching biosensor has high sensitivity, selectivity, and good stability. Graphical Abstract A novel solid-state electrochemiluminescence sensor for detection of cytochrome C based on Ceria Nanoparticles Decorated Reduced Graphene Oxide Nanocomposite.

A Novel Cobalt-Sensitive Fluorescent Chemosensor Based on Ligand Capped CdS Quantum Dots.

In this work, a ligand capped CdS QDs was synthesized, characterized and its fluorescence behavior was studied. The surface of the CdS QDs was modified using N-(3-methyl-2-(thiophene-2-carboxamido) phenyl) thiophene-2-carboxamide. The immobilized ligand on the surface of the CdS QDs can interact by cationic species due to the existence of donating atoms in its structures. Thus, effect of some metal cations on the fluorescent intensity of the ligand capped CdS QDs were studied. It was found that fluorescence intensity of the modified CdS QDs quenched selectively by addition of Co(II) ion in comparison with other cations tested. The ligand capped CdS QDs can be used as a fluorescent bulk chemosensor for detection of Co(II) ions. The fluorescent quenching is linear in the range of 1.0 × 10(-5) to 1.5 × 10(-4) mol L(-1) of Co(II) ions. The limit of detection was obtained 8.3 × 10(-7) mol L(-1). The nanosensor exhibits high selectivity toward Co(II) ions in comparison with common metal ions.

Sensitive determination of carbidopa through the electrochemiluminescence of luminol at graphene-modified electrodes.

Using the concept of electrogenerated chemiluminescence (ECL), a sensitive analytical method for the determination of carbidopa is described. Electro-oxidation of carbidopa on the surface of a graphene oxide (GO)-modified gold electrode (GE) leads to enhancement of the weak emission of oxidized luminol. Under optimum experimental conditions, the ECL signal increases linearly with increasing carbidopa concentrations over a range of 1.0 × 10(-9) -1.7 × 10(-7) M, with a detection limit of 7.4 × 10(-10) M. The proposed ECL method was successfully used for the determination of carbidopa in urine samples.

Rapid enzyme-free detection of miRNA-21 in human ovarian cancerous cells using a fluorescent nanobiosensor designed based on hairpin DNA-templated silver nanoclusters.

BACKGROUND: Cancer is known as one of the main non-communicable diseases and the leading cause of death in the new era. Early diagnosis of cancer requires the identification of special biomarkers. Currently, microRNAs (miRNAs) have attracted the attention of researchers as useful biomarkers for cancer early detection. Hence, various methods have been recently developed for detecting and monitoring miRNAs. Among all miRNAs, detection of miRNA-21 (miR-21) is important because it is abnormally overexpressed in most cancers. Here, a new biosensor based on silver nanoclusters (AgNCs) is introduced for detecting miR-21. RESULTS: As a fluorescent probe, a rationally designed hairpin sequence containing a poly-cytosine motif was used to facilitate the formation of AgNCs. A guanine-rich sequence was also employed to enhance the sensing signal. It was found that in the absence of miR-21, adding a guanine-rich sequence to the detecting probe caused only a slight change in the fluorescence emission intensity of AgNCs. While in the presence of miR-21, the emission signal enhanced. A direct correlation was observed between the increase in the fluorescence of AgNCs and the concentration of miR-21. The performance of the proposed biosensor was characterized thoroughly and confirmed. The biosensor detected miR-21 in an applicable linear range from 9 pM to 1.55 nM (LOD: 2 pM). SIGNIFICANCE: The designed biosensor was successfully applied for detecting miR-21 in human plasma samples and also in human normal and lung and ovarian cancer cells. This biosensing strategy can be used as a model for detecting other miRNAs. The designed nanobiosensor can measure miR-21 without using any enzymes, with fewer experimental steps, and at a low cost compared to the reported biosensors in this field.

Early fetal sex determination using a fluorescent DNA nanosensing platform capable of simultaneous detection of SRY and DYS14 sequences in cell-free fetal DNA.

Early fetal sex determination is of crucial importance in the management of prenatal diagnosis of X-linked genetic abnormalities and congenital adrenal hyperplasia. The development of an efficient and simple method for high-sensitivity, affordable, and rapid screening of cell-free fetal DNA (cffDNA) is crucial for fetal sex determination in early pregnancy. In this study, single- and dual-fluorophore DNA biosensors based on multi-walled carbon nanotubes (MWCNT) were fabricated for the individual and simultaneous detection of the SRY gene and DYS14 marker in cffDNA obtained from maternal plasma samples. This nanosensing platform is based on the immobilization of single-stranded DNA (ssDNA) probes, labeled with ROX or FAM fluorophores, on MWCNT, resulting in the quenching of fluorescence emission in the absence of the targets. Upon the addition of the complementary target DNA (ctDNA) to the hybridization reaction, the fluorescence emission of fluorophore-labeled probes was significantly recovered to 79.5 % for ROX-labeled probes (i.e. SRY-specific probes), 81.5 % for FAM-labeled probes (i.e. DYS14-specific probes), and 65.9 % for dual-fluorophore biosensor compared to the quenching mode. The limit of detection (LOD) for ROX, and FAM was determined to be 4.5 nM, and 7.6 nM, respectively. For dual-color probes, LOD was found to be 5.4 (ROX) and 9.2 nM (FAM). Finally, the clinical applicability of the proposed method was confirmed through the detection of both biomarkers in maternal plasma samples, suggesting that the proposed nanosensing platform may be useful for the early detection of fetal sex using cffDNA.

Simple detection of gluten in wheat-containing food samples of celiac diets with a novel fluorescent nanosensor made of folic acid-based carbon dots through molecularly imprinted technique.

A nanosensor is designed for rapid detection of the gluten content of wheat-containing samples. Gluten is a plant protein that causes allergy in individuals and leads to celiac disease. Since in a celiac diet trace amounts of gluten are able to prompt allergic reactions, a food-allergen label must be provided on foodstuffs and be seriously considered by food industries. Various analytical methods and commercial immunoassays are used for such analyses but prices per test, especially for low-income countries are high. Thus, a rapid, sensitive, simple, and inexpensive detecting tool seems essential. A solution can be designing a gluten optical nanosensor. The nanosensor is made of folic-acid-carbon dots and gluten molecularly templates embedded simultaneously in a silicate matrix. Adding gluten to the solution of this nanostructure and its adsorbing on the blank templated space on the nanostructure causes fluorescence enhancement. The concentration range of gluten detection was 0.36 to 2.20 µM.

Carbendazim trace analysis in different samples by using nanostructured modified carbon paste electrode as voltametric sensor.

Carbendazim (CBZ) as a fungicide is widely used to control fungal diseases in agriculture, veterinary medicine, and forestry. In this study, molecularly imprinted nano-size polymer was synthesized and then combined with multiwalled carbon nanotubes to be used as modifiers for carbon paste electrode to detect carbendazim in water, fruit, agricultural wastewater, and urine samples by using the square-wave technique. Some common ions and pesticides were investigated as interferences in analyte, to study the sensitivity and selectivity of the modified carbon paste electrode for carbendazim. The combination of molecular imprinted polymer and multiwalled carbon nanotubes showed a significant increase in peak current in electrocatalytic activity on electrochemical detection of the carbendazim. The linear range of 1 × 10-10 to 5 × 10-8 molL-1 was investigated. The lower detection limit was determined to be 0.2 × 10-10 molL-1, and the relative standard deviation for the target molecule analysis was 2.07%. The result reveals that the modified carbon paste sensor with Multi walled Carbon Nanotubes (MWCNTs) and Molecular Imprinted Polymer (MIPs) can be used easily, without preparation steps that have high selectivity and sensitivity to determine carbendazim in water, fruit, agricultural wastewater, and urine samples.