Nicotinamide-Functionalized Carbon Quantum Dot as New Sensing Platform for Portable Quantification of Vitamin B12 in Fluorescence, UV-Vis and Smartphone Triple Mode.

Development of an efficient, portable and simple nanosensor-based systems with reliable analytical performance for on-site monitoring of vitamin B12 (VB12) are still major problems and a challenging work for quality control of manufacturers. Herein, a new fluorescence, UV-Vis and smartphone triple mode nanosensors were designed for the simultaneous detection of VB12 with high sensitivity and accuracy. A novel nanosensor was synthesized through nicotinamide-functionalizing of carbon quantum dot (NA-CQDs) by an one-step microwave-assisted method with green approach. The NA-CQDs sensor showed excellent fluorescence properties and wide linear ranges from 0.1-60 µM with the detection limits of 31.7 nM. Moreover, color changes of NA-CQDs induced by the VB12 could also be detected by UV-Vis spectrophotometer and inhouse-developed application installed on smartphone as a signal reader, simultanusly. The Red, Green and Blue (RGB) intensities of the colorimetric images of NA-CQDs/VB12 system which taken by smartphone's camera converted into quantitative values by the application. A smartphone-integrated with NA-CQDs as colorimetric sensing platform displays good linear ranges (4.16 to 66.6 µM) for on-site determination of VB12 with detection limit of 1.40 µM. The method was successfully applied in the determination of VB12 in complex pharmaceutical supplement formulations without any sample pre-treatment and matrix interfering effects. The recovery results (96.52% to 105.10%) which were in agreement with the reference methods, demonstrating the capability of the smartphone-assisted colorimetric sensing platform in many on-site practical applications of quality controls.

Portable smartphone-based colorimetric system for simultaneous on-site microfluidic paper-based determination and mapping of phosphate, nitrite and silicate in coastal waters.

Early and on-site detection of environmental contaminations and physicochemical parameters of seawater is increasingly preferred to guarantee hazard minimization in many settings. In this paper, we describe a combination of microfluidic paper-based sensors (µPADs) and an Android-based smartphone application (App) for simultaneous on-site quantification of phosphate (PO4-P), silicate (SiO3-Si) and nitrite (NO2-N) in coastal seawater samples. The developed App can on-site capture, process, and quantify the µPAD colorimetric outputs. This App uses an image processing algorithm for quantifying color intensity and relating the RGB components to the analyte concentrations. The GPS-tagged data can be stored on the smartphone or sent via social networks. The significant factors affecting the detection of the analytes were optimized using Box-Behnken design. Under optimized parameters, the proposed method presented the linear ranges between 5 and 100 µg L-1 for phosphate (R2 = 0.9909), 5 to 100 µg L-1 (R2 = 0.9819) for nitrite and 10 to 600 µg L-1 (R2 = 0.9933) for silicate. The LODs of the method for detection of phosphate, nitrite and silicate were 1.52 µg L-1, 0.61 µg L-1 and 3.74 µg L-1, respectively. The device was successfully used to simultaneous analyze and map the PO4-P, SiO3-Si and NO2-N of Bushehr coastal seawater samples (Iran). The results were confirmed by the lab-based conventional colorimetric methods using spectrophotometer.

Multisensor-integrated organs-on-chips platform for automated and continual in situ monitoring of organoid behaviors.

Organ-on-a-chip systems are miniaturized microfluidic 3D human tissue and organ models designed to recapitulate the important biological and physiological parameters of their in vivo counterparts. They have recently emerged as a viable platform for personalized medicine and drug screening. These in vitro models, featuring biomimetic compositions, architectures, and functions, are expected to replace the conventional planar, static cell cultures and bridge the gap between the currently used preclinical animal models and the human body. Multiple organoid models may be further connected together through the microfluidics in a similar manner in which they are arranged in vivo, providing the capability to analyze multiorgan interactions. Although a wide variety of human organ-on-a-chip models have been created, there are limited efforts on the integration of multisensor systems. However, in situ continual measuring is critical in precise assessment of the microenvironment parameters and the dynamic responses of the organs to pharmaceutical compounds over extended periods of time. In addition, automated and noninvasive capability is strongly desired for long-term monitoring. Here, we report a fully integrated modular physical, biochemical, and optical sensing platform through a fluidics-routing breadboard, which operates organ-on-a-chip units in a continual, dynamic, and automated manner. We believe that this platform technology has paved a potential avenue to promote the performance of current organ-on-a-chip models in drug screening by integrating a multitude of real-time sensors to achieve automated in situ monitoring of biophysical and biochemical parameters.

Rapid and sensitive fluorescence and smartphone dual-mode detection of dopamine based on nitrogen-boron co-doped carbon quantum dots.

A dual-mode fluorescence and colorimetric biosensor based on nitrogen-boron co-doped carbon quantum dot (N-B CQDs) for rapid and sensitive detection of dopamine (DA) was developed. The quantum dot luminescent materials, N-B CQDs, were prepared by a one-step microwave-assisted method. The N-B CQDs were characterized using SEM, HR-TEM, XRD, FT-IR, Raman, fluorescence, and UV-Vis techniques. The dual-mode assays of fluorescence and colorimetric methods were used for detection of DA. The high fluorescent N-B CQDs mediated turn-off assay for the facile room temperature detection of dopamine via inner filter effect (IFE) and Forster resonance energy transfer (FRET) processes at basic pH. The colorimetric detection of DA was also developed via in-house android application using a smartphone and N-B CQD solution-based nanosensor. The smartphone-based colorimetric biosensors generated more reliable information for quantitative analysis of color changes than the naked eye. Furthermore, a smartphone application with N-B CQD solution-based nanosensor was integrated to monitor the color changes through the DA addition. Wide linear ranges were achieved for DA in the ranges 0.25-50 µM and 5-500 µM with fluorescence and smartphone-based method, respectively. The satisfactory results of the dual-mode detection of DA, not only in aqueous solution, but also in human urine and serum biological sample demonstrated its potential application in biosensing, as a point of care diagnostic tool. Graphical abstract.

Aptamer-Based Microfluidic Electrochemical Biosensor for Monitoring Cell-Secreted Trace Cardiac Biomarkers.

Continual monitoring of secreted biomarkers from organ-on-a-chip models is desired to understand their responses to drug exposure in a noninvasive manner. To achieve this goal, analytical methods capable of monitoring trace amounts of secreted biomarkers are of particular interest. However, a majority of existing biosensing techniques suffer from limited sensitivity, selectivity, stability, and require large working volumes, especially when cell culture medium is involved, which usually contains a plethora of nonspecific binding proteins and interfering compounds. Hence, novel analytical platforms are needed to provide noninvasive, accurate information on the status of organoids at low working volumes. Here, we report a novel microfluidic aptamer-based electrochemical biosensing platform for monitoring damage to cardiac organoids. The system is scalable, low-cost, and compatible with microfluidic platforms easing its integration with microfluidic bioreactors. To create the creatine kinase (CK)-MB biosensor, the microelectrode was functionalized with aptamers that are specific to CK-MB biomarker secreted from a damaged cardiac tissue. Compared to antibody-based sensors, the proposed aptamer-based system was highly sensitive, selective, and stable. The performance of the sensors was assessed using a heart-on-a-chip system constructed from human embryonic stem cell-derived cardiomyocytes following exposure to a cardiotoxic drug, doxorubicin. The aptamer-based biosensor was capable of measuring trace amounts of CK-MB secreted by the cardiac organoids upon drug treatments in a dose-dependent manner, which was in agreement with the beating behavior and cell viability analyses. We believe that, our microfluidic electrochemical biosensor using aptamer-based capture mechanism will find widespread applications in integration with organ-on-a-chip platforms for in situ detection of biomarkers at low abundance and high sensitivity.

Electrochemically controlled in-tube solid phase microextraction of naproxen from urine samples using an experimental design.

A new in-tube solid phase microextraction approach named electrochemically controlled in-tube solid phase microextraction (EC in-tube SPME) has been reported. In this approach, in which electrochemistry and in-tube SPME were combined, the total analysis time was decreased and the sensitivity was increased. After electropolymerization of pyrrole on the inner surface of a stainless steel tube, the polypyrrole (PPy)-coated in-tube SPME was coupled on-line to high performance liquid chromatography (HPLC) to achieve automated in-tube SPME-HPLC analysis. After the completion of the EC-in-tube SPME-HPLC system, the PPy-coated tube was used as a working electrode for the uptake of naproxen. It was found that the extraction efficiency could be significantly enhanced using the constant potential. Plackett-Burman design was employed for screening, to determine the variables significantly affecting the extraction efficiency. The significant factors were then optimized using a Box-Behnken design. The linear range and detection limit (S/N = 3) were 0.5-1000 and 0.07 µg L(-1), respectively. Urine samples were successfully analyzed by the proposed method.

Distribution of hydrogen sulfide, nitrogen and phosphorous species in inshore and offshore sediments of the south Caspian Sea.

This study aimed to geochemically investigate the sediments of the south Caspian Sea at different depths in summer and winter 2020. Sampling was conducted in 5 transects along the south coastline of the Caspian Sea and sediment grain size, hydrogen sulfide, Oxidation-reduction potential (Eh), total nitrogen, nitrite, nitrate, ammonium, total phosphorus, organic and inorganic phosphorous were measured. Eh values showed significant differences between seasons and between different transects (p < 0.05). Hydrogen sulfide ranged from 1.87 to 307.00 ppm. No significant difference was observed in hydrogen sulfide between seasons and among depths (p > 0.05). Total, inorganic and organic phosphorus contents were 782.96-1335.79 ppm, 639.66-1183.60 ppm, and 42.58-205.46 ppm, respectively. Total nitrogen revealed significant differences among transects (p < 0.05). Based on sediment quality guidelines, most sampling sites had alerting conditions for organic matter, and phosphorous contamination was detected at all stations. Anoxic condition was seen at most sites according to sedimentary Eh.

Distribution of microplastics in upstream and downstream surface waters of the Iranian rivers discharging to the southern Caspian Sea.

Microplastic pollution in the riverine ecosystems has caught many attentions in the scientific literatures. However, little information is available about the abundance and distribution of microplastics of the rivers discharging to the Caspian Sea. The aim of this study was to assess the spatial and seasonal distribution of microplastics in the surface waters of thirteen rivers discharging to the southern Caspian Sea. Microplastics were found in all stations with uneven distributions. The average concentrations of microplastics in the stations during snowmelt and dry seasons were 1.406 ± 0.1380 microplastics/m3 and 0.4070 ± 0.01500 microplastics/m3, respectively. Positive gradients of the rivers microplastics concentration from upstream to downstream were found. White/transparent polyethylene (PE) particles with the shape of fragment/film and the length (L) of ≤ 1 mm were the most common microplastics in the surface waters of the rivers discharging to the southern Caspian Sea. Also, the mean concentration of microplastics in spring snowmelt and runoff period was 3.45 times higher than in dry period. Factors such as sewage and household wastes; landfills; and recreational-tourism, fishing and agricultural activities along the rivers may contribute to microplastic contamination in downstream stations. Our data provide baseline information of microplastics in surface waters of rivers discharging to the southern Caspian Sea.

Sources and hotspots of microplastics of the rivers ending to the southern Caspian Sea.

The occurrence of microplastics (MPs) in beach sediments of the southern Caspian Sea was well documented, however, there are still many unknowns about the abundances and distributions of MPs in the rivers ending to the Caspian Sea. Here, bank sediments of 26 sites in the thirteen rivers were surveyed in two seasons. However, there was not any significant difference (p > 0.05) between the concentrations of MPs during the two seasons. MPs were detected in all samples with mean concentrations of 214.08 ± 14.35 MPs/kg. The most common size, shape, color, and polymer types of MPs were L < 300 µm, fragment/film, white/transparent, and polystyrene (PS), respectively. In all rivers, positive MP gradients from upstream to downstream were observed. Maximum concentrations of MPs were found in the downstream parts of Chalus, Haraz, and Safarud rivers. Recreational-tourism and fishing activities had significant positive relationships (p < 0.05) with concentration of MPs in the rivers.

Catalytic nanozyme Zn/Cl-doped carbon quantum dots as ratiometric fluorescent probe for sequential on-off-on detection of riboflavin, Cu2+ and thiamine.

A novel metal-doped Zn/Cl carbon quantum dots (Zn/Cl-CQDs) was developed successfully as ratiometric fluorescent probes for the sequential on-off-on detection of riboflavin, Cu2+ ion and thiamine. The excellent catalytic performance of the Zn/Cl-CQDs nanozyme serves as an ideal platform for sensitive detection of thiamine. Due to the addition of riboflavin to the Zn/Cl-CQDs, the blue emission peak of Zn/Cl-CQDs at 440 nm remains unaffected and used as an internal reference approach, while the green emission peak of riboflavin at 520 nm appeared and increased remarkably. Following the presence of Cu2+, a quenching blue fluorescence signal of Zn/Cl-CQDs was observed which resulted in consequent fluorescent 'turn-off' response toward Cu2+ ion. Finally, upon the addition of thiamine to the above solution under alkaline condition, the blue emission of Zn/Cl-CQDs was gradually recovered. The prepared Zn/Cl-CQDs could act as a nanozyme catalyst for directly catalyzing the oxidation of non-fluorescent substrate of thiamine to produce highly fluorescent substrate of thiochrome. As a result, the blue fluorescence emission peak at 440 nm was recovered. Eventually, the sequential detection properties of ratiometric probes for riboflavin, Cu2+ ion and thiamine were successfully applied in VB2 tablets, drinking water and VB1 tablet with good recoveries of 96.21%, 98.25% and 98.44%, respectively.

Microplastic pollution in inshore and offshore surface waters of the southern Caspian Sea.

In this study, as the first comprehensive monitoring, the occurrence of microplastics (MPs) in inshore and offshore surface waters of the southern Caspian Sea was investigated. Our data indicated that MPs, which were detected in all the samples, were widely distributed in the thirteen studied stations. Non-normally distribution of the MPs was observed among the studied stations (p<0.05). The average concentration of microplastics in the selected stations was 0.246 ± 0.020 MP/m3. In most of the transects, negative gradients of MPs from coastal waters to deeper waters were observed. The dominant size and color of MPs in the inshore and offshore water samples was 1000-5000 µm and white-transparent, respectively. Films and fibers constituted about 50% and 40% of the total number of MPs of the water samples, respectively. Also, polyethylene (PE), polypropylene (PP) and polyethylene terephthalate (PET) were the three main polymer types of microplastics in the inshore and offshore surface waters. Our data provide valuable evidence for the comparative assessing of future data regarding decreases or increases of MPs in the southern Caspian Sea.

Spatial distribution of microplastics in sandy beach and inshore-offshore sediments of the southern Caspian Sea.

The occurrence of microplastics (MPs) in nearshore zones of the southern Caspian coasts is well documented; however, no data are available on MP occurrence in offshore sediments. In this study, six sandy beach stations and 18 inshore-offshore stations (six transects) were surveyed. MPs were detected in all sediment samples. The mean abundances of MPs in the beach and inshore-offshore stations were 196.67 ± 11.58 and 103.15 ± 7.21 MPs/kg, respectively. Fibers constituted the most common shape of MPs. Polystyrene (PS) and polyethylene terephthalate (PET) were the major polymer types found in the beach and inshore-offshore sediments, respectively. In most transects, negative MP gradients were observed from nearshore to offshore, which showed that coastal fishing, tourism, and rivers were the main sources of MPs in this area. These results will improve our understanding on MPs pollution in the marine ecosystem. We recommend further MP studies in different parts of the Caspian Sea to develop appropriate management programs.

In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube.

In-tube magnetic solid phase microextraction (in-tube MSPME) of fluoroquinolones from water and urine samples based on the use of sodium dodecyl sulfate (SDS) coated Fe3O4 nanoparticles packed tube has been reported. After the preparation of Fe3O4 nanoparticles (NPs) by a batch synthesis, these NPs were introduced into a stainless steel tube by a syringe and then a strong magnet was placed around the tube, so that the Fe3O4 NPs were remained in the tube and the tube was used in the in-tube SPME-HPLC/UV for the analysis of fluoroquinolones in water and urine samples. Plackett-Burman design was employed for screening the variables significantly affecting the extraction efficiency. Then, the significant factors were more investigated by Box-Behnken design. Calibration curves were linear (R(2)>0.990) in the range of 0.1-1000µgL(-1) for ciprofloxacin (CIP) and 0.5-500µgL(-1) for enrofloxacin (ENR) and ofloxacin (OFL), respectively. LODs for all studied fluoroquinolones ranged from 0.01 to 0.05µgL(-1). The main advantages of this method were rapid and easy automation and analysis, short extraction time, high sensitivity, possibility of fully sorbent collection after analysis, wide linear range and no need to organic solvents in extraction.

Electrochemically controlled in-tube solid phase microextraction.

We report a new in-tube solid phase microextraction approach named electrochemically controlled in-tube solid phase microextraction (EC in-tube SPME). This approach, which combined electrochemistry and in-tube SPME, led to decrease in total analysis time and increase in sensitivity. At first, pyrrole was elctropolymerized on the inner surface of a stainless steel tube. Then, the polypyrrole (PPy)-coated in-tube SPME was coupled on-line to liquid chromatography (HPLC) to achieve automated in-tube SPME-HPLC analysis. After the completion of EC-in-tube SPME-HPLC setup, the PPy-coated tube was used as working electrode for uptake of diclofenac as target analyte. Extraction ability of the tube in presence and in absence of applied electrical field was investigated. It was found that, under the same extraction conditions, the extraction efficiency could be greatly enhanced by using the constant potential. Important factors are also optimized. The detection limit (S/N=3) and precision were 0.1 µg L(-1) and 4.4%, respectively.

Nanostructure conducting molecularly imprinted polypyrrole film as a selective sorbent for benzoate ion and its application in spectrophotometric analysis of beverage samples.

The benzoate anion was selectively extracted by electrochemically controlled solid-phase microextraction (EC-SPME) using a electro-synthesised nanostructure conducting molecularly imprinted polypyrrole (CMIP) film that imprinted for benzoate ions (template ion). The sorbent behaviors of CMIP were characterised using spectrophotometry analysis. The effect of pH, uptake and released times and potentials, template ion concentration, and interference were investigated, and experimental conditions optimised. The film exhibited excellent selectivity in the presence of potential interference from anions including salicylate, sorbate, citrate, phosphate, acetate and chloride ions. The calibration graph was linear (R(2)⩾ 0.993) in the range 1.1 × 10(-5)-5.5 × 10(-4) mol L(-1) and detection limit was 5.2 × 10(-6) mol L(-1). The relative standard deviation was less than 4.5% (n=3). The CMIP film, as a solid-phase micro-extraction absorbent, was applied for the selective clean up and quantification of benzoate in beverage samples using the EC-SPME-spectrophotometric method. The results were in agreement with those obtained using HPLC analysis. This method has a good selectivity and mechanical stability and is disposable simple to construct. However, HPLC method is more selective for determination of benzoate in some food products which have interference compounds such as vanilla and flavoring agents.