Standard Addition Research Articles

Hydrogen peroxide and glucose detection using surface plasmon resonance imaging biosensor with corrodible silver thin film

A surface plasmon resonance imaging (SPRI)-based biosensor is demonstrated for the detection of both hydrogen peroxide (H2O2) and glucose. The H2O2 to be detected acts as an oxidant and etch the silver film. This process gradually effects on resonance condition and consequently the reflected light intensity at a fixed angle. The etching rate of the silver film shows a clear relation with the H2O2 concentration. Therefore, monitoring the reflected light intensity progressively changing over a few minutes, enables accurate detection of H2O2 concentrations ranging from 0 to 200 μM (within physiological range of 0.25–50 μM), with a remarkable limit of detection (LOD) as low as 40 nM. In this regard, the behavior of the surface plasmon resonance (SPR) dip in response to the reduction of the silver film thickness is predicted by Winspall simulation software. These simulation results are in good agreement with the experimental results. Moreover, the proposed method can be applied to determine glucose concentrations ranging from 0 to 10 mM, encompassing the physiological range of 3–8 mM. This is achieved by observing the generated H2O2 through the enzymatic oxidation reaction between glucose and glucose oxidase (Gox). The sensor demonstrates remarkable sensitivity and selectivity, with a detection limit as low as 175 μM for glucose concentration. Furthermore, accurate measurement of glucose concentration in an actual human serum sample is achievable with the proposed sensor, using the standard addition method. The suggested glucose sensor shows promising prospects for use in routine glucose testing, employing a label-free, real-time, and multiplex detection approach.© 2017 Elsevier Inc. All rights reserved.

Adaptation of Conductometric Monoenzyme Biosensor for Rapid Quantitative Analysis of L-arginine in Dietary Supplements.

The present study reports on the development, adaptation, and optimization of a novel monoenzyme conductometric biosensor based on a recombinant arginine deiminase (ADI) for the determination of arginine in dietary supplements with a high accuracy of results. Aiming for the highly sensitive determination of arginine in real samples, we studied the effect of parameters of the working buffer solution (its pH, buffer capacity, ionic strength, temperature, and protein concentration) on the sensitivity of the biosensor to arginine. Thus, it was determined that the optimal buffer is a 5 mM phosphate buffer solution with pH 6.2, and the optimal temperature is 39.5 °C. The linear functioning range is 2.5-750 µM of L-arginine with a minimal limit of detection of 2 µM. The concentration of arginine in food additive samples was determined using the developed ADI-based biosensor. Based on the obtained results, the most effective method of biosensor analysis using the method of standard additions was chosen. It was also checked how the reproducibility of the biosensor changes during the analysis of pharmaceutical samples. The results of the determination of arginine in real samples using a conductometric biosensor based on ADI clearly correlated with the data obtained using the method of ion-exchange chromatography and enzymatic spectrophotometric analysis. We concluded that the developed biosensor would be effective for the accurate and selective determination of arginine in dietary supplements intended for the prevention and/or elimination of arginine deficiency.

A new composite electrode based on hemin/copper nanoparticles/oxidized graphitic nitride for sensitive detection of organophosphorus pesticide

A new composite of Hemin, copper oxide nanoparticle, and oxidized g-C3N4 (He/CuO/Oxi-gC3N4) is fabricated and successfully employed for electrocatalysis of the chlorinated Organo-Phosphorous pesticide, Dichlorvos. Hemin (He) is a well-known metalloporphyrin, which has an electroactive center of Fe3+. Pure hemin aggregates easily due to its poor solubility in an aqueous solution and hence is usually composited with other electroactive materials. The composite electrode has been thoroughly characterized including SEM, AFM, FT-IR, Raman spectroscopy, XPS, and Voltammetric techniques for the determination of Dichlorvos in water sample. Herein we have used a composite of Hemin with green synthesized copper oxide nanoparticle, (CuO)-Nps adsorbed on a porous oxidized graphitic carbon nitride surface (Oxi-gC3N4). The obtained linear range for Dichlorvos was found to be 2.5 × 10−10 to 62.5 × 10−10 M with a detection limit of 0.83×10−11 M. The composite electrode performance was further extended for use in real samples like lake water, well water, and tap water containing Dichlorvos. The analysis was carried out based on the standard addition method. Good recovery ranges from 99.0 to 100.0% were observed. Also, the He/CuO/Oxi-gC3N4 showed very good antibacterial activity against gram-positive and gram-negative bacteria.

Internal Standard Addition System for Online Breath Analysis.

Breath analysis with secondary electrospray ionization (SESI) coupled to mass spectrometry (MS) is a sensitive method for breath metabolomics. To enable quantitative assessments using SESI-MS, a system was developed to introduce controlled amounts of gases into breath samples and carry out standard addition experiments. The system combines gas standard generation through controlled evaporation, humidification, breath dilution, and standard injection with the help of mass-flow controllers. The system can also dilute breath, which affects the signal of the detected components. This response can be used to filter out contaminating compounds in an untargeted metabolomics workflow. The system's quantitative capabilities have been shown through standard addition of pyridine and butyric acid into breath in real time. This system can improve the quality and robustness of breath data.

Plastic Quantification and Polyethylene Overestimation in Agricultural Soil Using Large-Volume Pyrolysis and TD-GC-MS/MS.

Quantification of microplastics in soil is needed to understand their impact and fate in agricultural areas. Often, low sample volume and removal of organic matter (OM) limit representative quantification. We present a method which allows simultaneous quantification of microplastics in homogenized, large environmental samples (>1 g) and tested polyethylene (PE), polyethylene terephthalate (PET), and polystyrene (PS) (200-400 μm) overestimation by fresh and diagenetically altered OM in agricultural soils using a new combination of large-volume pyrolysis adsorption with thermal desorption-gas chromatography-tandem mass spectrometry (TD-GC-MS/MS). Characteristic MS/MS profiles for PE, PET, and PS were derived from plastic pyrolysis and allowed for a new mass separation of PET. Volume-defined standard particles (125 × 125 × 20 μm3) were developed with the respective weight (PE: 0.48 ± 0.12, PET: 0.50 ± 0.10, PS: 0.31 ± 0.08 μg), which can be spiked into solid samples. Diagenetically altered OM contained compounds that could be incorrectly identified as PE and suggest a mathematical correction to account for OM contribution. With a standard addition method, we quantified PS, PET, and PEcorrected in two agricultural soils. This provides a base to simultaneously quantify a variety of microplastics in many environmental matrices and agricultural soil.

Supramolecular Solvent-Based Liquid–Liquid Microextraction and Preconcentration of Rhodamine B, Methyl Violet, and Eriochrome Black T in Water, Cosmetics, and Food with Spectrophotometric Quantification

Dyes are complex organic compounds that are utilized in many industries. However, excessive exposure to dyes increases susceptibility to various diseases. Their concentrations are below the detection level of many available analytical techniques. Therefore, preconcentration methodology is highly needed prior to their quantification. Herein, a new supramolecular solvent decanol-tetrahydrofuran-based liquid-liquid microextraction method has been established for the first time for the determination of Rhodamine B (Rh B), methyl violet (MV), and Eriochrome black T (EBT) in commercial spices, cosmetics, and water before spectrophotometric quantification. 556, 590, and 530 nm were used for the measurement of Rhodamine B (Rh B), methyl violet (MV), and Eriochrome black T (EBT), respectively. The optimization experiments revealed the best performance at pH 7, 0.9 mL of decanol, 1.3 mL of tetrahydrofuran (THF), and 5 min of vortex time. Under optimized conditions, the limits of detection (LOD) (0.480–0.511 µg L−1), limits of quantification (LOQ) (1.455–1.549 µg L−1), preconcentration factor (PF) (15–20), enhancement factor (EF) (15–20), and relative standard deviation (RSD) (0.5–0.8%) were evaluated. The validation of the method was carried out by standard addition experiments for food, cosmetic, and environmental water samples. The recovery results from 95 ± 6 to 100 ± 4% demonstrate that the method can be successfully applied to practical analysis.

Fabrication and characterization of model wireless biosensor-based electrochemical impedance spectroscopy (EIS) for detecting HER2 in plasma as therapeutics

PurposeEarly prediction of any type of cancer is important for the treatment of this type of disease, therefore, our target to evaluate whether monitoring early changes in plasma human epidermal growth factor receptor 2 (HER2) levels (using EIS), could help in the treatment of breast cancer or not? Human epidermal growth factor receptor 2 (HER2) overexpression is an important biomarker for treatment selection in earlier stages of cancers. The combined detection of the HER2 gene in plasma for blood cancer provides an important reference index for the prognosis of metastasis to other tissues. For this purpose, the authors fabricated and characterized a model wireless biosensor-based electrochemical impedance spectroscopy (EIS) for detecting HER2 plasma as therapeutics.Design/methodology/approachMost sensors generally are fabricated based on a connection between component of the sensors and the external circuits through wires. Although these types of sensors provide suitable sensitivities and also quick responses, the connection wires can be limited to the sensing ability in various devices approximately. Therefore, the authors designed a wireless sensor, which can provide the advantages of in vivo sensing and also long-distance sensing, quickly.FindingsThe biosensor structure was designed for detection of HER2, HER3 and HER-4 from lab-on-chip approach with six units of screen-printed electrode (SPE), which is built of an electrochemical device of gold/silver, silver/silver or carbon electrodes. The results exhibited that the biosensor is completely selective at low concentrations of the plasma and HER2 detection via the standard addition approach has a linearity plot, therefore, by using this type of biosensors HER2 in plasma can be detected.Originality/valueThis is then followed by detecting HER2 in real plasma using standard way which proved to have great linearity (R2 = 0.991) proving that this technique can be used to detect HER2 solution in real patients.

Chemical Standardization of Milk Thistle (Silybum marianum L.) Extract Using UHPLC-MS/MS and the Method of Standard Addition.

Extracts prepared from the seeds of the medicinal plant milk thistle [Silybum marianum (L.) Gaertn. (Asteraceae)] are widely used as dietary supplements due to anti-inflammatory, antitumor, and hepatoprotective effects. Called silymarin, the main components of lipophilic extracts of milk thistle seeds are flavonoids and flavonolignans including silybin A, silybin B, isosilybin A, isosilybin B, silydianin, silychristin, taxifolin, and 2,3-dehydrosilybins. The aim of this study was to develop a method based on UHPLC-MS/MS for the chemical authentication and standardization of milk thistle silymarin. Validation included the method of standard addition to account for the lack of a blank matrix. Potential matrix effects were investigated by analyzing silymarin standards dissolved only in the initial UHPLC mobile phase. Measurements of six flavonolignans and taxifolin in the milk thistle extract using UHPLC-MS/MS with standard addition or external standard calibration produced similar results for all analytes except silydianin and 2,3-dehydrosilybin B, which showed significant peak enhancement during negative ion electrospray due to botanical matrix effects. The UHPLC-MS/MS-based method of standard addition requires <10 min per injection and is suitable for the standardization of silymarin from milk thistle in support of preclinical and clinical studies of safety and efficacy.

Does a postmortem redistribution affect the concentrations of the 7 azaindole-derived synthetic cannabinoid 5F-MDMB-P7AICA in tissues and body fluids following pulmonary administration to pigs?

Many fatal intoxications have been reported in connection with the consumption of newer, highly potent synthetic cannabinoids. Yet, a possible postmortem redistribution (PMR) might complicate reliable interpretation of analytical results. Thus, it is necessary to investigate the PMR-potential of new synthetic cannabinoids. The pig model has already proven to be suitable for this purpose. Hence, the aim of this study was to study the PMR of the synthetic cannabinoid 5F-MDMB-P7AICA and its main metabolite 5F-MDMB-P7AICA-dimethylbutanoic acid (DBA). 5F-MDMB-P7AICA (200 µg/kg body weight) was administered by inhalation to anesthetized and ventilated pigs. At the end of the experiment, the animals were euthanized and stored at room temperature for 3 days. Tissue and body fluid samples were taken daily. Specimens were analyzed after solid phase extraction using a standard addition method and LC–MS/MS, blood was quantified after protein precipitation using a validated method. In perimortem samples, 5F-MDMB-P7AICA was found mainly in adipose tissue, bile fluid, and duodenum contents. Small amounts of 5F-MDMB-P7AICA were found in blood, muscle, brain, liver, and lung. High concentrations of DBA were found primarily in bile fluid, duodenum contents, urine, and kidney/perirenal fat tissue. In the remaining tissues, rather low amounts could be found. In comparison to older synthetic cannabinoids, PMR of 5F-MDMB-P7AICA was less pronounced. Concentrations in blood also appear to remain relatively stable at a low level postmortem. Muscle, kidney, fat, and duodenum content are suitable alternative matrices for the detection of 5F-MDMB-P7AICA and DBA, if blood specimens are not available. In conclusion, concentrations of 5F-MDMB-P7AICA and its main metabolite DBA are not relevantly affected by PMR.

Study of the thermal diffusivity in low-response optical systems combining a thermal lensing approach with a standard addition method

Abstract Thermal lensing is a local effect produced by the incidence of a light beam that heats a part of an absorbent material. Mathematical modeling of this photothermal phenomenon allows the determination of the medium’s thermal diffusivity. A pumping-modulated laser (405nm) induces the thermal lensing effect, and a test laser (650nm) generates the photothermal signal measured as a function of the modulation. The thermal diffusivity is obtained from a curve fit of the signal (calibrated for ethanol). In this work, the thermal diffusion coefficients of low-absorbance nanoparticle suspensions are established. This was achieved through the application of a standard addition method. The added analyte, enhance the optical response of SiO 2 nanoparticle suspensions. Different aliquots of tartrazine (analyte) resulted in different values for the thermal diffusion of the samples. It was found that the experimental coefficients of this colloids agree with the theoretical model. Finally, a linear regression allowed to find the thermal coefficient in the zero concentration point.

Estimation of Imatinib Mesylate by Extractive Colorimetric Methods in Bulk and Pharmaceutical Dosage Form

Simple sensitive and accurate extractive spectrophotometric methods have developed for the estimation of Imatinib mesylate in pharmaceutical dosage form. The methods are based on the formation of coloured complexes by the drug with reagents like bromophenol blue, solochrome dark blue and bromocresol green in acidic medium. The ion associated complexes were formed and quantitatively extracted under the experimental condition in chloroform. The absorbance values were measured at 420 nm, 495 nm and 430 nm respectively. The proposed methods were validated statistically. Recoveries of methods were carried out by standard addition methods. The linearity was found to be 1-8 μg/ml, 2 -16μg/ml, 1-16 μg/ ml for methods 1, 2 and 3 respectively. The low values of standard deviation and percentage RSD indicate high precision of methods. Hence these methods are useful for routine estimation of Imatinib mesylate in tablets.

الاستخلاص الانتقائي للكليميبيرايد في المستحضرات الصيدلانية وفي مصل الانسان عن طريق تقنية MIP-SPE المركبة

This paper demonstrates that the synthesizing and storage of molecular-imprinted polymers (MIP) at room temperature using bulk polymerisation of Glimepiride (Glim.) is characterized by high sensitivity, reduced costs, increased stability, and extended life. The research used 1:15:20 mmol ratios of template, monomer and cross-linking agents for the polymerisation in order to ensure an appropriate adsorption capacity. Benzoyl peroxide BPO was employed as the initiator for the functional monomer Allyl chloride C3H5Cl , cross-linked with Ethylene glycol dimethacrylate EGDMA C10H14O4, thereby creating MIP for Glimepiride (Glim-MIP) that could be characterised with UV-Visible Spectrophotometry at 274.5nm, for pharmaceutical drugs. Fourier-transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) was used for the human serum. The elution process that was applied to the template (Glim.) from the Glim-MIP created cavities that were caused by the porogenic mixture solvents that were created from (acetic acid, methanol) 1:9 respectively, successfully removed by repeated washing for 20 hours, the polymer was dried at room temperature. The maximum adsorption capacity was 11.7797 µmol/g using (0.1) g weight of Glim-MIP. which adhered to the Langmuir isotherm model. A solid-phase extraction (SPE) syringe packed with molecular imprinted polymers (MIPs) was employed to selectively separate and pre-concentrate the Glimepiride in multiple pharmaceutical drugs from several sources. The human serum was based on the use of deionized water to dilute the serum, followed by heating of the serum with methanol. Subsequently, few drops of 1N hydrochloric acid were applied to detect Glimepiride at UV region 274.5 nm by applying the standard addition method.

Quantification of linear alkylbenzene sulphonates in complex sludge samples: Influence of matrix effects in calibration methods

Linear Alkylbenzene Sulfonates (LAS) are among the priority organic pollutants in sludge owing to their high concentrations, due to its use as a major cleaning agent (surfactant) in laundry detergents and household cleaning products, and to the concentration limits of 2,600 mg/kg outlined in the EU directive draft for land application of sludge. In this work, a method has been optimized and validated for the accurate quantification of LAS homologues C10-C13 in different types of samples in the sludge treatment and disposal process including primary, secondary, and digested sludge, compost, and soil. The type of matrix had a significant impact on the method’s validation process, resulting in the need of the use of distinct dilution factors for each matrix. Overall, the procedure propose involves a cost-effective and user-friendly technique that combines both extraction and clean-up in a single step (ultrasound-assisted extraction and dispersive solid phase extraction). Analytical determination is conducted using liquid chromatography-tandem mass spectrometry. The method demonstrated excellent accuracy (relative recoveries exceeding 84.5 % across all types of sludge samples) and the limit of quantification enables the measurement of LAS concentrations up to 1000 times lower than the concentration limits stipulated in the EU directive draft. For an accurate quantification, three calibration approaches were tested (external calibration, standard addition, and matrix-matched calibration). Standard addition was the preferred method for quantitative analysis. It helps mitigate matrix effects that could otherwise distort the accuracy of analyte measurements, making it crucial for quality control, especially in monitoring applications where matrix effects may introduce bias into concentration calculations.

Indirect Spectrophotometric Determination of Antidepressant Drugs by Oxidation Using Ponceau 4R Dye

A simple and sensitive indirect spectrophotometric method is developed for the assay of Adrenaline, Dopamine hydrochloride, and Methyldopa in their pure and pharmaceutical preparations. The method is based on the principle of oxidation of the above drugs with a known amount of the oxidizing agent, N-bromosuccinimide (NBS), in hydrochloric acid. The unreacted oxidant bleaches Ponceau 4R dye, then the absorbance of the remaining dye (ΔA) is measured at 507 nm. The method obeyed Beer’s law within the concentration range of 3.5-10, 4-15, and 5-20 μg/mL, with molar absorptivity values of 8.01×104, 5.32×104, and 4.93×104 L. mol-1cm-1 for Adrenaline, Dopamine hydrochloride and Methyldopa, respectively. The recovery ranged between 99.15 to 100.61%, and the relative standard deviation (RSD) was less than 1.42 % for all drug compounds. The method was applied successfully to pharmaceutical preparations for the studied medicinal compounds from different origins, as its results were in good agreement with the original content of the drugs in their pharmaceutical formulations and with the standard addition procedure, which proved that there was no interference by the excipients.

A Highly Sensitive and Selective Fluorescent Sensor for Folic Acid Detection Based on D-penicillamine Stabilized Ag/Cu Alloy Nanoclusters.

In this work, a highly sensitive and selective method for detecting folic acid (FA) was developed using D-penicillamine (DPA) stabilized Ag/Cu alloy nanoclusters (DPA@Ag/Cu NCs). The yellow emission of DPA@Ag/Cu NCs was found to be quenched upon the addition of FA to the system. The fluorescence intensity quenching value demonstrated a linear relationship with FA concentrations ranging from 0.01 to 1200 μM, with a limit of detection (LOD) of 5.3 nM. Furthermore, the detection mechanism was investigated through various characterization analyses, including high resolution transmission electron microscopy, fluorescence spectra, ultraviolet-visible absorption spectra, and fluorescence lifetime. The results indicated that the fluorescence quenching induced by FA was a result of electron transfer from FA to the ligands of DPA@Ag/Cu NCs. The selectivity of the FA sensor was also evaluated, showing that common amino acids and inorganic ions had minimal impact on the detection of FA. Moreover, the standard addition method was successfully applied to detect FA in human serum, chewable tablets and FA tablets with promising results. The use of DPA@Ag/Cu NCs demonstrates significant potential for detecting FA in complex biological samples.

Study on the correlation and difference of qualitative information among three types of UPLC-HRMS and potential generalization in metabolites annotation

The variation of qualitative information among different types of mainstream hyphenated instruments of ultra-performance liquid chromatography coupled to high-resolution mass spectrometry (UPLC-HRMS) makes data sharing and standardization, and further comparison of results consistency in metabolite annotation not easy to attain. In this work, a quantitative study of correlation and difference was first achieved to systematically investigate the variation of retention time (tR), precursor ion (MS1), and product fragment ions (MS2) generated by three typical UPLC-HRMS instruments commonly used in metabolomics area. In terms of the findings of systematic and correlated variation of tR, MS1, and MS2 between different instruments, a computational strategy for integrated metabolite annotation was proposed to reduce the influence of differential ions, which made full use of the characteristic (common) and non-common fragments for scoring assessment. The regular variations of MS2 among three instruments under four collision energy voltages of high, medium, low, and hybrid levels were respectively inspected with three technical replicates at each level. These discoveries could improve general metabolite annotation with a known database and similarity comparison. It should provide the potential for metabolite annotation to generalize qualitative information obtained under different experimental conditions or using instruments from various manufacturers, which is still a big headache in untargeted metabolomics. The mixture of standard compounds and serum samples with the addition of standards were applied to demonstrate the principle and performance of the proposed method. The results showed that it could be an optional strategy for general use in HRMS-based metabolomics to offset the difference in metabolite annotation. It has some potential in untargeted metabolomics.

Indicator displacement-based colorimetric assay for dibutyl phthalate in pharmaceutical products with titanium(IV)-pyridylazo resorcinol (PAR)

Taking advantage of the competitive binding affinity towards Ti(IV) between 4-(2-pyridylazo) resorcinol (PAR) and phthalate, a simple indicator displacement (ID)–based colorimetric assay was designed for indirect determination of a well-known phthalic acid ester, dibutyl phthalate (DBP). The indicator PAR and Ti(IV) formed a purplish-red-colored Ti(IV)-PAR complex (λmax = 540 nm) at a 1:1 ratio. In the presence of pre-hydrolyzed DBP, colorless complex formation of phthalate ion (emerging from alkaline hydrolysis of DBP) with Ti(IV) resulted in a hypsochromic shift in absorbance maximum, accompanying a color change from purplish-red to yellowish-orange (λmax = 390 nm) by the release of PAR from Ti(IV)-PAR system. Based on this mechanism, the linear response range of the system for DBP was found to lie between 0.16 and 0.37 mmol L–1 with an experimental detection limit of 11.6 µmol L–1. The recommended Ti(IV)-PAR system was successfully applied to DBP-containing pharmaceutical products (as real sample) after a simple clean-up process for removing possible water-soluble interferents. The analytical results obtained from the recommended method (by applying the standard addition approach) and the reference liquid chromatography-tandem mass spectrometric (LC–MS/MS) method were statistically compared using DBP-extract of the drug samples. Consequently, a simple and selective colorimetric ID strategy was proposed for the analysis of DBP in pharmaceuticals for the first time.

Analysis of Dimethylsiloxanes in Hydrocarbon Matrices like Marine Fuels Applying a Novel Enrichment Procedure and a Two-Column Gas Chromatography – Mass Spectrometry Measurement

Marine fuels are consumed worldwide in quantities of more than 200 million tons per year. It is not a uniform product, but rather heterogeneous mixtures of hydrocarbons with a wide range of viscosities. Due to the production processes, marine diesel contains dimethylsiloxanes. These lead to damage to marine exhaust catalysts in connection with combustion reactions in the ships’ engines. A novel analytical method, presented here, was developed that allows to investigate these processes and to monitor the dimethylsiloxane contents in complex marine fuel matrices. The key steps of the analytical procedure are analyte enrichment by solid phase extraction (SPE) using thermally activated silica gel and chromatographic separation and measurement by heart-cutting gas chromatography - mass spectrometry. Authentic reference substances for quantification by standard addition are used for the dimethylsiloxane analytes. The clean-up enabled a 90% reduction of the matrix content in the analysis solutions compared to the initial sample. Recovery rates in the range of 87.8% to 111.4% were determined for all analytes (Si3 to Si9). The detection limits of analytes ranged from 0.06 μg/L to 5.68 μg/L. Values of 0.71 μg/L to 23.6 μg/L were determined for the limits of quantification. The newly designed analytical method was successfully applied to real marine fuel samples. The analytical procedure is to be made available to commercial and industrial laboratories as a practical method for controlling siloxane contents in marine fuels to contribute this way to efficiently functioning marine exhaust gas purification.

Dual chemical bonding construction of electrochemical peptide sensor based on GDY/MOFs(Fe) composite for ultra-low determination of prostate-specific antigen

A novel “double chemical bonding” electrochemical peptide biosensor 2FcP-GA-GDY(Fe)@NMIL-B was developed for highly selective, ultrasensitive, and ultrastable identification of prostate-specific antigen (PSA). The C–Fe–O chemical bond linking Fe-Graphdiyne (Fe-GDY) with NH2-MIL88B(Fe) (NMIL88B) as the first chemical bonding of electrode carrier Fe-GDY@NH2-MIL88B(Fe) (GDY(Fe)@NMIL) significantly accelerates electron transport. With glutaraldehyde (GA) as a crosslinking agent, the Schiff-base –NC- formed by GDY(Fe)@NMIL nanocomposites links the two Fc molecules labeled peptides (2FcP) as the second chemical bonding, facilitating high-density attachment of peptides to the electrode carrier in a firm manner. When the PSA analyte is introduced to identify and cleave the specific peptide, the release of ferrocene from its head leads to a decrease in the electrical signal, enabling sensitive detection. The prepared sensing platform exhibits exceptional analytical performance for PSA with an extended linear response range from 10 fg mL−1 to 50 ng mL−1. Additionally, the detection limit has been significantly reduced to an ultra-low level of only 0.94 fg mL−1, surpassing those reported in most literature by several orders of magnitude. Moreover, the 2FcP-GA-GDY(Fe)@NMIL-B sensor has excellent selectivity and stability while also showcasing great potential for practical application of PSA detection in human serum using the standard addition method.

First-Order Derivative Spectrophotometry for Simultaneous Determination of Vitamin C and Nicotinamide: Application in Quantitative Analysis of Cocrystals.

Vitamin C (l-ascorbic acid, ASC) and the amide form of vitamin B3 nicotinamide (NIC) can form cocrystals through hydrogen bonding. Currently, there is a lack of fast and reliable alternatives for precisely quantifying cocrystal components and their purity. Spectrophotometric analysis for quantifying such vitamin preparations is challenging due to overlapping absorbance bands in a narrow wavelength range in the ultraviolet (UV) region. Moreover, ASC undergoes progressive degradation if not diluted in a proper medium, requiring stability during quantitative analysis. This study adopted a fast, simple, and reliable two-component spectrophotometric assay for simultaneously determining ASC and NIC based on the first-order derivative spectrophotometry (FODS) method using sodium oxalate as a stabilizer for vitamin C. The FODS method showed linearity between 2 and 24 μg·mL-1 and good precision. The standard addition method was employed to validate FODS, with high recovery percentages (96.5 to 102.4% for ASC and 95.3 to 101.9% for NIC). The FODS method was successfully applied to quantify ASC and NIC in bulk powder produced by the gas antisolvent method. The proposed method could estimate cocrystal purity through mass balance regarding the expected 1:1 stoichiometry, confirmed by PXRD and DSC. Cocrystal purity determined by the FODS method (58-100%) aligned well with results from LC-MS (62-100%), with an accuracy exceeding 97%. The FODS method is as sensitive and accurate as high-performance liquid chromatography for simultaneously determining vitamin concentrations deriving from cocrystals. However, it is less costly, more efficient, and a suitable alternative to classical solid-state methods for estimating cocrystal purity.