Green Analytical Procedure Index Research Articles

Implementation of green-assessed nanotechnology and quality by design approach for development of optical sensor for determination of tobramycin in ophthalmic formulations and spiked human plasma

A fast eco-friendly colorimetric method was developed for the determination of Tobramycin in drug substance, ophthalmic formulations, and spiked human plasma using silver nanoparticles optical sensor. Even though tobramycin is non-UV–visible absorbing, the developed method is based on measuring the absorbance quenching of silver nanoparticles resulting from the interaction with tobramycin. Different factors affecting the absorbance intensity were studied as; silver nanoparticle concentration, pH, buffer type, and reaction time using quality by design approach. Validation of the proposed method was performed according to ICH guidelines and was found to be accurate, precise, and sensitive. The linearity range of tobramycin was 0.35–4.0 μg/mL. The optical sensor was successfully applied for the determination of Tobramycin in ophthalmic formulations and spiked human plasma without pre-treatment. Additionally, the binding between Tobramycin and PVP- capped silver nanoparticles was studied using molecular docking software. The method was assessed and compared to colorimetric reported methods for the green character using Green Analytical Procedure Index (GAPI) and Analytical GREEnness calculator (AGREE) tools and found to be greener.

Innovative eco-friendly stability-indicating HPLC-PDA method for simultaneous determination of the emerging antiviral drugs against COVID-19 infection molnupiravir and favipiravir; degradation kinetic studies along with LC-MS based structure elucidation

The adoption of the principles of green chemistry in analytical procedures lowers the negative influence on both people and the environment, which presently has become the key goal. Additionally, the need for advanced analytical techniques for the simultaneous determination of antiviral combinations is highly recommended, one of those novel combinations that recently proved effective emerging antiviral drugs in the treatment of SARS-COV-2 is molnupiravir (MOL) and favipiravir (FAV). Therefore, the establishment of simple and precise stability-indicating HPLC-PDA method for their simultaneous determination is crucial for the probable co-formulation. The stability of MOL was studied along with FAV after forced degradation of both under different stress conditions Separation of MOL, FAV, and their corresponding degradation products was achieved by simple isocratic HPLC-PDA method using a mobile phase comprised of 25.0 mM phosphate buffer (pH 3.0 ± 0.05) − methanol (70:30, v/v) at flow rate 1.0 mL/min. A Zorbax C18 (250 × 4.6 mm, 5 μm; Agilent Technologies, USA) column was used for the separation of the components and the column oven was maintained at 30 °C, the selected wavelength for detection of both analytes and their degradation products was 230.0 nm. The method was linear over the range of 1.0 – 200.0 µg/mL for both MOL and FAV. MOL was found to be susceptible to all forced degradation conditions, namely, acid, alkali, oxidative, thermal, and photodegradation while FAV was susceptible only to acid, alkali, and oxidative degradation. The probable degradation mechanisms were assumed through the evaluation of the MS1 fragmentation pattern of the degradation products, also studying the kinetic behavior of the degradation reactions. Furthermore, the greenness profile for the proposed method was evaluated utilizing the new Complementary Green Analytical Procedure Index method (ComplexGAPI), and analytical greenness (AGREE) metrics with a score of the later one equals to 0.61 that indicated the greenness evaluation of the method. In addition, the new blue applicability grade index (BAGI) which is complementary to the green metrics showed a score of 85.0 that presents a good applicability potential of the method. The proposed method is the first sustainable, stability-indicating method developed for the simultaneous determination of this potential combination that would help in manufacturing both drugs in a fixed-dose drug combination.

Smart Chemometric‑Assisted Spectrophotometric Approaches for Simultaneous Quantification of Tertiary Combination Recommended for COVID-19 Supportive Treatments with Their Greenness Assessment.

There is an increasing interest of scientific community in developing innovative methodologies for their analysis needs within green analytical chemistry framework. UV spectrophotometry is one of the most promising eco-friendly methods, which is integrated with advanced chemometric tools to enhance the selectivity of the analysis of complex mixtures with severe overlapped signals. Simultaneous determination of a triple-combination of pseudoephedrine hydrochloride (PSE), carbinoxamine maleate (CRX), and paracetamol (PAR) using an artificial intelligence system and multivariate calibration methods. This combination is recently recommended for COVID-19 home-treated patients as part of a symptomatic treatment. Namely, the suggested models are: Artificial Neural Networks, Partial Least Squares, and Principal Component Regression. The proposed algorithms were optimized and developed with the aid of a five-level, three-factor experimental design. The investigated methods were applied over the concentration range of 100-180 μg/mL, 18-16 μg/mL, and 4-12 μg/mL for PSE, CRX, and PAR, respectively. The models validation results demonstrated excellent recoveries (around 98 to 102%), signaling the approaches outstanding resolution capacity for the cited compounds in the presence of common excipients. The outcomes of the studied methods were statistically compared to the official approaches, and no significant difference was found. The suggested models were efficiently employed to determine the selected drugs in their combined tablets without any initial separation steps. The impact of these methods on the environment was evaluated via greenness tools, namely; National Environmental Method Index, Raynie and Driver's green assessment method, analytical Eco-Scale, Green Analytical Procedure Index, and Analytical Greenness Metric. Green chemometric quality assessment of PSE, CRX, and PAR in their pure and pharmaceutical dosage forms. The established approaches are innovative, sustainable, smart, fast, selective, and cost-effective. These models are potential green nominees for routine analysis of the investigated mixture in quality control laboratories.

Rapid and ecofriendly ultra performance liquid chromatographic analytical methodology for the simultaneous determination of four drugs included in COVID-19 treatment protocol

The global spread of COVID-19 disease has increased the demand for new therapeutic approaches. The clinical studies revealed that remdesivir and molnupiravir have been effective against COVID-19. Remdesivir (REM) is the first FDA-approved antiviral drug for COVID-19, while molnupiravir is the first oral antiviral drug for SARS-CoV-2 infections. In addition to antivirals, anticoagulants such as apixaban (APX) and antibiotics such as levofloxacin (LVF) are also included in the treatment protocols. This study suggests and validates a rapid and selective method for the determination of the four drugs involved in the COVID-19 treatment protocol. The simultaneous separation and determination of REM, MLP, LVF, and APX in human plasma were achieved using UPLC with a fluorophenyl column and a mobile phase composed of acetonitrile and water acidified with formic acid (pH = 3) in the ratio of 45: 55, v/v, at a flow rate of 0.1 mL/min. The PDA detector was adjusted at 254 nm. The method could simultaneously determine the four drugs in a single run in less than 6 min. The method exhibited linearity over the concentration ranges of 1.0–15.0 µg/mL, 0.1–5.0 µg/mL, 0.1–2.0 µg /mL, and 0.1–5.0 µg/mL, for LVF, MLP, APX and REM, respectively. The proposed method was validated following the International Council on Harmonization Q2(R1) guidelines and the findings were compared statistically to previously reported methods. The recovery rates of the drugs from spiked human plasma were satisfactory. The greenness of the suggested method was evaluated using three metrics, namely, Analytical Eco-scale, Green Analytical Procedure Index (GAPI) metric, and the Analytical GREEnness measure approach (AGREE).

A green liquid phase microextraction using phthalic acid as switchable hydrophilicity solvent for the HPLC determination of sildenafil (Viagra®) in human urine

Herein, a green liquid phase microextraction protocol using phthalic acid as switchable hydrophilicity solvent (SHS) is reported for the quantification of sildenafil in authentic human urine. The analyte was extracted onto phthalic acid solid particles which were produced through acidification of the sample. Its solidification was accomplished at ambient conditions without sample cooling. The determination of the sildenafil was carried out using high performance liquid chromatography-ultraviolet detection (HPLC-UV). The microextraction parameters that affect the extraction efficiency of the drug (i.e. SHS type and its concentration, acid type and concentration, extraction time, filter type) have been studied. The optimized analytical protocol involved the mixing of 300 μL of phthalate solution (0.75 M) with 600 μL of sample, followed by the addition of 50 μL of concentrated H3PO4. The produced solid was collected using membrane syringe filter (0.45 μm) and was finally dissolved in 500 μL of CH3OH. Method validation data showed determination coefficient ≥ 0.99 for the linear range of 50 – 2000 ng/mL. The limit of detection (LOD) and the lower limit of quantitation (LLOQ) were 30 and 100 ng/mL, respectively. The accuracy (expressed as % recovery) of the method ranged between 88.0 – 108.9 % while the precision (expressed as % RSD) was less than 17.8 % in all cases. The robustness of the microextraction procedure and the instrumental method were investigated using Plackett-Burman experimental designs. The applicability of the method was demonstrated by analyzing both spiked and authentic human urine samples after oral administration of drug-containing pharmaceutical formulation. The developed protocol offers cost-efficiency, handling simplicity, and high throughput. Its green character was evaluated using Green Analytical Procedure Index and Blue Applicability Grade Index.

Development of a fluorescent nano-sensing probe for atomoxetine analysis: Additional clinical pharmacokinetic study

Atomoxetine is a psychostimulant drug used for the treatment of attention-deficit/hyperactivity disorder (ADHD) symptoms in people with autism. Herein, eco-friendly fluorescent carbon quantum dots (CQDs) were synthesized using black-eyed pea beans and characterized for the purpose of quantifying atomoxetine in pharmaceutical capsules and human plasma. The selectivity of these CQDs towards atomoxetine was improved by functionalizing their surface with an atomoxetine-tetraphenylborate ion complex. The quantification of atomoxetine is based on measuring the fluorescence quenching of the functionalized CQDs in response to varying concentrations of atomoxetine. The Stern-Volmer plot was employed to investigate the mechanism through which atomoxetine quenches the fluorescence intensity of the CQDs. The outcomes indicated a dynamic quenching mechanism. The applied method was optimized and validated in compliance with ICH requirements, resulting in excellent linearity across the concentration range of 50–800 ng/mL. The developed method was successfully used to quantify atomoxetine in pharmaceutical dosage form and human plasma with acceptable accuracy and precision outcomes. In addition, the method was applied for clinical pharmacokinetic study of atomoxetine in the plasma of children diagnosed with both autism and ADHD. Atomoxetine was rapidly absorbed after a single oral dose of 10 mg, reaching maximum concentration within two hours and having a half-life (t1/2) of 3.11 h. Moreover, the method demonstrates a notable degree of eco-friendliness, as evidenced by two greenness evaluation metrics; Green Analytical Procedure Index (GAPI) and Analytical GREEnness (AGREE).

Eco-friendly simultaneous estimation of atenolol and losartan potassium in spiked human plasma via synchronous fluorescence with sustainability assessment.

A green, sensitive, and fast spectrofluorimetric technique for the simultaneous determination of atenolol (ATN) and losartan potassium (LSR) was developed. The proposed technique relied on the implementation of a first derivative synchronous fluorescence spectroscopy for the determination of the investigated drugs simultaneously without pretreatment procedures. The synchronous fluorescence of both drugs was measured in methanol at Δλ of 100 nm, and the first derivative peak amplitudes (1D) were measured at 321 nm for ATN and 348 nm for LSR, each at the zero-crossing point of the other. The method was rectilinear over the concentration ranges of 100-1000 ng/mL and 50-500 ng/mL for ATN and LSR, respectively. The proposed technique was successfully applied for the determination of the studied drugs in their laboratory-prepared mixture and pharmaceutical formulations, demonstrating high mean recoveries of 100.54% for ATN and 100.62% for LSR, without interference from common excipients. The results were in good agreement with those obtained by the comparison method. Three recent greenness assessment tools, the Eco-Scale tool, the Green Analytical Procedure Index (GAPI) metric, and the Analytical GREEnness metric approach, were employed to affirm the greenness of the proposed method. The developed method was proven to be eco-friendly.

Development of an eco-friendly fluorescent probe for mefenamic acid sensing in pharmaceuticals and biofluids.

Mefenamic acid, renowned for its analgesic properties, stands as a reliable choice for alleviating mild to moderate pain. However, its versatility extends beyond pain relief, with ongoing research unveiling its promising therapeutic potential across diverse domains. A straightforward, environmentally friendly, and sensitive spectrofluorometric technique has been developed for the precise quantification of the analgesic medication, mefenamic acid. This method relies on the immediate reduction of fluorescence emitted by a probe upon interaction with varying concentrations of the drug. The fluorescent probe utilized, N-phenyl-1-naphthylamine (NPNA), was synthesized in a single step, and the fluorescence intensities were measured at 480 nm using synchronous fluorescence spectroscopy with a wavelength difference of 200 nm. Temperature variations and lifetime studies indicated that the quenching process was static. The calibration curve exhibited linearity within the concentration range of 0.50-9.00 μg/mL, with a detection limit of 60.00 ng/mL. Various experimental parameters affecting the quenching process were meticulously examined and optimized. The proposed technique was successfully applied to determine mefenamic acid in pharmaceutical formulations, plasma, and urine, yielding excellent recoveries ranging from 98% to 100.5%. The greenness of the developed method was evaluated using three metrics: the Analytical Eco-scale, AGREE, and the Green Analytical Procedure Index.

An eco-friendly first and second derivative synchronous spectrofluorimetry for quantification of florfenicol in presence of its different degradation products. Application to kinetic stability study.

Two rapid, simple, sensitive and selective derivative spectrofluorimetric methods (first and second derivative synchronous spectrofluorimetric (FDSFS and SDSFS) procedures) have been developed for the analysis of florfenicol in the presence of its various degradation products. FDSFS was applied to assay the drug in the presence of its alkaline, oxidative and photolytic degradation products while SDSFS was used to quantify it in the presence of its acidic degradation product. These methods permitted quantification of florfenicol at corresponding λ Em of 288, 287, 279 and 284 nm without interferences from any of its degradation products. Full validation procedures were applied to the suggested method according to International Conference of Harmonization guidelines. Moreover, different degradation kinetic parameters were calculated such as half-life (t 1/2), degradation rate constant (K) and activation energy (E a). Using the analytical eco-scale, green analytical procedure index and analytical greenness metric approach AGREE as greenness assessment tools, the proposed method was found to be environmentally friendly.

Green analytical quality by design RP-HPLC technique with fluorimetric detection for simultaneous assay of cinnarizine and dompridone.

A green and sensitive factorial design-assisted reversed-phase high-performance liquid chromatography (RP-HPLC) approach with fluorimetric detection has been developed for simultaneous determination of cinnarizine and domperidone in pure materials, commercial single and combined tablets. Both drugs are co-formulated in one dosage form and are commonly used for the effective treatment of motion sickness in the ratio of 4 : 3 for cinnarizine and domperidone, respectively. To achieve the developed method's best performance and reliability, a 23 full factorial design was applied during the optimization of chromatographic conditions. Subsequently, isocratic elution on a C18 column with a mobile phase mixture of methanol and 0.02 M potassium dihydrogen phosphate buffer (85 : 15 v/v, pH 3.0) was performed to achieve the best separation. Moreover, the flow rate of 0.8 ml min-1 was applied during the analysis with fluorescence detection at λex 283 nm/λem 324 nm. The elution process was time effective; it consumed less than 6 min for a complete run as retention time for cinnarizine and domperidone, was 4.5 and 3.5, respectively. Good linearity of the proposed method was achieved within the concentration ranges of 0.2-4.5 and 0.4-5.0 µg ml-1 for domperidone and cinnarizine, respectively. The suggested approach was carefully validated according to the International Council for Harmonization (ICH) guidelines. Moreover, green analytical procedure index (GAPI), national environmental methods index (NEMI), analytical greenness (AGREE) and analytical eco-scale methods were applied to assess and confirm method greenness.

Bridging Pharma and Sustainability: Green Electrochemical Analysis of Antiparkinsonian Drug in Pharmaceuticals and Plasma, Aligned with United Nations Goals via the NQS Index

This study presents a sustainable electrochemical investigation of pramipexole (PRA) in pharmaceuticals and human plasma, using cyclic and differential pulse voltammetry. Key parameters, including potential range, buffer pH, accumulation period, and scan rate were optimized, establishing efficient voltammetric methods for PRA analysis. The analytical range was 0.60–12.00 μg ml−1, with a detection limit of 0.14 μg ml−1 and a correlation coefficient of 0.9998. Recovery rates for PRA ranged from 98.60 ± 0.26% to 101.33 ± 0.38%, validating the methodology’s applicability in human plasma with an average recovery of 99.25 ± 0.45%. The study highlights the environmental sustainability of the developed voltammetric electrode, evaluated through SWOT analysis, and assesses the greenness impact using tools like Complementary Green Analytical Procedure Index (ComplexGAPI), Analytical greenness (AGREE) and Analytical greenness for sample preparation (AGREEprep). Significantly, this work aligns with numerous United Nations Sustainable Development Goals (UN-SDGs), specifically goals 3, 4, 5, 7, 9, 11, 12, 13, 14, 15, and 17, illustrating our commitment to sustainable pharmaceutical research. The sustainability of the method was further quantified using the newly introduced Need, Quality, Sustainability (NQS) index, demonstrating significant alignment with sustainable analytical practices.

A total scoring system and software for complex modified GAPI (ComplexMoGAPI) application in the assessment of method greenness

Evaluating analytical methods with innovative metrics is essential to ensure the effectiveness of analytical procedures. Various approaches have been proposed to assess the performance of an analytical method and its environmental consequences, as sustainable environment and green chemistry ideology are of high importance nowadays. Considering greenness evaluation of developed analytical procedures, Green Analytical Procedure Index (GAPI), one of these metrics, utilizes five distinct colored pentagons to evaluate the environmental footprint of the analytical process at different stages. An additional tool named Complementary Green Analytical Procedure Index (ComplexGAPI) was introduced to expand on GAPI by adding additional fields pertaining to the processes performed prior to the analytical procedure itself. Nevertheless, the existing ComplexGAPI lacks a comprehensive scoring system for individual methods, which would allow for even easier comparison of procedures using this tool. In response to queries from ComplexGAPI users, this study introduces a refined tool named ComplexMoGAPI, merging the visual appeal of ComplexGAPI with precise total scores. The accompanying software streamlines the application, facilitating quicker and simpler evaluations. This software is available as an open source on bit.ly/ComplexMoGAPI. We believe that, following ComplexGAPI success, this ComplexMoGAPI tool will also gain attention and eventually trust and acceptance from the chemical community.

Ecofriendly UPLC-MS/MS method for simultaneous assay of veterinary drugs residues; erythromycin, sulfadiazine and trimethoprim in edible chicken tissues, evaluation of method greenness and whiteness

Antibiotics are the key veterinary drugs used in animal food production. The uncontrolled widespread use of antibiotics may lead to the accumulation of their residues in foodstuff such as milk, eggs, meat and muscles. An Ultra-performance liquid chromatography-tandem mass spectrometry (UPLC/MS/MS) method was developed for simultaneous determination of triple combination of erythromycin thiocyanate (ERY), sulfadiazine sodium (SFD) and trimethoprim (TMP) in their dosage form and in different chicken tissues including muscles and liver samples. A Simple extraction and cleaning up procedure was applied using 0.1 N EDTA and methanol to remove the interfering substances and hence increase the efficiency of chromatographic separation. Moreover, separation was performed within 1.2 min on Agilent Poroshell 123EC-C18 column using a mobile phase mixture of methanol: water (90:10, v/v), at a flow rate of 0.5 mL/min using quadrupole tandem mass spectrometer detector. The method was validated according to Food and Drug Administration (FDA) guidelines and linearity was achieved in the range of 2.5–1000 ng/mL for ERY and TMP and in the range of for 5–2000 ng/mL for SFD using tamsulosin (TAM) as an internal standard. All the validation results were within the acceptable ranges. Moreover, Three green metric systems including Green Analytical Procedure Index (GAPI), Analytical Eco-Scale and Analytical GREEnness (AGREE) were used to assess the greenness of the developed method. As well as, the novel blue applicability grade index (BAGI) tool was applied to evaluate the practicality of the method. Results of these tools proved the low environmental impact of the method regarding solvent consumption, analysis time, amount of sample needed, sample treatment procedure, and waste product. The developed method has the privilege of high sensitivity and selectivity as well as short analysis time; hence it can be used to test the presence of the residues of studied drugs in various marketed meat samples to assure human safety and maintain public health. Moreover, it is the first developed method for their analysis in liver samples.

Sustainable HPLC technique for measurement of antidiabetic drugs: Appraisal of green and white metrics, content uniformity, and in vitro dissolution

Abstract Green chemistry and white chemistry are two approaches to chemistry that prioritize sustainability and environmental protection. The pursuit of green chemistry is to develop chemical processes and products that decrease or stop the use and generation of dangerous materials. In contrast, white chemistry focuses on developing energy-efficient, sustainable chemical processes that produce minimal waste. Our study evaluated the environmental friendliness of the suggested approach, using eight greenness appraisal techniques, including analytical eco-scale, analytical method volume intensity, HPLC-environmental assessment tool, analytical method greenness score, analytical greenness, analytical greenness metric for sample preparation, green analytical procedure index, and complexgreen analytical procedure index, in addition to the unique metric blue applicability grade index of white chemistry. We have developed and validated a highly effective and reliable method for concurrently analyzing designated pharmaceutical medications characterized in metformin (MET) and empagliflozin (EMP) formulations, including their degraded products. This method is cost-effective, specific, and environmentally friendly, utilizing reversed-phase high-performance liquid chromatography with an XBridge BEH C8 column (150 mm × 4.6 mm, 5 μm) at a flow rate of 1.0 mL·min−1, an injection volume of 5.0 μL, a column oven temperature of 50°C, a wavelength of 224 nm, and a mobile phase comprised of phosphate buffer adjusted at pH 6.8 and acetonitrile in gradient mode. In the HPLC method, linearity has been achieved over the concentration range of 10–106 and 30–1,050 µg·mL−1 for EMP and MET, respectively, with correlation coefficients more than 0.999 and good recoveries within 98–102%. An assessment of the content uniformity of finished products confirmed that they met the declaration’s acceptance standards (85–115%). A comparative study has been successfully conducted on generic and reference products, demonstrating their similarity. The suggested approach was validated by adhering to international council for harmonisation criteria.

Cutting-edge HPLC and MCR techniques for synchronically quantifying anticholinergic drugs in the presence of C12 and C14 homologs: Robust application to green and white chemistry.

Green and white chemistry are vital to revolutionizing the chemical industry through their unparalleled potential to enhance sustainability and efficiency. In this study, nine sustainability tools of both green and white metrics, including green analytical procedure index (GAPI), ComplexGAPI, analytical greenness, analytical greenness metric for sample preparation, Analytical Eco-Scale (ESA), analytical method greenness score, high-performance liquid chromatography- environmental assessment tool (HPLC-EAT), analytical method volume intensity, and blue applicability grade index (BAGI), have been developed for appraising environmental friendliness for both innovative and straightforward mean centering of ratio spectra (MCR) and reversed-phase high-performance liquid chromatography (RP-HPLC)strategies utilized for concurrent analysis and separation of cyclopentolate (CYC) and C12 and C14 homologs of benzalkonium chloride (BNZ) in pure and ophthalmic solution. The mobile phase, formed of buffer phosphate and acetonitrile (35:65, v/v), was adjusted to pH 6.3, and 215-nm UV detection was used. The experimental flow rate was 2.0 mL min-1, and the analytical column was L11 Inertsil Ph-3 (150 mm × 4.6 mm, 5 µm). All sequences were run at 25°C in the column oven. The MCR approach effectively resolved the drug's spectral overlapping. CYC and BNZ employed this approach at 227.5 and 220.4 nm, respectively. As part of the HPLC analysis, an isocratic method was employed with phosphate buffer and acetonitrile in the mobile phase at 35:65. A correlation coefficient greater than 0.999 was observed between the calibration curves for the HPLC and MCR methods in the ranges of 20-320 µg mL-1 and 5-30 µg mL-1 for all drugs. The technique yields excellent primary recovery rates, ranging from 97.2% to 100.5%. The recommended approach has been validated according to International Council for Harmonizationguidelines.

A practical and eco-friendly method for the determination of polycyclic aromatic hydrocarbons in açaí-based food products by vacuum-assisted sorbent extraction coupled to gas chromatography-mass spectrometry

For the first time, a method for the simultaneous analysis of fifteen polycyclic aromatic hydrocarbons (PAHs), including light and heavy PAHs, in açaí-based food products (AFPs) was developed using vacuum-assisted sorbent extraction (VASE) combined with gas chromatography-mass spectrometry (GC–MS). The method requires no organic solvents and is amenable to full automation. To achieve optimal analytical extraction conditions, VASE parameters including stirring rate, extraction time, desorption temperature, desorption time, preheat time, and preheat temperature were optimized using sequential multivariate optimization. The method was validated and yielded limits of quantification below 1 µg kg−1 for all analytes, with recoveries ranging from 65 % to 112 % and good precision (≤11 % relative standard deviation). Additionally, the greenness and practical aspects of the method were investigated using the Green Analytical Procedure Index (GAPI), eco-scale, and the Blue Applicability Grade Index (BAGI), respectively. The VASE-GC–MS approach is suitable for routine analysis and exhibits characteristics of a green analytical method. No PAHs were detected above the limits of detection in thirty samples of AFPs.

Anisaldehyde-based deep eutectic solvent dispersive liquid–liquid microextraction (DES-DLLME) followed by UPLC–MS/MS for simultaneous determination of selected parabens and bisphenols in food products: Method development and assessment of the ecological implications

A rapid and environmentally friendly method based on dispersive liquid–liquid microextraction (DLLME) technique, coupled with UPLC–MS/MS analysis was employed for simultaneous determination of selected bisphenols and parabens residues in food products. In this research, anisaldehyde and decanoic acid with a molar ration of 3:1 was prepared as a natural deep eutectic extracting solvent. Various extraction parameters such as the volume of the natural deep eutectic solvent, vortex duration, centrifugation duration, sample volume and pH were systematically explored and optimized. Determination coefficients of ≥0.9990 were achieved for the analyzed compounds under the optimal conditions. The limits detection were in the range of 0.0005 to 0.02 µg/L, while extraction recoveries ranged from 97.8 % to 100.2 % with relative standard deviations (%RSD) not exceeding 6.8 %. To assess the practical applicability of the proposed method, it was employed for the determination of five parabens and three bisphenols in eighty food products including soft drinks, energy drinks, sauces and juices collected from the Saudi market. The environmental implications of the proposed method were assessed using the following evaluation tools, Eco-Scale Assessment (ESA), Green Analytical Procedure Index (GAPI) and Analytical GREEnness metric (AGREE). To the best of our knowledge, this is the first study to determine the investigated analytes using anisaldehyde based deep eutectic solvent.

Bioinspired Carbon Dots-Based Fluorescent Sensor for the Selective Determination of a Potent Anti-Inflammatory Drug in the Presence of Its Photodegradation Products.

Herein, we synthesized biogenic carbon dots (CDs) with blue-shifted maximum excitation (λex/λem of 320/404 nm) from largely wasted tangerine seeds for the first time via a one-step hydrothermal method. The biogenic CDs exhibit a maximum excitation wavelength that overlaps with the absorption spectrum of ketorolac tromethamine (KETO) at 320 nm. The developed CDs serve as a turn-off fluorescent probe via an inner filter effect (IFE) quenching mechanism. The resulting CDs have high quantum yield (QY) (39% ± 2.89%, n = 5) and exhibited great performance toward KETO over a concentration range of 0.50-16.00 μg/mL with a limit of detection (LOD) = 0.17 μg/mL. The nanoprobe achieved a high % recovery in assaying KETO in tablet dosage form and had not been significantly affected by various interferents including co-formulated and co-administered drugs. The nanoprobe shows selectivity toward KETO, even in the presence of its photocatalytic degradation products. It can effectively investigate the elimination of KETO from aquatic systems and test its stability in pharmaceutical preparations. The developed nanoprobe underwent a comprehensive evaluation of its environmental impact using analytical eco-scale (AES), complex green analytical procedure index (Complex GAPI), and the Analytical GREEnness calculator (AGREE). The sustainability of the developed nano sensor was assessed and compared to the reported metal-based quantum dots probe for KETO using the innovative RGB 12 model, considering 12 white analytical chemistry (WAC) perspectives.

Stability-Indicating TLC-Densitometric and HPLC Methods for Simultaneous Determination of Teneligliptin and Pioglitazone in Pharmaceutical Dosage Forms with Eco-Friendly Assessment.

The combination of teneligliptin hydrobromide hydrate and pioglitazone hydrochloride in pharmaceutical formulations has improved type 2 diabetes management. Two chromatographic methods TLC-densitometry and RP-HPLC were developed for simultaneous quantification of teneligliptin hydrobromide hydrate and pioglitazone hydrochloride in pharmaceutical formulations, ensuring accuracy and stability assessment. The TLC method uses a mobile phase of methanol, toluene, ethyl acetate and triethylamine (1:7:2:0.1, v/v/v/v) on TLC silica gel plates, scanned at 268nm. The RP-HPLC method employs isocratic elution with acetonitrile and sodium acetate buffer (adjust pH3.6 with glacial acetic acid, 60:40v/v) on a shimpack C18 column (250 × 4.6mm i.d., 5μm), detected at 235nm. Both methods offer high accuracy and reliability, making them valuable for pharmaceutical quality control. Additionally, an environmental impact assessment was conducted using eco-scale, Analytical Greenness Metric Approach, Green Analytical Procedure Index, and national environmental method index to evaluate solvent consumption, waste generation and energy usage. Statistical comparisons (t-tests and F-tests) validate the outcomes of both methods, ensuring their effectiveness in drug formulation analysis. These methods can enhance pharmaceutical quality control while fulfilling environmental responsibilities.

Innovative Molecularly Imprinted Electrochemical Sensor for Selective Nanomolar Detection of the Anti-COVID-19 Medication Molnupiravir

For the first time, a green ecofriendly approach is applied, to develop a molecularly imprinted polymer (MIP) electrochemical for the assay of the oral anti-viral molnupiravir (MLN) in various matrices as confirmed by referring to analytical eco-scale, green analytical procedure index (GAPI), Raynie and Driver, analytical greenness metric (AGREE), and national environmental index (NEMI). AuNPs were chronoamperometry deposited on the glassy carbon electrode surface (GCE) using 0.01 gm ml−1 gold solution (HAuCl4.3H2O) in 0.5 M H2SO4 at a constant potential of −0.4 V for 60 s. Then, the MIP was created by electropolymerizing OPDA on the surface of AuNPs GCE using cyclic voltammetry in the potential range between −0.5 and +1 V for 15 cycles (scan rate: 50 mV.s−1). To optimize the sensor’s performance, factors such as number of electropolymerization cycles, template: monomer ratio, binding and rebinding time, pH of rebinding buffer, extraction solvent, deposition time of Au nanoparticles, order of deposition on the electrode; surface, as well as differential pulse voltammetry parameters including accumulation potential and time, and potential step, were all investigated. The detection limit was set at 0.00098 ng ml−1 (3 × 10−12M) and the linearity range of MLN was between 0.033 ng ml−1 and 164 ng ml−1 (1 × 10−10–5 × 10−7 M). The MIP sensor was employed for MLN determination in its pharmaceutical product (capsules), spiked human plasma, and human urine samples with mean recovery % ± mean relative standard deviation (RSD) (99.82% ± 0.53), (99.88% ± 0.62), and (97.90% ± 0.70), respectively. The investigated sensor provided good reproducibility, repeatability, and durability. Acceptable selectivity regarding MLN when mixed with structurally comparable compounds was proved with mean recovery % ± mean RSD (97.10% ± 0.03). Additionally, when molnupiravir was exposed to oxidative, hydrolytic, and thermal stress conditions, good results in stability-indicating studies served as an indicator of sensor selectivity. The developed electrode is coupled with a portable potentiostat, making it a promising point-of-care diagnostic platform for on-site measurements.