Efficient and straightforward spectrophotometric analysis of 5-hydroxymethylfurfural (HMF) using citrate@Fe3O4 nanoparticles as an adsorbent.

In this study, we developed a spectrophotometry method for the analysis of 5-hydroxymethylfurfuraldehyde (HMF) in pharmaceutical formulations using citrate@Fe3O4 adsorbent. As bare magnetite (Fe3O4) has certain limitations, such as aggregation and oxidation, surface modifications are commonly used to improve its properties. We successfully coated Fe3O4 with sodium citrate to create a magnetic adsorbent for isolating HMF from samples. We confirmed the successful surface coating of Fe3O4 with citrate using Fourier Transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Zeta potential, and scanning electron microscopy (SEM). The high adsorption capacity of citrate@Fe3O4 is due to the abundance of carboxyl and hydroxyl groups on the surface of the adsorbent, making it ideal for HMF extraction. The HMF concentration was then quantified using spectrophotometry. Citrate@Fe3O4 exhibited a high surface area and strong interaction with HMF. We analyzed the individual influential factors affecting the magnetic solid phase extraction (MSPE) setup. Validation parameters were also provided to confirm the reliability of the method. Under optimal parameters, the method exhibited excellent linearity in the range of 0.05-30.00 µg/ml with the lower limit of quantification (LLOQ) of 0.05 µg/ml. Relative standard deviations (RSD) values for precision were better than 10% and the method's trueness were better than 10%. Recoveries were found to be in the range of 85% to 106%, indicating excellent accuracy and reliability. We used this method to identify and measure HMF in six different dextrose pharmaceutical dosage forms as intravenous injectable solutions and three honey samples.

Application of Carbon-based Nano Adsorbents in the Extraction of Amphetamines from Urine Samples.

Amphetamines, as psychoactive drugs, are extensively abused in society and cause serious mental and physical disorders among young people. Furthermore, the extremely euphoric and excited sense of stimulant consumption leads to dramatic social problems. Determination of various analytes and related metabolites in the complex biological matrices at trace levels has made sample preparation an indispensable part of forensic sciences. According to the problems above, providing high sensitivity, solving some analytical problems like matrix effects in LCMS-MS, and needing a cleaner extract are remarkable aspects of novel sample preparation methods in drug analysis. Application of nanotechnology and carbon-based nanocomposites seems to bring the above properties in developed and novel sample preparation methods. This review will try to provide an overview of different carbonic nano adsorbents used in sample preparation methods of amphetamines and discuss their superiority over the other nanomaterials.

Magnetic Nanomaterials for Sample Preparation of Disease-related Biomarkers.

Measuring clinically relevant biomarkers is critical for disease screening, diagnosis, and therapeutic monitoring. However, analyzing trace biomarkers in complex biological fluids remains challenging. Magnetic solid phase extraction (MSPE) has recently emerged as a promising sample preparation approach due to its simplicity, efficiency, and ability to selectively isolate biomarkers. Databases, including PubMed, Web of Science, and Scopus, were systematically searched for studies on MSPE for clinical biomarkers. Key findings on nanomaterial synthesis strategies, surface modifications, and applications in biomarker isolation were synthesized. Recent research demonstrates magnetic nanoparticles with tailored surface chemistry can selectively extract biomarkers like cancer antigens, neurotransmitters, and pharmaceuticals from matrices such as plasma, urine, and serum. MSPE enables clinically relevant limits of detection, high recovery, and purification in a rapid and simple workflow. This technique shows significant potential to improve clinical diagnostics. Further research on novel magnetic materials and surface functionalization is warranted. This review provides insights for researchers aiming to develop MSPE methods for sensitive and selective analysis of clinical biomarkers.

Nanoparticle-based delivery platforms for the enhanced oral delivery of peptides/proteins.

Biopharmaceutical products are currently well-established in nearly all branches of medicine and are believed to have great potential for the treatment of a broad spectrum of diseases. Peptide/protein drugs exhibit a predominant class of new biopharmaceuticals coming on the market in recent years. Oral delivery of peptides/proteins as a non-invasive therapeutic technique has become an appealing alternative to the parenteral route. However, the efficient oral delivery of peptides/proteins is limited because of their high molecular weight, poor stability and low biodistribution. Nanoparticles (NPs) have shown excellent results in peptide/protein delivery research. In this paper, the use of NPs as delivery systems for peptides/proteins and their ability to be efficiently delivered via the oral route have been described.

Medicines made from peptides and proteins have become important for treating various diseases. One challenge is delivering them effectively through the mouth, as they can be fragile and may not distribute well in the body. Scientists have been studying the use of tiny particles called nanoparticles (NPs) to help solve these problems. In this article, we explore how NPs can enhance the delivery of peptide/protein medicines when taken orally. By using NPs as delivery platforms, these medicines can be protected and absorbed more efficiently, leading to better treatment outcomes.

Assessment of Undeclared Synthetic Drugs in Dietary Supplements in an Analytical View: A Comprehensive Review.

Dietary supplements have gained widespread attention globally as they are supposed to be healthier than synthetic pharmaceutical compounds with fewer side effects. Unlike common prescription drugs, dietary supplements are readily available to the general public. However, over the past few years, all kinds of legal and illegal drugs, have been detected in dietary supplements without labeling to defraud consumers, resulting in serious public health consequences. Due to the increasing number of drug frauds in dietary supplements, their consumption will undoubtedly risk consumers. Therefore; the importance of high-tech analytical methods in their assessment for controlling food quality seems undeniable. The current review examines the analytical techniques that focus on adulterating health products with undeclared pharmaceuticals, including registered and banned drugs. The present study referred to a survey from 2004 to 2021 based on articles in the Scopus database.

Recent Advances in Solid-Phase Extraction as a Platform for Sample Preparation in Biomarker Assay.

Low levels of biomarkers and the complexity of bio sample make the analytical assay of several biomarkers a challenging issue. Suitable sample preparation run remain a vital part of the puzzle of diagnostic level. Enhancing the detection limit of bioanalytical methods start during the sample preparation procedure. A robust sample preparation method is needed to evaluate the number of biomarkers. As worldwide environmental issues attract expanding consideration, all the more harmless to the ecosystem investigations are liked. Solid-phase extraction (SPE) is an appealing strategy among the sample treatment methods due to the versatility of sorbent materials, less solvent consumption, and compatibility with analytical devices. Miniaturization of the SPE gives the chance to integrate the other analytical steps in a single run, known as an easy-to-use and effective method. SPE utilizes various SPE sorbent beds such as packed beads, porous polymer monoliths, molecularly imprinted polymers, membranes, or other magnetic form microstructures to achieve high surface-to-volume ratio and appropriate chemical properties effective extraction. Also, SPE is the methodology of interest to fulfill high recovery and efficiency demands. In this review, we intend to explain more recent methods for the rational design of SPE and miniaturized SPE to determine biomarkers from biological media. The headlines are subdivided into (1) packing materials in SPE, (2) setups for sample preparation by magnetic SPE, and (3) and future perspective for the application of SPE in sample preparation for analysis of biomarkers.

Hydrogels as Novel and Efficient Materials in Sorbent-Based Sample Preparation Techniques.

Recently, the application of hydrogel materials in sample preparation techniques has increased dramatically. This review discusses application of hydrogels in the field of sample preparation and focuses on extraction techniques practiced with hydrogel materials as sorbent and coating materials, and discusses their synthesis route. After introducing hydrogels, their applications in a variety of solid phase extraction methods (as one of the types of sample preparation techniques) are described. These methods include solid-phase microextraction (SPME), micro solid-phase extraction (µ-SPE) and magnetic solid-phase extraction (MSPE), in which hydrogels are used as the main adsorbent for the extraction and pre-concentration of heavy metals, pesticides, herbicides, insecticides, drugs and pigments. Also, the mechanism of adsorption of the above analytes by different hydrogels and the advantages of using hydrogels in the solid-phase extraction techniques are discussed. In the following, applications of pH-sensitive hydrogels as stimuli-responsive polymers, are discussed in the sample preparation field. Finally, conclusions and future perspectives are covered in the last section that will be very helpful for future studies.

Amin-modified graphene oxide as a promising adsorbent for selective extraction of dexamethasone adulterant from herbal supplements.

In most cases, herbal supplements found in illegal centers and herbal medicine stores have harmful content that causes irreparable damage to people. As a representative of the green chemistry method, a rapid and efficient dispersive micro solid-phase extraction (D-mSPE) method was applied to extract dexamethasone adulterant from handmade supplements sold as power natural enhancing materials. The quantification of the analyte was performed by high performance liquid chromatography with an ultraviolet detector. Effective parameters on the extraction recovery, including the type and amount of adsorbent, the kind of elution solvent, and the time of extraction and elution, were systematically investigated. The limit of detection of the method was 0.05 µg mL-1. Furthermore, inter-day precisions calculated as relative standard deviations were better than 10%. Ten dietary supplements, including liquid, capsule, tablet forms, and powder, were analyzed using the developed method, and four of them were detected as adulterated with dexamethasone. The developed method purifies the complex plant-based samples and results in a clean analysis with separation instruments.

Application of Liquid-Liquid Extraction for the Determination of Antibiotics in the Foodstuff: Recent Trends and Developments.

Nowadays, the presence of antibiotic residues in foods with animal origin has become an important challenge for public health authorities in many countries. Antibiotic residues are associated with several health problems in the human body such as acute allergic or toxic reactions, chronic toxic effects, and disturption of the natural balance of intestinal microflora as well as the emergence of antimicrobial resistance pathogenic bacteria. In order to determine the trace levels of antibiotics in the foodstuff, the development of rapid, sensitive and accurate analytical methods is necessary. Besides the great advances in the development of analytical instruments in recent years, sample preparation remains a critical step of any analytical procedure. Since food samples have complex and heterogeneous matrices, the sample preparation method can affect the accuracy, precision and overall performance of an analytical technique. Liquid-liquid extraction (LLE) is one of the most commonly used techniques for sample preparation which allows the selective concentration of target analytes in the aqueous samples. The aim of this study was to provide an updated overview of the recent trends and development in LLE techniques over the past 5 years. Different variations of this method such as hollow fiber liquid-phase microextraction, dispersive liquid-liquid microextraction, salting-out LLE, and aqueous two-phase system extraction are given in the present study. This review is focused on recent innovations and modifications in the LLE procedure which try to improve the efficiency and safety of this technique.

Micro Solid Phase Extraction Using Novel Adsorbents.

Metal organic frameworks (MOFs) are classified as metal clusters with high surface area, commutable structure and pore size, chemical and thermal stability with wide applications in different scientific subjects. Designing of novel adsorbents for sample preparation methods attends high attention towards MOFs and they are good candidates for this purpose. In the present review, recently applied MOF-based materials as micro solid phase extraction technique adsorbents for extraction of environmental, food, and biological samples are comprehensively overviewed.

Current trends in sample preparation by solid-phase extraction techniques for the determination of antibiotic residues in foodstuffs: a review.

The presence of antibiotic residues in foodstuff has been of growing concern in recent years. They are associated with several adverse effects on human health such as the transmission of antibiotic-resistant pathogenic bacteria through the contaminated food, weakness of the immune system, allergic or toxic reactions and imbalance of the gut microbiota. Therefore, monitoring of the levels of antibiotic residues in animal-derived food is necessary to guarantee the safety of food products as well as the public health. Since the residual antibiotics in the foodstuff are in trace levels which are often lower than the limits of detection of analytical instruments, the sample preparation before the analysis is very important. This step is an essential part of an analytical process, especially for the extraction of chemical residues from a sample, preconcentration of the extract and elimination of any matrix interferences that may affect the selectivity, sensitivity and the overall performance of the analytical methods. Solid-phase extraction (SPE) is one of the most widely used techniques for the sample preparation that provides an efficient and reproducible method for selective concentration of target analytes in complex matrices. The objective of this research was to provide an updated overview of the recent trends in SPE techniques over the past five years. Different variations of this method, including solid-phase microextraction, stir bar sorptive extraction, matrix solid-phase dispersion, micro-solid-phase extraction, dispersive micro solid-phase extraction, magnetic solid-phase extraction, and molecularly imprinted solid-phase extraction are also given in the present study. The review is focused on recent developments and innovations in the SPE which tries to improve the efficiency, safety and performance of sample preparation.

Dispersive Micro-Solid Phase Extraction for Sensitive Determination of Methotrexate from Human Saliva Followed by Spectrophotometric Method.

For biological assessing of hospital personnel occupationally exposed to antineoplastic drugs, highly sensitive and accurate methods are required. Methotrexate (MTX) is an anticancer agent that is widely used in a variety of human cancers. For the first time, dispersive-micro solid phase extraction (D-µ-SPE) has been applied for determination of low levels of MTX in saliva samples. The method is based on rapid extraction of MTX using graphene oxide adsorbent. The sample preparation time is decreased by the fact that the adsorbent dispersed in the sample solution and extraction equilibrium can be reached very fast. This significant feature which obtained with this method is of key interest for routine trace laboratory analysis. The influence of different variables on D-µ-SPE was investigated. Under optimum conditions, the calibration graph was linear over the range of 10-1000 ng/ml. The relative standard deviations are better than 9.0%. The proposed method was successfully applied for the determination of MTX in patient samples.

Dispersive micro solid phase extraction of busulfan from plasma samples using novel mesoporous sorbent prior to determination by HPLC-MS/MS.

Determination of busulfan concentration in patients undergoing bone marrow transplantation is necessary in order to reduce toxic effects and/or graft rejection due to unadjusted dose exposure. A new extraction method namely dispersive micro solid phase extraction (DMSPE) based on mesoporous sorbent was used for cleaning-up the plasma samples. DMSPE coupling with liquid chromatography with tandem mass spectrometry (LC-MS/MS) was implemented for the determination of busulfan dosage in plasma samples. The linear range was found from 10 to 2000 ng/ml. The precision and accuracy were found better than 15% according to Food and drug Administration (FDA) guideline. This method was successfully used to determine the busulfan in patients administrated busulfan as part of the preparative regimen for bone marrow transplantation.

Preparation and characterization of PLGA-PEG-PLGA polymeric nanoparticles for co-delivery of 5-Fluorouracil and Chrysin.

Despite significant advances in cancer therapy, chemotherapeutic agents are still the main types of drugs used to treat cancer patients. 5-Fluorouracil (5-FU) is the first-line treatment in several types of human cancers, however, nonspecific function, low plasma half-life, and high doses toxicity are the important barrier to achieve efficient response in cancer patients. The use of polymeric nanoparticles (NPs) for tumor targeted delivery of 5-FU in combination with other potent anticancer agent is considered an important strategy to enhance the therapeutic efficacy of 5-FU. In this study, we proposed to use PLGA-PEG-PLGA NPs to co-encapsulate 5-FU and Chrysin, a natural compound known to enhance the therapeutic efficacy of chemotherapy. NPs were prepared by double emulsion method and characterized for size and drug encapsulation efficacy. The cell growth inhibitory effect of prepared NPs was assessed by MTT assay in HT29 human colon cancer cell line. The analysis of NPs by dynamic light scattering showed that the developed NPs have average size of 40 nm. The encapsulation efficiency of NPs was 81.3% and 97.5% for 5-FU and Chrysin, respectively. Furthermore, the NPs showed a remarkable uptake in HT29 cells. NPs loaded with both 5-FU and Chrysin (5-FU@Chrysin loaded NPs) were found to have significantly higher growth inhibitory effects compared with NPs loaded with each drug alone in HT29 cell line. The synergistic anticancer effects of 5-FU and Chrysin loaded in NPs were confirmed with the combination index (CI) being 0.35. CI for combination therapy with free 5-FU and Chrysin was found to be 0.73, indicating weaker synergistic anticancer effects of these two drugs in free forms as compared with 5-FU@Chrysin loaded NPs. These finding indicates that co-delivery of 5-FU and Chrysin with PLGA-PEG-PLGA copolymer can be used to improve the therapeutic and functional delivery efficacy of 5-FU and Chrysin in cancer.

Mixed hemimicelle magnetic dispersive solid-phase extraction using carbon-coated magnetic nanoparticles for the determination of tramadol in urine samples.

Ionic liquid carbon-coated magnetic nanoparticles were successfully applied as an adsorbent in a mixed hemimicelle magnetic dispersive solid-phase extraction method for the determination of tramadol from urine samples coupled with high-performance liquid chromatography with UV-vis detection. The significant parameters affect the extraction efficiency including type and amount of adsorbent, sample volume, pH, ionic strength, type and amount of elution solvent, time of extraction and desorption, time of ionic liquid loading on the adsorbent and stirring rate were studied and optimized. The proposed method provided a fast, straightforward, environmentally friendly and adsorbent recyclable approach for tramadol analysis. The linear range for the tramadol determination was from 100 to 1500 ng/mL. Precisions and accuracies were within 6%. The applicability of the proposed method in clinical trial was tried successfully on determination of tramadol in addicted subjects under tramadol therapy. The mean percent recovery of the patient samples was 94%. The results proved that the proposed method could be applied in clinical and forensic laboratories for determination of tramadol from biological urine samples.

A novel mixed hemimicelles dispersive micro-solid phase extraction using ionic liquid functionalized magnetic graphene oxide/polypyrrole for extraction and pre-concentration of methotrexate from urine samples followed by the spectrophotometric method.

Methotrexate (MTX) is an anticancer drug that is widely used in a variety of cancers including primary central nervous system lymphoma. It is also administrated in the treatment of some autoimmune diseases. A simple, accurate, sensitive, and precise mixed hemimicelles dispersive micro-solid phase extraction was proposed for MTX quantification in human urine samples. MTX was quantified by spectrophotometer after dispersive micro-solid phase extraction using ionic liquid functionalized magnetic graphene oxide/polypyrrole. Interactions of adsorbent and MTX were modeled by molecular docking and the interaction energy was predicted to be -8.35 kcal/mol. A larger absolute value of binding energy represents larger adsorption strength, indicating that graphene oxide nanosheets could perform higher adsorption strength toward MTX. The concentrations of MTX were proportional to analytical response in amounts ranging from 10 to 1000 ng/mL with a good correlation (R2 = 0.99). Inter- and intra-day precisions and accuracies were within the acceptable limit according to FDA guideline (15% for biological determination). The recoveries were ranging from 89 to 93% and the method was specific for routine analysis of MTX. This protocol was applied to the urine of two patients under MTX therapy received an intravenous administration of 1 mg/kg/dose of MTX with acute lymphoblastic leukemia. The accuracy of the method was confirmed by HPLC measurements.

Solid Phase Microextraction Techniques in Determination of Biomarkers.

The detection and quantification of biomarkers is gaining attention in medical research and diagnostics communities. Biomarkers cover a range from gases to biological macromolecules. Because of the nanomolar range levels of typical biomarkers in plasma, blood, urine, exhalation samples, and other biological fluids as well as complex matrix of biological media, adequate sample preparation methods should be used for quantification of biomarkers. The performance of an analytical method for biomarkers should support reproducible and accurate data. In the present paper, recent progress in well-established solid phase microextraction (SPME) methods for the clinical analysis are reviewed and discussed.

Dispersive micro-solid-phase extraction using carbon-based adsorbents for the sensitive determination of verapamil in plasma samples coupled with capillary electrophoresis.

A dispersive micro-solid-phase extraction procedure coupled with capillary electrophoresis ultraviolet detection was developed for determination of verapamil in plasma samples. Graphene oxide/polydopamin was synthesized by a one-step polymerization method, and graphene oxide/Fe3 O4 (magnetic graphene oxide) nanocomposite was prepared by coprecipitation method. Moreover, they were fully characterized. The use of hazardous and water-immiscible solvents was scaled down, and only 500 µL of acetone was required as the desorption solvent. The detector response concentration plots were linear in the range of 5-500 ng/mL, and the proposed method was validated according to guidelines. The precision and accuracy were less than 15%. Dispersive micro-solid-phase extraction method provides a rapid, environmentally friendly, and sensitive analysis for the verapamil in patient plasma samples, which is adequate for therapeutic drug monitoring and pharmacokinetic studies.