Abstract: The dual-signal output self-calibration mode reduces false positive or negative signals of electrochemiluminescence (ECL) aptamer sensors. A competitive dual-signal ECL platform was designed for ultrasensitive detection of kanamycin (KAN)using zirconium metal-organic frameworks (Zr MOFs) and Luminol as ECL emitters. To enhance the ECL efficiency, co-reactant (polyethyleneimine, PEI) was covalently bound to Zr MOFs to achieve the self-enhanced ECL. Based on the selective interaction between KAN and its aptamer, the Luminol/KAN/Zr MOFs-PEI "sandwich" structure was immobilized on the electrode surface. The competition for PEI between emitters increased the Luminol ECL signal and decreased the Zr MOFs ECL signal. The ratio in ECL signals between the two competitive emitters enabled the quantitative analysis of KAN, achieving a detection limit as low as 7.86 × 10-4 ng/mL. This study elucidated the synergistic mechanism between self-enhanceding ECL and ECL competition, offering a novel approach for constructing dual-signal ECL sensors using a single co-reactant.

Abstract: N-Methyl-2-pyrrolidone (NMP) is a standard processing solvent for lithium ion battery electrode dispersions. Since NMP is toxic for reproduction, its concentration in laboratory air should be monitored. The time resolved observation of the contamination level exhibits sub-processes, that pose higher or lower risks for an exceedance of the limit values. A method based on thermal desorption coupled to gas chromatography – mass spectrometry (TD-GC-MS) was developed for the quantification of NMP in concentrations close to the derived no-effect level (DNEL). Thermal desorption uses tubes filled with a sorbent material. Air samples are drawn through the tubes. While air passes the sorbent material, contaminations are retained on the material. For analysis, the samples are thermally desorbed and detected by GC-MS. Method parameters like desorption temperature, desorption flow and desorption duration as well as breakthrough were evaluated. The method was applied for the quantification of NMP during a coating process of lithium ion battery electrodes. Determined values for the contamination of laboratory air with NMP in this case study were found to be below DNEL. TD GC MS is a fast and easy to apply method for the quantification of volatile organic compounds like NMP. It offers high desorption efficiency, quick sampling and no need for any solvents, except for calibration purposes.

Abstract: The study and preservation of illuminated manuscripts, particularly miniatures on parchment, are crucial for understanding the artistic, cultural, and technological history of the past. This research investigates the materials used in a 16th-century illuminated scroll, analyzing both the miniatures and the written text through non-invasive techniques. A multi-analytical approach was applied, including optical microscopy, Hypercolorimetric Multispectral Imaging (HMI), Infrared Reflectography in the 950-1700 nm range, Fiber Optics Reflectance Spectra (FORS), macro X-ray fluorescence (MA-XRF) spectroscopy, Raman spectroscopy and External Reflection-Fourier Transform Infrared spectroscopy (ER-FTIR). These methods provided a comprehensive characterization of the chemical composition and artistic techniques employed, revealing new information on Renaissance materials and practices. The mineral-based pigments identified include smalt, vermillion, lead white, rouaite or gerhardtite. Aluminosilicate and calcite were used as fillers or substrates for organic dyes used for pink hues. Moreover, gold and silver were employed in decorations both as foils and shell pigments. Finally, the capital letters were created with smalt and vermillion, while the black text ink is composed by iron gall ink, commonly used on parchments.

Abstract: In photoelectrochemical biosensing, efficient electron-hole separation is crucial to obtain preferred photocurrent response and analytical performance; thus, constructing developed heterointerfaces with high carriers transfer efficiency is an effective way for sensitive evaluation of analytes. Herein, 1D ZnIn2S4 nanosheet decorated 2D In2O3 tube was developed to integrate with prostate antigen (PSA)-sensitive aptamer for PSA sensitive detection. Benefiting from photoelectric effect and specific 1D/2D hierarchical structure, In2O3-ZnIn2S4 displayed enhanced optical absorption and photocarrier separation, thus superior photoelectrochemical response. Proposed bioassay protocol possessed the linear range from 0.001 to 50 ng/mL and a detection limit at 0.00037 ng/mL. In addition, this biosensor exhibited satisfy anti-interface ability and stability, which also could be extended to other quantitative platforms for detecting else proteins.

Abstract: Drink spiking is a significant public safety issue, often linked to crimes such as theft and sexual assault. The detection of drugs used in these incidents is challenging due to the low concentrations (<ng) and complex matrices involved. This review explores the application of gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS) for identifying drugs in spiked beverages. GC-MS offers high sensitivity and specificity, capable of detecting drugs at ng/mL levels and distinguishing between compounds with similar structures. The review highlights the advantages of GC-MS, including its ability to analyze multiple substances simultaneously and provide detailed molecular information. Various methods for detecting gamma-hydroxybutyrate (GHB), benzodiazepines, and other drugs in beverages are discussed, emphasizing the importance of derivatization to enhance volatility and chromatographic performance. The paper also addresses the challenges of analyzing complex beverage matrices and the need for continuous improvement in detection techniques to keep pace with the evolving drug market. Overall, GC and GC-MS are powerful tools for forensic analysis in drink spiking cases, offering reliable and accurate results essential for legal and investigative processes.

Abstract: Upcycling horticulture residues offers a sustainable solution to reduce environmental impact, maximize resource utilization, mitigate climate change, and contribute to the circular economy. We synthesized and characterized fourteen natural deep eutectic solvents (NADESs) and applied them to upcycle horticulture residues offering an innovative valorization approach. With initial many factors at a time (MFAT) screening followed by a rotatable central composite response surface methodology (RCCRSM) for optimization, quadratic models fitted the response data for all the synthesized NADESs given: TPC (R2 = 0.984, p < 0.0001), TFC (R2= 0.9999, p < 0.0001), and AA- CUPRAC (R2 = 0.918, p < 0.0001), FRAP (R2 =1.000, P < 0001), and DPPH (R2 = 0.9992, p < 0.0001). Ultrasound temperature 45°C, extraction time 5 min, solvent volume 25 mL, and solvent concentration 90% (v/v) were considered the optimal conditions for maximum desirability (0.9936) of TPC yield; 30°C, 5 min, 25 ml, and 90% (v/v) for maximum desirability (0.9003) for TFC and CUPRAC with maximum desirability (1.00). The maximum desirability for FRAP was (0.9605) at conditions of 45°C, 25 min, 25 ml, and 50%, while DPPH with maximum desirability of (0.9313) had 50°C, 15 min, 15 mL, and 70% (v/v) as the optimized conditions respectively.

Abstract:

This review systematically summarizes the novel preparation methods of cyclodextrin-based chromatographic stationary phases and their applications for chiral recognition in separation techniques such as capillary gas chromatography and high performance liquid chromatography. Aiming at the current situation that enantiomers of chiral compounds present significant differences at the pharmacological, pharmacodynamic and toxicological levels, the core value of chromatographic chiral separation technology in the field of drug discovery and development is emphasized. By analyzing the unique cavity structure and excellent stereoselective properties of cyclodextrins, the mechanism of its action as a chromatographic stationary phase was elaborated. Combined with the typical applications of different derivatized cyclodextrin stationary phases in drug analysis, environmental testing and biological samples, the value and potential of cyclodextrin stationary phases in stereoisomer separation are systematically demonstrated.

Abstract: Purity determination of precious metal is very crucial due to the economic value and hence metals like gold used for making jewelry must reflect the true value. Quantitative determination of jewelry is very important to ensure product integrity and consumer protection. The aim of the current study is to assess and compare the performance of EDXRF technique in the quality determination of gold jewelry. A total of 119 jewelry items containing gold of varying purity were assessed in the study and compared with fire assay. In conclusion, EDXRF technique appears to be a comparable alternative for rapid determination of elemental composition of gold in alloys especially for finished and semifinished ornaments. Further refinements in analytical accuracy may even replace destructive methods in practice.

Abstract: The detection of endocrine disruptors in the environment suggests that human health will be adversely affected by them, and the presence of endocrine disruptors in food is even more hazardous to health.There is a wide range of endocrine disruptors, including antimicrobials, preservatives, plastic additives and photoinitiators.The level of endocrine disruptor contamination in honey, a widely used everyday food, is closely related to human health.In this study, a method for the simultaneous determination of seven typical endocrine disruptors (triclosan (TCS), triclocarban (TCC), methyltriclosan (MTCS), methylparaben (MeP), propylparaben (PrP), bisphenol F (BPF), and 4-hydroxybenzophenone (4HBP)) in honey by ultrasonication-assisted dispersive liquid-liquid microextraction (UALLME) coupled with high-performance liquid chromatography (HPLC) was developed.The actual sample spiked recoveries were 89.70-102.2% with RSD values of 1.1-3.9%, and intra-day precision was in the range of 0.6-1.6% and inter-day precision was in the range of 0.2-1.2%.It also tested 47 honey samples from 7 countries, 12 nectar sources and 5 materials of packaging.The results showed that the total detection rates of TCS and TCC were 29.79% and 19.15%, respectively, the maximum detected concentration of TCS was 144.6 g/kg, the detected concentrations of TCC were below the limit of quantification (LOQ), and MTCS was not detected.The total detection rates of BPF, 4HBP, MeP and PrP in honey samples were 97.87%, 36.17%, 82.98% and 80.85%, respectively, and the maximum detected concentrations were 1194 g/kg, 294.9 g/kg, 439.5 g/kg and 136.7 g/kg, respectively. TCS in citrus nectar, TCC in motherwort nectar, and 4HBP in multifloral nectar were the most frequently detected, and BPF, MeP, and PrP were detected in all nectar sources.Foreign honey samples had a wider range of TCS, BPF, 4HBP and MeP contamination than domestic samples.The concentrations of TCS, BPF, MeP and PrP in honey packed in PET were the highest among all materials.Seven typical endocrine disruptors in honey were found to pose a low risk to adult health through a health risk assessment.However, the health risk of BPAF exposure through honey consumption is high for infants one year of age and younger.Therefore, it is recommended that infants should avoid honey foods and that contamination and monitoring of typical endocrine disruptors during food processing should be enhanced.

Abstract: Tablet surface defects are typically controlled by visual inspection in pharmaceutical industry. This is an insufficient response variable for knowledge-based formulation and process development, and it results in a rather limited robustness of the control strategy. In this article, we present an analytical method for the quantitative characterization of visual tablet surface defects. The method involves analysis of the tablet surface by a digital microscope to obtain optical images and three-dimensional surface scans. Pre-processing procedures are applied for the simplification of the data to allow the detection of the imprint characters and tablet surface structures by a Faster R-CNN object detection model. Geometrical measured variables like perimeter and area were derived from the results of the object detection model and statistically analyzed for a selected number of tablets. The analysis allowed the development of product specific acceptance criteria by a small reference dataset, and the quantitative evaluation of sticking, picking, chipping and abrasion defects. The method showed high precision and sensitivity and demonstrated robust detection of visual tablet surface defects without false negative results. The image analysis was automated, and the developed algorithm can be operated by a simple routine on a standard computer in a few minutes. The method is suitable for industrial use and enables an advancement for industrial formulation and process development, while providing a novel opportunity for the quality control of visual tablet surface defects.

Abstract: A sol-gel approach was used to prepare a thin hydrogel membrane based on an organic-inorganic polymer matrix embedded with pre-synthesized gold nanoparticles (AuNPs). The organic polymers utilized were poly(vinyl alcohol) (PVA) and poly(ethylene oxide) 400 (PEO), while tetraethoxysilane (TEOS) served as a precursor for the inorganic silica polymer. AuNPs were synthesized using D-glucose as a reducing agent and starch as a capping agent. A mixture of PVA, PEO, pre-hydrolyzed TEOS, and AuNP dispersions was cast and dried at 50 °C to obtain the hybrid hydrogel membrane. The structure, morphology, and optical properties of the nanocomposite membrane were analyzed using TEM, SEM, XRD, and UV-Vis spectroscopy. The newly designed hybrid hydrogel membrane was utilized as an efficient sorbent for the simultaneous speciation analysis of chromium and manganese in water samples via solid-phase extraction. The study re-vealed that Cr(III) and Mn(II) could be selectively adsorbed onto the PVA/PEO/TEOS/AuNPs membrane at pH 9, while Cr(VI) and Mn(VII) remained in solution due to their inability to bind under these conditions. Under optimized parameters, detection limits and relative standard deviations were determined for chromium and manganese species. The developed analytical method was successfully applied for the simultaneous speciation analysis of chromium and manganese in drinking water and wastewater samples.

Abstract:

The history of cannabis research spans centuries, with a focus on isolating and understanding its active compounds. Although plants like opium and coca yielded active alkaloids relatively early, cannabis posed unique challenges due to its active substances existing in oily mixtures that were difficult to isolate. Early studies in the 19th century, such as Ferdinand Tscheppe’s 1821 research, debunked claims of opioid-like substances in hemp, setting the stage for further exploration. In the late 19th and early 20th centuries, key figures like Sir William Brooke O’Shaughnessy and Robert Sidney Cahn made significant contributions to the understanding of cannabis’s chemical components, though major breakthroughs were delayed due to technical limitations. In the 1940s, Ghosh and Adams independently elucidated the structure of cannabinol, marking the first cannabinoid identified from cannabis. Subsequent work, including Šantavý’s 1964 and Mechoulam and Gaoni’s 1964 identification of ∆⁹-THC, confirmed the psychoactive compound’s structure and absolute configuration. This article traces these incremental advancements, highlighting the critical role of each researcher’s contributions in piecing together the puzzle of cannabinoid chemistry, underscoring that scientific progress thrives on collaboration and shared knowledge.

Abstract:

An effective deposition of cinchonine layer on platinum metal surface can be easily achieved by the cathodic reduction of cinchonine hydrochloride methanolic solution at a controlled potential of -220 mV vs. the silver standard electrode (SSE). A coated screen-printed platinum electrode has proven suitable for cinchonine determination in water, urine and serum at ug L-1 level concentrations by differential pulse voltammetry in phosphate buffer solution (pH=7.0). The limits of detection (LOD) and the limits of quantitation (LOQ) are 0.6 ug L-1 and 1.8 ug L-1 respectively.

Abstract: A project to assess air pollution at the National Archeological Museum in Naples was carried out. The main goal of the project was to develop and test a reliable, yet simple, monitoring system to be adopted at the same time in several exposition rooms. Nitrogen dioxide, hydrogen chloride, nitrous acid, and sulphur dioxide were the chemical species addressed by the technique. Monitoring was simultaneously performed in five rooms and pollutant concentrations were determined using two passive samplers. The sampling time was approximately one month per period. In addition to passive samplers, environmental data loggers were used to obtain temperature and relative humidity data. Results show high concentrations of nitrogen dioxide inside rooms, consistent with those found in outdoor environments and are close to the values calculated considering the air exchange rates, estimated through time gradients of ambient temperature. The minimum values were recorded in a basement room, having a low ventilation rate. The conversion of nitrogen dioxide to real surfaces produces nitric acid and nitrous acid. Large amounts of nitrous acid were found in exposition rooms up to 15 µg/m3, with maximum values in the basement room, where the air exchange rate is limited and the surface-to-volume ratio is the highest among the monitored rooms. Data analysis demonstrate that the system could discriminate between nitrous acid and nitrogen dioxide. The results show that, for the first time, passive samplers can overcome the problem of mutual interference between nitrogen-containing species. It was found that the nitrates and nitrites found in the alkaline passive sampler is not due to the interference of nitrogen dioxide. Nitric acid was also found in the gas phase, likely generated by dissociation of ammonium nitrate in particulate matter. Hydrogen chloride and sulphur dioxide are present at few µg/m3. Nitrous acid is the most relevant acidic species found indoors. The presence of pollutants was discussed in terms of the reliability of the analytical procedure and its significance for indoor air pollution.

Abstract: Pectin is a complex and versatile polysaccharide crucial for various industries. It functions as a thickener, gelling agent, emulsifier, and low-calorie food. Its anti-inflammatory and immunomodulatory properties have attracted biomedical interest, while its biodegradability and biocompatibility make it valuable for biomaterial applications. The effectiveness of these applications depends on the quality of pectin extraction procedures While traditional extraction methods exist, green methodologies and alternative techniques have improved pectin's physicochemical properties—a significant advantage for industrial applications. Pectin can be extracted from various sources, with its molecular structure and functional groups analyzed through different characterization techniques. Modern green extraction methods include ultrasound-assisted extraction, pulsed ultrasound-assisted extraction, pulsed electric field, moderate electric field mediated extraction, microwave-assisted extraction, subcritical water extraction, enzyme-assisted extraction, ohmic heating-assisted extraction, ultrasound-assisted microwave extraction, ultrasound-assisted ohmic heating extraction, hydrothermal processing, high-pressure processing extraction, and dielectric barrier discharge extraction. This review examines these methods' advantages and disadvantages, along with their applications and future possibilities; it serves as a comprehensive guide for researchers exploring new pectin-rich sources and green extraction technologies for commercial applications.

Abstract: An electrochemical sensor for identification and monitoring of chronic alcohol abuse and alcoholism was preclinically validated by the analysis of plasma from polydrug-consuming rats (alcohol and cocaine). The sensor measures the glycosylation level of transferrin as an electrochemical index of glycosylation (EIG). Three rat groups were designed: saline group, cocaine group and cocaine-alcohol group. Moreover, two periods of withdrawal were studied, after 2 days and 30 days. The alcohol-cocaine group after 2 days of withdrawal showed significantly lower EIG values (p<0.1) than the rest of groups (saline groups, cocaine groups and alcohol-cocaine group after 30 days of withdrawal), so the sensor was able to identify the alcohol abuse in rats and the recovery of glycosylation level after 30 days of withdrawal, even combined with cocaine. Furthermore, the effect of sex was also considered. Receiver operating characteristic (ROC) curves were developed for each sex and the corresponding cut-off values were determined. The sensor showed a clinical sensitivity of 70% for male and 75% for female, and a specificity of 67% for both sexes. This preclinical validation demonstrated the possibilities of this sensor for point of care testing of chronic alcohol abuse, even in cocaine addicts, making it a potential tool for diagnosis and monitoring of alcohol consumption in detox treatments for humans.

Abstract: Gas chromatography – ion mobility spectrometry (GC-IMS) is a powerful technique in the field of food and flavor analysis specifically, as well as for the determination of volatile organic compounds (VOC) in general. It offers high sensitivity and selectivity, combined with a robust design. Sample preparation is typically not required and operating principles under ambient conditions facilitate routine analysis and usage at points of care. Up to now, a plethora of applications of GC-IMS exist in the fields of food analysis, primarily for determining flavors and evaluating the authenticity of food. However, the general issue of peak tailing is so far non-addressed in IMS. Typical drift tube applications (DTIMS) are designed with emphasis to high detection sensitivities and feature large void volumes. This study aimed at developing an optimized IMS instrument design (“focus IMS”), which allows for a signal mapping of the eluting compounds. Due to an optimized flow architecture of sample and drift gas, in combination with an increased drift tube temperature, IMS peak tailing is decreased significantly. In this study, the influence of drift gas flow and IMS cell temperature on the peak shape of several relevant allergenic terpenes was investigated. The peak quality optimization of DTIMS approaches for especially high-boiling substances facilitates the analysis of complex matrices, such as cosmetics, Citrus peel and essence oils as well as terpenes and terpenoids in general.

Abstract: Inductively coupled plasma mass spectrometry (ICP-MS) is important in the biological and biochemical fields as it can quantify trace elements. Confocal laser Raman micros-copy (CLRM), a powerful tool for the compositional analysis of biological samples, or-ganic materials, and inorganic materials, can be used to analyze samples in aqueous solutions. Despite their analytical strength, the quantitative evaluation of proteins bound to mesoporous silica (SiO2) microspheres, which are promising candidates for drug delivery systems and vaccine carriers, has not been sufficiently explored. Therefore, we investigated the applicability of ICP-MS and CLRM to quantify lactoferrin (LF), a widely studied iron-containing protein bound to mesoporous SiO2 microspheres (SBA24). The bound LF amount was measured using ICP-MS, selectively monitoring iron derived from LF as a marker element, and CLRM. The results were compared with those obtained using a conventional bulk analysis technique. The amounts and trends of the signal intensities obtained using ICP-MS and CLRM agreed with each other and with the bulk analysis results. Our findings demonstrate that ICP-MS and CLRM are applicable for the quantitative evaluation of iron-containing proteins bound to SBA24. These methods offer a reliable platform for quantification of biomolecules on micro-particles and provide valuable insights for biomedical research and quality control in related industries.

Abstract: The extraction processes for medicinal plants, particularly the distillation of aromatic plants, generate significant quantities of by-products, consisting of fibrous biomass and hydrosols. These by-products pose challenges for disposal and recovery. Consequently, it is imperative to make the entire, highly energy-intensive process more sustainable by valorizing all derivatives. This study aims to recover bioactive compounds, particularly polyphenols, from these biomasses. Polyphenols represent a large class of compounds known for their biological activities. Artemisia dracunculus, Echinacea purpurea, Helichrysum italicum (from the Asteraceae family), and Lavandula angustifolia, Lavandula x intermedia, Melissa officinalis, Salvia officinalis, Salvia sclarea, and Salvia rosmarinus (from the Lamiaceae family) were subjected to steam distillation. The essential oils obtained were characterized using gas chromatography, and the residual biomasses were processed with innovative extraction methods. The study investigated the use of natural deep eutectic solvents (NADES) for extracting polyphenols from the residual biomasses. Comparisons were made between the extracts obtained using NADES and those obtained using ethanol, a traditional solvent commonly employed for such purposes. The chemical characterization of the extracted compounds was performed using advanced analytical techniques, including HPLC-DAD and UHPLC-HRMS. The application of NADES demonstrated superior extraction efficiency for biomasses from both the Asteraceae and Lamiaceae families. Additionally, NADES exhibited several environmentally friendly characteristics, enhancing their sustainability profile. For these reasons, NADES present a viable alternative system for the recovery of bioactive compounds and could be used to formulate new products for the food, pharmaceutical, and cosmetic industries.

Abstract: Tegoprazan is a potassium ion-competitive acid blocker (P-CAB) and novel inhibitor of gastric acid secretion. The crystal is available in two polymorphs, A and B, but their crystal structures have not yet been reported. Liquid and solid-state NMR were used to investigate the tautomeric state, which was found to be identical in both phases. Using these tautomers, the crystal structures of both polymorphs were determined from the X-ray diffraction data obtained with a laboratory powder X-ray diffractometer, employing simulated annealing and Rietveld refinement. It was found that both phases crystallized in the monoclinic space group P21, Z = 4, with the asymmetric unit containing two symmetrically independent molecules.