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Surface Enhanced Raman Spectroscopy (SERS) technique is an effective analytical technique in which fingerprint information about analytes can be obtained, can provide detection limit performance at the single molecule level, and analyzes are performed in a single step without any intermediate steps. SERS technique offers additional benefits rather than other analytical techniques including high selectivity, ultrasensitive detection, uncomplicated protocols, in situ sampling, on-set capability and cost-effectiveness. As a result of the combination of developments in materials and nanotechnology science with the SERS analysis technique, this technique strengthens its use advantage day by day. The most important factor that limited the use of this technique was the fact that the solution containing the desired analyte(s) was dropped onto the SERS substrate and the same substrate could not be reused in subsequent analyses. To solve this problem, scientists have focused on developing reusable SERS substrates in recent years. In these studies, scientists basically used three SERS substrate cleaning applications (1) washing the SERS substrate with a suitable solvent that can elute the analyte from SERS surface after analysis, (2) cleaning the SERS substrate with catalytic degradation of analytes after analysis by modifying them with catalytic active materials and (3) Applying plasma cleaning procedure to SERS substrate after analysis and (4) applying adsorption and desorption procedure prior to SERS analysis. Herein, the aim of this review article is to evaluate the reusable SERS substrates-based methods based on their level of development and their potential to recycle. This review offers a coherent discussion on a wide range of sensing schemes employed in fabricating the SERS substrates. We utilized a critical approach in which elaborative examples were selected to highlight key shortcomings of various experimental configurations. In the same vein, there is a discussion of the advantages and limitations concerning the key instrumental advances and the expansion of the recent methods developed in this area.

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With the global increase in the use of dietary supplements to provide nutrients in one's regular diet, these supplements' potential health risks and benefits have become a topic of significant interest. Interestingly, as dietary supplements, the Food and Drug Administration (FDA) in the United States (USA), Europe, and most countries do not require manufacturers and distributors to obtain approval or provide safety assessments before marketing those products. This research explores for the first time 16 heavy, trace and macro-elemental contents, namely, As, Ni, Cd, Pb, Cu, Co, Mn, Cr, Zn, V, Fe, Al, K, Na, Mg, and Ca, within 24 nutraceutical and herbal supplements marketed in Oman. The research is focusing on ensuring their compositions, concentrations, and freedom of toxic elements. ICP-OES was utilized, preceded by a microwave digestion technique to digest the samples in concentrated HNO3 and HCl (3:1, v/v). The method was validated within linear ranges of 0.03-5.00 ppm and 1.0-200.0 ppm for micro- and macro-elements, respectively, with %recoveries ranging from 90 to 104%. The limits of detection ranged from 0.01 to 0.09 and 0.14 to 0.30 ppm, while the limits of quantification ranged from 0.03 to 0.28 and 0.46 to 0.91 ppm for micro- and macro-elements, respectively. The detected levels were compared to online databases for risk assessment. Although As and Cd were not detected in all samples, Pb was found in nine samples, with some exceeding regulated limits of exposure. About 80% of the samples contained Al, of which two samples were susceptible to serious health risks of exceeding exposure limits in their compiled doses. The locally harvested Omani herbal supplements revealed significant amounts of Zn, Mg, Mn, and Cu. The results highlighted the potential risks associated with both dosage compliance and labeling discrepancies.

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Understanding the presence, transfer dynamics and depletion of gunshot residues (GSR) on various surfaces is crucial for preserving evidence, reconstructing shooting incidents, and linking suspects to crime scenes. This study aims to explore the transfer and loss of GSR on commonly encountered surfaces such as ceramic, glass, metal, paper, and plastic, as well as the influence of different common hand cleaning methods on secondary transfer. Using scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX) and automated detection software, we quantified highly indicative three-component characteristic particles (lead, barium, and antimony) on cups made from ceramic, glass, metal, paper, and plastic. Furthermore, we evaluated the amount of secondary transferred particles on these surfaces following various post-discharge hand cleaning methods: washing with water and soap, washing with only water, wiping with wet wipes, or using paper towels. The results demonstrate that counts of secondarily transferred GSR particles vary significantly among surfaces. Specifically, the transferred GSR count was highest on paper, followed by plastic, ceramic, metal, and glass respectively. Post-discharge hand cleaning methods, including washing with water and soap, washing with only water, cleaning with wet wipes, or with paper towel, resulted in substantial loss of GSR count on transferred surfaces. Among these methods, washing with water and soap showed the highest depletion. The empirical evidence provided by our results underscores the importance of considering surface properties, post-shooting activities, and the methods of sample collection and analysis when interpreting transferred GSR analysis. Despite challenges, these insights enhance our ability to link suspects to shooting crimes through careful consideration of the entire context.

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Covalent organic frameworks (COFs) are featured with large specific surface areas, good thermal stability, and abundant pores. These properties are exactly what the sorbents used for extraction or adsorption of interest substances are desired with. While, the low density and hydrophobicity of COFs often makes them difficult to be dispersed evenly and recovered from the aqueous solution. Magnetic covalent organic frameworks (MCOFs) inherit magnetic property of the magnetic particles and porous structure of COFs. They have improved dispersity in aqueous solution and phase separation can be rapidly achieved via external magnetic fields. This review summarized the synthesis strategies for MCOFs, and their application in trace environmental organic pollutants analysis by chromatography techniques. The selection of COFs types and modification with active groups for a certain adsorption purpose is discussed, along with the exploration of adsorption mechanisms, which is beneficial for the design and synthesis of MCOFs.

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INTRODUCTION: Due to the high toxicity of antineoplastic drugs, handling their packaging could lead to the chemical contamination of hospital environments and exposure risks to healthcare professionals and patients. This study aimed to assess the contamination of two main surfaces: the outer primary packaging of oral antineoplastic drug formulations (n = 36) available on the Swiss market and the surface of secondary packaging of injectable antineoplastic drug preparations (n = 60) produced by the pharmacy of a Swiss hospital and carriers used for transport (n = 5). METHODS: Samples were collected using a validated wipe sampling method. The simultaneous analysis of 24 antineoplastic drugs: 5-fluorouracil, busulfan, carboplatin, cyclophosphamide, cytarabine, dacarbazine, daunorubicin, docetaxel, doxorubicin, epirubicin, etoposide, gemcitabine, idarubicin, ifosfamide, irinotecan, methotrexate, oxaliplatin, paclitaxel, pemetrexed, raltitrexed, topotecan, treosulfan, vinblastine, vincristine) and 1 antiviral compound (ganciclovir) was performed by UHPLC-MS/MS. RESULTS: A total of 58% and 90% positive results were obtained for the primary packaging of oral chemotherapies and for the secondary packaging of injectable preparations, respectively. The highest quantities found on the primary packaging for oral chemotherapies and on the surface of closed leak-proof bags were 111 ng of methotrexate and 19 ng of gemcitabine, respectively. Gemcitabine (69%) and cyclophosphamide (38%) were the two most common contaminants found on the packaging of injectable preparations and carriers, regardless of the chemotherapy preparations. CONCLUSION: Trace levels (ng) of antineoplastic drugs can be found on most surfaces of all evaluated pharmaceutical products. Thus, suitable personal protective equipment is mandatory for healthcare professional handling antineoplastic drugs.

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Raman spectroscopy is a non-destructive analytical technique for characterizing organic and inorganic materials with spatial resolution in the micrometer range. This makes it a method of choice for space-mission sample characterization, whether on return or in situ. To enhance its sensitivity, we use signal amplification via interaction with plasmonic silver-based colloids, which corresponds to surface-enhanced Raman scattering (SERS). In this study, we focus on the analysis of biomolecules of prebiotic interest on extraterrestrial dust trapped in silica aerogel, jointly with the Japanese Tanpopo mission. The aim is twofold: to prepare samples as close as possible to the real ones, and to optimize analysis by SERS for this specific context. Serpentinite was chosen as the inorganic matrix and adenine as the target biomolecule. The dust was projected at high velocity into the trapping aerogel and then mechanically extracted. A quantitative study shows effective detection even for adenine doping from a 5·10-9mol/L solution. After the dust has been expelled from the aerogel using a solvent, SERS mapping enables unambiguous adenine detection over the entire dust surface. This study shows the potential of SERS as a key technique not only for return samples, but also for upcoming new explorations.

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Globally, per- and polyfluoroalkyl substances (PFAS)-related research on paper products has focused on food packaging with less consideration on the presence of PFAS at different stages of the paper recycling chain. This study analysed the prevalence of PFAS in paper grades used for the manufacture of recycled paperboard. The presence of PFAS was attributed to the use of PFAS-containing additives, consumer usage, exposure to packed goods as well as contamination during mingling, sorting, collection, and recovery of paper recycling material. Q Orbitrap mass spectrometry was used to analyse the paper samples after accelerated solvent extraction and solid phase extraction. The distribution and possible propagation of 22 PFAS were determined in pre-consumer, retail and post-consumer paper products. Post-consumer samples had the highest combined average concentration (ΣPFAS) at 213 ng/g, while the ΣPFAS in retail (159 ng/g) and pre-consumer samples (121 ng/g) was detected at lower concentrations. This study showed that waste collection and recycling protocols may influence PFAS propagation and that measures must be developed to minimise and possibly eliminate exposure opportunities.

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The SERS response of adenine is one of the most studied, due to its outstanding exaltation. However, the spectra obtained strongly differ according to the experimental conditions and still remain not well understood. To be able to search for the presence of this molecule in complex environments, it is essential to better understand the SERS response of adenine alone. After a brief presentation of the literature on the subject, we present results suggesting that the experimental spectra would result from the overlap of different spectroscopic signatures, that may probably be due to different non-covalent interactions or different electromagnetic fields experienced by adenine molecules. An independent component analysis is reported. Our results underline the difficulty to precisely analyze the experimental data, the need to continue this research and to constitute data banks that would allow comparing the spectra obtained in different laboratories according to the experimental conditions.

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To sensitively determine 99Tc, a new method for internal quantification of its most common and stable species, [99Tc]Tc O 4 - , was developed. Anion-exchange chromatography (IC) was coupled to inductively coupled plasma-mass spectrometry (ICP-MS) and equipped with an aerosol desolvation system to provide enhanced detection power. Due to a lack of commercial Tc standards, an isotope dilution-like approach using a Ru spike and called isobaric dilution analysis (IBDA) was used for internal quantification of 99Tc. This approach required knowledge of the sensitivities of 99Ru and 99Tc in ICP-MS. The latter was determined using an in-house prepared standard manufactured from decayed medical 99mTc-generator eluates. This standard was cleaned and preconcentrated using extraction chromatography with TEVA resin and quantified via total reflection X-ray fluorescence (TXRF) analysis. IC coupled to ICP-MS enabled to separate, detect and quantify [99Tc]Tc O 4 - as most stable Tc species in complex environments, which was demonstrated in a proof of concept. We quantified this species in untreated and undiluted raw urine collected from a patient, who previously underwent scintigraphy with a 99mTc-tracer, and determined a concentration of 19.6 ± 0.5 ng L-1. The developed method has a high utility to characterize a range of Tc-based radiopharmaceuticals, to determine concentrations, purity, and degradation products in complex samples without the need to assess activity parameters of 99(m)Tc.

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High silicon alloyed ductile cast iron (Si-DCI) can show unpredictable brittle fracture which currently prevents a widespread application of this material. The brittleness is associated with local superstructure formation due to silicon segregation which influences the deformation mechanisms of the matrix phase. In order to understand the effect of silicon segregation on the mechanical properties of Si-DCI under monotonous loading, three alloys with different cooling conditions were examined and micromechanical simulations were carried out by using the phenomenological crystal plasticity model. Here, the segregation profiles were determined through multi phase field simulations. The influence of segregation on the mechanical properties was only evident from the model but not from the experimental results. The simulated results show that the toughness of Si-DCI decreases with stronger silicon segregation when ductile damage is considered.

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Non-steroidal anti-inflammatory drugs (NSAIDs) have been recognized as a potentially serious threat to the natural environment. NSAIDs are popular painkillers, and the main pathway for them to reach natural water is via discharge from wastewater and sewage treatment plants. In order to monitor contamination caused by these drugs, as well as their impact on the environment, a new material based on Silica Gel 60, functionalized with a dendrimeric copolymer of methylamine and 1,4-butanediol diglycidyl ether (named MA-BDDE), was prepared. Initial physicochemical characterization of the MA-BDDE material was carried out using ATR FT-IR spectroscopy as well as solid-state carbon-13 NMR spectroscopy. Its effectiveness at NSAID extraction was evaluated by the application of five select drugs in dispersive solid-phase extraction (dSPE): aspirin, ketoprofen, naproxen, diclofenac and ibuprofen. This was followed by their simultaneous determination using the HPLC-UV/Vis system demonstrating good sensitivity, with limits of detection values within the 63-265 ng mL-1 range. A comparison of the sorption capacity of each pharmaceutical with unmodified base silica showed an at least tenfold increase in capacity after modification. Initial MA-BDDE application in a quick, low-waste extraction procedure of those select NSAIDs from spiked surface water samples yielded promising results for its use as a sorbent, as recovery values of analytes adsorbed from various samples were found to exceed 72%.

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The accurate analysis of ultra-trace (e.g. <10-4 ng/mL) substances in complex matrices is a burdensome but vital problem in pharmaceutical analysis, with important implications for precise quality control of drugs, discovery of innovative medicines and elucidation of pharmacological mechanisms. Herein, an innovative constant-flow perfusion nano-electrospray ionization (PnESI) technique was developed firstly features significant quantitative advantages in high-sensitivity ambient MS analysis of complex matrix sample. More importantly, double-labeled addition enrichment quantitation strategies of gas-liquid microextraction (GLME) were proposed for the first time, allowing highly selective extraction and enrichment of specific target analytes in a green and ultra-efficient (>1000-fold) manner. Using complex processed Aconitum herbs as example, PnESI-MS directly enabled the qualitative and absolute quantitative analysis of the processed Aconitum extracts and characterized the target toxic diester alkaloids with high sensitivity, high stability, wide linearity range, and strong resistance to matrix interference. Further, GLME device was applied to obtain the highly specific enrichment of the target diester alkaloids more than 1000-fold, and accurate absolute quantitation of trace aconitine, mesaconitine, and hypaconitine in the extracts of Heishunpian, Zhichuanwu and Zhicaowu was accomplished (e.g., 0.098 pg/mL and 0.143 pg/mL), with the quantitation results well below the LODs of aconitines from any analytical instruments available. This study built a systematic strategy for accurate quantitation of ultra-trace substances in complex matrix sample and expected to provide a technological revolution in many fields of pharmaceutical research.

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Theory of mind (ToM) has been argued to be a multidimensional construct, with ToM inferences depending on distinct processes across affective and cognitive ToM tasks and across first-order cognitive and second-order cognitive ToM tasks. Behavioural evidence for a multidimensional account has primarily depended on dissociations identified via analysis of variance, a statistical approach insufficient for assessing dimensionality. Instead, state-trace analysis (STA) is a more appropriate statistical technique to uncover dimensionality. The current study first applied STA to two summary datasets that had previously identified key dissociations between cognitive and affective ToM; these reanalyses did not support a multidimensional account of ToM. Next, STA was applied to a more detailed dataset to reveal whether ToM is based on multiple processes in a sample of 115 older adults aged 60-85 years (M = 68.5, SD = 5.92, 61.7% female) with higher or lower emotion perception ability. Participants made ToM judgements about different social exchanges (e.g., sarcasm or lying). STA results supported a multidimensional account of ToM across first-order cognitive, second-order cognitive, and affective ToM subdomains. These results lay a more rigorous foundation for subsequent studies to further examine the dimensionality of ToM and to apply formal modelling, progressing the field's understanding and measurement of the cognitive processes driving ToM judgements.

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A convenient and reliable surface-enhanced Raman scattering (SERS) substrate has been developed for the surface corrosion analysis of bronze artifacts. The substrate consists of oriented alginate nanofiber membranes containing silver nanoparticles (Ag NPs), which were obtained through electrostatic spinning, ion exchange, and in-situ reduction. By controlling the reduction time, Ag/alginate nanofiber membranes with different contents, sizes, and distributions were obtained. The Ag/alginate nanofiber#20 membranes, obtained with a reduction time of 20 min, reached a detection limit of 10-12 M for R6G with an enhancement factor of 6.64 × 107. In the trace detection of bronze patina, the intensity of the characteristic peaks of harmful patina located at 513, 846, 911, and 974 cm-1 were increased by more than 500 %. This was due to the uniform loading of a large number of Ag NPs on the surface of the nanofiber membrane obtained by reduction for 20 min, and the formation of a large number of hot spots between the oriented nanofibers. This significantly improved the SERS performance of the flexible substrate layer under the joint action with the Ag NPs. These results indicate that the flexible substrate layer can greatly enhance the Raman characteristic peaks of alkali copper chloride and be effectively used for trace analysis of the surface composition of bronze artifacts.

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The present study focused on the pretreatment and detection of GLY and its four metabolites AMPA, N-acetyl AMPA, N-methyl GLY and N-acetyl GLY in plasma samples. Multi-walled carbon nanotube-modified quaternary amine-functionalized polymers (QA-PDNV@MWCNTs) were synthesized in a controlled manner by self-assembly, and its morphology and composition were extensively characterized. The QA-PDNV@MWCNTs microspheres were then used as an SPE adsorbent for the preparation and rapid determination of GLY and its four metabolites in plasma samples combined with ultra-performance liquid chromatography-high resolution mass spectrometry (UPLCHRMS). The SPE conditions based on QA-PDNV@MWCNTs were optimized for GLY and its metabolites to obtain the best purification efficiency. The experimental results show that when the adsorbent contains 8% MWCNTs, it can balance the adsorption of target analytes and the purification performance of the adsorbent for impurities. In addition, this study compared the QA-PDNV@MWCNTs based SPE method with the commercial Waters Oasis MAX SPE cartridge and the results showed that the developed method in this study has better resistance to matrix interference. Under optimal conditions, the recoveries of GLY and its metabolites spiked in plasma were 82.6-99.4 % with relative standard deviations (RSDs) of 1.0-7.8 %. The limits of detection (LODs, S/N ≥ 3) and limits of quantification (LOQs, S/N ≥ 9) of the method were 0.05-0.33 µg/L and 0.15-1.00 µg/L, respectively. Finally, the developed QA-PDNV@MWCNTs based SPE-UPLCHRMS method was used to confirm GLY poisoning not only on the basis of the detection of the GLY prototype, but also on the basis of its four metabolites.

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The biopharmaceutical industry faces the challenge of efficiently characterising impurity profiles of therapeutical peptides, also due to their complex polar and ionisable attributes. This research explores the potential of advanced chromatographic techniques to address this challenge. The study compares dynamic electrostatic repulsion reversed phase (d-ERRP) to its counterparts (static ERRP and ion pair reversed phase IP-RP) in analysing Icatibant and its elusive epimeric impurity, [L-Arg]1-Icatibant and highlights its exceptional capabilities in generating symmetric peaks, mitigating the common tailing phenomenon, and serving as a steadfast guardian of column longevity. The result highlights d-ERRP as a pioneering tool in the domain of liquid chromatography, fostering its role as a reference technique for the analysis of therapeutic peptides.

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Detecting trace amounts of explosives is important for maintaining national security due to the growing threat of terror attacks. Particularly challenging is the increasing use of homemade explosives. Therefore, there is a constant need to improve existing technologies for detecting trace amounts of explosives. This paper describes the design of a stationary device (a gate) for detecting trace amounts of explosives and explosive taggants and the design of differential ion mobility spectrometers with a focus on the gas system. Nitromethane (NM), trimeric acetone peroxide (TATP), hexamine peroxide (HMTD), and explosive taggants 2,3-dimethyl-2,3-dinitrobutane (DMDNB) and 4-nitrotoluene (4NT) were used in this study. Gate measurements were carried out by taking air from the hands, pocket area, and shoes of the tested person. Two differential ion mobility spectrometers operating in two different modes were used as explosive detectors: a mode with a semi-permeable membrane to detect explosives with high vapor pressures (such as TATP) and a mode without a semi-permeable membrane (using direct introduction of the sample into the measuring chamber) to detect explosives with low vapor pressures (such as HMTD). The device was able to detect trace amounts of selected explosives/explosive taggants in 5 s.

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Three penicillin-based ß-lactam antibiotics (benzylpenicillin, amoxicillin, and ampicillin) were extracted by electromembrane extraction (EME) and determined in the resulting extracts by capillary zone electrophoresis (CZE) with UV-Vis detection. The EME was optimized for the simultaneous clean-up of complex samples and preconcentration of the three antibiotics and employed 1-octanol as the organic phase interface (impregnated in the pores of a hollow fiber), acidified donor solution (pH 3), and phosphate buffer (pH 5.6) as the acceptor solution. The EMEs were carried out for 20 min at 300 V and constant stirring (750 rpm) of the donor solution. At the optimized EME-CZE conditions, the sensitivity of the analytical method was sufficient for the determination of the three ß-lactam antibiotics in undiluted cow's milk at concentrations below the EU maximum residue limits (4 µg/L) in foodstuffs. The method was simple, rapid, and convenient and offered extraction recoveries of 13.5 - 87.3 %, enrichment factors of 23.6 - 152.8, repeatability (RSD values) better than 7.6 %, linear analytical response in the 1 - 100 µg/L (3 - 100 µg/L for benzylpenicillin) concentration range with correlation coefficients ≥ 0.9997, and limits of detection from 0.2 to 1.2 µg/L. The proposed analytical concept was used for the rapid control of milk quality (i.e. assessment of excessive use of antibiotics in dairy animals), moreover, it was further extended to the trace determination of ß-lactam antibiotics in other complex samples, such as in wastewater.

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Secondary fluorescence (SF) is known to be a potential source of error in electron probe microanalysis (EPMA) when analyzing for a trace or minor element near a phase boundary. This often overlooked effect leads to a concentration enhancement whenever the neighboring phase contains a high concentration of the analyzed element. Here we show that SF may also lead to a concentration decrease, which can be mistakenly interpreted as a depletion. To examine this issue, we compare Ni profiles measured on well-characterized, homogeneous olivine [(Mg,Fe)2SiO4] grains embedded in basaltic glass, with semi-analytical calculations and numerical simulations of SF across phase boundaries. We find that the Ni content consistently decreases with decreasing distance to the interface or grain radius, deviating from the expected concentration by ∼2-5% at 10 µm from the interface. This decrease is explained by the lower bremsstrahlung fluorescence emitted from the sample as compared to that emitted from the standard. The analytical error due to boundary fluorescence affecting other elements of petrologic importance in olivine is discussed.

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This study uses a rapid tandem mass-spectrometry method to determine water content in complex organic solutions. Emphasis is placed on trace-water analysis by a fast and accurate alternative to the Karl-Fischer method. In this new method, water is captured by a charge-labeled molecular probe. Water binds strongly with high specificity to the strongly electrophilic aldehyde site in a charge-labelled molecule (N-methylpyridinium); competitive binding by other analytes is effectively discriminated against in the mass-measurement step. Quantitative determinations are made over a wide concentration range, 0.001 % (10 ppm) to 99 %, with better than 10 % relative standard deviation, along with short (1 min) analysis times using small sample volumes (several µL). Applications include water measurement in simple organic solvents, for example, deuterated solvents, as well as in complex mixtures, for example, organic reaction mixtures. Additionally, this method allows for water monitoring in levitated droplets. Mechanistic investigations into the impact of water on important chemical processes in organic synthesis and environmental science are reported.