Analytical Challenges Research Articles

A review of particulate matter (PM) in Indonesia: trends, health impact, challenges, and options.

This study reviews particulate matter (PM) research in Indonesia, focusing on current trends, health impacts, challenges, and future research directions. As the largest archipelago country, Indonesia faces severe pollution annually due to rapid urbanization, industrial activities, vehicle emissions, and forest fires. PM levels often exceed WHO and NAAQS standards, especially in urban areas and during forest fire seasons, posing significant health risks to vulnerable populations. Most PM studies have been conducted in major cities, primarily concentrated on Java Island. While there are several studies in Sumatra and Borneo, they commonly focus on the effects of peatland fires, and research in the eastern part of Indonesia remains limited. Substantial gaps in PM studies have been highlighted, including limited monitoring infrastructure, technology, data inconsistencies, and socio-economic challenges. Recent studies emphasize the need for more research on size-segregated PM, including ultrafine particles (UFPs), to fully understand their behavior in the atmosphere, sources, distribution, and health impacts. Chemical analysis and source apportionment studies are also crucial but currently limited due to equipment and analytical challenges. To improve PM management, the study proposes strategic options, including adopting advanced monitoring technologies along with low-cost samplers, increasing funding and technical training, enhancing coordination among stakeholders, and fostering international collaboration. Furthermore, public awareness campaigns and community-based monitoring are essential for effective air quality management.

Current Analytical Methods and Challenges for the Clinical Diagnosis of Invasive Pulmonary Aspergillosis Infection

In the last decade, pulmonary fungal infections such as invasive pulmonary aspergillosis (IPA) have increased in incidence due to the increased number of immunocompromised individuals. This increase is especially problematic when considering mortality rates associated with IPA are upwards of 70%. This high mortality rate is due to, in part, the length of time it takes to diagnose a patient with IPA. When diagnosed early, mortality rates of IPA decrease by as much as 30%. In this review, we discuss current technologies employed in both medical and research laboratories to diagnose IPA, including culture, imaging, polymerase chain reaction, peptide nucleic acid–fluorescence in situ hybridization, enzyme-linked immunosorbent assay, lateral flow assay, and liquid chromatography mass spectrometry. For each technique, we discuss both promising results and potential areas for improvement that would lead to decreased diagnosis time for patients suspected of contracting IPA. Further study into methods that offer increased speed and both analytical and clinical sensitivity to decrease diagnosis time for IPA is warranted.

A brief review on recent high-performance platforms for electrochemical sensing of azo dye Allura Red (E129): food safety and pharmaceutical applications

Artificial dyes are increasingly widespread, especially in foodstuffs and pharmaceutical products as an industry marketing strategy to attract consumers. Consumption of the synthetic azo dye Allura Red (AR) has potential risks to human health and can cause several adverse health effects such as genotoxicity, carcinogenicity, attention deficit hyperactivity disorder, allergic and asthmatic diseases in children. The limited number of electrochemical sensing platforms for AR successfully applied for safety assessment of foods, beverages, and drug formulations testifies that the food and pharmaceutical matrices present significant analytical challenges and there is still a need to amplify the analytical performances of these systems. The authors intensively reviewed recent papers (mainly since 2019) emphasizing electrode engineering, strategies for electrochemical signal amplification, and analytical applications in food and drug control. A critical discussion on the latest interesting innovations and perspectives of the most promising electrochemical tools for AR electro­analysis is presented. The challenges and limitations in the design of electrochemical sensors for AR analysis are also discussed with a view to providing new directions for future research and development of sustainable sensing devices, paving the way for advancements in this field.

Latest trends in the environmental analysis of PFAS including nontarget analysis and EOF-, AOF-, and TOP-based methodologies.

Ubiquitous environmental occurrence of per- and polyfluoroalkyl substances (PFAS) underscores the critical need to broaden investigative efforts in effective screening, risk assessment, and remediation. Owing to thebroad spectrum of PFAS, various analytical techniques have been extensively utilized to attain inclusivity, with notable attention given to methods such as extractable organic fluorine (EOF), adsorbable organic fluorine (AOF), and the total oxidizable precursor (TOP) assay. These techniques expand the scope of PFAS analysis by estimating perfluoroalkyl acid precursors or the total organochlorine fraction. This review offers a comprehensive comparative overview of up-to-date methodologies, alongside acknowledging the inherent limitations associated with their applications. When coupled with target analysis via low-resolution tandem mass spectrometry, these techniques offer a potential estimation of total PFAS concentrations. Yet, analytical challenges such as the limited availability of reference analytical standards, partial PFAS adsorption, and the entrapment of fluorinated inorganic anions on adsorbent materials often restrict the comprehensiveness of PFAS analysis. So, integrating nontarget analysis using high-resolution mass spectrometry (HRMS) tools fortifies these PFAS mass balance approaches, enabling the development of a more holistic approach for anenvironmental analysis framework. This review provides additional insights into the comparative advantages of PFAS analytical approaches and explores various data prioritization strategies in nontarget screening methods. It advocates for the necessary optimization of PFAS extraction methods, asserting that integrating the nontarget approach would foster the establishment of a comprehensive monitoring framework across diverse environmental matrices. Such integration holds promise for enhancing scientific comprehension of PFAS contamination across diverse environmental matrices.

Simultaneously quantifying a novel five-component anti- migraine formulation containing ergotamine, propyphenazone, caffeine, camylofin, and mecloxamine using UV spectrophotometry and chemometric models

This study presents a new method for simultaneously quantifying a complex anti-migraine formulation containing five components (ergotamine, propyphenazone, caffeine, camylofin, and mecloxamine) using UV spectrophotometry and chemometric models. The formulation presents analytical challenges due to the wide variation in component concentrations (ERG: PRO: CAF: CAM: MEC ratio of 0.075:20:8:5:4) and highly overlapping UV spectra. To create a comprehensive validation dataset, the Kennard-Stone Clustering Algorithm was used to address the limitations of arbitrary data partitioning in chemometric methods. Three different chemometric models were evaluated: Classical Least Squares (CLS), Partial Least Squares (PLS), and Multivariate Curve Resolution-Alternating Least Squares (MCR-ALS). Among these, MCR-ALS demonstrated excellent performance, achieving recovery values of 98–102% for all components, accompanied by minimal root mean square errors of calibration (0.072–0.378) and prediction (0.077–0.404). Moreover, the model exhibited high accuracy, with relative errors ranging from 1.936 to 3.121%, bias-corrected mean square errors between 0.074 and 0.389, and a good sensitivity (0.2097–1.2898 μg mL−1) for all components. The Elliptical Joint Confidence Region analysis further confirmed the predictive performance of the models, with MCR-ALS consistently showing the smallest ellipses closest to the ideal point (slope = 1, intercept = 0) for most analytes, indicating superior accuracy and precision. The approach's sustainability was rigorously assessed using six advanced metrics, validating its environmental friendliness, economic viability, and practical application. This approach effectively resolves complex pharmaceutical formulations, contributing to sustainable development objectives in quality control processes.

Case study of adjacent integral bridges supported on continuous secant piled walls

Integral bridges are often the preferred way of construction for short and medium span bridges in the UK. However, the behaviour of integral bridges is influenced by complex soil-structure interaction behaviour that may be cumbersome to predict and analyse when dealing with unusual structural arrangements. This paper presents a case study for the design of two single span bridges carrying a roundabout over a dual carriageway, supported on continuous secant piled walls. One of the bridges is fully integral while the adjacent structure is articulated at one end due to its skew. An alternative detail for the articulated end is proposed, to eliminate soil pressures and settlements at the back of the abutments as well as reduce the risk of water ingress to the bearings. The complex nature of the structural arrangement presented analytical challenges, that were solved by developing an advanced modelling approach, exploring two proposals. The first is to evaluate the geotechnical model for a range of imposed top of abutment displacements from the onset. The second, using unique non-linear springs and derived P-Y curves describes the more realistic variable nature of soil-structure interaction over the length of the walls leading to reduced soil pressures enhancing design feasibility.

Stable isotope analyses of lacustrine chitinous invertebrate remains: Analytical advances, challenges and potential

This review examines recent developments in the application of stable isotope analyses (δ18O, δ13C, δ15N, δD) to lacustrine invertebrate remains. These remains are ubiquitous in lacustrine sediments and thus provide an opportunity to measure changes in stable isotope ratios across a range of timescales and environments and allow interpretive power beyond taxonomic studies. To date they have been relatively understudied in comparison to carbonate fossils and offer both opportunities and challenges and we explore both themes in this review. This review will explore improvements to analytical instrumentation and the opportunities that this presents, it will look at a range of new studies of the modern lacustrine environment and how these studies allow a more nuanced palaeoenvironmental approach. We review recent studies that have used these advancements in understanding to help to reveal new knowledge of past climates, environments and ecology. In addition, we explore new studies that help to elucidate the role of methane-derived carbon to lacustrine food webs and the drivers behind this, including new data to estimate the contribution of methane derived carbon to an arctic lake. We conclude that major progress is currently being made in invertebrate-isotope analyses, and we expect this to continue apace.

Improved differentiation of NPS analogs through the application of chemometric methods to GC-solid deposition-FTIR spectra

Novel psychoactive substances pose a significant analytical challenge for forensic laboratories. Gas Chromatography with Infrared Spectroscopy (GC-IR) is typically presented as producing visually distinct spectra. However, this is not the case for all compounds. In this study, we showcase three synthetic cathinone analogs (methylone, N-ethylpentylone, and pentylone) which produce extremely visually similar solid state IR spectra.A primary dataset of these analogs was generated at the Amsterdam Police Laboratory. Libraries were created using two different sample preparation methods. The same compounds were also analyzed at the Virginia Department of Forensic Science (DFS). It was observed that changes in either instrument or sample preparation were enough to pose challenges to both the visual assessment and a library matching algorithm. Additionally, week-to-week variation was observed within the primary dataset. Principal Component Analysis (PCA) in combination with mahalanobis distances for objective comparison was assessed. A leave-one-sample-out cross validation accurately identified 100% of the samples in the primary dataset.This study shows how the application of chemometrics to spectral GC-IR data can substantiate the instrument’s differentiation capabilities and provide valuable objective support for a compound identification. In addition, limitations in the consistency of GC-IR spectra over time and across instruments and sample preparation methods were observed which could affect how the forensic community utilizes these techniques. Specifically, this study shows that shared GC-IR libraries might pose selectivity limitations. Therefore, laboratories must exercise caution if shared/generic GC-IR libraries are utilized for casework, and it is recommended that instrument and solvent specific libraries are generated.

Inter-chromosomal contacts demarcate genome topology along a spatial gradient

Non-homologous chromosomal contacts (NHCCs) between different chromosomes participate considerably in gene and genome regulation. Due to analytical challenges, NHCCs are currently considered as singular, stochastic events, and their extent and fundamental principles across cell types remain controversial. We develop a supervised and unsupervised learning algorithm, termed Signature, to call NHCCs in Hi-C datasets to advance our understanding of genome topology. Signature reveals 40,282 NHCCs and their properties across 62 Hi-C datasets of 53 diploid human cell types. Genomic regions of NHCCs are gene-dense, highly expressed, and harbor genes for cell-specific and sex-specific functions. Extensive inter-telomeric and inter-centromeric clustering occurs across cell types [Rabl’s configuration] and 61 NHCCs are consistently found at the nuclear speckles. These constitutive ‘anchor loci’ facilitate an axis of genome activity whilst cell-type-specific NHCCs act in discrete hubs. Our results suggest that non-random chromosome positioning is supported by constitutive NHCCs that shape genome topology along an off-centered spatial gradient of genome activity.

WEST is an ensemble method for spatial transcriptomics analysis

Spatial transcriptomics is a groundbreaking technology, enabling simultaneous profiling of gene expression and spatial orientation within biological tissues. Yet when analyzing spatial transcriptomics data, effective integration of expression and spatial information poses considerable analytical challenges. Although many methods have been developed to address this issue, many are platform specific and lack the general applicability to analyze diverse datasets. In this article, we propose a method called the weighted ensemble method for spatial transcriptomics (WEST) that utilizes ensemble techniques to improve the performance and robustness of spatial transcriptomics data analytics. Wecompare the performance of WEST with six methods on both synthetic and real-world datasets. WEST represents a significant advance in detecting spatial domains, offering improved accuracy andflexibility compared to existing methods, making it a valuable tool for spatial transcriptomics data analytics.

Recent and emerging food packaging alternatives: Chemical safety risks, current regulations, and analytical challenges.

Food contact materials should not release their constituent substances into food at levels harmful to human health nor change the food composition, taste, or odor unacceptably. The historical evolution of food packaging shows that the use of plastics has increased dramatically, because of its convenience, lightweight, and cost effectiveness, but carries a significant environmental impact. Influenced by trends such as growing awareness of the environmental footprint and stricter safety requirements, conventional packaging is now progressively evolving toward new alternatives. All stakeholders in the agrifood system are involved in the journey to transform food packaging to more sustainable alternatives, while maintaining the important functionalities of suitable food packaging. The current most promising food packaging alternatives are presented in this review with their benefits, limitations, and associated potential safety hazards, with a focus on chemical hazards. Although some potential hazards are common to conventional packaging, others are specific to the new alternatives. Identification of potential chemical hazards associated with these new packaging alternatives is important to anticipate any risks posed to consumer safety. With much diversity in packaging types and rules aimed at ensuring safety drastically varying between jurisdictions, it is not always easy to determine the best way to assess the safety of food packaging. International guidance on principles for safe food packaging could help drive global harmonization and would play a crucial role in ensuring a consistent and science-based framework for the safety and compliance of new and emerging food packaging.

Development and application of an LC-MS/MS method for the combined quantification of oxysterols and bile acids

Oxysterols and bile acids are interconnected bioactive lipids playing pivotal roles in diverse physiological and pathological processes. For this reason, they are increasingly studied together for their implications in various diseases. However, due to analytical challenges inherent to the nature of these analytes, very few methods have been developed for the simultaneous analysis of these lipids. We here report the development of a sensitive LC-MS/MS method for the combined quantification of 18 oxysterols, 11 unconjugated, 15 conjugated bile acids, and 1 bile acid precursor, using 8 isotope-labeled internal standards, addressing the need for a more comprehensive analysis of these interesting lipid families. During the method development, we investigated different extraction protocols, set up a purification step, and achieved chromatographic separation for these lipids, overcoming challenges such as the large number of analytes, isomers, and wide range of polarity across the analytes. Finally, the method was successfully applied to the analysis of preclinical and clinical samples, quantifying 12 oxysterols and 14 bile acids in human plasma, 10 oxysterols and 18 bile acids in mouse plasma from the vena cava, and 10 oxysterols and 20 bile acids in mouse plasma from the portal vein within a single chromatographic run.

Analytical Challenges in Novel Pentavalent Meningococcal Conjugate Vaccine (A, C, Y, W, X).

Multivalent meningococcal conjugate vaccines are a significant focus for the scientific community in light of the WHO's mission to defeat meningitidis by 2030. Well-known meningococcal vaccines such as MenAfriVac, Nimenrix, Menveo, and MenQuadfi are licensed in various parts of the world and have been successful. Recently, the World Health Organization (WHO) qualified MenFive (meningococcal A, C, Y, W, and X) conjugate vaccine, further enhancing the battery of vaccines against meningitis. The antigenic nature of the current and new serogroups, the selection of carrier proteins, and the optimal formulation of these biomolecules are pivotal parameters for determining whether a biological preparation qualifies as a vaccine candidate. Creating appropriate quality control analytical tools for a complex biological formulation is challenging. A scoping review aims to identify the main challenges and gaps in analyzing multivalent vaccines, especially in the case of novel serogroups, such as X, as the limited literature addresses these analytical challenges. In summary, the similarities in polysaccharide backbones between meningococcal serogroups (C, Y, W sharing a sialic acid backbone and A, X sharing a phosphorous backbone) along with various conjugation chemistries (such as CNBr activation, reductive amination, CDAP, CPIP, thioether bond formation, N-hydroxy succinimide activation, and carbodiimide-mediated coupling) resulting into a wide variety of polysaccharide -protein conjugates. The challenge in analyzing carrier proteins used in conjugation (such as diphtheria toxoid, tetanus toxoid, CRM diphtheria protein, and recombinant CRM) is assessing their purity (whether they are monomeric or polymeric in nature as well as their polydispersity). Additional analytical challenges include the impact of excipients, potential interference from serogroups, selection and establishment of standards, age-dependent behavior of biomolecules indicated by molecular size distributions, and process-driven variations. This article explains the analytical insights gained (polysaccharide content, free saccharide, free proteins, MSD) during the development of the MenFive vaccine and highlights the crucial gaps and challenges in testing.

In-Syringe Vortex-Assisted Liquid-Liquid Microextraction Based on Natural Deep Eutectic Solvent for Simultaneous Determination of the Two Anticancer Polyphenols Chrysin and Resveratrol.

The simultaneous determination of multiple anticancer drugs in combination therapy poses a significant analytical challenge due to their complex nature and low concentrations. In this study, we propose an in-syringe vortex-assisted liquid-liquid microextraction (IS-VA-LLME), based on a green natural deep eutectic solvent (NaDES) for the simultaneous determination of two coadministered anticancer drugs (resveratrol and chrysin) prior to the HPLC-UV analysis, for the first time. The key parameters affecting the extraction efficiency, such as extraction solvent, vortex time, pH, and ionic strength were optimized. Under optimal conditions, the method demonstrates good linearity over the range of 0.05-15.0 μg/mL for RVT and 0.50-15.0 μg/mL for CHR with low limits of detection (LODs) of 16.78 and 161.60 ng/mL for RVT and CHR, respectively, confirming the high sensitivity of the method. The interday and intraday precision values, expressed as %RSDs, are below 2.0%, indicating good repeatability and reproducibility. Furthermore, the proposed method could be efficiently applied for the determination of the two drugs in human plasma and river water. The obtained results show satisfactory % recoveries (97.80%-102.04%), highlighting the accuracy and reliability of the developed method. The sustainability of the method was comprehensively evaluated using seven different tools. In conclusion, the developed IS-VA-LLME-NaDES allows for enhanced extraction efficiency, reduced extraction time, and improved recovery of the target analytes. This method holds great promise for applications in clinical and environmental research, enabling the precise quantification of these anticancer drugs in complex matrices.

Characterization of Trivalently Crosslinked C-Terminal Telopeptide of Type I Collagen (CTX) Species in Human Plasma and Serum Using High-Resolution Mass Spectrometry.

With an aging population, the increased interest in the monitoring of skeletal diseases such as osteoporosis led to significant progress in the discovery and measurement of bone turnover biomarkers since the 2000s. Multiple markers derived from type I collagen, such as CTX, NTX, PINP, and ICTP, have been developed. Extensive efforts have been devoted to characterizing these molecules; however, their complex crosslinked structures have posed significant analytical challenges, and to date, these biomarkers remain poorly characterized. Previous attempts at characterization involved gel-based separation methods and MALDI-TOF analysis on collagen peptides directly extracted from bone. However, using bone powder, which is rich in collagen, does not represent the true structure of the peptides in the biofluids as it was cleaved. In this study, our goal was to characterize plasma and serum CTX for subsequent LC-MS/MS method development. We extracted and characterized type I collagen peptides directly from human plasma and serum using a proteomics workflow that integrates preparative LC, affinity chromatography, and HR-MS. Subsequently, we successfully identified numerous CTX species, providing valuable insights into the characterization of these crucial biomarkers.

Comprehensive targeted profiling of multiple steroid classes in rodent plasma using liquid chromatography-mass spectrometry

BackgroundReliable quantification of multiple steroid classes in biological fluids within a single method remains an analytical challenge despite many previously published methods. Crosstalk of positional isomers, overlap of stereoisomer fragmentation patterns, differing proton affinities, in-source fragmentation, varying stability of protonated ions in the gas phase across steroid classes, and non-existence of steroid-free matrix are the main challenges limiting the number of simultaneously profiled steroids. ResultsIn this study, we focused on the development of a derivatization-free, achiral, high-throughput, and cost-effective UHPLC-MS/MS approach that allows simultaneous profiling of a spectrum of 38 steroids covering progestogens, androgens, corticosteroids, and estrogens, while properly addressing the hurdles of steroid analysis. Within a 20-min method, 16 stereoisomers and 15 positional isomers were fully resolved within a single run while separated from 7 additional non-interfering steroids and matrix interferences in rodent plasma. Protein precipitation (PP) and supported liquid extraction (SLE) methods using only 40 μL of sample were developed to achieve the lowest possible limits of quantification. Nevertheless, 5α-dihydroprogesterone and 3α,5α-THDOC could be only qualitatively assessed when using PP. In contrast, DHEA-S could not be quantified or identified when using SLE. A novel surrogate matrix-background subtraction approach, using rat plasma after the animal's adrenalectomy, has been implemented into the optimized PP-UHPLC-MS/MS workflow, successfully validated according to the unified ICH/EMA M10 guidelines, and compared to the traditional quantification strategies. Moreover, the validity of the newly adopted approach has been verified by the targeted profiling of multiple biologically active endogenous steroids in more than 500 samples of mouse plasma in total. SignificanceUnderestimation of hurdles associated with steroid analysis often compromises the accurate steroid quantification. Our comprehensive, fully validated UHPLC-MS/MS method targeting a wide spectrum of endogenous steroids, mitigating steroid crosstalk and using a minimal sample volume together with a novel surrogate matrix-background subtraction approach significantly advances steroid analysis for research and clinical applications covering multiple biological scopes.

Exploring the utility of complementary separations in liquid chromatography

An alternative strategy is explored for the separation of samples by liquid chromatography (LC). Unlike traditional approaches that aim to resolve all components in a given sample within a single LC separation, the proposed strategy uses two or more distinct separations carried out with a different gradient program and/or using different separation chemistries i.e., a different set of mobile and stationary phase. This set of complementary incomplete separations (CIS) is selected such that each component is at least fully resolved once, meaning the most critical pairs of each individual separation can be left unseparated. This allows for a significant time saving per separation. To investigate whether such an approach can lead to overall shorter analysis times than is possible with the fastest single-run gradient separation, a comprehensive in silico study covering a statistically significant number of samples is undertaken. The investigation shows that, for the presently considered sample sets and chemistries, CIS has a substantially higher probability, about two times greater for the simplest samples considered in this work and as much as 30 times greater for more complex samples, to fully resolve an unknown sample compared to a single gradient separation. Comparing separation speeds, the CIS approach can achieve complete sample resolution on average approximately four times faster than a single separation. Our findings thus demonstrate the potential of CIS in enhancing separation efficiency and offer insights regarding their use for solving analytical challenges.

Characterisation of rouaite, an unusual copper-containing pigment in early modern English wall paintings, by synchrotron micro X-Ray diffraction and micro X-Ray absorption spectroscopy

Although the use of verditer, a synthetically produced copper carbonate pigment chemically analogous to azurite (Cu3(CO3)2(OH)2), in early modern wall paintings is regularly reported in grey literature, its detection in wall paintings is typically unavailable in a public forum. This article focusses on two particular samples (M9 and T1) initially suspected to contain copper blue pigments from decorative wall painting schemes in domestic houses across a range of status groups, in eastern and south-eastern England, dated to 1550-1650. Interest in verditer synthesis procedures is found in textual sources including both historic manuals and current scientific literature. The unreliability of the synthesis, particularly for blue verditer, however, is widely documented. Here, we report a multimodal study employing SEM-EDX, SR-μ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mu$$\\end{document}PXRD mapping, and SR-μ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\mu$$\\end{document}XANES spectroscopy to characterise the phases present in two wall painting samples, one c. 1600/early 1600s (M9) and the other c. 1600 (T1). In addition to assessment of the presence of verditer, this study presents the first identification of rouaite, a synthetic copper hydroxynitrate mineral (Cu2(NO3)(OH)3), in wall painting samples. Rouaite, shown in a previous publication to be a common byproduct of replications of the historical verditer synthetic recipes, appears in combination with verditer and alone. Its infrequent identification in paintings and murals is considered in light of analytical challenges. The presence of copper hydroxychlorides is also discussed in the context of rouaite stability and degradation. These results represent a significant development in our knowledge of the early modern palette in England and historical verditer synthesis and advances our understanding of how these painting schemes may be best preserved in the future.

Alcohol ink-modified microfluidic paper-based analytical devices for enhanced white detection in simultaneous determination of multiple water quality indicators.

White detection remains a critical limitation in using colorimetry to determinesubstances with microfluidic paper-based analytical devices (µPADs). Here, we introduced a simple, safe alcohol ink-modified µPAD for the straightforward and facile detection of white color in precipitation reactions. Although absolute alcohol ink was found to cause device leakage, dilution of the ink with water was the key to successfully precoat wax-created µPADs. Device utility was demonstrated through simultaneous detection of sulfate, phosphate, and waterhardness via precipitation reactions. While phosphate interfered with sulfate detection by Ba2+, in situ distance-based quantification of phosphate was implemented. Aside from anions, the modified µPADs could be extended to detect cationic analytes such as total hardness. The limits of detection (LODs) for sulfate, phosphate, and hardness were 0.005mmol L-1, 0.005mmol L-1, and 0.5mmol L-1, respectively, with the linear ranges of 0.01-10.0mmol L-1, 0.005-1.0mmol L-1, and 0.001-0.5mol L-1. The µPADs were applied to real water samples, demonstrating results that were consistent with standard methods at a 95% confidence level. By incorporating white detection, these alcohol ink-modified µPADs offer enhanced versatility for addressing a broader array of analytical challenges in real-world settings.

On the fractionation of lignin oligomers by stepwise gradient reversed-phase liquid chromatography

With the increased interest in lignin valorization, the analytical challenge to separate a complex mixture of a vast number of phenolics has made chromatography an indispensable step in lignin analysis. High-resolution separations, such as gas chromatography, reversed-phase liquid chromatography and supercritical fluid chromatography have typically been targeting low-molecular-weight compounds, while larger lignin oligomers have received less attention. These compounds have proven to be difficult to separate due to the inherent complexity of the high-molecular-weight fraction of lignins, in fact, even high-resolving linear reversed-phase gradients elute them as one wide zone. To tackle this, in this study we show that a crude fractionation of lignin oligomers can be achieved by applying stepwise reversed-phase gradients. A commonly employed reversed-phase system with water:acetonitrile mobile phase is evaluated for this task. Special attention was devoted to uncovering the molecular level explanation of the retention phenomenon. Our results indicate that separation is mainly governed by reversed-phase retention phenomena without any major exclusion or viscosity-related effects, shown by great fits to linear retention models (R2avg = 0.9599 for five different oligomers) and apparent differences in retentivity between different stationary phases. The influence of the gradient shape was demonstrated by the comparison of stepwise gradients with different number and frequency of steps, leading to the conclusion that gradients with a low number of steps yield fewer, but better resolved fractions, while finer multi-step gradients can be used to distinguish more fractions.