Liquid Samples Research Articles

Thermal lensing and photoacoustics as potential tools for nanomaterial characterization: a review

AbstractThis comprehensive review highlights the versatile applications of photothermal techniques, particularly thermal lens spectrometry (TLS) and photoacoustic spectrometry (PAS), in the field of nanomaterials characterization. TLS is an effective technique in the trace detection of different compounds in liquid samples, photodegradation studies, and analysis of photocatalytic reaction rate, as well as the study of molecular dynamics, impacting both environmental and catalytical research. It enables the optimization of thermal diffusivity in soot nanofluids and offers insights into seed germination and plant yield enhancement in nanobiophotonics. The review also explores the thermal and elastic characterization of Fe2O3 polymorphs by photoacoustic spectroscopy (PAS). Investigating the metal mirror demonstrates PAS’s efficacy in determining its reflection coefficient and thermal diffusivity. ZnO nanoparticles’ strong absorption on diatomite surfaces is revealed through PAS, emphasizing their effectiveness in light absorption enhancement. Furthermore, PA techniques address working frequency limitations in studying silicon-based nanomaterials. Thus, thermal lens and photoacoustic spectroscopy assume pivotal roles in unveiling the nuanced attributes of various nanostructured materials, thereby propelling advancements in the realms of science and technology.

Sunlight-Driven Smart Windows with a Wide Temperature Range of Optical Switching Based on Chiral Nematic Liquid Crystals.

Photoresponsive liquid crystals are promising materials for sunlight-driven smart windows, which can automatically change their optical states in response to sunlight and control energy flow between the inside and outside of a building. Herein, liquid-crystalline systems are developed that show a transparent-scattering transition upon irradiation with sunlight in a wide temperature range. Push-pull azobenzenes with axial chirality have been newly developed as photochromic chiral dopants to allow changes in mesostructures of liquid crystals in response to sunlight. To realize optical switching, photochromic and photoinert chiral compounds with opposite handedness of helical twisting are doped in liquid crystals. This liquid crystalline sample with a compensated nematic phase is transparent in its initial state. Upon irradiation with sunlight, this sample transforms to a scattering state due to the formation of helical mesostructures along with photoisomerization of azobenzene moieties and the change in the helical twisting power. After the cease of irradiation, the sample reverts to the transparent state through thermal back isomerization of azobenzene moieties. This system significantly improves the operating temperature range of sunlight-driven smart windows based on liquid crystals: the transparent-scattering transition is observed at 4-42 °C. The present mechanism allows development of autonomous and wireless smart windows adaptable to various environments.

Quantification of Zr in simulated dissolver solution of U–Zr fuel by laser-induced breakdown spectroscopy

Abstract Estimation of Zr in fresh and irradiated metal alloy fuel is important. The homogeneous dissolver solution represents the fuel composition better compared to a highly heterogeneous solid pellet. The present study employs LIBS to determine Zr in the simulated dissolver solution. Four different compositions of U–Zr samples where the Zr/U ratio varies from 0.04 to 0.18 % are analyzed by LIBS with an in-house designed liquid sample cell. A good correlation coefficient is achieved for the measurements in the calibration plot. The results for identifying non-overlapping peaks, calibration plot, precision, deviation, and detection limit are discussed in detail. Two set of solid samples, an oxide pellet and metal alloy with similar Zr/U composition, are also analyzed by LIBS. The results obtained from these three set of samples are inter-compared, and the reason for getting a better Zr/U intensity ratio for a dried coating of sample on aluminium for a given composition is explained.

Proposal for a New Differential High-Sensitivity Refractometer for the Simultaneous Measurement of Two Refractive Indices and Their Differences

The refractive index of a liquid serves as a fundamental parameter reflecting its composition, thereby enabling the determination of component concentrations in various fields such as chemical research, the food industry, and environmental monitoring. Traditional methods for refractive index (RI) measurement rely on light deflection angles at interfaces between the liquid and a material with a known refractive index. In this paper, the authors present a new differential refractometer for the highly sensitive measurement of RI differences between two liquid samples. Using a configuration with two cells equipped with flat parallel plates as measuring elements, the instrument facilitates accurate analysis. Namely, the sensor signals from both the solution and the solvent cuvette are generated simultaneously with one laser pulse, reducing the possible fluctuations in the laser radiation intensity. Our evaluation shows the high sensitivity of RI measurements < 7 × 10−6, so this differential refractometer can be proposed not only as a high-sensitivity sensing tool that can be used for mobile detection of nanoparticles in solution samples but also to determine the level of environmental nano-pollution using water (including rain, snow) samples from various natural as well as industrial sources, thus helping to solve some important environmental problems.

Colorimetric Detection of Fentanyl Powder on Surfaces Using a Supramolecular Displacement Assay.

Fentanyl is a potent synthetic opioid with an alarmingly low lethal dosage of 2 mg. The equipment necessary to detect fentanyl in field settings (e.g., hand-held spectrometers) is restricted to highly trained, well-funded, and specialized personnel. Established point-of-need technologies, such as lateral flow immunochromatographic strips, are available; however, they often involve multiple contact-based steps (e.g., collection, mixing) that pose a higher risk to users handling unknown substances. Herein, we developed a colorimetric displacement assay capable of contactless detection of fentanyl in liquid or solid samples. The basis of our assay relies on the presence of fentanyl to displace a redox mediator, ferrocene carboxylic acid, inclusively bound in the cavity of a supramolecular host, CB[7]. The displacement is only possible in the presence of high affinity binding guests, like fentanyl (KA ∼ 106 M-1). The liberated redox guest can then react with indicator reagents that are free in solution, producing either: (i) a distinct blue color to indicate the presence of fentanyl or (ii) a pale blue tint in the absence of fentanyl. We demonstrate rapid and specific detection of fentanyl free base and fentanyl derivatives (e.g., acetyl fentanyl and furanyl fentanyl) against a panel of 9 other common drugs of abuse (e.g., morphine, cocaine, and heroin). Furthermore, we highlight the intended use of this assay by testing grains of fentanyl derivatives on a surface with a drop (i.e., 25 μL) of the assay reagent. We anticipate that this approach can be applied broadly to identify the presence of fentanyl at the point of need.

Evaluation of the Tasso+ blood self-collection device for quantitation of plasma cytomegalovirus (CMV) DNAemia in adult solid organ transplant recipients (SOTr).

We evaluate an FDA-cleared blood self-collection device (Tasso+) and demonstrate that it is patient-acceptable and yields a liquid blood sample with quantitative CMV DNAemia results comparable to those of standard venipuncture samples. This opens up possibilities for self-blood collection to monitor for CMV and potentially other viruses in transplant and other at-risk populations.

RLab Calorimetry: an internet-enabled calorimeter using Arduino for local or remote lab activities

This study presents an internet-connected calorimeter allowing both face-to-face and online laboratory activities. This device aims to create an environment that facilitates enquiry-based teaching strategies. There are three ways to access the device: (i) remotely via the web (WAN—Wide Area Network), locally (ii) through the local network (LAN—Local Area Network), or (iii) as a stand-alone device. It was designed with a client-server structure and utilised the Flask framework in Python. The instrument consists of two isolated containers (calorimeters), allowing for investigative activities that include comparing two liquid samples. The system was built using low-cost components based on the Arduino platform. Unlike virtual laboratories, measurements are performed on real devices. We present the results of direct electrical heating for a short time and record the temperature step of the samples. This straightforward method has proven to be suitable as a learning activity because of its conceptual clarity and effectiveness in teaching and learning. The use of a mechanical stirrer to homogenise the temperature of the liquids is crucial for obtaining high-quality experimental results. The system described in this paper is part of ‘RLab project’, an initiative to develop a platform for remote Experimental Physics Activities in Physics Teaching for public schools in Brazil. This experimental setup can be highly beneficial for implementing an experimental learning methodology, especially in the case of—but not restricted to—distance learning.

Visualizing Dynamic Single Atom Catalysis.

Many industrial chemical processes, including for producing fuels, foods, pharmaceuticals, chemicals and environmental controls, employ heterogeneous solid state catalysts at elevated temperatures in gas or liquid environments. Dynamic reactions at the atomic level play a critical role in catalyst stability and functionality. In-situ visualization and analysis of atomic-scale processes in real time under controlled reaction environments can provide important insights into practical frameworks to improve catalytic processes and materials. This review focuses on innovative real time in-situ EM methods, including recent progress in analytical in-situ environmental (scanning) transmission EM (ESTEM and ETEM) with single atom resolution for visualizing dynamic single atom catalysis under controlled flowing gas reaction environments. ESTEM studies of single atom dynamics of reactions, and of sintering deactivation, contribute to a better-informed understanding of the yield and stability of catalyst operations. Advances in in-situ technologies, including gas and liquid sample holders, nano-tomography and higher voltages, as well as challenges and opportunities in tracking reacting atoms, are highlighted. The findings show that the understanding and application of fundamental processes in catalysis can be improved, with valuable economic, environmental, and societal benefits. This article is protected by copyright. All rights reserved.

Determination of radiocarbon content in liquid fuel blends by accelerator mass spectrometry and liquid scintillation counting in the gliwice radiocarbon and mass spectrometry laboratory

Abstract The increase in biobased material usage requires the methods of verification to investigate the actual content of biocarbon in such materials, including liquid fuels. The determination of biocarbon in liquid samples using 14C required adaptation of existing sample preparation methods. In this study, both accelerator mass spectrometry (AMS) and liquid scintillation counting (LSC) methods were used to determine the content of 14C in six different liquid fuel blends produced from purely bio-based hydrotreated vegetable oil (HVO) and a 14C-free petrodiesel sample (ON/UF-BC). The results obtained for pure petrodiesel provide background values. The results indicate a good agreement between LSC and AMS, and a linear correlation between the 14C measurement results for blended samples and HVO content affirmed the reproducibility between the two methods. The repeatability of AMS results was tested on 10 aliquots of one of the blends, and the results were deemed reproducible.

The Influence of Blood and Serum Microenvironment on Spin-Labeled Magnetic Nanoparticles

The investigation and clarification of the properties of surface-functionalized superparamagnetic nanoparticles in a biological environment are key challenges prior to their medical applications. In the present work, electron paramagnetic resonance spectroscopy (EPR) combined with the spin labeling technique was utilized to better understand the behavior of nitroxides attached to magnetite nanoparticles dispersed in body fluid. EPR spectra of spin-labeled, silane-coated Fe3O4 nanoparticles in human serum and whole blood were recorded and analyzed for both room- and low-temperature values. In all cases, the obtained EPR signal consisted of a broad line from magnetite cores and a characteristic signal from the attached 4-Amino-2,2,6,6-tetramethylpiperidine-1-oxyl (4-amino-TEMPO). Even for liquid samples, the anisotropic components of magnetic tensors did not fully average out, which was reflected in the differences in the intensity of three narrow hyperfine lines from nitroxide. At 230 K the irregular slow-motion signal from the attached radical was also simulated using the EasySpin toolbox, which allowed to determine the parameters related to magnetic tensors and the dynamics of the spin label. The study showed that the anisotropy of the motion of the spin label 4-amino-TEMPO reflects its interactions with the surrounding medium and the manner of the attachment of the nitroxide to the surface of nanoparticles.

One‐step synthesis of a spongy flexible substrate for surface enhanced Raman spectroscopy comprising a silver nanoparticles‐loaded poly(amidoamine) dendrimer crosslinked with glutaraldehyde

AbstractA composite comprising a silver nanoparticles‐loaded poly(amidoamine) (PAMAM) dendrimer crosslinked with glutaraldehyde (PAMAM/AgNPs) is synthesized using a one‐step method under vortex at room temperature. The structure of glutaraldehyde‐crosslinked PAMAM dendrimer is characterized using FTIR and high‐resolution magic angle spinning–carbon 13 nuclear magnetic resonance (HRMAS 13C NMR) spectroscopy. The crosslinking structure ensures the uniformity and stability of the Ag nanoparticles, and the flexibility of the PAMAM/AgNPs composite. X‐ray diffraction (XRD) analysis and energy dispersive spectroscopy (EDS) confirm the formation of Ag nanoparticles in the PAMAM/AgNPs composite. Scanning electron microscopy (SEM) and three‐dimensional (3D) micro‐Raman images reveal the coarsely porous 3D micro‐structure of the PAMAM/AgNPs composite. This unique micro‐3D architecture provides the PAMAM/AgNPs composite with spongy flexibility and a swab‐like nature, which is advantageous for the rapid and effective absorption of liquid samples on the surfaces of objects. Surface enhanced Raman spectroscopy (SERS) indicates that the detection limits of both rhodamine 6G (R6G) and thiram are 1.0 × 10−5 mol L−1, and the SERS enhancement factor of R6G is determined to be 1.35 × 104. The spongy flexible PAMAM/AgNPs SERS substrate therefore has potential for use in Raman active compound detection.

Bioinspired integrated triboelectric electronic tongue

An electronic tongue (E-tongue) comprises a series of sensors that simulate human perception of taste and embedded artificial intelligence (AI) for data analysis and recognition. Traditional E-tongues based on electrochemical methods suffer from a bulky size and require larger sample volumes and extra power sources, limiting their applications in in vivo medical diagnosis and analytical chemistry. Inspired by the mechanics of the human tongue, triboelectric components have been incorporated into E-tongue platforms to overcome these limitations. In this study, an integrated multichannel triboelectric bioinspired E-tongue (TBIET) device was developed on a single glass slide chip to improve the device’s taste classification accuracy by utilizing numerous sensory signals. The detection capability of the TBIET was further validated using various test samples, including representative human body, environmental, and beverage samples. The TBIET achieved a remarkably high classification accuracy. For instance, chemical solutions showed 100% identification accuracy, environmental samples reached 98.3% accuracy, and four typical teas demonstrated 97.0% accuracy. Additionally, the classification accuracy of NaCl solutions with five different concentrations reached 96.9%. The innovative TBIET exhibits a remarkable capacity to detect and analyze droplets with ultrahigh sensitivity to their electrical properties. Moreover, it offers a high degree of reliability in accurately detecting and analyzing various liquid samples within a short timeframe. The development of a self-powered portable triboelectric E-tongue prototype is a notable advancement in the field and is one that can greatly enhance the feasibility of rapid on-site detection of liquid samples in various settings.

The Development of a Specific Nanofiber Bioreceptor for Detection of Escherichia coli and Staphylococcus aureus from Air.

Polluted air and the presence of numerous airborne pathogens affect our daily lives. The sensitive and fast detection of pollutants and pathogens is crucial for environmental monitoring and effective medical diagnostics. Compared to conventional detection methods (PCR, ELISA, metabolic tests, etc.), biosensors bring a very attractive possibility to detect chemicals and organic particles with the mentioned reliability and sensitivity in real time. Moreover, by integrating nanomaterials into the biosensor structure, it is possible to increase the sensitivity and specificity of the device significantly. However, air quality monitoring could be more problematic even with such devices. The greatest challenge with conservative and sensing methods for detecting organic matter such as bacteria is the need to use liquid samples, which slows down the detection procedure and makes it more difficult. In this work, we present the development of a polyacrylonitrile nanofiber bioreceptor functionalized with antibodies against bacterial antigens for the specific interception of bacterial cells directly from the air. We tested the presented novel nanofiber bioreceptor using a unique air filtration system we had previously created. The prepared antibody-functionalized nanofiber membranes for air filtration and pathogen detection (with model organisms E. coli and S. aureus) show a statistically significant increase in bacterial interception compared to unmodified nanofibers. Creating such a bioreceptor could lead to the development of an inexpensive, fast, sensitive, and incredibly selective bionanosensor for detecting bacterial polluted air in commercial premises or medical facilities.

Abstract PO1-07-02: Sensitive tumor detection, accurate quantification, and ER subtyping using low-pass methylome of liquid biopsy samples from patients (pts) with metastatic breast cancer (mBC)

Abstract Background The presence and amount of blood circulating tumor DNA (Tumor Content, TC) is emerging as a clinically relevant factor in many cancers, including BC. In the metastatic setting, a commonly used tumor tissue agnostic approach involves analyzing Copy Number Alterations (CNA) from low-pass whole-genome sequencing (lpWGS) by ichorCNA. However, with a lower limit of detection of 3%, it is unsuitable for low TC applications, such as monitoring disease in response to treatment. Here we report on the use of low-pass whole genome bisulfite sequencing (lpWGBS) coupled with a novel tool, METER (METhylation analyzER), to overcome current limitations of lpWGS, enabling sensitive TC detection, accurate quantification, and ER subtyping from mBC liquid biopsies. Methods METER is a computational tool to analyse TC exploiting BC-specific Differentially Methylated Sites (DMS) and Regions (DMR) in lpWGBS data. To define BC DMSs and DMRs, Rocker-meth was applied to the WGBS profiles of 30 BC tissue (BASIS dataset) and 23 healthy donor cell free DNA (cfDNA) (Fox-Fisher 2021). METER consists of three modules: 1) METER-quant, a DMS-based quantifier of TC; 2) METER-detect, a DMR-based z-score method to classify samples as TC+ (METER+) or TC- (METER-); 3) METER-subtype, to infer ER status via Robust Partial Correlation applied to ER+ vs. ER- BC DMR. We generated lpWGBS data (coverage 0.5-1X) of 135 cfDNA samples from 58 pts (45 ER+, 13 ER-, 55 (95%) up to 3 previous lines of treatment; before starting treatment (T0, n=58), after the first cycle (T1, n=25), and at progression (T2, n=22)) and 30 from healthy individuals as controls. ichorCNA using sensitive parameters (allowing normal fraction up to 0.99) was used to estimate reference TC. A leave-one-out strategy applied to the control samples was used to estimate the false discovery rate (FDR) of METER-detect classification. METER+/- pts were tested for association with OS and PFS using the log-rank test and compared with ichorCNA detection (TC by ichorCNA above or below 3%, ichorCNA+/-). Results TC of 105 cfDNA BC samples by METER-quant was concordant with estimates from the state-of-the-art tool ichorCNA (R >0.90, p< 1e-10). In 22 pts with complete longitudinal data, METER-quant median TC of 0.05 at T0 (IQR 0.02-0.12), 0.02 at T1 (0.01-0.07), and 0.06 at T2 (0.03-0.11) were obtained, with significant difference observed for T0 vs T1 and T2 vs T1 (paired Wilcoxon p< 0.05). Across all time points, METER-detect classified 43% of the n=42 ichorCNA- samples as METER+. The reliability and prognostic performance of METER and ichorCNA detection classification were then compared using clinical outcome data. Based on T0 data, METER+ pts had significantly worse OS than METER- (HR=4.2 CI=2.0-8.9, p< 0.001). This effect was stronger than using ichorCNA (HR=2.3 CI=1.3-4.0, p=0.006). Worse PFS at T0 was observed for METER+ compared with METER- pts (HR=3.7 CI=1.8-7.9, p< 0.001), while no significant association was observed for ichorCNA+ pts (HR=1.4 CI=0.8-2.5, p=0.2). Of note, ichorCNA-/METER+ pts (N=11) at T0 had worse PFS compared with ichorCNA-/METER- (N=11) (HR=3.7 CI 1.4-9.7, p=0.005). Considering the 73 METER+ and 53 samples with METER-quant >5%, METER-subtype showed an accuracy of 0.84 (CI=0.73-0.92) and 0.94 (CI=0.83-0.99) respectively in classifying ER status based on IHC. Discussion lpWGBS enables tumor tissue agnostic analysis and concurrent investigation of complementary molecular features, including CNA and DNA methylation patterns. In a small and heterogeneous cohort, METER showed comparable performance to state-of-the-art tools in terms of TC quantification (ichorCNA) and ER subtyping (IHC), while offering enhanced sensitivity and ensuring a low FDR. METER showed promising prognostic stratification capabilities, particularly for patients with low TC. Validation in an extended prospective cohort is currently ongoing. Citation Format: Marta Paoli, Agostina Nardone, Francesca Galardi, Chiara Biagioni, Dario Romagnoli, Francesca De Luca, Gian Marco Franceschini, Ilenia Migliaccio, Marta Pestrin, Giuseppina Sanna, Emanuela Risi, Luca Livraghi, Erica Moretti, Laura Biganzoli, Luca Malorni, Francesca Demichelis, Matteo Benelli. Sensitive tumor detection, accurate quantification, and ER subtyping using low-pass methylome of liquid biopsy samples from patients (pts) with metastatic breast cancer (mBC) [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO1-07-02.

Abstract PO2-16-05: ESR1 mutations (ESR1mut) in HR(+)HER2(-)patients with metastatic breast cancer (MBC): prevalence along treatment course and predictive value for endocrine therapy (ET) resistance in real-world practice

Abstract Background: ET combined with CDK4/6 inhibitors (CDKi) is the standard of care for HR(+)HER2(-) patients with MBC. ESR1mut is an acquired resistance mechanism to ET, especially aromatase inhibitors (AI). The prevalence and behavior of ESR1mut in patients receiving the selective estrogen receptor degrader (SERD) fulvestrant remains in question. This study aimed to characterize the prevalence of ESR1mut at start of successive lines of therapy and to evaluate clinical outcomes of ET by ESR1 status in 1st line therapy in real-world practice. Methods: This study included patients with HR(+)HER2(-) MBC who underwent genomic testing using Foundation Medicine tissue or liquid comprehensive genomic profiling (CGP) assays, with specimens collected within 60 days of therapy initiation. Patient clinical data was obtained by the nationwide (US-based) de-identified Flatiron Health and Foundation Medicine real-world clinicogenomic breast database (FH-FMI CGDB), originated from ~280 US cancer clinics (~800 sites of care) between 01/2011 and 04/2023. ESR1mut prevalence was calculated in tissue and liquid samples collected in the 1st, 2nd, and 3rd lines of therapy. Real-world progression free-survival (rwPFS), time to treatment discontinuation (rwTTD), and overall survival (rwOS) were compared between patients who received AI + CDKi and between patients receiving fulvestrant + CDKi 1st line therapy [ESR1mut vs. ESR1 wild-type (wt) by tissue CGP] by Cox models. Multivariable analyses adjusted for adjuvant therapy, age, ECOG, menopausal status, histology, stage at diagnosis, metastatic site, and specific ESR1mut (Y537S, D538G, E380W, or others) were performed. Results: The prevalence of ESR1mut in tissue samples collected in 1st, 2nd, and 3rd lines of therapy was 7.9% (n=159/2004), 26.4% (n=66/250), and 34.0% (n=68/200), respectively. The prevalence of ESR1mut in liquid samples collected in the 1st, 2nd, and 3rd lines of therapy was 11.6% (n=30/259) 34.4% (n=63/183), and 35.9% (n=42/117), respectively. Among patients receiving AI + CDKi 1st line therapy (n=485), those with ESR1mut vs. ESR1wt had less favorable rwPFS [median 6.1 vs. 20.8 months, hazard ratio (HR) 2.36, 95% CI 1.35-4.14, p=0.003]. rwTTD and rwOS assessments were consistent with the magnitude of effect of rwPFS. Among patients receiving fulvestrant + CDKi 1st line therapy (n=302), those with ESR1mut vs. ESR1wt had less favorable rwPFS (median 10.5 vs. 14.5 months, HR 1.5, 95% CI 1.05-2.15, p=0.025), but no difference was observed for rwTTD and rwOS (p >0.05). Notably, the multivariable analyses found the independent association of ESR1mut and less favorable rwPFS (HR 2.18, 95% CI 1.15-4.1, p=0.018), rwTTD (HR 3.34, 95% CI, 1.84-6.1, p< 0.001), and rwOS (HR 2.46, 95% CI 1.04-5.9, p=0.041) in patients receiving AI + CDKi. The multivariable analyses confirmed no association between ESR1mut and outcomes in patients receiving fulvestrant + CDKi (p >0.05). No substantial differential associations were observed between specific ESR1mut and clinical outcomes in the multivariable analyses. Conclusion: In our dataset, ESR1mut is prevalent in about 8-11% of baseline tissue and liquid samples of patients with HR(+)HER2(-) MBC. Baseline ESR1mut is associated with less favorable outcomes in patients receiving AI + CDKi 1st line therapy, but not in patients receiving fulvestrant + CDKi. Specific ESR1mut do not seem to be associated with different outcomes to ET. ESR1mut prevalence increased during treatment course. Further investigation is warranted to determine optimal endocrine partner with CDKi based upon ESR1 status, particularly with development of oral SERDs. Citation Format: Manali Bhave, Julia Quintanilha, Ryon Graf, Takara Scott, Hanna Tukachinsky, Gerald Li, Alexa Schrock, Geoffrey Oxnard, Mia Levy, Kevin Kalinsky. ESR1 mutations (ESR1mut) in HR(+)HER2(-)patients with metastatic breast cancer (MBC): prevalence along treatment course and predictive value for endocrine therapy (ET) resistance in real-world practice [abstract]. In: Proceedings of the 2023 San Antonio Breast Cancer Symposium; 2023 Dec 5-9; San Antonio, TX. Philadelphia (PA): AACR; Cancer Res 2024;84(9 Suppl):Abstract nr PO2-16-05.

Optimization of carbon-based thin film microextraction supports for simultaneous detection of heavy metals using LIBS

One of the most versatile and effective methods to improve LIBS analysis of liquids is Thin Film Microextraction (TFME).This approach generally uses carbon-based adsorbent films to extract analytes from a liquid sample and bind them into a solid matrix, which is ideal for LIBS. In a previous work, we demonstrated the feasibility of TFME supports based on graphene prepared by Pulsed Laser Ablation in Liquid (PLAL) for LIBS analysis.In this paper, we optimized the preparation of such supports for the analysis of heavy metals in aqueous samples (i.e. chromium, lead and nickel), by analyzing both standard solutions and real samples. The feasibility of coupling TFME with NELIBS approach was also exploited. The procedure was applied to the analysis of both mineral water and well water samples.We obtained a standardized procedure for the extraction of three analytes (Pb, Cr and Ni) and estimated LOD values in spiked mineral water of the order of 0.6 mg/L for LIBS and 0.2 mg/L for NELIBS.

Dual structure-switching aptamer-mediated signal amplification cascade for SARS-CoV-2 detection

Since the outbreak of the novel severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) at the end of 2019, the spread of the virus has posed a significant threat to public health and the global economy. This work proposed a one-step, dual-structure-switching aptamer-mediated signal amplification cascade for rapid and sensitive detection of the SARS-CoV-2 nucleocapsid protein. This system consisted of two DNA aptamers with structure-switching functionality and fuel DNA, where a cascade of strand hybridization and displacement triggered fluorescence generation and signal amplification. This aptamer-based amplification cascade required neither an amplification stage using enzymes nor pre-processing steps such as washing, viral isolation, and gene extraction. The assay could distinguish SARS-CoV-2 from other respiratory viruses and detect up to 1.0 PFU/assay of SARS-CoV-2 within 30 min at room temperature. In 35 nasopharyngeal clinical samples, the assay accurately assessed 25 positive and 10 negative clinical swab samples, which were confirmed using quantitative polymerase chain reaction. The strategy reported herein can help detect newly emerging pathogens and biomarkers of various diseases in liquid samples. In addition, the developed detection system consisting of only DNA and fluorophores can be widely integrated into liquid biopsy platforms for disease diagnosis.

Facile and fast elemental analysis using glass fiber filter by X-ray fluorescence

Analysis of elements in liquid samples via X-ray fluorescence (XRF) faces challenges due to diverse matrix effects. To address this, the use of glass fiber filters (GFFs) as effective substrates for XRF analysis was explored. The matrix compositions of various commercial GFFs were comprehensively analyzed and compared to assess their applicability in liquid analysis. Most GFFs do not contain heavy elements, exhibit highly consistent filter weights, and have matrix element contents with relative standard deviations (RSDs) below 3%, which are ideal for detecting heavy elements. GFFs were also demonstrated to have superior analytical sensitivity compared to alternative filters. Optimal analytical performance can be achieved by utilizing a 30 mm sample holder, dripping 50 μL of the sample on the uniformly pressed GFFs, and drying it via infrared heating. Most heavy elements showed wide linear concentration ranges spanning over three orders of magnitudes and limits of detection (LOD) lower than mg/L. The results of standard addition and recoveries in natural lake water were promising. Furthermore, GFFs proved capable of verifying the composition and quality of particulate materials. The used GFFs can also be easily regenerated through acid washing for reuse. Therefore, GFFs are optimal XRF substrates for analyzing liquid samples containing heavy metal ions and materials.

Co-gasification of lignite and spent tea waste for the generation of hydrogen-rich syngas in a fluidized bed gasifier

The co-gasification of high moisture and high volatile content low-rank lignite (LG) coal and a common waste generated from the brewed tea leaves was studied in a fluidized bed gasification unit. Multiple experiments were conducted at different temperatures, ranging from 800 °C to 900 °C, at fixed operating parameters to elucidate the catalytic thermo-chemical impact on the gasifier performance parameters. The catalytic effect of alkali and alkaline earth metals (AAEMs), especially CaO, K2O, and Na2O present in the spent tea waste (STW) sample, on the product gas composition and performance parameters during the co-gasification experiments with LG was demonstrated. Mixed blends of LG and STW showed enhancement in the overall reactivity of the steam gasification runs, compared to the LG-only feed, primarily due to the change in the surface morphology, textures, and pore structures of the solid product ash samples, as identified with the electron spectroscopy analysis. Liquid and product samples were analyzed using characterization techniques such as Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) analytical techniques, along with the proximate, ultimate, and X-ray fluorescence (XRF) analysis of the gasification feed samples. An optimized blend ratio of 20 wt % of STW with LG sample enhanced the volumetric gas composition of H2 and CH4 gases from 52.03 % to 61.32 % and 3.98 %–5.45 % (on a dry-N2-free basis) with a relatively constant CO gas composition. It showed a reduced CO2 composition from 28.64 % to 18.25 % (on a dry-N2-free basis) for the gasification temperature of 900 °C. Even at the lower gasification temperatures of 800 °C and 850 °C with LG + STW feed, steam gasification experiments showed relatively comparable or superior performance to gasification experiments at 900 °C with LG-only feed. The present study indicated a holistic way to utilize the spent tea waste generated from millions of homes and commercial establishments in various parts of the world with potential application towards synergistic gasification process with other conventional carbon-source materials.

Automated analyses of dried blood spots collected by volumetric microsampling devices

BackgroundDried blood spot (DBS) sampling on cellulose cards suffers from varying blood haematocrit levels and from chromatographic effects, which have a direct impact on quantitative DBS analyses. Commercial volumetric microsampling devices were, therefore, introduced to mitigate these effects, however, these devices are not compatible with automated DBS processing systems and must be processed manually. ResultsCapillary electrophoresis (CE) instruments use fused-silica (FS) capillaries for precise and accurate liquid handling as well as for injection, separation, and quantitative analyses of liquid samples. These inherent features of an Agilent 7100 CE instrument were employed for the automated processing (elution and homogenization) of DBSs collected by hemaPEN® volumetric devices (2.74 μL of capillary blood per spot). The hemaPEN® samples were processed directly in CE vials by consecutive transfers of 56 μL of methanol and 14 μL of deionized water through the FS capillary in a sequence of 39 DBSs with repeatability of the liquid transfers better than 1.4%. The resulting DBS eluates were homogenized by a quick air flush through the capillary and analyzed by the same capillary and CE instrument. Creatinine was selected as a clinically relevant model analyte and its endogenous concentrations in DBSs were determined by CE with capacitively coupled contactless conductivity detection (CE-C4D) in a background electrolyte solution consisting of 50 mM acetic acid and 0.1% (v/v) Tween 20 (pH 3.0). The overall repeatability of the automated DBS processing and CE-C4D analyses of 39 DBSs was ≤ 7.1% (peak areas) and ≤ 0.6% (migration times), the calibration curve was linear in the 25 – 500 μM range (R2 = 0.9993) and covered all endogenous blood creatinine levels, the limit of detection was 5.0 μM, and sample throughput was > 12 DBSs per hour. DBS ageing for 60 days and varying blood haematocrit levels (20 – 70%) did not affect creatinine quantitative results (≤ 6.9% for peak areas). Inter-capillary and inter-instrument repeatability was ≤ 7.7% (peak areas) and ≤ 3.4% (migration times) and demonstrated an excellent transferability of the proposed analytical concept among laboratories. Significance and NoveltyThis contribution is the first-ever report on the use of a single off-the-shelf analytical instrument for fully automated analyses of DBSs collected by commercial volumetric microsampling devices and holds great promise for future unmanned quantitative DBS analyses.