Analysis Of Liquid Samples Research Articles

Near-petahertz fieldoscopy of liquid

AbstractMeasuring transient optical fields is pivotal not only for understanding ultrafast phenomena but also for the quantitative detection of various molecular species in a sample. Here we demonstrate near-petahertz electric field detection of a few femtosecond pulses with 200 attosecond temporal resolution and subfemtojoule detection sensitivity. By field-resolved detection of the impulsively excited molecules in the liquid phase, termed femtosecond fieldoscopy, we demonstrate temporal isolation of the response of the target molecules from those of the environment and the excitation pulse. In a proof-of-concept analysis of aqueous and liquid samples, we demonstrate field-sensitive detection of combination bands of 4.13 μmol ethanol for the first time. This method expands the scope of aqueous sample analysis to higher detection sensitivity and dynamic range, while the simultaneous direct measurements of phase and intensity information pave the path towards high-resolution biological spectro-microscopy.

Electrochemical sensing at the fingertips: Wearable glove-based sensors for detection of 4-nitrophenol, picric acid and diazepam

A wearable glove-based sensor is a portable and practical approach for onsite detection/monitoring of a variety of chemical threats. Herein, we report a flexible and sensitive wearable sensor fabricated on the nitrile glove fingertips by stencil-printing technique. The working electrodes were modified with multiwalled carbon nanotubes (MWCNTs)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) for sensitive and real-time analyses of hazardous or chemical treats, as picric acid (PA) explosive, diazepam (DZ) as drug-facilitated crimes and the emerging pollutant 4-nitrophenol (4-NP). The multi-sensing platform towards PA, 4-NP, and DZ offers the ability of in-situ qualitative and quantitative analyses of powder and liquid samples. A simple sampling by touching or swiping the fingertip sensor on the sample or surface under investigation using an ionic hydrogel combined with fast voltammetry measurement provides timely point-of-need analyses. The wearable glove-based sensor uses the square wave voltammetry (SWV) technique and exhibited excellent performance to detect PA, 4-NP, and DZ, resulting in limits of detection (LOD) of 0.24 μM, 0.35 μM, 0.06 μM, respectively, in a wide concentration range (from 0.5 μM to 100 μM). Also, we obtained excellent manufacturing reproducibility with relative standard deviations (RSD) in the range of 3.65%–4.61% using 7 different wearable devices (n = 7) and stability in the range of 4.86%–6.61% using different electrodes stored for 10 days at room temperature (n = 10), demonstrating the excellent sensor-to-sensor reproducibility and stability for reliable in-field measurements. The stretchable sensor presented great mechanical robustness, supporting up to 80 bending or stretching deformation cycles without significant voltammetric changes. Collectively, our wearable glove-based sensor may be employed for analyses of chemical contaminants of concern, such as explosives (PA), drugs (DZ), and emerging pollutants (4-NP), helping in environmental and public safety control.

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.

Gene expression markers in peripheral blood and outcome in patients with platinum-resistant ovarian cancer: A study of the European GANNET53 consortium.

Disease progression is a major problem in ovarian cancer. There are very few treatment options for patients with platinum-resistant ovarian cancer (PROC), and therefore, these patients have a particularly poor prognosis. The aim of the present study was to identify markers for monitoring the response of 123 PROC patients enrolled in the Phase I/II GANNET53 clinical trial, which evaluated the efficacy of Ganetespib in combination with standard chemotherapy versus standard chemotherapy alone. In total, 474 blood samples were collected, comprising baseline samples taken before the first administration of the study drugs and serial samples taken during treatment until further disease progression (PD). After microfluidic enrichment, 27 gene transcripts were analyzed using quantitative polymerase chain reaction and their utility for disease monitoring was evaluated. At baseline, ERCC1 was associated with an increased risk of PD (hazard ratio [HR] 1.75, 95% confidence interval [CI]: 1.20-2.55; p = 0.005), while baseline CDH1 and ESR1 may have a risk-reducing effect (CDH1 HR 0.66, 95% CI: 0.46-0.96; p = 0.024; ESR1 HR 0.58, 95% CI: 0.39-0.86; p = 0.002). ERCC1 was observed significantly more often (72.7% vs. 53.9%; p = 0.032) and ESR1 significantly less frequently (59.1% vs. 78.3%; p = 0.018) in blood samples taken at radiologically confirmed PD than at controlled disease. At any time during treatment, ERCC1-presence and ESR1-absence were associated with short PFS and with higher odds of PD within 6 months (odds ratio 12.77, 95% CI: 4.08-39.97; p < 0.001). Our study demonstrates the clinical relevance of ESR1 and ERCC1 and may encourage the analysis of liquid biopsy samples for the management of PROC patients.

Chemical structure and characterization of bio-oils isolated from walnut shells by different processes

This study investigated the products and properties of bio-yields obtained from different types of processes using the extraction and pyrolysis of walnut shells. Pyrolysis experiments were carried out with 10 g walnut shells at a pyrolysis temperature of 550 °C, a heating rate of 10 °C /1 min, a particle size of 1-1.5 mm, and a specific nitrogen gas flow rate. Aqueous extracts were obtained by placing the solid sample in a glass jar with methanol-chloroform (1:1 v/w) solvent indoors and away from light for five days. The obtained liquid samples were analyzed by Gas chromatography-mass spectrometry (GC-MS), Liquid Chromatography Mass Spectrometry (LC/MS-MS), and Fourier Transform Infrared Spectroscopy (FT-IR). Chemical composition analysis of the bio-oils revealed that phenol compounds were more concentrated in the aqueous extract process and volatile oil compounds that were more dominant in the pyrolysis process. The structural analysis results of the bio-oil showed that bio-oil products obtained from walnut shells can be used as fuel, composite film for different purposes, and value-added products. It can be said that the content analysis of liquid samples obtained as a result of pyrolysis and extraction of walnut shells was elucidated with advanced analytical techniques such as LC-MS/MS and GC-MS. The test results revealed that these products will be used in different areas such as energy and high-value-added products. This study provides researchers with a concrete prediction about the suitability of content-analyzed walnut shells.

Optically induced dielectrophoresis for continuous separation and purification of C. vulgaris and H. pluvialis

Marine microalgae are widely present in the natural environment, exhibiting a significant economic value. However, during the inoculation and cultivation process of microalgae, the introduction of unwanted algae is bound to trigger nutrient competition, leading to a decrease in the growth rate of microalgae and consequently impacting their economic value in production. To address this issue, this study integrates the optically induced dielectrophoresis (ODEP) manipulation technology based on the continuous flow in a microfluidic system. A two-stage cell filter, utilizing two virtual optical spots, is designed and manufactured. Leveraging the size differences between microalgae, continuous separation and purification of mixed samples containing Chlorella vulgaris and Haematococcus pluvialis are achieved within microchannels. Additionally, optimal ODEP manipulation conditions for mixed algal liquid samples, comprising C. vulgaris and H. pluvialis, are demonstrated, including appropriate alternating current voltage (6 V), alternating current frequency (100 kHz), light spot width (40 μm), and sample flow rate (0.9 μl/min). Analysis of mixed liquid samples collected at the chip's outlet reveals a reduction in the proportion of H. pluvialis from 37.5% to 1.2% after separation. In summary, this study proposes an ODEP microfluidic system capable of continuously separating and purifying microalgae with different biological characteristics, showcasing its potential as an alternative to traditional labor-intensive microalgae separation techniques.

Low-cost high-resolution distributed optical fiber system for spectrophotometric analysis of liquid samples: Application to detection of azo dyes

A distributed optical fiber system for spectrophotometric analysis of liquid samples based on light diffusing fiber (LDF) is presented. The sensor is based on a high-density white light emitting diode (LED) strip, which is side coupled to a glass based light-diffusing fiber (LDF) that acts as distributed optical receiver. The light emitted from a single LED propagates through the sample medium, is collected by the LDF and is then detected at the end of the fiber by a mini spectrometer. By sequentially turning on one LED at a time, the system permits the spectrophotometric analysis of the sample medium along the entire fiber length. This approach is capable of a continuous monitoring of absorbance spatial profile of liquid sample in the whole visible spectrum with a single low-cost spectrometer. The experimental results confirm the possibility of distributed measurements with a spatial resolution of about 12 mm over 1 m of measurement range. The approach has been successfully employed to the distributed detection and localization of azo dyes in water with a limit of detection lower than 1 ppm.

Optrode-Assisted Multiparametric Near-Infrared Spectroscopy for the Analysis of Liquids

We demonstrate a sensing scheme for liquid analytes that integrates multiple optical fiber sensors in a near-infrared spectrometer. With a simple optofluidic method, a broadband radiation is encoded in a time-domain interferogram and distributed to different sensing units that interrogate the sample simultaneously; the spectral readout of each unit is extracted from its output signal by a Fourier transform routine. The proposed method allows performing a multiparametric analysis of liquid samples in a compact setup where the radiation source, measurement units, and spectral readout are all integrated in a robust telecom optical fiber. An experimental validation is provided by combining a plasmonic nanostructured fiber probe and a transmission cuvette in the setup and demonstrating the simultaneous measurement of the absorption spectrum and the refractive index of water–methanol solutions.

Elemental analysis of liquid samples by nanoparticle-enhanced laser-induced breakdown spectroscopy: using ordered nano-arrays with a tunable nanoparticle size and inter-particle distance

NELIBS analysis of liquid samples using ordered nanoparticle arrays with a precisely tunable nanoparticle size and inter-particle distance, which provide excellent homogeneity to ensure signal reproducibility and enhancement.

Diverse thermal desorption combined with self-aspirating corona discharge ionization for direct mass spectrometry analysis of complex samples.

The thermal desorption (TD) technique is widely employed in modern mass spectrometry to facilitate the detection of non-volatile analytes. In this study, we developed a compact TD device based on a small resistance wire and coupled it with a self-aspirating corona discharge ionization (CDI) source to conduct direct MS analysis of various liquid and solid samples. Due to its small size and low heat capacity, the temperature of the TD module can be flexibly and rapidly modulated by controlling the power sequence. Multiple heating modes, including pulse heating (PH), isothermal heating, and step heating (SH), are realized and characterized, and then applied for the detection of different real samples. In particular, the PH mode is suitable for the simultaneous detection of multiple components in samples with relatively simple matrices, while the SH mode is capable of component separation. In addition, the sensitivity and quantitative capability of the TD-CDI system for DEP solutions were tested, showing acceptable stability with a relative standard deviation of about 6.7% and a detection limit of 0.088 ng. Overall, the developed TD-CDI system provides a simple, convenient, and versatile tool for direct mass spectrometry analysis of real samples.

A simple method for elemental analysis of liquids in sprayed microdroplets by laser-induced breakdown spectroscopy

The study shows that paper spray and laser-induced breakdown spectroscopy (PS-LIBS) analyze trace elements in aqueous solutions, addressing challenges in bulk analysis. Its efficiency highlights its potential for in situ liquid sample analysis.

OpenASAP: An affordable 3D printed atmospheric solids analysis probe (ASAP) mass spectrometry system for direct analysis of solid and liquid samples

Atmospheric Solids Analysis Probe (ASAP) mass spectrometry is a versatile technique allowing direct sampling of solid and liquid samples, but its adoption is limited due to the high cost of commercial ASAP systems. To address this, we present OpenASAP, an open-source ASAP system for mass spectrometers that can be fabricated for $20 or less using 3D-printing. Our design is readily adaptable to instruments from different manufacturers and can be produced with a variety of additive manufacturing techniques on consumer-grade 3D-printers. The probe allows for rapid sampling of solid and liquid samples without sample preparation, making it useful for high throughput screening, investigating spatial localization and function of analytes in biological samples, and incorporating mass spectrometry in instructional settings. We demonstrate its effectiveness by obtaining mass spectra of three natural product standards at levels as low as 10 ng/ml in liquid samples, and detecting these metabolites in microbial cultures that are difficult to analyze due to complex sample matrices or analyte properties. Furthermore, we demonstrate direct sampling of thin layer chromatography (TLC) spots of these cultures.

FLIIMP - a community software for the processing, calibration, and reporting of liquid water isotope measurements on cavity-ring down spectrometers

Precise and accurate measurements of the stable isotope composition from precipitation, land ice, runoff, and oceans provide critical information on Earth's water cycle. The analysis, post-processing, and calibration of raw analytical signals from laser spectrometers during sample analysis involves a number of critical procedures to counteract instrumental drift, inter-sample memory effects, and the quantification of total uncertainty. We present a new software tool for the post-processing and calibration named FLIIMP (FARLAB Liquid Water Isotope Measurement Processor). FLIIMP facilitates sample processing by (1) a graphical user interface that guides the user along the processing steps from corrections for memory effects, drift, and mixing ratio to calibration, and (2) allows to monitor long-term measurement system behaviour, currently for Picarro-brand water isotope analysers. Final data files are accompanied by a detailed calibration report. Being an open-source software for the major operating systems, users can adapt FLIIMP to their laboratory environment, and the community can contribute the software development.•FLIIMP facilitates post-processing, calibration and reporting for stable water isotope liquid sample analysis.•The stepwise, interactive graphical user interface reduces possibility of errors and shortens processing time.•Open source software enables future development of FLIIMP by the user community.

TOTAL OXYGEN CONTENT IN LIQUID STEEL AS A CRITERION FOR EVALUATING NONMETALLIC INCLUSIONS IN PIPE STEELS

A statistical analysis of the total oxygen content in samples of pipe steels at the stage of continuous casting at the continuous-casting machines of the casting and rolling complex of JSC “Vyksa Metallurgical Plant” was carried out. The microstructures of rolled samples were studied, and the chemical composition of non-metallic inclusions was determined by X-ray spectral microanalysis. A laboratory analysis of liquid steel samples and hot-rolled steel products of the casting and rolling complex was carried out using the method of reduction melting in an inert gas flow. Relationships have been constructed between the duration of metal presence in a steel-pouring ladle and the magnesium content in non-metallic inclusions, as well as between the average score of non-metallic inclusions in rolled metal and the total oxygen content in liquid steel at the stage of continuous steel casting.

Fiber-Based SERS-Fluidic Polymeric Platforms for Improved Optical Analysis of Liquids.

Downsizing surface-enhanced Raman spectroscopy (SERS) within microfluidic devices has opened interesting perspectives for the development of low-cost and portable (bio)sensors for the optical analysis of liquid samples. Despite the research efforts, SERS-fluidic devices still rely either on the use of expensive bulky set-ups or on polymeric devices giving spurious background signals fabricated via expensive manufacturing processes. Here, polymeric platforms integrating fluidics and optics were fabricated with versatile designs allowing easy coupling with fiber-based Raman systems. For the first time, anti-fouling photocurable perfluoropolyether (PFPE) was explored for high-throughput SERS-integrating chip fabrication via replica molding of negative stamps obtained through standard and advanced fabrication processes. The PFPE devices comprised networks of channels for fluid handling and for optical fiber housing with multiple orientations. Embedded microfeatures were used to control the relative positioning of the fibers, thus guaranteeing the highest signal delivering and collection. The feasibility of PFPE devices as fiber-based SERS fluidic platforms was demonstrated through the straightforward acquisition of Raman-SERS spectra of a mixture of gold nanoparticles as SERS substrates with rhodamine 6G (Rh6G) at decreasing concentrations. In the presence of high-performing gold nanostars, the Rh6G signal was detectable at dilutions down to the nanomolar level even without tight focusing and working at low laser power-a key aspect for analyte detection in real-world biomedical and environmental applications.

Porous Chitosan Composite Membrane Tandem Laser-Induced Breakdown Spectroscopy for Detection of Metal Elements in Liquid Samples

Laser-induced breakdown spectroscopy (LIBS) is currently one of the most popular techniques for direct element analysis of solid samples. However, when directly used for liquid sample analysis, there are disadvantages, including sample splashing, plasma quenching, and poor signal stability. These problems can be overcome through liquid-solid matrix conversion; at the same time, LIBS signal enhancement can be realized, and the sensitivity of detection of liquid samples can be improved. For this research, the authors used chitosan (CS) as a raw material, and introduced poly(vinyl alcohol) (PVA) and polyethyleneimine (PEI) to finally synthesize a new type of porous membrane material with better stability and more functional group content. The membrane was used as a liquid-solid conversion matrix material combined with LIBS technology to successfully achieve rapid separation and detection of Cu, Ag, Pb, and Cr, and the corresponding detection limits can reach 0.038, 0.069, 0.012, and 0.009 mg/L, respectively. This method further improves the sensitivity of the LIBS method. Combining it with membrane materials will replace inactive membranes and open up a new way for the rapid analysis of solution samples using LIBS technology.

Abstract 2316: Automating ctDNA liquid biopsy workflow for mutation testing: From sample extraction to dPCR analysis utilizing the Maxprep™ Liquid Handler, Maxwell® extraction system, and high-plex detection assays

Abstract Liquid biopsies are a minimally-invasive sampling approach to overcome the heterogeneity of tumors and represent a valuable source of circulating tumor DNA (ctDNA) for oncological biomarker analysis. The use of ctDNA as a surrogate for tissue DNA is increasingly popular, and advances in the detection and characterization of ctDNA has enabled liquid biopsy assay integration into clinical utilization. However, an innate challenge with measurement of ctDNA is the requirement for highly sensitive quantitation to reliably detect rare genetic aberrations. Digital PCR has emerged as a powerful technology addressing the needs for next-generation analysis of liquid biopsies samples. Having reliable assays for analysis of key oncology targets help drive adoption of this technology into real-world applications. The exquisite sensitivity of digital PCR requires sample preparation methods that reduce variation, making automation of any manual steps highly desirable. Automation also provides flexibility to scale up as testing volumes increase while simultaneously decreasing overall complexity for the operator. Here we present an automated workflow for ctDNA extraction and analysis using the Maxprep™ Liquid Handler, Maxwell® extraction system (Promega Corporation), and a new, high-throughput digital PCR consumable, the Ruby Chip (Stilla Technologies). This ultra-sensitive detection for liquid biopsy samples was performed using a high-plex dPCR assay. Citation Format: Michael Granitsiotis, Kimberly Gutierrez, Doug Horejsh, Monica Yue. Automating ctDNA liquid biopsy workflow for mutation testing: From sample extraction to dPCR analysis utilizing the Maxprep™ Liquid Handler, Maxwell® extraction system, and high-plex detection assays [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 2316.

Two Fast GC-MS Methods for the Measurement of Nicotine, Propylene Glycol, Vegetable Glycol, Ethylmaltol, Diacetyl, and Acetylpropionyl in Refill Liquids for E-Cigarettes.

The use of e-cigarettes (ECs) has become increasingly popular worldwide, even though scientific results have not established their safety. Diacetyl (DA) and acetylpropionyl (AP), which can be present in ECs, are linked with lung diseases. Ethyl maltol (EM)-the most commonly used flavoring agent-can be present in toxic concentrations. Until now, there is no methodology for the determination of nicotine, propylene glycol (PG), vegetable glycerin (VG), EM, DA, and acetylpropionyl in e-liquids that can be used as a quality control procedure. Herein, gas chromatography coupled with mass spectrometry (GC-MS) was applied for the development of analytical methodologies for these substances. Two GC-MS methodologies were developed and fully validated, fulfilling the standards for the integration in a routine quality control procedure by manufacturers. As proof of applicability, the methodology was applied for the analysis of several e-liquids. Differences were observed between the labeled and the experimental levels of PG, VG, and nicotine. Three samples contained EM at higher concentrations compared to the other samples, while only one contained DA. These validated methodologies can be used for the quality control analysis of EC liquid samples regarding nicotine, PG, and VG amounts, as well as for the measurement of the EM.

Diagnostics of laser-induced plasma on carbon-based polymer material using atomic and molecular emission spectra

Time-integrated optical emission analysis of laser-induced plasma on Teflon is presented. Plasma was induced under atmospheric pressure air using transversely excited atmospheric CO2 laser pulses. Teflon is a C-based polymer that is, among other things, interesting as a substrate for laser-induced breakdown spectroscopy analysis of liquid samples. This study aimed to determine the optimal experimental conditions for obtaining neutral and ionized C spectral lines and C2 and CN molecular band emission suitable for spectrochemical purposes. Evaluation of plasma parameters was done using several spectroscopic techniques. Stark profiles of appropriate C ionic lines were used to determine electron number density. The ratio of the integral intensity of ionic-to-atomic C spectral lines was used to determine the ionization temperature. A spectral emission of C2 Swan and CN violet bands system was used to determine the temperature of the colder, peripheral parts of plasma. We critically analyzed the use of molecular emission bands as a tool for plasma diagnostics and suggested methods for possible improvements.

Comparison of digital PCR systems for the analysis of liquid biopsy samples of patients affected by lung and colorectal cancer

Background and aimsHighly sensitive technologies are available for the molecular characterization of solid tumors, including digital PCR (dPCR). Liquid biopsy, based on the analysis of cell-free DNA (cfDNA), is often used to assess EGFR or RAS alterations in lung and colorectal cancers. Our study aimed to compare the results of two different dPCR platforms for the detection of mutations in cfDNA. MethodsPlasma samples from lung and colorectal cancer patients collected as per routine procedures have been tested. cfDNA Was extracted from plasma, and samples were screened on the droplet digital PCR (ddPCR, BioRad) and solid dPCR QIAcuity (Qiagen). ResultsA total of 42 samples were analyzed, obtained from 20 Non-Small Cell Lung Cancer (NSCLC) patients carrying an EGFR or a KRAS mutation on tissue at diagnosis, and from 22 samples of colorectal cancer (CRC) patients, 10 of which presenting a KRAS mutation. EGFR mutation detection was 58.8% for ddPCR and 100% for dPCR (κ = 0.54; 95% CI, 0.37–0.71), compared to tissue results. The detection rate for RAS mutations was 72.7% for ddPCR and 86.4% for dPCR (κ = 0.34; 95% CI, 0.01–0.68), compared to tissue results. ConclusionsThis study showed moderate agreement between dPCR and ddPCR. Sampling effect or threshold settings may potentially explain the differences in the cfDNA data between the two different platforms.