Complex Permittivity Characterization of Liquid Samples Based on a Split Ring Resonator (SRR).

A complex permittivity characterization method for liquid samples has been proposed. The measurement is carried out based on a self-designed microwave sensor with a split ring resonator (SRR), the unload resonant frequency of which is 5.05 GHz. The liquid samples in capillary are placed in the resonant zone of the fabricated senor for high sensitivity measurement. The frequency shift of 58.7 MHz is achieved when the capillary is filled with ethanol, corresponding a sensitivity of 97.46 MHz/µL. The complex permittivity of methanol, ethanol, isopropanol (IPA) and deionized water at the resonant frequency are measured and calibrated by the first order Debye model. Then, the complex permittivity of different concentrations of aqueous solutions of these materials are measured by using the calibrated sensor system. The results show that the proposed sensor has high sensitivity and accuracy in measuring the complex permittivity of liquid samples with volumes as small as 0.13 µL. It provides a useful reference for the complex permittivity characterization of small amount of liquid chemical samples. In addition, the characterization of an important biological sample (inositol) is carried out by using the proposed sensor.

Merits of online electrochemistry liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS).

A new online electrochemistry/liquid sample desorption electrospray ionization mass spectrometry (EC/LS DESI MS) system with a simple electrochemical thin-layer flow-through cell was developed and tested using N,N-dimethyl-p-phenylenediamine (DMPA) as a model probe. Although oxidation of DMPA is observed as a result of ionization of LS in positive ion mode LS DESI, application of voltage to the online electrochemical (EC) cell in EC/LS DESI MS increases yields of oxidation products. An advantage of LS DESI MS is its sensitivity in aqueous electrolyte solutions, which improves efficiency of electrochemical reactions in EC/LS DESI MS. In highly conductive low pH aqueous buffer solutions, oxidation efficiency is close to 100%. EC/ESI MS typically requires mixed aqueous/organic solvents and low electrolyte concentrations for efficient ionization in MS, limiting efficiency of electrochemistry online with MS. Independently, the results verify higher electrochemical oxidation efficiency during positive mode ESI than during LS DESI.

Rapid and ultra-sensitive trace metals detection of water by partial Leidenfrost superhydrophobic array surface enhanced laser-induced breakdown spectroscopy.

The rapid and ultra-sensitive detection of trace elements in liquid is a primary concern for researchers. In this study, a partial Leidenfrost effect superhydrophobic (PLSHB) array surface was used for rapid in situ evaporation enrichment of sample droplets. Within 4 min, a 50 µL droplet sample was completely evaporated, resulting in all solutes in it being concentrated within a circular range measuring approximately 350 µm in diameter, without the formation of a coffee ring structure. The limits of detection for six metals (Pb, Ba, Be, Mn, Cr, Cu) in water were determined to be as follows: 0.82 µgL-1, 0.27 µgL-1, 0.033 µgL-1, 0.136 µgL-1, 0.241 µgL-1, and 0.083 µgL-1. Furthermore, laser-induced breakdown spectroscopy (LIBS) was employed to detect the enriched solutes from ten liquid samples with identical concentrations on the PLSHB array surface; these measurements exhibited a relative standard deviation (RSD) of only 3.7%. Spike experiments involving the addition of the aforementioned six metals into drinking water demonstrated recovery rates ranging from 85.7% to 117.7%. Therefore, the application potential of PLSHB array surface enhanced LIBS for rapid, stable, and ultra-sensitive detection and analysis of trace metal elements across various fields such as industry, environmental science, and biomedicine might be highly promising.

Parallel Accelerator and Molecular Mass Spectrometry Measurement of Carbon-14-Labeled Analytes.

Parallel accelerator and molecular mass spectrometry (PAMMS) is a powerful analytical technique capable of simultaneous quantitation of carbon-14 tracer and structural characterization of 14C-labeled biomolecules. Here we describe the use of PAMMS for the analysis of biological molecules separated by high-performance liquid chromatography. This protocol is intended to serve as a guide for researchers who need to perform PAMMS experiments using instrumentation available at resource centers such as the National User Resource for Biological Accelerator Mass Spectrometry at Lawrence Livermore National Laboratory.

Fast Air-to-Liquid Sampler Detects Surges in SARS-CoV-2 Aerosol Levels in Hospital Rooms.

The COVID-19 pandemic highlighted the dangers of airborne pathogen transmission. SARS-CoV-2 is known to be transmitted through aerosols; however, little is known about the dynamics of these aerosols in real environments, the conditions, and the minimum viral load required for infection. Efficiently measuring and capturing pathogens present in the air would help to understand the infection process. Air samplers usually take several hours to obtain an air sample. In this work a fast (1-2 min) method for capturing bioaerosols into a liquid medium has been tested in hospital rooms with COVID-19 patients. This fast sampling allows detecting transient levels of aerosols in the air. SARS-CoV-2 RNA is detected in aerosols from several hospital rooms at different levels. Interestingly, there are sudden boosts of the SARS-CoV-2 load in the air, suggesting that SARS-CoV-2 could be released abundantly at certain moments. These results show that the distribution of SARS-CoV-2-containing aerosols is not homogeneous in the hospital room. This technology is a fast and effective tool for capturing airborne matter in a very short time, which allows for fast decision-making any kind of hazard in the air is detected. It is also useful for a better understanding of aerosols dynamics.

In-situ induced ethanol-water phase separation extraction of phthalate esters in alcoholic liquid sample using potassium triphosphate and analysis by gas chromatography-mass spectrometry.

A novel and efficient analytical method consisting of in-situ potassium triphosphate induced ethanol-water phase separation extraction and followed by gas chromatography-mass spectrometry (GC-MS) detection was developed for determination of eighteen phthalate esters (PAEs) in alcoholic liquid samples. Experimental parameters affecting the extraction efficiency were studied and optimized by univariate analysis. The effects of salt type and concentration, concentration of ethanol, redissolve solvent, vortex and standing time, solution pH on extraction efficiency were investigated. The developed method exhibited good linearity at a concentration range of 5-2500 µg·L-1 for diisononyl phthalate and 1-500 µg·L-1 for other PAEs. In addition, the coefficients of determination (R2) for all PAEs ranged from 0.9979 to 0.9999, the detection limits (LODs) and the limits of quantification (LOQs) were in the range of 0.014-0.530 µg·L-1 and 0.047-1.767 µg·L-1, respectively, the spiked recoveries were in the range of 92.2%-110.2% with the relative standard deviation (RSD) less than 8.6%. As ethanol within alcoholic liquid samples was used to separate PAEs with none solvent added at extraction processing, the proposed method could be considered simple and environmentally friendly.

Evaluation of a Thermoelectric Cooler as a Sample Pre-Treatment Method for Laser-Induced Breakdown Spectroscopy (LIBS) Analysis of Liquid Samples.

In this study, the performance of a thermoelectric cooler (TEC) as a simple and easy-to-assemble freezing instrument has been evaluated. Experiments were carried out using samples with different viscosity ranging from 44.07 to 16 965.80 MPa. The analysis of sodium component of the samples by direct laser irradiation of frozen samples showed emission enhancement and higher signal-to-noise ratio compared to that of liquids. This work also focused on using chemometrics methods such as principal component analysis (PCA) to compare the principal component score separation and clustering pattern between frozen and liquid samples. The PCA was constructed by dividing the samples into two different categories: (i) type (paste, cream, gel, and oil) and (ii) viscosity (more than and less than 10 000 MPa). The frozen samples showed a more established separation and clustering compared to that acquired from the liquid samples. However, poorer clustering pattern of some frozen samples could be due to the heat transfer during laser-sample interaction inducing surface melting and splashing. The average laser-induced breakdown spectroscopy (LIBS) spectra were taken at as many different surface areas as possible to ensure the sample surface always maintain similar freezing temperature. This work showed that the TEC pre-treatment method had improved the LIBS measurement of the liquid samples.

Rapid alpha spectrometry from liquids doped with ²°9Po and ²4¹Am using simplified sample processing.

Rapid detection of alpha-particle emitting radionuclides from liquids doped with (209)Po and (241)Am was investigated. These nuclides may mimic or be among those that could be used as threat agents in malevolent actions such as deliberate poisoning of refreshments. The liquids investigated here by using a semiconductor alpha detector in vacuum were coffee, beer and apple juice. Methods for the sample processing were rapid evaporation of the liquids and filtration. Both methods produced samples, which gave alpha spectra that could be readily analyzed by an unfolding program. The doped radionuclides were easily identified from the spectra, but the samples were too thick for reliable activity determination. Determination of the activity ratios is possible if the peak shapes are equal. However, radionuclides may behave differently during the sample preparation, which must be accounted for in the activity ratio determination.

Influence of Sulfolane on ESI-MS Measurements of Protein-Ligand Affinities.

The results of an investigation into the influence of sulfolane, a commonly used supercharging agent, on electrospray ionization mass spectrometry (ESI-MS) measurements of protein-ligand affinities are described. Binding measurements carried out on four protein-carbohydrate complexes, lysozyme with ß-D-GlcNAc-(1→4)-ß-D-GlcNAc-(1→4)-ß-D-GlcNAc-(1→4)-D-GlcNAc, a single chain variable fragment and α-D-Gal-(1→2)-[α-D-Abe-(1→3)]-α-D-Man-OCH3, cholera toxin B subunit homopentamer with ß-D-Gal-(1→3)-ß-D-GalNAc-(1→4)[α-D-Neu5Ac-(2→3)]-ß-D-Gal-(1→4)-ß-D-Glc, and a fragment of galectin 3 and α-L-Fuc-(1→2)-ß-D-Gal-(1→3)-ß-D-GlcNAc-(1→3)-ß-D-Gal-(1→4)-ß-D-Glc, revealed that sulfolane generally reduces the apparent (as measured by ESI-MS) protein-ligand affinities. To establish the origin of this effect, a detailed study was undertaken using the lysozyme-tetrasaccharide interaction as a model system. Measurements carried out using isothermal titration calorimetry (ITC), circular dichroism, and nuclear magnetic resonance spectroscopies reveal that sulfolane reduces the binding affinity in solution but does not cause any significant change in the higher order structure of lysozyme or to the intermolecular interactions. These observations confirm that changes to the structure of lysozyme in bulk solution are not responsible for the supercharging effect induced by sulfolane. Moreover, the agreement between the ESI-MS and ITC-derived affinities indicates that there is no dissociation of the complex during ESI or in the gas phase (i.e., in-source dissociation). This finding suggests that supercharging of lysozyme by sulfolane is not related to protein unfolding during the ESI process. Binding measurements performed using liquid sample desorption ESI-MS revealed that protein supercharging with sulfolane can be achieved without a reduction in affinity.

Rapid prototyping of pneumatically actuated hydrocarbon gel valves for centrifugal microfluidic devices.

A novel, easy to prototype hydrocarbon gel-based active valve was developed for use in centrifugal microfluidic devices. The valve has been demonstrated to restrict flow by an additional 1000 revolutions per minute (RPM) when compared to a passive capillary valve of the same size located at the same radius. Opening of the valve is accomplished in a contactless manner using a stream of focused compressed air. The ease of fabrication, low cost and small dimensions of the gel valve offer the potential for integration of multiple valves of this type into multi-process centrifugal microfluidic systems.