Fused-silica Capillary Research Articles

Simultaneous quantification of chlorogenic acid, quercetin, and kaempferol in Urceola rosea leaves by CE and HPLC techniques: method validation and comparative study

Two analytical methods, CE and HPLC, were developed, validated, and compared for simultaneously determining chlorogenic acid, quercetin, and kaempferol in Urceola rosea leaves collected from twelve different sources of Thailand. The determination was accomplished by CE on the uncoated fused silica capillary tube and by HPLC on the ZORBAX Eclipse Plus C18 column. Chlorogenic acid was found to have the highest average amount in U. rosea leaves, followed by kaempferol and quercetin, respectively. Compared to CE, HPLC is considered to provide higher sensitivity and robustness as indicated by lower LOD and LOQ values as well as % RSD of robustness for all analytes. Overall, the present study first demonstrated that both methods were selective, sensitive, and robust, allowing reliable simultaneous quantification of three major bioactive compounds in U. rosea leaves, which could be beneficially applied for quality control assessment of this plant material, particularly those cultivated in Thailand.

Simple simultaneous analysis of various cardiovascular drug mixtures with vincamine: comparative eco-friendly assessment

The development of two eco-friendly analytical methods for the simultaneous determination of eight cardiovascular drugs; hydrochlorothiazide (HCT), captopril (CPL), lisinopril (LSP), valsartan (VAL), atorvastatin (ATR), bisoprolol (BSL), amlodipine (AML) and carvedilol (CVL); alongside with the nutraceutical vincamine (VIC) is essential for sustainable pharmaceutical analysis. This study explores the application of Micellar Electro Kinetic Chromatography (MEKC) and High-Performance Liquid Chromatography (HPLC) for this purpose. In MEKC method, the separation was done using fused silica capillary (41.5 cm × 50 µm id) and a back ground electrolyte consisting of 50 mM borate buffer (pH 9) containing 50 mM sodium lauryl sulphate (SLS) and 10% organic modifier (Acetonitrile). In HPLC method, separation was performed on a ZORBAX Extend-C18 (4.6 × 250 mm, 5 µm) column, using a gradient mobile phase consisting of 50 mM phosphate buffer pH 3 and methanol. Both methods attained good linearity (r ≥ 0.9996) with low values of LOD and LOQ. Both methods were successfully applied in the determination of co-administered single, binary and ternary dosage form of the studied drugs. Moreover, application of various combinations of co-administered dosage forms was achieved in rat plasma, confirming the applicability of these methods in different matrices. The use of micellar solutions in MEKC enhances separation efficiency while reducing the need for organic solvents, aligning with green chemistry principles. HPLC methods were optimized using environmentally benign solvents, ensuring reduced toxicity and waste production. The methodologies were evaluated through green, white, and blue metrics to ensure comprehensive sustainability, considering ecological impact, safety, and practical efficiency. These methods were not only cost-effective and time-saving but achieved high efficiency, sensitivity, and reproducibility making them ideal for routine use in pharmaceutical analysis.

A simple method to remove polyimide coating from fused silica capillaries for capillary electrophoresis

A simple and cost-effective method for making capillary electrophoresis (CE) detection windows is reported. A low-cost laser engraving machine equipped with a 450 nm high-power blue laser was used to remove the polyimide coating from the fused silica capillary by laser scanning the desired section. The entire process is automated and controlled in real time by software. This method can be easily adopted by many CE users for routine practice and is scalable for high-throughput production of detection windows across multiple capillaries.

A robust polymetallic-coated sheathless interface with high acid and alkali resistance for coupling capillary electrophoresis with mass spectrometry

A robust interface for coupling capillary electrophoresis (CE) to mass spectrometry (MS) was critical to maintain high separation efficiency of CE while achieving high sensitivity of MS. Current interfaces often suffer from problems such as reproducibility and ruggedness. For this purpose, a new polymetallic-coated sheathless interface was developed for the coupling of CE with MS. The electrical contact of the interface was achieved by etching one end of the fused silica capillary into a tapered tip using hydrofluoric acid (HF) solution, and then depositing a thin layer of chromium followed by a layer of platinum on it via physical vapor deposition technique. The performance of the new sheathless interface was systematically evaluated for the effect of flow rate and electrospray ionization (ESI) voltage on MS signal intensity, as well as the sample loading volume on CE separation efficiency and repeatability by using peptide standards and tryptic digest of bovine serum albumin (BSA). The interface was capable of generating stable electrospray even at ultra-low flow rate of 12.2 nL/min. In addition, the acid and alkali resistance of the polymetallic- coated emitter was tested by immersing it into 1M HCL and 1M NaOH solution, respectively. The results showed that polymetallic coating was still intact even after continuous immersion in the alkaline solution for 8 days (192 h) and a longer period in the acidic solution, indicating its excellent chemical stability. All the experimental results indicated that the sheathless interface fabricated by the new method in this study was robust and stable, making it promising for both sensitive and robust CE-MS sample analysis.

Getting the Best out of Capillary Electrophoresis and Capillary Electrophoresis-Mass Spectrometry by Quantifying Sources of Peak Broadening for Proteins Using Polyelectrolyte Multilayer Coated Fused Silica Capillaries.

Capillary electrophoresis (CE) has emerged as a relevant technique for protein and biopharmaceutical analysis, as it combines high separation efficiency, sensitivity, and versatility. The use of capillary coatings, including successive multiple ionic-polymer layers (SMILs), reduces interactions between analytes and the capillary, further improving the CE performance. Nevertheless, separations done on SMIL coatings rarely surpass 500 × 103 plates/m. To obtain the best out of the CE, it is interesting to have a detailed look at the sources of peak dispersion. Separations of a mix of model proteins were performed on (poly(diallyldimethylammonium chloride)/poly(styrenesulfonate))2.5-coated capillaries at different electrical field strengths, leading to plate height H against migration velocity u plots that enabled a quantitative analysis of each contribution. Using this model, capillary lengths and injected volumes were systematically varied. For the first time, the contribution of sample electrophoretic heterogeneity to the total peak dispersion was deciphered for model proteins and a monoclonal antibody. Dispersion due to electromigration was seen to have an impact on plate heights in the case of triangular peaks of small molecules but not for proteins under the present conditions. UV and mass spectrometry detections were compared on the same capillary, providing valuable information on the impact of the detection type on separation efficiency. Close to 1 million plates/m were reached in the best conditions.

Development of a HPLC system using a phase-separation multiphase flow as an eluent: an influence of column pressure on phase separation and chromatogram at room temperature.

We have developed a HPLC system where phase-separation multiphase flow works in the separation column as an eluent. We call the novel separation mechanism a phase-separation mode. The ternary mixed solution of water/acetonitrile/ethyl acetate, which is one of the two-phase-separation mixed solutions, caused the phase-separation multiphase flow via phase change from homogeneous to heterogeneous with the temperature effect (from 20 to 0°C). In this study, we tried to perform phase-separation multiphase flow with the pressure effect instead of the temperature one. The fused-silica capillary tube (50cm length and 50µm inner diameter) was allied to the downstream of the column to apply the pressure of 5.5MPa to the system. Model analytes of 2,6-naphthalenedisulfonic acid (2,6-NDS) and 1-naphthol (1-NA) were examined. For example, solutions (the volume% of water/acetonitrile/ethyl acetate; 20:55:25, organic-rich) and (60:30:10, water-rich) were used as eluent. The model analytes were not separated with both solutions at the pressure of 1.5MPa and 20°C. But with the organic-rich solution, 1-NA and 2,6-NDS were separated in this order and with the water-rich solution, they were separated in the reverse order at the pressure of 5.5MPa and 20°C. The phase-separation mode could be performed at the high pressure even at the room temperature.

Investigation of induced electroosmotic flow in small-scale capillary electrophoresis devices: Strategies for control and reversal.

Electroosmotic flow (EOF) is the bulk flow of solution in a capillary or microchannel induced by an applied electric potential. For capillary and microchip electrophoresis, the EOF enables analysis of both cations and anions in one separation and can be varied to modify separation speed and resolution. The EOF arises from an electrical double layer at the capillary wall and is normally controlled through the pH and ionic strength of the background buffer or with the use of additives. Understanding and controlling the electrical double layer is therefore critical for maintaining acceptable repeatability during method development. Surprisingly, in fused silica capillaries at low pH, studies observe an EOF even though the capillary surface should be neutralized. Previous work has suggested the presence of an "induced electroosmotic flow" from radial electric fields generated across the capillary wall due to the separation voltage and grounded components external to the capillary. Using thin-wall (15µm) fused silica separation capillaries to facilitate the study of radial fields, we show that the EOF mobility depends on both the separation voltage and the location of external grounds. This is consistent with the induced EOF model, in which radial electric fields embed positive charges at the capillary walls to create an electrical double layer. The magnitude of the effect is characterized and shown to have long-range influences that are difficult to completely null by moving grounded components away from the separation capillary. Instead, active EOF control using externally applied potentials or a passive approach using a negative separation voltage are discussed as two possible methods for controlling the induced EOF. Both methods can reverse the EOF and improve the resolution and peak efficiency in amino acid separations.

Simultaneous Determination of Glycerol and Carbohydrates in Sweat by Capillary Electrophoresis with Amperometric Detection

Background: Glycerol, sucrose, lactose, glucose, and fructose are important biomarkers in human sweat because their contents can reflect physiological status and health conditions. It is of high importance to determine them in sweat for health monitoring, disease diagnosis, physical training, etc. Aim: The aim of this work is to develop a method based on capillary electrophoresis and amperometric detection for the simultaneous determination of glycerol and carbohydrates in sweat. Objective: A capillary electrophoretic method based on pipette-tip-based detection electrodes and micro-injectors was developed for the simultaneous determination of glycerol, sucrose, lactose, glucose, and fructose in sweat samples Method: Sweat samples diluted in the background electrolyte of 75 mM NaOH aqueous solution were electrokinetically introduced into a piece of separation capillary via pipette tip-based microinjectors. Glycerol, sucrose, lactose, glucose, and fructose were determined by capillary electrophoresis in combination with a pipette-tip-based copper electrode. Results: At a DC voltage of 12 kV, the capillary electrophoretic separation of the five analytes could be achieved in less than 11 min in a piece of 40 cm long fused silica capillary containing 75 mM NaOH aqueous solution. Linearity was observed between the currents and concentrations, with the limits of detection ranging from 0.21 to 0.72 µM at a detection potential of 0.65 V. Glycerol, sucrose, lactose, glucose, and fructose in sweat samples were positively identified and accurately measured. Conclusion: The method was successfully applied in the simultaneous determination of glycerol and carbohydrates in sweat samples with satisfactory assay results. It will find a wide range of applications in clinical diagnosis, health monitoring, and drug and food analysis.

Aptamer based hybrid monolithic pipette tips supported by melamine sponge for enrichment of proteins

BackgroundThe convenient preparation and application of functionalized organic-inorganic hybrid monolithic materials have obtained substantial interest in the pretreatment of complex samples by solid-phase extraction (SPE). Compared to the in-tube solid-phase microextraction in fused-silica capillaries, micro SPE in plastic pipette tips have fascinating merits for the easily operated enrichment of trace target analytes from biological samples. However, the poor compatibility of organic-inorganic hybrid monoliths with plastics leads to the rare appearance of commercial hybrid monolithic pipette tips (HMPTs). Therefore, how to synthesize the organic-inorganic hybrid monolithic materials with better extraction performance in plastic pipette tips becomes a challenge. ResultsWe develop a facile and cheap strategy to immobilize organic-inorganic hybrid monoliths in pipette tips. Melamine sponge was employed as the supporting skeleton to in situ assemble amine- and thiol-bifunctionalized hybrid monolithic material via “one pot” in a pipette tip, and gold nanoparticles (GNPs) and thiol-modified aptamer against human α-thrombin were sequentially attached to the hybrid monolith within the HMPTs. The average coverage density of the aptamer with GNPs as an intermediary reached as high as 818.5 pmol μL−1. The enriched thrombin concentration was determined by a sensitive enzymatic chromogenic assay with the limit of detection of 2 nM. The extraction recovery of thrombin at 10 nM in human serum was 86.1 % with a relative standard deviation of 6.1 %. This proposed protocol has been applied to the enrichment and determination of thrombin in real serum sample with strong anti-interference ability, low limit of detection and high recovery. SignificanceThe amine- and thiol-bifunctionalized HMPTs prepared with sponge as the skeleton frame provided a novel substrate material to decorate aptamers for efficient enrichment of proteins. This enlightens us that we can take advantage of the tunability of sponge assisted HMPTs to produce and tailor a variety of micro SPE pipette tips for broader applications on the analysis of trace targets in complex biological, clinic and environmental samples.

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.

Electrochemical detection of cocaine metabolites (benzoylecgonine and ecgonine) at the miniaturized electrified liquid-liquid interface

The main urinary cocaine metabolites are benzoylecgonine and ecgonine methyl ester. These molecules possess two chemical functional groups that can be charged within the conventional pH range, this is the tertiary amine group (both) and the carboxylic group (benzoylecgonine). We have found that in the pH range from 2 to 6 (for benzoylecgonine) and pH from 2 to 4 (for ecgonine methyl ester) both molecules can be detected at the electrified liquid-liquid interface (eLLI) by following the interfacial ion transfer reactions triggered in the presence of the concerned metabolites in the aqueous phase. The presence of the benzene ring in the benzoylecgonine structure increases its hydrophobicity (on the formal Galvani potential difference scale) by around 200 mV as compared with ecgonine methyl ester which transfer is overlaid with the inorganic cations crossing the LLI at the positive end of the potential window. Macroscopic eLLI was used during physicochemical ecgonine methyl ester and benzoylecgonine characterization as we have defined their diffusion coefficients, ion partition, and concentration fraction diagrams (only for the latter). The miniaturized platform was used during electroanalytical studies focused on benzoylecgonine giving a few µM limit of detection. For this purpose, we have used the fused silica capillary as the eLLI support. All our findings allowed us to use this system first to develop the electroanalytical protocol for benzoylecgonine quantification to finally detect it in the spiked urine sample with nearly 100 % recovery.

Capillary Electrophoresis as a Complementary Analytical Tool for the Separation and Detection of Nanoplastic Particles.

Capillary electrophoresis (CE) is presented as a technique for the separation of polystyrene nanoparticles (NPs, particle diameters ranging from 30 to 300 nm) through a bare fused silica capillary and ultraviolet detection. The proposed strategy was also assessed for other types of nanoplastics, finding that stronger alkaline conditions, with an ammonium hydroxide buffer (7.5%, pH = 11.9), enabled the separation of poly(methyl methacrylate), polypropylene, and polyethylene NP for the first time by means of CE for particle diameters below 200 nm. Particle behavior has been investigated in terms of its effective electrophoretic mobility, showing an increasing absolute value of effective electrophoretic mobility from the smaller to the larger sizes. On the other hand, the absolute value of surface charge density decreased with increasing size of NPs. It was demonstrated and quantified that the separation mechanism was a combination of linear and nonlinear electrophoretic effects. This work is the first report on the quantification of nonlinear electrophoretic effects on nanoplastic particles in a CE system.

Effective method for simultaneous determination of abscisic acid, 3-indolacetic acid and gibberellic acid in commercial plant biostimulants by capillary electrophoresis with diode array detection

Phytohormones, also known as plant hormones, are naturally occurring chemical compounds that regulate various physiological processes in plants. In this work, a capillary electrophoretic coupled to a diode array detector (CE-DAD) method was developed and validated for the simultaneous quantification of abscisic acid (ABA), 3-indolacetic acid (IAA), and gibberellic acid (GA3) in commercial plant biostimulants. Sample preparation was carried out by liquid-liquid extraction using ethyl acetate. CE separation was performed in a fused-silica capillary and background electrolyte (BGE) consisting of borate buffer (50 mM, pH 9.3) applying a high voltage of 20 kV, a pressure of 50 mbar, and injection time of 35 s. The ABA, IAA, and GA3 were detected at 254, 220 and 195 nm respectively. The CE-DAD method validation results showed acceptable specificity, linearity, accuracy, and precision in the concentration range of 10-100 µg/mL for all compounds according to the (International Conference Harmonisation) ICH guidelines. The proposed method was satisfactory applied to the analysis of cited plant hormones in biostimulants and suggest that sample preparation is a reliable step for extraction of phytohormones containing carboxyl groups. Therefore, the developed and validated method could be implemented as a low-cost and fast analytical tool for quality control purposes.

Protein analysis using capillary electrophoresis coupled to mass spectrometry through vibrating sharp-edge spray ionization.

Capillary electrophoresis (CE) interfaced to mass spectrometry (MS) with electrospray ionization typically incorporates acidic additives or organic solvents to assist in ionization. Vibrating sharp-edge spray ionization (VSSI) is a voltage-free method to interface CE and MS that does not require these additives, making it appealing for protein analyses. CE-VSSI nanoflow sheath separations are performed with low ionic strength aqueous solutions in the sheath to reduce suppression. Serine is also included in the sheath to reduce analyte adduction. Proteins are detected in the 2.5-10µM range, corresponding to an injected mass range of 0.1-1.2ng. The anionic proteins β-lactoglobulin and transferrin are resolved using an unmodified fused silica capillary because they do not exhibit nonspecific surface adsorption. Conversely, separations of cationic proteins cytochrome c, ribonuclease A, and α-chymotrypsinogen A in an unmodified capillary require acidic background electrolytes to overcome adsorption. Alternatively, a semipermanent coating comprised self-assembled lipids overcomes surface adsorption at a neutral pH. Separations with zwitterionic and hybrid cationic coatings are complete within 15 or 6min, respectively. The dimeric form of triosephosphate isomerase was observed at a 60µM, corresponding to a mass of 19ng, by dropping the temperature of the MS inlet.

Solid-Phase Microextraction-Aided Capillary Zone Electrophoresis-Mass Spectrometry: Toward Bottom-Up Proteomics of Single Human Cells.

Capillary zone electrophoresis-mass spectrometry (CZE-MS) has been recognized as a valuable technique for the proteomics of mass-limited biological samples (i.e., single cells). However, its broad adoption for single cell proteomics (SCP) of human cells has been impeded by the low sample loading capacity of CZE, only allowing us to use less than 5% of the available peptide material for each measurement. Here we present a reversed-phase-based solid-phase microextraction (RP-SPME)-CZE-MS platform to solve the issue, paving the way for SCP of human cells using CZE-MS. The RP-SPME-CZE system was constructed in one fused silica capillary with zero dead volume for connection via in situ synthesis of a frit, followed by packing C8 beads into the capillary to form a roughly 2 mm long SPME section. Peptides captured by SPME were eluted with a buffer containing 30% (v/v) acetonitrile and 50 mM ammonium acetate (pH 6.5), followed by dynamic pH junction-based CZE-MS. The SPME-CZE-MS enabled the injection of nearly 40% of the available peptide sample for each measurement. The system identified 257 ± 24 proteins and 523 ± 69 peptides (N = 2) using a Q-Exactive HF mass spectrometer when only 0.25 ng of a commercial HeLa cell digest was available in the sample vial and 0.1 ng of the sample was injected. The amount of available peptide is equivalent to the protein mass of one HeLa cell. The data indicate that SPME-CZE-MS is ready for SCP of human cells.

Insights into nucleoside hydrolase from Leishmania donovani inhibition: A new bioaffinity chromatography-based screening assay and docking studies

Leishmaniasis, a group of neglected infectious diseases, encompasses a serious health concern, particularly with visceral leishmaniasis exhibiting potentially fatal outcomes. Nucleoside hydrolase (NH) has a fundamental role in the purine salvage pathway, crucial for Leishmania donovani survival, and presents a promising target for developing new drugs for visceral leishmaniasis treatment. In this study, LdNH was immobilized into fused silica capillaries, resulting in immobilized enzyme reactors (IMERs). The LdNH-IMER activity was monitored on-flow in a multidimensional liquid chromatography system, with the IMER in the first dimension. A C18 analytical column in the second dimension furnished the rapid separation of the substrate (inosine) and product (hypoxanthine), enabling direct enzyme activity monitoring through product quantification. LdNH-IMER exhibited high stability and was characterized by determining the Michaelis-Menten constant. A known inhibitor (1-(β-d-Ribofuranosyl)-4-quinolone derivative) was used as a model to validate the established method in inhibitor recognition. Screening of three additional derivatives of 1-(β-d-Ribofuranosyl)-4-quinolone led to the discovery of novel inhibitors, with compound 2a exhibiting superior inhibitory activity (Ki = 23.37 ± 3.64 µmol/L) compared to the employed model inhibitor. Docking and Molecular Dynamics studies provided crucial insights into inhibitor interactions at the enzyme active site, offering valuable information for developing new LdNH inhibitors. Therefore, this study presents a novel screening assay and contributes to the development of potent LdNH inhibitors.

Exploring the performance of cellulose tris-3,5-dichlorophenylcarbamate as a stationary phase for the chiral electro-chromatographic separation of azole antifungals

In this study, the enantiorecognition and separation performance of cellulose tris-3,5-dichlorophenylcarbamate (CDCPC) as the chiral selector for the enantioseparation of some chiral antifungal compounds was investigated. The CDCPC was bonded to 5 µm porous silica particles and the stationary phase packed into fused silica capillaries (250 mm x 75 µm I.D.) using the "slurry method". The column was used for the separation of twelve selected azole compounds in their enantiomers by capillary electrochromatography (CEC). To study chiral recognition, the mobile phase was modified changing the organic solvent, water content, buffer type, concentration, and pH. Each change resulted in the enhancement of specific interactions at the expense of others, leading to chiral recognition. Their effects on retention factors, enantiomeric resolution, and peak broadening are critically discussed. The developed methodology was used as an appropriate test bench to evaluate the stability of the stationary phase under different mobile phase conditions, demonstrating a remarkable enantioselective capacity even after several tens of hours of continuous use. The optimized CEC-UV method was very effective in the enantiomeric separation of seven out of twelve azole fungicides, totaling fourteen separated peaks in a single 30 min run analysis.

Evaluation of deep eutectic solvents in the synthesis of molecularly imprinted fibers for the solid-phase microextraction of triazines in soil samples.

Nowadays, molecularly imprinted polymers (MIPs) are well established and are considered excellent materials for performing selective extractions. However, with the progressive implementation of the principles of green chemistry, it is necessary to find greener alternatives for both the synthesis and further use of MIPs in sample preparation. Accordingly, in the present work, different deep eutectic solvents (DES, both hydrophilic and hydrophobic), as an alternative to conventional organic solvents (i.e., toluene), were evaluated as porogens for the synthesis of imprinted fibers (monoliths), using fused silica capillaries as molds, for solid-phase microextraction (SPME). From this study, the polymer prepared with propazine (dummy template), methacrylic acid (monomer), ethylene glycol dimethacrylate (cross-linker), and a formic acid:L-menthol (1:1) DES (porogen) showed the best performance for selective rebinding of triazines. After optimization of the different variables involved in SPME, the new imprinted fibers were successfully applied to the extraction of target analytes (desisopropylatrazine, desethylatrazine, simazine, and atrazine) from soil sample extracts, providing relative recoveries ranging from 75.7 to 120.1%, reaching limits of detection within the range of 6.2-15.7ngg-1, depending upon the analyte.

Sample Injection for Real-Time Analysis (SIRTA) Using GC-MS with Cold EI.

There is a continual demand for advanced methods and instruments for real-time analysis (RTA). Most of the current RTA techniques based on MS involve ambient desorption ionization technology. However, flow injection of liquid extracted samples is another option without added modifications or cost to existing LC-MS instruments. In this work, we introduce a new RTA approach named sample injection for real-time analysis (SIRTA) using GC-MS with Cold EI. In SIRTA, the standard GC column is replaced with a 1 m long 0.1 mm I.D. fused silica capillary that connects the GC injector to the MS transfer-line of Cold EI. Thus, SIRTA with Cold EI imposes no need for any additional instrumentation; hence, it is characterized by zero added cost. Like in flow injection in MS of LC-MS, the sample is dissolved in ∼1 mL methanol or another solvent. Subsequently, the vial is placed in the GC-MS autosampler while using a standard syringe for injection without any GC separation. The analysis takes merely 0.2-0.7 min, ensuring rapid and consecutive analyses. Unlike standard EI, Cold EI enables SIRTA by taking advantage of its fly through open ion source to avoid overwhelming the ion source during the elution of solvents while still providing enhanced molecular ions for nearly all analytes. In this study, we demonstrated SIRTA Cold EI analysis of 12 compounds and 7 mixtures, including various prescription and illicit drugs, cannabis and petroleum samples, and other synthetic organic compounds including those with molecular weight up to 800 g/mol.

Ultrahigh-sensitivity temperature sensor based on an elastic TPU capillary whispering gallery resonator.

An ultrahigh sensitivity temperature sensor based on an elastic thermoplastic urethane (TPU) capillary whispering-gallery mode (WGM) microcavity is proposed. The temperature sensor comprises a dye-doped TPU capillary and two sealed fused silica capillaries covered at both ends and is fabricated via a thin film assembly and wet etching. The fused silica capillaries limit the thermal volume expansion of the air within it. The volume of the exposed part of the elastic TPU capillary, which has an ultrahigh sensitivity to temperature compared with the thermal volume expansion of material, is increased; the designed elastic TPU capillary WGM microcavity exhibited an ultrahigh sensitivity of 11.28 nm/°C.