Silica Capillary Research Articles

Optical Fiber Hydrogen Sensor Based on the EVA/Pd Coated Hollow Fiber

A novel optical fiber hydrogen sensor based on the dielectric/metal coated hollow fiber structure is proposed. The palladium (Pd) and ethylene-vinyl acetate (EVA) layers are sequentially coated on the inner surface of the hollow core of the silica capillary to fabricate the EVA/Pd coated hollow fiber sensor. Theoretical ray transmission model is carried out to analyze the influence of the thicknesses of the Pd and EVA films. The experimental transmission spectra of the proposed sensor filled with hydrogen gas of different concentrations are measured. The experimental results show that the interference peak in the spectrum has a red shift with the increase of hydrogen concentration. Then the hydrogen concentration can be obtained by measuring the wavelength of the interference peak. In the range of 0–4% hydrogen concentration, the total shift is 10.64nm and the average sensitivity is 2.66 nm/%. Compared to other optical fiber hydrogen sensors, the proposed sensor has the advantages of simple structure, easy fabrication, low cost, high sensitivity and good safety performance.

Demonstration of Coherent Interference between Acoustic Waves Using a Fiber Ring Resonator.

Optical fibers were previously demonstrated to propagate and detect acoustic modes that were converted from Lamb waves for structural health-monitoring applications; typically, a fiber Bragg grating sensor in the optical fiber is used to detect acoustic modes. Acoustic modes can transfer from one fiber to another through a simple adhesive bond coupler, preserving the waveform of the acoustic mode. This paper experimentally investigates the coherence of acoustic waves through the adhesive coupler, using a fiber ring resonator (FRR) configuration. This configuration was chosen because the wave coupled to the second fiber interferes with the original wave after it encircles the fiber ring. We performed this experiment using different geometries of optical fibers in the ring, including a standard single-mode optical fiber, a hollow silica capillary tube, and a large-diameter multi-mode fiber. The results demonstrate that the acoustic wave, when transferring through an adhesive coupler, interferes coherently even when the main and ring fibers are of different types. Finally, we demonstrate that the FRR can be applied for sensing applications by measuring the mode attenuations in the ring due to a changing external environment (water-level sensing) and measuring the optical-path length change in the ring (temperature sensing).

Low-cost high-sensitivity pH sensor based on a droplet-shaped single-mode fiber Mach–Zehnder interferometer

In this paper, we present the fabrication of a new fiber-optic pH sensor based on the macro-bending loss properties in a droplet-shaped single-mode fiber (SMF) bending structure for the first time. To form the droplet-shaped probe, a segment of straight SMF is properly bent into a droplet shape using a short length of a thin silica capillary tube and without any splicing. By gradually varying the bending diameter of the droplet-shaped structure, interference results between the core and cladding modes, and a Mach–Zehnder interferometer (MZI) is effectively introduced within the bending section. Sodium hydroxide (NaOH) or hydrochloric acid (HCl) were added to the pH indicator utilizing buffers solution to achieve a wide pH range from 1 to 14. Experimental results show that the proposed sensor exhibits maximum sensitivity of 3.264 nm/pH and 5.336 nm/pH for acidic and alkaline solutions, respectively. In addition to the high sensitivity, the proposed sensor structure provides high sensitivity with a high linear response and good repeatability.

Classification of clinical Cutibacterium acnes isolates at phylotype level by capillary electrophoretic methods in roughened fused silica capillary

Despite being commensal bacterium involved in the maintenance of healthy skin, Cutibacterium acnes is also associated with inflammatory diseases. Since inflammatory and immunogenic properties vary between C. acnes phylotypes, reliable classification of clinical C. acnes isolates is important for determining their pathogenicity. Combination of optimized separation methods, polymer-enhanced transient isotachophoresis and sweeping of the charged bacterial cells in micellar electrokinetic chromatography in the roughened fused silica capillary, was used for the separation of twenty clinical C. acnes isolates. Their correct classification into the individual phylotypes was achieved in 20 min at laboratory temperature. In addition, decrease in the separation temperature to 15 °C led to the separation of the individual isolates of some phylotypes. Relative standard deviations of migration times of both intra- and inter-day analyses did not exceed 1.7%. Linearity of the proposed method in the concentration range from 5 × 105 to 1 × 107 cells mL−1 was characterized by the coefficient of determination R2 = 0.9985. Limit of detection of 5 × 105 cells mL−1 (50 cells in 100 nL of the injected sample) was determined for all the examined bacteria.

Flow-Through Atmospheric Pressure-Atomic Layer Deposition Reactor for Thin-Film Deposition in Capillary Columns.

We demonstrate the development of a new atmospheric pressure-atomic layer deposition(AP-ALD) system to coat the inner walls of capillary columns for gas chromatography (GC). Unlike traditional ALD, this reactor operates at near-atmospheric pressure and addresses the challenges of depositing thin films inside capillaries, which include long pump down times, deposition in high-aspect-ratio materials, and temperature control. We show ALD of alumina in 5 and 12 m capillaries (0.53 mm ID) via sequential half reactions of trimethylaluminum and water. Our system yields pinhole-free, uniform thin films. It includes small witness chambers for witness silicon shards before and after the capillary. An engineering flow/transport analysis of the device is provided. Our ALD alumina thin films are characterized by spectroscopic ellipsometry (SE), X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy. Alumina film growth achieved is 1.4-1.5 Å/cycle, which is consistent with previously reported results. Film thickness measurements by SE on witness shards of silicon and by TEM at both ends of the capillary are in good agreement. A capillary column coated with alumina is used to separate different gases by GC, although the retention times of gases are essentially the same as with an untreated fused silica capillary. This successful deposition of ALD alumina in long capillaries opens the door for other possible ALD coatings, including hybrid organic-inorganic coatings, using the 450+ ALD precursors available today.

Silica nanolayer coated capillary by hydrothermal sol-gel process for amines separation and detection of tyramine in food products.

A hydrothermal sol–gel method for reproducible formation of silica nanolayer on the wall of silica capillaries was developed for electrochromatography. The formulation was optimized by observation of uniform gel formation on an optical microscope. The variables of the formulation include types of solvent, water-TEOS ratio, CTAB and urea contents, and mixing method. The procedure produced a coating of silica ca. 100 nm thick layer on the wall of the capillary. Surface morphology of the coating was characterized by SEM, contact angle and chemical composition by FT-IR spectroscopy and X-ray powder diffraction. The coating reduced the electroosmotic mobility producing enhanced separation performance. Eight standard amines (including tyramine and benzhydrylamine, as an internal standard) were separated with peak resolution Rs ≥ 2 for all adjacent peaks and plate number N ≥ 3.0 × 104 m-1. Calibration was linear from 5 to 200 µg L-1, with r2 > 0.9985 and instrumental LOD of 4.9 μg L-1. Five samples of food products were diluted and analyzed for the amines using the coated capillary and only tyramine was detected. Intra-day and inter-day precisions were less than 1.2%RSD. Percent recoveries of spiked tyramine in samples were 95 ± 3 to 106 ± 7% (n = 3).

Two-step micelle-to-solvent stacking of arsenic species from foods in permanently coated tubing for capillary electrophoresis

An effective and sensitive two-step stacking of arsenic species by electrokinetic injection and micelle-to-solvent stacking (MSS) using zwitterionic surfactant 3-(N,N-dimethylpalmitylammonio) propane sulfonate was successfully developed in a co-electro-osmotic flow (co-EOF) capillary zone electrophoresis (CZE). The fused silica capillaries were coated with 1% hexadimethrine bromide solution to satisfy the condition of the same EOF direction between the test anions and capillary. The background solution was 100 mM borax buffer (pH 9.2). The proposed method was performed by a CZE system equipped with a diode array detector, and the detection wavelength was monitored at 192 nm. The separation voltage was −20 kV. The group of micelles and target analytes was stacked by field-enhanced sample injection at −10 kV for 180 s. The second stacking step used 60% MeOH to serve as an organic solvent where the analytes were brought by the micelles to the MSS boundary. The enrichment factors of As(Ⅴ), As(Ⅲ), disodium methyl arsonate hexahydrate (MMA), and dimethylarsinic acid (DMA) were 1230, 840, 3820, and 1450, respectively, compared to typical injections in CZE. The limits of detection (S/N = 3) ranged from 0.382 to 0.911 ng mL−1. The intracapillary repeatabilities (%RSD, n = 3) were 0.5–1.0% for migration time and 0.3–0.7% for peak areas. The technology of two-step stacking by MSS in co-EOF CZE together with a simple extraction procedure for As(Ⅴ), As(Ⅲ), MMA and DMA were demonstrated in kelp and rice samples.

Sprayed Water Microdroplets Are Able to Generate Hydrogen Peroxide Spontaneously.

Ultrapure N2 gas was bubbled through water, and the humidified output containing undetectable concentrations of ozone filled a closed chamber in which 18 MΩ-cm water was sprayed through a silica capillary to form microdroplets. Analysis of the collected microdroplets by NMR spectroscopy showed the presence of hydrogen peroxide at a concentration level ranging from 0.3 to 1.5 μM depending on the flow conditions. This was confirmed using a spectrofluorometric assay. We suggest that this finding establishes that when sprayed to form microdroplets, water has the ability to produce hydrogen peroxide by itself. When the N2 gas is replaced by compressed air or O2 gas, the concentration of hydrogen peroxide is found to increase, indicating that gas-surface interactions with O2 in aqueous microdroplets promote the formation of hydrogen peroxide.

Validated Method for the Determination of Five Membered Heterocyclic Polar Compound Imidazole in Drug Substances Using Capillary Electrophoresis and UV Detection

A simple and sensitive method based on capillary electrophoresis with UV detection was developed, optimized, and validated for the determination of five membered heterocyclic polar compound, imidazole in pharmaceutical drug substances. Separation was achieved on bare fused silica capillary using a simple running buffer, potassium dihydrogen phosphate at pH 4.0. Capillary temperature set at 25°C. The applied voltage was 25 kV across the capillary and the samples were injected by hydrodynamically at a pressure of 50 mbar for 5 s. Analyte was monitored at 210 nm. The achieved limit of detection value was 0.005%w/w, limit of quantification value was 0.014%w/w, and the average accuracy value was 98.4% for imidazole. The aim of present study is to develop a specific and sensitive method for the determination of imidazole to overcome the void volume and sample matrix interferences.

Sustainable quantitative determination of allopurinol in fixed dose combinations with benzbromarone and thioctic acid by capillary zone electrophoresis and spectrophotometry: Validation, greenness and whiteness studies

The design of novel validated methodologies targeting many goals such as simplicity, greenness, analytical efficiency and sustainability, has gained great concern in quality control units. In this sense, fast, white and sustainable analytical procedures were optimized and validated for estimation of Allopurinol (ALP) with either Benzbromarone (BZB) or Thioctic acid (TIO) in their fixed dose combinations. In procedure I, capillary zone electrophoresis (CZE) was performed using fused silica capillary (50 cm, 50 μm id), a background electrolyte solution of 50 mM borate buffer (pH 8.5) with 17 s injection time and 30 kV voltage. The diode array detector was operated at 210 nm for the three drugs. Separation occurred in 4 min with migration times 2.9, 3.3 and 3.6 min for ALP, BZB and TIO respectively. Linearity range was 10–200 μg/mL for the three drugs. Additionally, simple spectrophotometric methods were designed for simultaneous estimation of the two binary mixtures. Method I was direct absorbance measurement for determination of ALP and TIO simultaneously at 250 and 330 nm respectively. Similarly, direct Amax measurement at 356 nm was implemented for estimation of BZB in mixture with ALP. Methods II and III were based on the ratio difference and ratio spectra derivative measurements for the quantitation of ALP using BZB as divisor. The developed methods were validated conforming to the ICH guidelines and assessed for greenness and sustainability using AGREE model and the hexagon tool. On studying the whiteness features, the suggested methods were compared with 7 reported methods using the recently introduced RGB12 model.

Characterization of photo-isomerization-induced refractive index response for azobenzene solution based on capillary-assisted Mach-Zehnder interferometer under 473 nm laser excitation

We propose a compact silica-capillary-assisted Mach-Zehnder interferometer (SCAMZI) to investigate the light power and polarization dependences of refractive indices in the near-infrared region for ethyl orange (EO) solution, which is one type of azo-based photo-sensitive functional material. Owing to photo-induced trans-to-cis isomerization of azo material, interference dips of the proposed MZI are highly sensitive to applied excitation laser power density, showing a maximum wavelength sensitivity of 0.1959 nm/(mW⋅cm−2) for the silica capillary of 325 μm in length and EO percentage weight of 0.08 wt%. The experimentally observed spectral responses to applied laser power density show good light-controlled spectral reversibility and repeatability. And by adjusting the polarization angle of 473 nm excitation laser, polarization-dependent refractive index of EO solution have been characterized and thus optical birefringence responses can be acquired as well, which provides an important reference for understanding the mechanism of photo-isomerization-induced optical response and the development of related light-controlled photonic devices.

Determination of ultrahigh molar mass of polyelectrolytes by Taylor dispersion analysis

Taylor dispersion analysis (TDA) was successfully applied to obtain broadly distributed, ultrahigh molar masses of industrial anionic polyacrylamides (IPAMs) up to 25×106g/mol, far beyond the limits of Size Exclusion Chromatography (SEC) (about 7.3×106g/mol for anionic polyacrylamides standards (APAM)). Two protocols of TDA differing in capillary surface and rinsing procedure were employed: (i) bare fused silica capillaries under intensive between-run rinsing with 1M NaOH, and (ii) fused silica capillaries coated with polyelectrolyte multilayers composed of polydiallyldimethylammonium chloride polycation and sodium polystyrenesulfonate polyanion under simple rinsing with background electrolyte. Both cases led to similar results and in agreement with those obtained by static light scattering, the rinsing capillary step being much shorter in the second case (8min instead of 30min). The data processing of the obtained taylorgrams was realized using multiple-Gaussian fitting of the overall taylorgrams, by separating the contribution of low molar mass impurities from the polymeric profiles, and by determining the mean hydrodynamic radii and diffusion coefficients of the polymers. The molar masses of ultra-high molar mass industrial anionic polyacrylamides (IPAM) were derived from the hydrodynamic radii according to logRh versus logMw linear correlation established with APAM standards. Compared to capillary gel electrophoresis for which the size separation was only feasible up to Mw ∼ 10×106g/mol due to field induced polymer aggregation, TDA largely extended the range of accessible molar mass with easy-to-run and time saving assays.

Inexpensive portable capillary electrophoresis instrument for Monitoring Zinc(II) in remote areas

A compact, inexpensive capillary electrophoresis instrument was developed for monitoring metal ions and evaluated for Zn(II) in remote contaminated locations in western Tasmania, Australia. The portable instrument, measuring 21 cm x 10 cm x 7 cm, was powered from the USB port of a laptop computer and built from off-the-shelf components costing ∼$1200 USD. Electrophoretic separations were conducted using a fused silica capillary (10–50 µm I.D.), applying 8.5 kV over capillaries ranging from 25 cm to 40 cm in length. The capillary inlet was connected with an electrically grounded cross-piece as flow-through injection interface. Automated fluidic management was achieved by controlling four mini peristaltic pumps and a solenoid valve. Detection was realised using a purpose-built visible LED absorption detector, optimised for the detection of Co(II), Cu(II) and Zn(II) after complexation with 4-(2-Pyridylazo) resorcinol (PAR). Limits of detection of sub-µM were obtained. The instrument was tested for continuous operation in the laboratory for up to 3 months, and relative standard deviations of <5.4% were found over 945 consecutive injections. In the field, the system was able to measure 106 samples within 11 h, the time it can be powered from the laptop computer. As Field measurement of Zn(II) in western Tasmania was demonstrated to show capability for on-site metal testing.

Open tubular nano-liquid chromatography with a new polylysine grafted on graphene oxide stationary phase for the separation and determination of casein protein variants in milk

In this study, a novel narrow capillary (i.e., 20 µm i.d.) coating procedure was reported for the preparation and application of open-tubular (OT) column for the separation of casein (CN) protein variants in milk. Based on this approach, a new poly-L-lysine (PLL) grafted on graphene oxide stationary phase was developed for OT nano-liquid chromatography (OT-nano LC). In this preparation, methacryloyl graphene oxide nanoparticles (MGONPs) were synthesized and used as reactive monomer. Fused silica capillaries with 20 µm i.d. were used for the preparation of OT column. After silanization of the capillary column, the stationary phase was prepared by MGONPs graft polymerization and PLL modification. It was shown that the use of MGONPs amount was important for the capillary coating. A column without PLL modification was also prepared for comparing the effect of PLL. SEM images of the column showed that MGONPs were bound to the surface of capillary in a dense monolayer. Alkylbenzenes (ABs) were used for the chromatographic characterization of the OT column. The results showed that the modification was successfully performed and allowed satisfactory separation of ABs. The developed OT column in the ProFlow nano-LC was applied to the separation of casein (CN) protein variants, including αs1-CN, αs2-CN, β-CN and Ƙ-CN. Results indicated that the column provided a promising separation of casein protein variants due to both hydrophobic interactions and repulsive electrostatic interactions. Run-to-run and column-to-column reproducibilities were satisfactory (i.e., ≤3.12%). Real sample application of the OT column was demonstrated using a milk sample. Several isoforms of αs1-CN could be detected. All results demonstrated that the developed OT column with a novel coating procedure was promising for advanced nano-liquid chromatographic separations.

Compact Optical Fiber Sensor Based on Silica Capillary Tube for Simultaneous High Temperature and Transverse Load Measurement

An optical fiber sensor is proposed and experimentally demonstrated for simultaneous measurement of high temperature and transverse load. The sensor is designed by splicing a silica capillary tube (SCT) to a single-mode fiber (SMF) and then heating the SCT to form an air bubble. SCT simultaneously functions as a Fabry Perot (F-P) microcavity and an anti-resonant reflection waveguide. These sensing mechanisms lead to high contrast sensitivity values of temperature and transverse load (1.89pm/°C,190.48pm/N and 24.93pm/°C, 16.68pm/N). Remarkably, the temperature sensitivity of this sensor is eleven times higher than that of the current fiber-tip micro-cavity (2.1 pm/°C). The sensor is also more advantageous in quantitative production and practical application due to its low cost, ease of fabrication, good mechanical strength, and convenient reflection probe.

Validated Capillary Zone Electrophoresis Method for Impurity Profiling and Determination of NiII(3-OMe-Salophene)

A capillary zone electrophoresis method was developed for the determination of NiII(3-OMe-salophene), a substance with anticancer activity in vitro. A fused silica capillary (56 cm × 100 µm) was used for this purpose. The method was optimized in terms of parameters affecting the electrophoretic conditions in order to optimize separation efficiency and total time of migration. The analysis was best performed using an operating buffer of 50 mM borate, adjusted to pH 9.3, mixed with acetonitrile (50%, v/v) as organic modifier. Injections were performed hydrodynamically by applying a pressure of 50 mbar for 8 s, and a 30 kV separation voltage was selected at 25 °C. Detection was carried out at 250 nm using diode array detector (DAD). The method allowed the separation of NiII(3-OMe-salophene) from four other structurally related impurities in a total migration time (tm) of 8 min. Peak identification was achieved using the standard reference of individual impurities. The purity of the migrated NiII(3-OMe-salophene) was confirmed by Ultra-violet (UV) scan overlay depending on DAD. The linear ranges for the determination of NiII(3-OMe-salophene) was 400–20,000 ng mL−1 with limit of detection (LOD) of 120 ng mL−1. Acceptable intra-day and inter-day precisions were achieved (%relative standard deviation (RSD) results were less than 0.76% and 0.30%, respectively). The proposed method was assessed for greenness and compared to reported methodologies to prove superiority.

Enantioselective analysis of the methamphetamine precursors ephedrine and pseudoephedrine by capillary electrokinetic chromatography using cyclodextrins as chiral selectors

Ephedrine and pseudoephedrine can be used as precursors for the illicit synthesis of stimulant drugs, such as methamphetamine and methcathinone. For this reason, an enantioselective capillary electrokinetic chromatography method was developed for the separation of ephedrine and pseudoephedrine enantiomers. After testing two different charged or chargeable cyclodextrins (β-cyclodextrin sulphate and carboxymethyl-β-cyclodextrin) and a few mixtures as possible chiral selectors, a mixture of 3 mM carboxymethyl-β-cyclodextrin and 3 mM heptakis(2,6-di-O-methyl)-β-cyclodextrin in pH 3.4 acetate buffer was used as the enantioselective background electrolyte and the separation was carried out in an uncoated silica capillary (75 µm internal diameter, 48.6 cm total length, 40.0 cm effective length). Analytical method performance was then evaluated in terms of linearity, precision, selectivity and accuracy with good results. Proof of concept application to mixtures simulating illicit methamphetamine (containing small amounts of ephedrine and pseudoephedrine as possible residual synthesis impurities) provided satisfactory results for the identification and quantitation of the four analyte diastereomers.

Open tubular capillary ion chromatography with online dilution for small ions determination in drinks

This work aims to develop a more robust, easy-to-use, low-pressure, and cost-effective nonsuppressed open tubular capillary ion chromatography (NS-OTIC) approach with online dialysis for small ions determination in drinks. The fabricated device was applied for two selected columns, including poly(butadiene-maleic acid) on a 50-μm bore and AS18 Latex on 25-µm bore fused silica capillaries, for the separation of mixed cations (Na+, K+, Ca2+, Mg2+) and mixed anions (Cl−, Br−, NO2−, NO3−), respectively. High concentrations of ions (up to 100 mM) level can be directly introduced into the NS-OTIC system without an off-line (manual) dilution step. The linear relationship of the peak area and concentration of model ions can be obtained with a resolution > 1.1. The repeatability of the peak area for both OTIC columns was < 6% RSD. Juice and tea samples were successfully analyzed with % recoveries of 77–112 and 90–119 for cation and anion determinations, respectively.

Sensitive identification of milk protein allergens using on-line combination of transient isotachophoresis/micellar electrokinetic chromatography and capillary isoelectric focusing in fused silica capillary with roughened part

A method for on-line concentration of milk proteins from large sample volumes using combination of transient isotachophoresis (tITP) and micellar electrokinetic chromatography (MEKC) in fused silica capillary with an inner roughened part has been developed. The method utilizes reversible dynamic adsorption of proteins onto a thin layer of PEG 4000 on the roughened surface of the capillary. In addition, the tITP/MEKC method was combined with capillary isoelectric focusing (CIEF) for on-line concentration, separation, identification and sensitive determination of proteins in skimmed milk. The method allows analysis of up to 50 μL of sample. This study has focused on the four important whey proteins, bovine serum albumin (BSA), α-lactalbumin (α-LA), and two genetic variants of β-lactoglobulin (β-LG A and β-LG B). The proteins were identified on the basis of their migration times and characteristic pI values. The pI values of BSA, α-LA, β-LG A, and β-LG B were determined as 4.7, 4.4, 5.1, and 5.2, respectively. Limits of detection for BSA, α-LA and both β-LG variants were found as 1.2, 1.0 and 1.0 pg mL−1, respectively. The linearity of calibration curves was characterized by the R2 = 0.9982. The method provided highly reproducible results as the relative standard deviations of the migration times and peak areas of the examined proteins did not exceed 1.6%.

Liquid Modified Anti-Resonant Reflecting Guidance in Silica Capillary for Sensing Applications

In this work, the transmission characteristic of a single mode fiber-silica capillary-single mode fiber (SMF-Capillary-SMF) structure is modified by introducing liquids inside and outside the silica capillary. The anti-resonant reflecting guidance mechanism in the silica capillary is influenced by the presence of the liquids. By immersing a section of liquid-filled SMF-Capillary-SMF structure into liquids, both the resonant wavelength and transmission intensity are altered due to a liquid-modified resonant condition. Temperature change will lead to the refractive index (RI) variation of liquids, causing the resonant wavelength to shift. Experimental results indicate that the temperature sensitivity is dependent on the RI value of the liquids, and the liquid temperature sensitivity of 2.99 nm/℃ is experimentally achieved in the temperature range of 25 ℃-60 ℃ when the liquid RI is 1.39. On the other hand, the transmission intensity at resonant wavelength, which is determined by the reflectivity at the inner and outer surfaces of the ring cladding, can be affected when the RI of the ambient liquid changes. The intensity at resonant wavelength increases as the ambient RI rises, and the RI sensitivity varies from 240 dB/RIU to 60 dB/RIU in the RI range of 1.31 to 1.39. Such a device is simple and easy to fabricate, which can find wide applications in liquid environments like biochemical and pharmacy industries.