The development of rapid and precise methods for detecting metal ions has emerged as a critical concern. In this study, we present a novel and highly miniaturized glass capillary system designed for the specific, rapid, and cost-effective detection of heavy metal ions, focusing on chromium (Cr3+) as a representative example.
Applied capillaries were made of fused silica (tailored and drawn in-house), and their used pieces accommodated volumes as low as 2.9 µL. The measurement setup consisted of the laser source and optical detector collecting spectra in the wavelength range of 200-900 nm. The specificity of the detection in the system was provided by the engineered green fluorescent protein (eGFP, developed in-house), which undergoes conformational changes upon interaction between its engineered metal-binding loop - and specific metal ion. Consequently, the fluorescence emission of eGFP is either emitted or enhanced.
The obtained results clearly demonstrate distinct changes in fluorescence intensity corresponding to varying concentrations (50 pM to 50 µM) of metal ions. Detection of 500 pM was feasible even with the mere presence of ng of the receptor protein - eGFP.
This work describes an experimental study towards label-free sensing of C-reactive protein (CRP) – a protein recognized as a inflammation marker. A multimode optical fiber with a section of its core coated with indium tin oxide (ITO) thin film was used as a sensor. ITO film allows for guiding lossy modes and can simultaneously be used as a transparent electrode for electrochemical measurements. Therefore, optical and electrochemical detection based on a single sensor was possible. Such a dual-domain approach is practical, especially when the results in one of the domains are not accurate enough, which was the case in this work. A case of different functionalization methods of ITO surface was also pointed out. The proposed sensor allows for recognition as low as ng/mL.
Tomasz Gabler, Karthika Kappalakandy Valapil, Elżbieta Jarosińska, Andrzej Krześniak, Monika Janik, Marcin Koba, Emilia Witkowska-Nery, Martin Jönsson-Niedziółka, Mateusz Śmietana
Nowadays, multi-domain systems are crucial for accurate measurements since they improve error avoidance in empirical observations by supplementing one domain with the other. Such an approach also yields more useful information about the sample under study. In this work, we present the results obtained from a sensing system composed of a microcavity inline Mach-Zehnder interferometer (μIMZI) combined with indium tin oxide (ITO) electrodes, which is the first approach to two-domain, real-time, and label-free observation of cell behavior. The µIMZI structure was manufactured with a femtosecond laser ablation process in the side surface of single-mode optical fiber. It is susceptible to refractive index (RI) change within its volume, i.e., hundreds of picolitres. The μIMZI sensitivity to RI reaches over 15,000 nm/RIU. The μIMZI was attached to the glass plate with eight ITO electrodes formed using laser irradiation. This optical and electrochemical domain system was used for cell medium measurements, followed by one hour of HepG2 cells monitoring. Finally, trypsin was added to the solution, and its effects on the HepG2 cells were investigated optically and electrochemically. The presented monitoring setup and obtained results are proof of concept for a multi-domain cell monitoring system.
The work discusses the possible impact of the electric charge of biological material on the properties of label-free biosensors, in particular those operating in dual domains, i.e., optical and electrochemical. Optical fiber lossy-mode resonance (LMR) sensors based on indium tin oxide (ITO) were investigated as label-free biosensors with a model biological receptor-target pair, i.e., biotin-avidin. Each of the used biological materials shows different properties, i.e., size, isoelectric point, and, therefore, also charge. The investigations were performed in two electrolytes with differently charged redox couples to better identify the possible influence of chargé of biological material on the optical readout. The obtained results clearly indicate that in designing label-free biosensing solutions, consideration of a broader range of biological materials properties than just refractive index, such as their charge, is required.
Nitrogen-vacancy (NV) centers are crystallographic defects which provide diamonds with unique physical properties. The centers are known for their intensive, time-stable fluorescence, and an electron spin, which exhibits long coherence time and may be manipulated using external stimuli. Nanodiamonds containing the NV centers are promising tools in biolabeling, biosensing, and drug delivery due to the aforementioned properties of the defects combined with a chemical inertness of a core and an easily functionalized surface of the diamond.
Many biochemical reactions are pH-sensitive, therefore, in order to utilize the NV centers for monitoring of such processes, the pH-dependency of the properties of the nanodiamonds needs to be well-understood. Functionalization of the nanodiamonds’ surfaces with biological molecules undergoing pH-triggered changes of conformation, e.g. poly-L-lysine, could not only increase the particles’ biocompatibility and promote cell adhesion, but also possibly enhance pH-sensitivity.
In the present study, an impact of pH on the fluorescence, a zeta potential, and a contact angle of the NV centers-containing nanodiamonds dispersed in liquid media is examined. The suspensions were made of commercially available, fluorescent diamond particles in an as-received, unmodified state, and after the poly-L-lysine had been attached to their surfaces via two different procedures – in aqueous, and anhydrous environment. Values of pH of dispersion media were specifically chosen to induce diverse conformation of the poly-L-lysine: from a fully relaxed conformation, through a state of being neither wholly extended, nor helical, to a complete α-helix conformation.
The intensity of the photoluminescence emitted by the NV centers has been found to depend on the pH-triggered conformation of the poly-L-lysine attached to the surfaces of the nanodiamonds. The impact of the conformation of the poly-L-lysine on the electric charge of the nanoparticles has also been analyzed. This study confirms the potential of the nitrogen-vacancy centers for optical sensing of pH-triggered processes.
This paper discusses refractive index (n) measurement capabilities of interferometers based on micro-cavities of various diameters (d = 50 and 60 μm) fabricated in optical fibers by a femtosecond laser. In comparison to previously presented structures, the reported sensor operates in the near-infrared spectral range. Bottom of the cavity intersected the fiber’s core (5.2 μm in diameter), which induced the Mach-Zehnder interferometer effect. After filling the cavity, a set of minima can be observed in the transmission spectrum, and they shift in wavelength with a change in n. The fabricated sensors exhibit high and linear sensitivity and can measure sub-nanoliter volumes of liquids, what make this sensor perfect for various diagnostic medical or biochemical applications.
This work presents combined long-period grating (LPG) and a micro-cavity in-line Mach-Zehnder interferometer (μIMZI), both induced in the same single-mode optical fiber. In order to increase refractive index (RI) sensitivity of the LPG, it has been nanocoated with aluminum oxide (Al2O3). Next, the μIMZI has been fabricated as a cylindrical cavity (d = 60 μm) in the center of the LPG. In transmission measurements for various RI in the cavity and around the LPG we have observed two effects coming from two independently working sensors. There was no significant impact on one or the other in terms of their functional properties. Such a combination of sensorial effects can be applied for cross-reference measurements of the two different parameters at the same time or for discrimination of influence of other parameters on the RI measurements.
There is a critical need of a fast, specific and reliable assay for biological species. To address this need, long period fiber gratings (LPFG) among other fiber optic sensors can be used because of their high sensitivity to changes in surrounding medium. In this work we fabricated and used two over-etched LPFGs. One of them was covered with T4 Phage and the other was covered with MS2 phage that both specifically bind with Escherichia coli (E. coli) bacteria. This bacterium is a major cause of the food contaminations and outbreaks. We showed achieving a highest sensitivity region of the LPFG and the way to fine tune to that region by over-etching the grating. Finally, using the highly sensitive LPFG platform we could detect E. coli at concentrations as low as 100 colony forming units (CFU), by covering the LPFG with an optimized bio-functionalization of the fiber surface with MS2 bacteriophage.
This work presents an application of reactive ion etching (RIE) for an effective tuning of the spectral response and the refractive-index (RI) sensitivity of the micro-cavity in-line Mach-Zehnder interferometer (μIMZI). The μIMZIs were fabricated using femtosecond laser micromachining in a standard single-mode fiber as a form circular holes with a diameter of 54 μm. The application of RIE with SF6 and O2 used as reactive gas allows for an efficient and well controlled etching of the fabricated structure. The process resulted in cleaning the bottom of the micro-cavity and smoothening of its sidewalls. In transmission measurements, the effect of the plasma processing was observed as an increase in both spectral depths of the minima and RI sensitivity of the structure, as well as improved wettability of the micro-cavity surface, which made the measurements faster and easier.
A micro-cavity in-line Mach-Zehnder interferometer (μIMZI) is an optical sensing structure fabricated in an optical fiber. Its design allows for refractive index sensing of liquid and gas in picoliter volumes, making it suitable for biochemical and medical sensing where measured material is often scarce. The fabricated structures show satisfactory levels of sensitivity, from about 400 nm/RIU in the near-water range of solutions (nD 1.336±0.003 RIU) to about 16 000 nm/RIU for solutions in approximate range from nD = 1.35 RIU to nD = 1.4 RIU. The structures were subjected to oxygen plasma, the process which was supposed to modify physical parameters of the structures, i.e., cavity surface wettability and roughness, and in consequence their sensitivity. As a result of the oxygen plasma modification we have observed a improved wettability of the structure surface, what makes it easier to introduce liquid into the cavity and simplifies the measurement process. In the case where the plasma processing is preceded by biological layer deposition, the bottom surface of the structure is smoothed and slightly deepened, causing a shift in the transmission spectrum and change in sensitivity.
This paper discusses refractive index (n) measurement capabilities of micro-cavity with various diameters (d = 40, 54 and 60μm) fabricated in optical fibers by a femtosecond laser. The bottom of the cavity intersected the fiber’s core and the Mach-Zehnder interferometer effect was induced, allowing the measurement of the n of the liquid filling the cavity. After filling the cavity, a set of minima can be observed in fiber transmission spectrum which shift with change in n. Fabricated sensors exhibit high and linear sensitivity, which in the range of n=1.3333 to 1.3500 RIU barely depends on the cavity diameter in case of first observed minima. Next for different micro-cavity diameters the minima do not overlap in refractive index domain thus it is impossible to compare them in terms of the sensitivity. The highest sensitivity of up to more than 27 000 nm/RIU was obtained for the smallest cavity and the third observed minimum.
In this paper we focus on refractive index (RI) sensing properties of a micro-size In-fiber Mach-Zehnder Interferometer (μIMZI). The μIMZI structure was fabricated as a precisely controlled side opening of a single-mode fiber using a femtosecond laser. The sensitivity to RI change in the micro-cavity has been measured and two RI sensitivity regions have been found for RI 1.33-1.36 and 1.37-1.40 RIU. The sensitivity in the first region is over 12,000 nm/RIU, and in the higher RI region is close to 50% higher. The obtained structures are an excellent solution for RI sensing with negligible temperature cross-sensitivity, especially where small amounts of liquid are available, e.g. in lab-on-chip, microfluidics.
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