Search Results (24)

The replacement of celestine (SrSO₄) by strontianite (SrCO₃) has extensively been studied over the past few decades. It also represents an ideal reaction to in situ study the kinetic and fundamental mechanistic details of mineral replacement reactions in aqueous solutions via fluid-cell Raman spectroscopy. This technique allows us to study the reaction process in real time by continuously analysing the solution or by imaging the solid–liquid interface where the reaction takes place and while the replacement process is ongoing. Two sets of experiments were conducted, the first of which was carried out with celestine powder and an equimolar Na₂CO₃ solution in a heated fluid cell between 30 and 60 °C. The progress of the reaction was followed by Raman spectroscopic in situ measurements of the solution. Another experiment was performed with a polished cuboid cut from a single celestine crystal and a 1 M Na₂CO₃ solution in a fluid cell at room temperature (21 °C). In this experiment, the reaction was studied in situ, spatially resolved, and in real time. The results of both types of experiments revealed that the replacement occurs via a coupled dissolution–precipitation mechanism and that the evolution of the solution composition cannot fully be explained by a single rate law derived from a shrinking core model. By applying the model-independent time-to-a-given-fraction method, three kinetic regimes could be identified and the associated activation energies quantified. Full article

Aiming at the fundamental understanding of solvent effects in amphiphilic polymer systems, we considered poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO-PPO-PEO) block copolymers in water mixed with an ionic liquid—ethylammonium nitrate (EAN), 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF₆), or 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄)—and we investigated the hexagonal lyotropic liquid crystal structures by means of small-angle X-ray scattering (SAXS). At 50% polymer, the hexagonal structure (cylinders of self-assembled block copolymer) was maintained across the solvent mixing ratio. The effects of the ionic liquids were reflected in the characteristic length scales of the hexagonal structure and were interpreted in terms of the location of the ionic liquid in the self-assembled block copolymer domains. The protic ionic liquid EAN was evenly distributed within the aqueous domains and showed no affinity for the interface, whereas BMIMPF₆ preferred to swell PEO and was located at the interface so as to reduce contact with water. BMIMBF₄ was also interfacially active, but to a lesser extent. Full article

Elongated ellipsoidal liquid crystal microdroplet reorientation dynamics are discussed in this paper for biosensor applications. To investigate the effect of elongated droplets on nematic liquid crystal droplet biosensors, we simulated a model of a liquid crystal droplet using ellipse geometry. Director reorientation is examined in relation to the elongated droplet shape. In addition, we examined aspect ratio as a factor affecting biosensor response time in relation to surface viscosity and anchoring energy. Finally, the findings suggest that the aspect ratio should be taken into account when designing biosensors. These results can be used to develop more effective biosensors for a variety of applications. This model then predicts the director reorientation angle, which is dependent on the anchoring energy and surface viscosity. This model further suggests that both surface viscosity and homeotropic anchoring energy play an important role when it comes to the director reorientation angle. We developed and applied a nonlinear unsteady-state mathematical model utilizing torque balance and Frank free energy according to the Leslie–Ericksen continuum theory for simulating elongated nematic liquid crystal biosensor droplets with aqueous interfaces. Using the Euler–Lagrange equation, a transient liquid crystal–aqueous interface realignment is modeled by changing the easy axis when surfactant molecules are added to the interface. The realignment at the surface of the droplet is assumed to be driven by the effect of the surfactant, which causes an anchoring transition. According to the results, the response time of the biosensor depends on the aspect ratio. Therefore, the elongation has the potential to control biosensing response time. The result of our study provides a better understanding of director reorientation in elongated liquid crystal droplets in biosensing applications through the numerical results which are presented in this paper. Full article

The numerical results from the modeling of liquid crystals dispersed in aqueous solutions in the form of axially symmetric droplets, with the aim of helping to facilitate the development of liquid crystal biosensors, were obtained. We developed a transient two-dimensional nonlinear model obtained via torque balance that incorporates Frank’s elastic free energy. In order to perform parametric studies, we defined the scaled parameters based on the surface viscosity and the homeotropic anchoring energy at the droplet interface. To evaluate the performance of the biosensor, the average angle and characteristic time were defined as performance criteria. Using these results, we studied the bulk reorientation of liquid crystal droplets in aqueous solutions caused by biomolecular interaction. Furthermore, we examined how surface viscosity affects the performance of a biosensor in the case of weak planar anchoring. The droplet interface ordering was modeled using the Euler–Lagrange equation. The droplets’ equilibrium was determined by minimizing their total distortion energy based on the interaction between their surface and bulk elastic energy. Two factors that contributed to the biosensor performance were homeotropic strength and surface viscosity. This highlights the importance of controlling the surface and physicochemical properties to achieve the desired liquid crystal orientation. In addition, our results provide insight into the role that surface viscosity plays in controlling radial configuration. Full article

The development of novel drug delivery systems (DDSs) with promising antibacterial properties is essential for facing the emergency of increasing resistance to antimicrobial agents. The antibacterial features of quercetin and its metal complexes have been broadly investigated. However, several drawbacks affect their activity and effectiveness. In this work, we propose a DDS based on a pH-responsive cobalt(II)-coordinated assembly containing quercetin and polyacrylic acid. This system is suggested to trigger the release of the model drug in a pH-dependent mode by exploiting the localized acidic environment at the bacterial infection sites under anaerobic conditions. The delivery system has been designed by accurately examining the species and the multiple equilibria occurring in solution among the assembly components. The formation of cobalt(II) complexes with quercetin in the absence or presence of the pH-responsive polyacrylic acid was investigated in buffered aqueous solution at pH 7.4 using spectrophotometric (UV-Vis) and calorimetric (ITC) techniques. The determined binding affinities and thermodynamic parameters that resulted are essential for the development of a DDS with improved binding and release capabilities. Furthermore, the affinity of the polymer–cobalt(II) complex toward the model antimicrobial flavonoid was explored at the solid–liquid interface by quartz crystal microbalance (QCM-D) experiments, which provided marked evidence for drug loading and release under pH control. Full article

In the context of the circular economy, used coffee grounds were transformed into powdered activated carbon by chemical activation using potassium hydroxide. Its characterisation was conducted in comparison with that of a commercial activated carbon by scanning electron microscopy (SEM) coupled with energy dispersive X-ray microanalysis (EDX), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Boehm titration, and point zero charge (pH_PZC) and by determination of the methylene blue number (MBN) and the iodine number (IN). Performance of the prepared activated carbon was tested in the adsorption of the cationic dye crystal violet (CV) and hexavalent chromium. Batch adsorption tests were carried out and the effects of operating parameters were studied. The results collected on the adsorption kinetics show that the adsorption followed pseudo-second order kinetics and that the Langmuir isotherm best fits the equilibrium data for crystal violet and hexavalent chromium. The thermodynamic study showed that the adsorption of both adsorbates is spontaneous and exothermic and leads to a decrease in disorder at the solid–liquid interfaces. These results indicate that this activated carbon can be used as an alternative adsorbent to remove cationic dyes and heavy metals from aqueous solutions. Full article

The bilayer’s formations of amphiphilic molecules or polyions of different ionogenity comprise the basic building units of most organic biological and non-biological systems. A theory has evolved to explain their behaviour during the creation of those organized structures, such as anisotropic liquid crystal (LC) in lyotropic (especially hydrotropic) systems and polyelectrolyte multilayer (PEM) assemblies. Particular attention has been paid to the temperature and the important role of water in the formation and behaviour of the bilayers. A novel insight into the formation of hydrotropic liquid LC systems and their thermotropic behaviour is presented. In this context, the systems PEM assemblies are also discussed. Essentially, a structuralised form of water fills out continuous and discontinuous, i.e., confined, nano-spaces among hydrophilic interfaces of bilayers, controlling their supramolecular structure through a system of attractive and repulsive hydration forces. The character of those sophisticated bonding hydration systems is predestined by the composition and type of these hydrophilic interface groups. The miscellaneous complexity of the bilayer’s aqueous systems suggests the need to study these examples in greater detail. Therefore, the bilayer’s processes connected with disruption as far as destruction of bilayers are mentioned, i.e., the processes with the highest potential to combat bacteria, fungi, and viruses, such as in a situation where a person exhales a breath of micro-droplets containing virus nanoparticles (e.g., the COVID-19 virus). Full article

Rational design of thermotropic liquid crystal (LC)-based sensors utilizing different mesophases holds great promise to open up novel detection modalities for various chemical and biological applications. In this context, we present a dissipative particle dynamics study to explore the unique anchoring behavior of nematic and smectic LCs at amphiphile-laden aqueous-LC interface. By increasing the surface coverage of amphiphiles, two distinct anchoring sequences, a continuous planar-tilted-homeotropic transition and a discontinuous planar-to-homeotropic transition, can be observed for the nematic and smectic LCs, respectively. More importantly, the latter occurs at a much lower surface coverage of amphiphiles, demonstrating an outstanding sensitivity for the smectic-based sensors. The dynamics of reorientation further reveals that the formation of homeotropic smectic anchoring is mainly governed by the synchronous growth of smectic layers through the LCs, which is significantly different from the mechanism of interface-to-bulk ordering propagation in nematic anchoring. Furthermore, the smectic LCs have also been proven to possess a potential selectivity in response to a subtle change in the chain rigidity of amphiphiles. These simulation findings are promising and would be valuable for the development of novel smectic-based sensors. Full article

A nonlinear unsteady-state mathematical model employing torque balance and Frank free energy according to the Leslie-Ericksen continuum theory is developed and implemented to simulate the performance of nematic liquid crystal biosensor films with aqueous interfaces. A transient liquid crystal-aqueous interface realignment is modeled using the Euler–Lagrange equation by changing the easy axis when the surfactant molecules at the interface are introduced. In our study, we evaluated the dynamics between bulk and interface by controlling surface properties of the interface, such as homeotropic anchoring energy and surface viscosity. In addition, transient optical interference and response time have been examined in this study. Our parametric study results indicated that both homeotropic anchoring energy and surface viscosity at the interface contribute to bulk reorientation. Furthermore, the obtained numerical results indicate that as homeotropic anchoring strength increases, the effective birefringence decreases more gradual due to the increasing surfactant concentration at the aqueous interface, consistent with available experimental observations. Our results have been validated and compared to experimental results from thin-film liquid crystal biosensors in this study. Full article

Indium and its compounds have many industrial applications and are widely used in the manufacture of liquid crystal displays, semiconductors, low temperature soldering, and infrared photodetectors. Indium does not have its own minerals in the Earth’s crust, and most commonly, indium is associated with the ores of zinc, lead, copper and tin. Therefore, it must be recovered as a by-product from other metallurgical processes or from secondary raw materials. The aim of this study is to investigate the adsorption properties for recovering indium from aqueous solutions using iron–magnesium composite (MgFe₂O₄). In addition, the results show that the material offers very efficient desorption in 15% HCl solution, being used for 10 adsorption–desorption cycle test. These results provide a simple and effective process for recovering indium. Present study was focuses on the synthesis and characterization of the material by physico-chemical methods such as: X-ray diffraction, FT-IR spectroscopy, followed by the adsorption tests. The XRD indicates that the MgFe₂O₄ phase was obtained, and the crystallite size was about 8 nm. New prepared adsorbent materials have a point of zero charge of 9.2. Studies have been performed to determine the influence of pH, initial indium solution concentration, material/solution contact time and temperature on the adsorption capacity of the material. Adsorption mechanism was established by kinetic, thermodynamic and equilibrium studies. At equilibrium a maximum adsorption capacity of 46.4 mg/g has been obtained. From kinetic and thermodynamic studies was proved that the studied adsorption process is homogeneous, spontaneous, endothermic and temperature dependent. Based on Weber and Morris model, we can conclude that the In (III) ions takes place at the MgFe₂O₄/In (III) solution–material interface. Full article

Liquid crystals (LCs) have been widely used as sensitive elements to construct LC biosensors based on the principle that specific bonding events between biomolecules can affect the orientation of LC molecules. On the basis of the sensing interface of LC molecules, LC biosensors can be classified into three types: LC–solid interface sensing platforms, LC–aqueous interface sensing platforms, and LC–droplet interface sensing platforms. In addition, as a signal amplification method, the combination of LCs and whispering gallery mode (WGM) optical microcavities can provide higher detection sensitivity due to the extremely high quality factor and the small mode volume of the WGM optical microcavity, which enhances the interaction between the light field and biotargets. In this review, we present an overview of the basic principles, the structure, and the applications of LC biosensors. We discuss the important properties of LC and the principle of LC biosensors. The different geometries of LCs in the biosensing systems as well as their applications in the biological detection are then described. The fabrication and the application of the LC-based WGM microcavity optofluidic sensor in the biological detection are also introduced. Finally, challenges and potential research opportunities in the development of LC-based biosensors are discussed. Full article

The working principle for a liquid crystal (LC)-based biosensor relies on the disturbance in the orderly aligned LC molecules induced by analytes at the LC-aqueous or LC-solid interface to produce optical signals that can be typically observed under a polarizing optical microscope (POM). Our previous studies demonstrate that such optical response can be enhanced by imposing a weak electric field on LCs so that they are readily tilted from the homeotropic alignment in response to lower concentrations of analytes at the LC-glass interface. In this study, an alternative approach toward signal amplification is proposed by taking advantage of the marginally tilted alignment configuration without applying an electric field. The surface of glass substrates was modified with a binary aligning agent of poly(vinyl alcohol) (PVA) and dimethyloctadecyl[3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP), in which the amount of PVA was fine-tuned so that the interfacing LC molecules were slightly tilted but remained virtually homeotropically aligned to yield no light leakage under the POM in the absence of an analyte. Two nematic LCs, E7 and 5CB, were each sandwiched between two parallel glass substrates coated with the PVA/DMOAP composite for the detection of bovine serum albumin (BSA), a model protein, and cortisol, a small-molecule steroid hormone. Through image analysis of the optical appearance of E7 observed under the POM, a limit of detection (LOD) of 2.5 × 10⁻⁸ μg/mL for BSA and that of 3 × 10⁻⁶ μg/mL for cortisol were deduced. Both values are significantly lower than that obtained with only DMOAP as the alignment layers, which correspond to signal amplification of more than six orders of magnitude. The new approach for signal amplification reported in this work enables analytes of a wide range of molecular weights to be detected with high sensitivity. Full article

In this study, we developed a liquid crystal (LC) droplet-based sensing platform for the detection of carboxylesterase (CES) and its inhibitors. The LC droplet patterns in contact with myristoylcholine chloride (Myr) exhibited dark cross appearances, corresponding to homeotropic anchoring of the LCs at the aqueous/LC interface. However, in the presence of CES, Myr was hydrolyzed; therefore, the optical images of the LC patterns changed to bright fan-shaped textures, corresponding to a planar orientation of LCs at the interface. In contrast, the presence of CES inhibitors, such as benzil, inhibits the hydrolysis of Myr; as a result, the LC patterns exhibit dark cross textures. This principle led to the development of an LC droplet-based sensing method with a detection limit of 2.8 U/L and 10 μM, for CES detection and its inhibitor, respectively. The developed biosensor not only enables simple and label-free detection of CES but also shows high promise for the detection of CES inhibitors. Full article

The use of drugs derived from benzothiadiazine, a bicyclic heterocyclic benzene derivative, has become a widespread treatment for diseases such as hypertension, low blood sugar or the human immunodeficiency virus, among others. In this work we have investigated the interactions of benzothiadiazine and four of its derivatives designed in silico with model zwitterionic cell membranes formed by dioleoylphosphatidylcholine, 1,2-dioleoyl-sn-glycero-3-phosphoserine and cholesterol at the liquid–crystal phase inside aqueous potassium chloride solution. We have elucidated the local structure of benzothiadiazine by means of microsecond molecular dynamics simulations of systems including a benzothiadiazine molecule or one of its derivatives. Such derivatives were obtained by the substitution of a single hydrogen site of benzothiadiazine by two different classes of chemical groups, one of them electron-donating groups (methyl and ethyl) and another one by electron-accepting groups (fluorine and trifluoromethyl). Our data have revealed that benzothiadiazine derivatives have a strong affinity to stay at the cell membrane interface although their solvation characteristics can vary significantly—they can be fully solvated by water in short periods of time or continuously attached to specific lipid sites during intervals of 10–70 ns. Furthermore, benzothiadiazines are able to bind lipids and cholesterol chains by means of single and double hydrogen-bonds of characteristic lengths between 1.6 and 2.1 Å. Full article

This focused review presents various approaches or formats in which liquid crystals (LCs) have been used as stimuli-responsive sensors. In these sensors, the LC molecules adopt some well-defined arrangement based on the sensor composition and the chemistry of the system. The sensor usually consists of a molecule or functionality in the system that engages in some form of specific interaction with the analyte of interest. The presence of analyte brings about the specific interaction, which then triggers an orientational transition of the LC molecules, which is optically discernible via a polarized optical image that shows up as dark or bright, depending on the orientation of the LC molecules in the system (usually a homeotropic or planar arrangement). The various applications of LCs as biosensors for glucose, protein and peptide detection, biomarkers, drug molecules and metabolites are extensively reviewed. The review also presents applications of LC-based sensors in the detection of heavy metals, anionic species, gases, volatile organic compounds (VOCs), toxic substances and in pH monitoring. Additionally discussed are the various ways in which LCs have been used in the field of material science. Specific attention has been given to the sensing mechanism of each sensor and it is important to note that in all cases, LC-based sensing involves some form of orientational transition of the LC molecules in the presence of a given analyte. Finally, the review concludes by giving future perspectives on LC-based sensors. Full article