Development of calix[4]arene-functionalized microcantilever array sensing system for the rapid, sensitive and simultaneous detection of metal ions in aqueous solutions

The work described in this thesis was conducted with the aim of: 1) investigating the binding capabilities of calix[4]arene-functionalized microcantilevers towards specific metal ions and 2) developing a new16-microcantilever array sensing system for the rapid, and simultaneous detection of metal ions in fresh water. Part I of this thesis reports on the use of three new bimodal calix[4]arenes (methoxy, ethoxy and crown) as potential host/guest sensing layers for detecting selected ions in dilute aqueous solutions using single microcantilever experimental system. In this work it was shown that modifying the upper rim of the calix[4]arenes with a thioacetate end group allow calix[4]arenes to self-assemble on Au(111) forming complete highly ordered monolayers. It was also found that incubating the microcantilevers coated with 5 nm of Inconel and 40 nm of Au for 1 h in a 1.0 M solution of calix[4]arene produced the highest sensitivity. Methoxy-functionalized microcantilevers showed a definite preference for Ca²⁺ ions over other cationic guests and were able to detect trace concentration as low as 10⁻¹² M in aqueous solutions. Microcantilevers modified with ethoxy calix[4]arene displayed their highest sensitivity towards Sr²⁺ and to a lesser extent Ca²⁺ ions. Crown calix[4]arene-modified microcantilevers were however found to bind selectively towards Cs⁺ ions. In addition, the counter anion was also found to contribute to the deflection. For example methoxy calix[4]arene-modified microcantilever was found to be more sensitive to CaCl₂ over other water-soluble calcium salts such as Ca(NO₃)₂ , CaBr₂ and CaI₂. These findings suggest that the response of calix[4]arene-modified microcantilevers should be attributed to the target ionic species as a whole instead of only considering the specific cation and/or anion. Part II presents the development of a 16-microcantilever sensor setup. The implementation of this system involved the creation of data analysis software that incorporates data from the motorized actuator and a two-axis photosensitive detector to obtain the deflection signal originating from each individual microcantilever in the array. The system was shown to be capable of simultaneous measurements of multiple microcantilevers with different coatings. A functionalization unit was also developed that allows four microcantilevers in the array to be coated with an individual sensing layer one at the time. Because of the variability of the spring constants of different cantilevers within the array, results presented were quoted in units of surface stress unit in order to compare values between the microcantilevers in the array

Using Principal Component Analysis for Temperature Readings from YF3:Pr3+ Luminescence

The method of measuring temperature using luminescence by analyzing the emission spectra of Pr3+-doped YF3 using principal component analysis is presented. The Pr3+-doped YF3 is synthesized using a solid-state technique, and its single-phase orthorhombic crystal structure is confirmed using X-ray diffraction. The emission spectra measured within the 93–473 K temperature range displays characteristic Pr3+ f-f electronic transitions. The red emission from the 3P0,1→3H6,3F2 electronic transition mostly dominates the spectra. However, at low temperatures, the intensity of the green emissions from the 3P0,1→3H5, deep-red 3P0,1→3F4, and the deep-red emissions from the 3P0,1→3F4 transitions are considerably lower compared to the intensity of the red emissions. Temperature variations directly impact the photoluminescent spectra, causing a notable increase in the green and deep-red emissions from the 3P1 excited state. We utilized the entire spectrum as an input for principal component analysis, considering each temperature as an independent group of data. The first principal component explained 99.3% of the variance in emission spectra caused by temperature and we further used it as a reliable temperature indicator for luminescence thermometry. The approach has a maximum absolute sensitivity of around 0.012 K−1. The average accuracy and precision values are 0.7 K and 0.5 K, respectively

Synthesis, structures and Lewis‐Acid‐Induced isomerization of 8‐Methoxy[2.2]metaparacyclophanes and a DFT study

Methyl substituted 8‐methoxy[2.2]MPCPs 8 a–b were obtained via thiacyclophane and its oxidized products. Lewis acid‐catalyzed (AlCl3‐MeNO2) reactions of 5‐tert‐butyl‐8‐methoxy‐12,13,15,16‐tetramethyl[2.2]MPCP 8 b under various conditions led to transannular cyclization and isomerization reactions, affording the considerably less‐strained 5‐tert‐butyl‐8‐methoxy[2.2]MPCP 9, 5‐tert‐butyl‐8‐hydroxy‐14,16,17,18‐tetramethyl[2.2]metacyclophane 10 and pyrene derivatives 11 and 12. However,on prolonging the reaction time to 3 h for 8 b, the major product is 5‐tert‐butyl‐8‐hydroxy[2.2]MPCP 10. These reactions are strongly affected by the size and properties of the C‐8 substitutents as well as the methyl substitutents on the para‐linked benzene rings, which increase the strain in the molecules. The 1H NMR spectra and X‐ray crystallographic analysis of 8 b revealed that it adopts a syn‐conformation both in solution and in the solid state

Utilizing photothermally induced oscillation damping parameters for the determination of bacterial load suspended in microfluidic resonators

Microchannel resonators containing a miniaturized volume of a solution can have various applications in different fields. In this study, a microchannel cantilever was loaded with a solution containing a very small number of Pseudomonas fluorescens bacteria suspended in M9 growth medium. The liquid-filled microchannel cantilever was irradiated with a 532-nm laser. The shift in the frequency of the cantilever due to varying bacterial loads is less reliable; therefore, it could not be used for monitoring the bacterial concentration. The energy loss of the cantilever extracted from the quality factor exhibited reliable results and a very strong correlation with the bacterial concentration. The results showed a linear relation between the damping factor of the cantilever and the bacterial concentration. Accordingly, these findings were expected because the bacteria inside the solution can be considered as particles acting against the cantilever motion due to the solution’s viscosity. Thus, more bacteria caused more damping, in agreement with the experimental observations. A semiquantitative experiment was conducted with a heat source (i.e., laser beam) that focused at the cantilever tip to demonstrate the redistribution of the bacterial load within the solution due to the thermal gradient

Exploring the anticancer and antibacterial potential of naphthoquinone derivatives: a comprehensive computational investigation

This study investigates the potential of 2-(4-butylbenzyl)-3-hydroxynaphthalene-1,4-dione (11) and its 12 derivatives as anticancer and biofilm formation inhibitors for methicillin-resistant staphylococcus aureus using in silico methods. The study employed various computational methods, including molecular dynamics simulation molecular docking, density functional theory, and global chemical descriptors, to evaluate the interactions between the compounds and the target proteins. The docking results revealed that compounds 9, 11, 13, and ofloxacin exhibited binding affinities of −7.6, −7.9, −7.5, and −7.8 kcal mol−1, respectively, against peptide methionine sulfoxide reductase msrA/msrB (PDB: 3E0M). Ligand (11) showed better inhibition for methicillin-resistant staphylococcus aureus msrA/msrB enzyme. The complex of the 3E0M-ligand 11 remained highly stable across all tested temperatures (300, 305, 310, and 320 K). Principal Component Analysis (PCA) was employed to evaluate the behavior of the complex at various temperatures (300, 305, 310, and 320 K), demonstrating a total variance of 85%. Convergence was confirmed by the eigenvector’s cosine content value of 0.43, consistently displaying low RMSD values, with the minimum observed at 310 K. Furthermore, ligand 11 emerges as the most promising candidate among the compounds examined, showcasing notable potential when considering a combination of in vitro, in vivo, and now in silico data. While the naphthoquinone derivative (11) remains the primary candidate based on comprehensive in silico studies, further analysis using Frontier molecular orbital (FMO) suggests while the Egap value of compound 11 (2.980 eV) and compound 13 (2.975 eV) is lower than ofloxacin (4.369 eV), indicating their potential, so it can be a statement that compound 13 can also be investigated in further research

Studies on Lewis-Acid Induced Reactions of 8-Methoxy[2.2]metacyclophanes: A New Synthetic Route to Alkylated Pyrenes

Anti-8-methoxy[2.2]metacyclophanes (MCPs) 5 a–b were obtained via pyrolysis of the corresponding syn-thiatetraoxide cyclophanes 4 a–b. Coupling reactions of 4-tert-butyl-1-methoxy-2,6-bis(mercaptomethyl)benzenes 1 a–b and 1,5-bis(chloro-methyl)-2,4-dimethylbenzene 2 under high dilution conditions afforded only the syn-conformers of 9-methoxy-2,11-dithia[3.3]metacyclophanes 3 a–b, which with m-CPBA formed the corresponding syn-tetraoxides 4 a–b. Lewis acid (TICl4/AlCl3-MeNO2) or iodine-catalyzed reactions of 5 b under various conditions led to transannular cyclization to afford tetrahydropyrene 6 b and pyrene derivative 7 b and/or de-tert-butylated 6 a. Iodine-catalyzed reaction of 5 a afforded tetrahydropyrene 6 a. These findings suggest the potential for a new route to alkylated pyrenes via strained and alkylated metacyclophanes. Density functional theory (DFT) studies were carried out to investigate the conformational characteristics of 3–5

Graphene oxide integrated silicon photonics for detection of vapour phase volatile organic compounds

From Springer Nature via Jisc Publications RouterHistory: received 2020-01-07, accepted 2020-05-17, registration 2020-05-20, pub-electronic 2020-06-12, online 2020-06-12, collection 2020-12Publication status: PublishedAbstract: The optical response of a graphene oxide integrated silicon micro-ring resonator (GOMRR) to a range of vapour phase Volatile Organic Compounds (VOCs) is reported. The response of the GOMRR to all but one (hexane) of the VOCs tested is significantly higher than that of the uncoated (control) silicon MRR, for the same vapour flow rate. An iterative Finite Difference Eigenmode (FDE) simulation reveals that the sensitivity of the GO integrated device (in terms of RIU/nm) is enhanced by a factor of ~2, which is coupled with a lower limit of detection. Critically, the simulations reveal that the strength of the optical response is determined by molecular specific changes in the local refractive index probed by the evanescent field of the guided optical mode in the device. Analytical modelling of the experimental data, based on Hill-Langmuir adsorption characteristics, suggests that these changes in the local refractive index are determined by the degree of molecular cooperativity, which is enhanced for molecules with a polarity that is high, relative to their kinetic diameter. We believe this reflects a molecular dependent capillary condensation within the graphene oxide interlayers, which, when combined with highly sensitive optical detection, provides a potential route for discriminating between different vapour phase VOCs

The impact of law enforcement on the dispensing antibiotics without prescription in Saudi Arabia : findings and implications

Background: Dispensing of antibiotics without a prescription (DAwP) has been widely practised in Saudi Arabia despite being illegal. This is a concern increasing AMR. In May 2018, the law and regulations were enforced including fines up to 100,000 SR (equivalent to US$26,666) and cancellation of licences. Consequently, we wanted to evaluate the impact. Methods: Mixed method study among 116 community pharmacies in two phases. Pre-law enforcement phase between December 2017 and March 2018 and post-law enforcement phase one year later. Each phase consisted of a cross-sectional questionnaire-based survey and a simulated client method (SCM). In the SCM, clients presented with either pharyngitis or urinary tract infections (UTI) with 3 levels: level 1 – SC asked for something to relieve the symptoms, level 2 – SC asked for something stronger if an antibiotic was not dispensed, level 3 – SC requested an antibiotic. In SCM for each phase, all 116 pharmacies were visited with at least one of the scenarios. Results: Before the law enforcement, 70.7% of community pharmacists reported DAwP was common. 96.6% and 87.7% of participating pharmacies dispensed antibiotics without a prescription for pharyngitis and UTI respectively. After law enforcement, only 12.9% of community pharmacists indicated that DAwP was common, with only 12.1% and 5.2% dispensing antibiotics without prescriptions for pharyngitis and UTI respectively and mostly after level 3. Conclusion: Law enforcement was effective. However, there is still further scope for improvement as community pharmacists are worried patients may go elsewhere if no antibiotic dispensed on request. This could include educational activities

MXene-Embedded Porous Carbon-Based Cu₂O Nanocomposites for Non-Enzymatic Glucose Sensors

This work explores the use of MXene-embedded porous carbon-based Cu2O nanocomposite (Cu2O/M/AC) as a sensing material for the electrochemical sensing of glucose. The composite was prepared using the coprecipitation method and further analyzed for its morphological and structural characteristics. The highly porous scaffold of activated (porous) carbon facilitated the incorporation of MXene and copper oxide inside the pores and also acted as a medium for charge transfer. In the Cu2O/ M/AC composite, MXene and Cu2O influence the sensingparameters, which were confirmed using electrochemical techniques such as cyclic voltammetry, electrochemical impedance spectroscopy, and amperometric analysis. The prepared composite shows two sets of linear ranges for glucose with a limit of detection (LOD) of 1.96 μM. The linear range was found to be 0.004 to 13.3 mM and 15.3 to 28.4 mM, with sensitivity values of 430.3 and 240.5 μA mM−1 cm−2, respectively. These materials suggest that the prepared Cu2O/M/AC nanocomposite can be utilized as a sensing material for non-enzymatic glucose sensors

The impact of law enforcement on dispensing antibiotics without prescription: a multi-methods study from Saudi Arabia

Background: Dispensing of antibiotics without a prescription (DAwP) has been widely practised among community pharmacies in Saudi Arabia despite being illegal. However, in May 2018, the law and regulations were enforced alongside fines. Consequently, we wanted to evaluate the impact of these changes. Methods: A study was conducted among 116 community pharmacies in two phases. A pre-law enforcement phase between December 2017 and March 2018 and a post-law enforcement phase one year later. Each phase consisted of a cross-sectional questionnaire-based survey and a simulated client method (SCM) approach. In the SCM, clients presented with either pharyngitis or urinary tract infections (UTI). In SCM, for each phase, all 116 pharmacies were visited with one of the scenarios. Results: Before the law enforcement, 70.7% of community pharmacists reported that DAwP was common with 96.6% and 87.7% of participating pharmacies dispensed antibiotics without a prescription for pharyngitis and UTI respectively. After the law enforcement, only 12.9% reported that DAwP is still a common practice, with only 12.1% and 5.2% dispensing antibiotics without prescriptions for pharyngitis and UTI respectively. Conclusion: law enforcement was effective. However, there is still further scope for improvement. This could include further educational activities with pharmacists, physicians and the public