Development of a MIP-Based QCM Sensor for Selective Detection of Penicillins in Aqueous Media

Pharmaceuticals wastes have been recognized as emerging pollutants to the environment. Among those, antibiotics in the aquatic environment are one of the major sources of concern, as chronic, low-dose exposure can lead to antibiotic resistance. Herein, we report on molecularly imprinted polymers (MIP) to recognize penicillin V potassium salt (PenV-K), penicillin G potassium salt (PenG-K), and amoxicillin sodium salt (Amo-Na), which belong to the most widespread group of antibiotics worldwide. Characterization and optimization led to two MIPs comprising methacrylic acid as the monomer and roughly 55% ethylene glycol dimethacrylate as the crosslinker. The obtained layers led to sensitive, selective, repeatable, and reusable sensor responses on quartz crystal microbalances (QCM). The LoD for PenV-K, PenG-K, and Amo-Na sensors are 0.25 mM, 0.30 mM, and 0.28 mM, respectively; imprinting factors reach at least around three. Furthermore, the sensors displayed relative selectivity factors of up to 50% among the three penicillins, which is appreciable given their structural similarity.

Poly(2-Hydroxyethyl methacrylate-co-N,N-dimethylacrylamide)-Coated Quartz Crystal Microbalance Sensor: Membrane Characterization and Proof of Concept

Application-oriented hydrogel properties can be obtained by modifying the synthesis conditions of the materials. The purpose of this study is to achieve customized properties for sensing applications of hydrogel membranes based on poly(2-hydroxyethyl methacrylate), HEMA and N,N-dimethylacrylamide, DMAa. Copolymer p(HEMA-co-DMAa) hydrogels were prepared by varying the DMAa monomer ratio from 0–100% in 20% increments. Hydrogel membranes were characterized by attenuated infrared spectroscopy. Swelling and sorption were evaluated using cation solutions. Copolymers were also synthesized on the gold surface of quartz crystal microbalances (QCM) as coating membranes. A proof of concept was conducted for approaching the design and development of QCM sensors based on P(DMAa-co-HEMA)-membranes. Results showed that the water and ion adsorption capacity of hydrogel membranes increased with higher DMAa content. Membranes are not selective to a specific location but did show different transport features with each cation. The QCM coated with the selected membrane presented linear relationships between resonance frequency and ions concentration in solution (10–120 ppm). As a consequence, hydrogel membranes obtained are promising for the development of future biosensing devices.

Polymer–Plasticizer Coatings for BTEX Detection Using Quartz Crystal Microbalance

Sensing films based on polymer–plasticizer coatings have been developed to detect volatile organic compounds (VOCs) in the atmosphere at low concentrations (ppm) using quartz crystal microbalances (QCMs). Of particular interest in this work are the VOCs benzene, ethylbenzene, and toluene which, along with xylene, are collectively referred to as BTEX. The combinations of four glassy polymers with five plasticizers were studied as prospective sensor films for this application, with PEMA-DINCH (5%) and PEMA-DIOA (5%) demonstrating optimal performance. This work shows how the sensitivity and selectivity of a glassy polymer film for BTEX detection can be altered by adding a precise amount and type of plasticizer. To quantify the film saturation dynamics and model the absorption of BTEX analyte molecules into the bulk of the sensing film, a diffusion study was performed in which the frequency–time curve obtained via QCM was correlated with gas-phase analyte composition and the infinite dilution partition coefficients of each constituent. The model was able to quantify the respective concentrations of each analyte from binary and ternary mixtures based on the difference in response time (τ) values using a single polymer–plasticizer film as opposed to the traditional approach of using a sensor array. This work presents a set of polymer–plasticizer coatings that can be used for detecting and quantifying the BTEX in air, and discusses the selection of an optimum film based on τ, infinite dilution partition coefficients, and stability over a period of time.

Measuring contamination levels in external induced atmosphere of Russian orbital stations and the Russian Segment of the International Space Station

In view of the increasing number of science experiments being carried out in the Russian Segment of the International Space Station, there is a growing interest in the state of the environment where they are conducted, especially, in the contaminating effects of the external induced contamination are firings of control as dust particles the outgassing system thrusters remaining on atmosphere. Sources of the induced atmosphere of non-metallic materials of the outer coatings, and exhausts the external of various venting systems, as well surfaces after launch from Earth, atmospheric aerosols and space dust. The paper presents results of quartz crystal microbalances molecular depositions measurements that were used for evaluating contamination in the induced atmosphere of the first Soviet orbital stations Salyut-7 and Mir, as well as modules Pirs and Poisk of the Russian Segment of the International Space Station. The results of the experiments show a significant effect of illumination and thermal conditions of the contamination source and the quartz microbalance sensor on the measurement results.

A Hairpin DNA-Based Piezoelectric E-Nose: Exploring the Performances of Heptamer Loops for the Detection of Volatile Organic Compounds

A hairpin DNA (hpDNA) piezoelectric gas sensors array with heptamer loops as sensing elements was designed, realized, and challenged with pure volatile organic compounds VOCs and real samples (beer). The virtual binding versus five chemical classes (alcohols, aldehydes, esters, hydrocarbons, and ketones) of the entire combinatorial library of heptamer loops (16,384 elements) was studied by molecular modelling. Six heptamer loops, having the largest variance in binding the chemical classes, were selected to build the array. The six gas sensors were realized by immobilizing onto gold nanoparticles (AuNPs) via a thiol spacer the hpDNA constituted by the heptamer loops and the same double helix stem of four base pairs (GAAG at 5′ and CTTC at 3′ end). The HpDNA-AuNP was used to modify the surface of 20 MHz quartz crystal microbalances (QCMs). The realized E-nose was able to clearly discriminate among 15 pure VOCs of different chemical classes, as demonstrated by hierarchical cluster analysis. The analysis of real beer samples during fermentation was also carried out. In such a challenging matrix consisting of 23 different VOCs, the hpDNA E-nose with heptamer loops was able to discriminate among different fermentation times with high success rate. Class assignment using the Bayes theorem gave an excellent 98% correct beer samples classification in cross-validation.

Studying the Bulk and Contour Ice Nucleation of Water Droplets via Quartz Crystal Microbalances

Due to the stochastic and time-dependent character of the ice embryo formation and growth (i.e., a process that can be analyzed statistically, but cannot be predicted precisely), the heterogeneous ice nucleation on atmospheric aerosols or macroscopic solid surfaces is still shrouded in mystery, regardless of the extremely active research and exponential progress within this scientific field. For instance, whether the icing appears from outside-in or inside-out is a subject of intense controversy, with practicability in designing passive icephobic coatings or improving the effectiveness of the cryopreservation technologies. Here, we propose an artful technique for quantitative analysis of the different modes of water freezing using super-nonwettable soot-coated quartz crystal microbalances (QCMs). To achieve this goal, a set of 5 MHz QCMs are loaded one at a time with a 50 μL droplet, whose bulk or contour solidification is detected in real-time. The obtained experimental results show that our sensor devices recognize explicitly if the ice nuclei form predominantly at the liquid–solid interface or spread along the droplet’s entire outer shell by triggering individual reproducible responses in terms of the direction of signal evolution in time. Our results may serve as a foundation for the future incorporation of QCM devices in different freezing assays, where gaining information about the ice adhesion forces and ice layer’s thickness is mandatory.

An Adaptive Measurement System for the Simultaneous Evaluation of Frequency Shift and Series Resistance of QCM in Liquid

In this paper, a novel measurement system based on Quartz Crystal Microbalances is presented. The proposed solution was conceived specifically to overcome the measurement problems related to Quartz Crystal Microbalance (QCM) applications in dielectric liquids where the Q-factor of the resonant system is severely reduced with respect to in-gas applications. The QCM is placed in a Meacham oscillator embedding an amplifier with adjustable gain, an automatic strategy for gain tuning allows for maintaining the oscillator frequency close to the series resonance frequency of the quartz, which is related in a simple way with the physical parameters of interest. The proposed system can be used to monitor simultaneously both the series resonant frequency and the equivalent electromechanical resistance of the quartz. The feasibility and the performance of the proposed method are proven by means of measurements obtained with a prototype based on a 10-MHz AT-cut quartz.