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In this study, multiple particle binding-liposomes (MPB-Lips), encapsulating the luminophore tris(2',2-bipyridyl)ruthenium (II) complex ([Ru(bpy)3]2+), were developed as an electrochemiluminescence (ECL) signal amplifier and were applied to detect the model analyte streptavidin (SA) using the indirect competitive ECL method. The MPB-Lips were prepared by mixing various ratios of two different liposomes-one containing a phospholipid with a primary amine group and a biotinyl group (BIO/NH2-Lip) and one containing a phospholipid with an N-hydroxysuccinimide group (NHS-Lip) to allow binding between particles via amide bonds. Quartz crystal microbalance analysis using SA-modified gold-coated quartz crystals showed that the frequency shift values of MPB-Lips gradually decreased in the order BIO/NH2-Lip:NHS-Lip = 1:0 < 1:1 < 1:3 < 1:5. This indicated that MPB-Lips were successfully formed. The indirect competitive ECL method using SA-modified gold electrodes showed that the 1:5-Lip system had greater sensitivity than the 1:0-Lip system-the limit of detection and quantification values for the systems were 1.84 and 6.30 µg mL-1 for 1:0-Lip, and 1.20 and 1.74 µg mL-1 for 1:5-Lip. Finally, the recovery of SA spiked in fetal bovine serum samples using the 1:5-Lip system showed good accuracy and precision with a recovery rate of 83-106% and relative standard deviation of 4-14%. Our study demonstrated that the MPB-Lips system was an effective and useful ECL amplifier and the ECL method using MPB-Lips could be applied to detect an analyte in a real sample.

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Cellulose nanofibrils (CNFs) from non-woody biomass, including citrus peel (CpCNFs), are promising naturally occurring nanomaterials; however, their properties depend on the composition of non-cellulosic components, including pectin. In this study, the effects of pectin modifications on CpCNFs were examined, including demethylesterification using alkaline treatment and enzymatic degradation of pectin using pectinase. CpCNFs could be redispersed in water with little aggregation after drying; however, the redispersibilities of both alkaline-treated (AT-CpCNFs) and pectinase-treated CpCNFs (PT-CpCNFs) were improved. Both AT-CpCNFs and PT-CpCNFs exhibited higher viscosity than untreated CpCNFs (UT-CpCNFs); redispersion in water after drying further increased the viscosity. A quartz crystal microbalance revealed that interactions between AT-CpCNFs were barely detectable, and interactions between PT-CpCNFs were stronger than those between UT-CpCNFs. The increase in the carboxylate groups of pectin due to demethylesterification in AT-CpCNF may have increased the viscosity and reduced the interactions between AT-CpCNFs, explaining the improved redispersibility. The increase in the viscosity of PT-CpCNFs may be attributed to the increased purity of CNFs, which is assumed to be more viscous than pectin. Our results show that the properties of CpCNFs are affected by the structure, properties, and content of pectin and can be controlled by pectin modification.

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A reflective surface plasmon resonance (SPR) sensor was evaluated for real-time monitoring of scale deposition. The sensor consists of an optical fiber, only 5 mm at the gold-coated tip of the sensing area. The effect of silica growth on the sensor response was evaluated using a Na2SiO3 solution. The sensitivity of the sensor to silica was 1.6 ± 0.3 nm per one immersion in the solution of 1000 mg/L (as SiO2) at 85 °C and subsequnt air drying, as indicated by the SPR peak shift. The amount of silica deposited on the gold surface was measured by the quartz crystal microbalance method, and the SPR sensitivity of 0.089 nm/ng to silica mass was obtained. The detection limit (3σ) of the SPR sensor was 17 ng, corresponding to a thickness of 2.5 nm for amorphous silica. The SPR sensor was tested in geothermal brine sampled at the Sumikawa Geothermal Power Plant, where a clear SPR shift was observed, suggesting the effectiveness of the SPR sensor for scale monitoring.

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This study presents and compares two methods for identifying the types of extracellular vesicles (EVs) from different cell lines. Through SDS-PAGE analysis, we discovered that the ratio of CD63 to CD81 in different EVs is consistent and distinct, making it a reliable characteristic for recognizing EVs secreted by cancer cells. However, the electrophoresis and imaging processes may introduce errors in the concentration values, especially at lower concentrations, rendering this method potentially less effective. An alternative approach involves the use of quartz crystal microbalance (QCM) and electroanalytical interdigitated electrode (IDT) biosensors for EV type identification and quantification. The QCM frequency shift caused by EVs is directly proportional to their concentration, while electroanalysis relies on measuring the curvature of the I-V curve as a distinguishing feature, which is also proportional to EV concentration. Linear regression lines for the QCM frequency shift and the electroanalysis curvature of various EV types are plotted separately, enabling the estimation of the corresponding concentration for an unknown EV type on the graphs. By intersecting the results from both biosensors, the unknown EV type can be identified. The biosensor analysis method proves to be an effective means of analyzing both the type and concentration of EVs from different cell lines.

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This article reports on a bioanalytical sensor device that hosts three different transducer principles: impedance spectroscopy, quartz-crystal microbalance with dissipation monitoring, and the thermal-current-based heat-transfer method. These principles utilize a single chip, allowing one to perform either microbalance and heat transfer measurements in parallel or heat transfer and impedance measurements. When taking specific precautions, the three measurement modalities can even be used truly simultaneously. The probed parameters are distinctly different, so that one may speak about multiparametric or "orthogonal" sensing without crosstalk between the sensing circuits. Hence, this sensor allows one to identify which of these label-free sensing principles performs best for a given bioanalytical application in terms of a high signal amplitude and signal-to-noise ratio. As a proof-of-concept, the three-parameter sensor was validated by studying the spontaneous, collective detachment of eukaryotic cells in the presence of a temperature gradient between the QCM chip and the supernatant liquid. In addition to heat transfer, detachment can also be monitored by the impedance- and QCM-related signals. These features allow for the distinguishing between different yeast strains that differ in their flocculation genes, and the sensor device enables proliferation monitoring of yeast colonies over time.

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Quartz Crystal Microbalances (QCMs) are versatile sensors employed in various fields, from environmental monitoring to biomedical applications, owing mainly to their very high sensitivity. However, the assessment of their metrological performance, including the impact of conditioning circuits, digital processing algorithms, and working conditions, is a complex and novel area of study. The purpose of this work is to investigate and understand the measurement errors associated with different QCM measurement techniques, specifically focusing on the influence of conditioning electronic circuits. Through a tailored and novel experimental setup, two measurement architectures-a Quartz Crystal Microbalance with dissipation monitoring (QCM-D) system and an oscillator-based QCM-R system-were compared under the same mechanical load conditions. Through rigorous experimentation and signal processing techniques, the study elucidated the complexities of accurately assessing QCM parameters, especially in liquid environments and under large mechanical loads. The comparison between the two different techniques allows for highlighting the critical aspects of the measurement techniques. The experimental results were discussed and interpreted based on models allowing for a deep understanding of the measurement problems encountered with QCM-based measurement systems. The performance of the different techniques was derived, showing that while the QCM-D technique exhibited higher accuracy, the QCM-R technique offered greater precision with a simpler design. This research advances our understanding of QCM-based measurements, providing insights for designing robust measurement systems adaptable to diverse conditions, thus enhancing their effectiveness in various applications.

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The misregulation of protein phosphatases is a key factor in the development of many human diseases, notably cancers. Here, based on a 100 MHz quartz crystal microbalance (QCM) biosensing platform, the dephosphorylation process of phosphopeptide (P-peptide) caused by protein tyrosine phosphatase 1B (PTP1B) was monitored in real time for the first time and PTP1B activity was assayed rapidly and sensitively. The QCM chip, coated with a gold (Au) film, was used to immobilized thiol-labeled single-stranded 5'-phosphate-DNAs (P-DNA) through Au-S bond. The P-peptide, specific to PTP1B, was then connected to the P-DNA via chelation between Zr4+ and phosphate groups. When PTP1B was injected into the QCM flow cell where the P-peptide/Zr4+/MCH/P-DNA/Au chip was placed, the P-peptide was dephosphorylated and released from the Au chip surface, resulting in an increase in the frequency of the QCM Au chip. This allowed the real-time monitoring of the P-peptide dephosphorylation process and sensitive detection of PTP1B activity within 6 min with a linear detection range of 0.01-100 pM and a detection limit of 0.008 pM. In addition, the maximum inhibitory ratios of inhibitors were evaluated using this proposed 100 MHz QCM biosensor. The developed 100 MHz QCM biosensing platform shows immense potential for early diagnosis of diseases related to protein phosphatases and the development of drugs targeting protein phosphatases.

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As one class of molecular imprinted polymers (MIPs), surface imprinted polymer (SIP)-based biosensors show great potential in direct whole-bacteria detection. Micro-contact imprinting, that involves stamping the template bacteria immobilized on a substrate into a pre-polymerized polymer matrix, is the most straightforward and prominent method to obtain SIP-based biosensors. However, the major drawbacks of the method arise from the requirement for fresh template bacteria and often non-reproducible bacteria distribution on the stamp substrate. Herein, we developed a positive master stamp containing photolithographic mimics of the template bacteria (E. coli) enabling reproducible fabrication of biomimetic SIP-based biosensors without the need for the "real" bacteria cells. By using atomic force and scanning electron microscopy imaging techniques, respectively, the E. coli-capturing ability of the SIP samples was tested, and compared with non-imprinted polymer (NIP)-based samples and control SIP samples, in which the cavity geometry does not match with E. coli cells. It was revealed that the presence of the biomimetic E. coli imprints with a specifically designed geometry increases the sensor E. coli-capturing ability by an "imprinting factor" of about 3. These findings show the importance of geometry-guided physical recognition in bacterial detection using SIP-based biosensors. In addition, this imprinting strategy was employed to interdigitated electrodes and QCM (quartz crystal microbalance) chips. E. coli detection performance of the sensors was demonstrated with electrochemical impedance spectroscopy (EIS) and QCM measurements with dissipation monitoring technique (QCM-D).

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In this study, a quartz crystal microbalance (QCM) aptasensor for carcinoembryonic antigen (CEA), a well-known biomarker for various cancer types, was reported, utilizing two different aptamers. To achieve this, a nanofilm of 4-mercaptophenyl was electrochemically attached to gold-coated QCM crystal surfaces via the reduction of 4-mercaptobenzenediazonium salt (4 MB-DAT) using cyclic voltammetry. Subsequently, gold nanoparticles (AuNP) were affixed to this structure, and then aptamers (antiCEA1 and antiCEA2) modified with SH-functional ends bound to AuNPs completed the modification. The analytical performance of the CEA sensor was evaluated through simultaneous QCM measurements employing CEA solutions ranging from 0.1 ng/mL to 25 ng/mL. The detection limit (LOD) for CEA was determined to be 102 pg/mL for antiCEA1 and 108 pg/mL for antiCEA2 aptamers. Interday and intraday precision and accuracy tests yielded maximum results of 4.3 and + 3.8, respectively, for both aptasensors, as measured by relative standard deviation (RSD%) and relative error (RE%). The kinetic data of the aptasensors resulted in affinity values (KD) of 0.43 ± 0.14 nM for antiCEA1 and 0.75 ± 0.42 nM for antiCEA2. These values were lower than the reported values of 3.9 nM and 37.8 nM for both aptamers, respectively. The selectivity of the aptasensor was evaluated by measuring the signal changes caused by alpha-fetoprotein (AFP), cancer antigen (CA-125), and vascular endothelial growth factor (VEGF-165) individually and together at a concentration of 500 ng/mL, resulting in a maximum 4.1 % change, which was comparable to precision and accuracy values reported in the literature. After confirming the selectivity of the aptamers, recovery experiments were conducted using spiked commercial serum samples to simulate real samples, and the lowest recovery value obtained was 95.4 %. It was determined that two different aptasensors could be successfully used for the QCM-based detection of CEA in this study.

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The interactions of viral fusion peptides from influenza (E4K and Ac-E4K) and human immunodeficiency virus (gp41 and Ac-gp41) with planar lipid bilayers and monolayers was investigated herein. A combination of surface-sensitive techniques, including quartz crystal microbalance with dissipation (QCM-D), Langmuir-Blodgett area-pressure isotherms with Micro-Brewster angle microscopy, and neutron reflectometry, was employed. Differences in the interactions of the viral fusion peptides with lipid bilayers featuring ordered and disordered phases, as well as lipid rafts, were revealed. The HIV fusion peptide (gp41) exhibited strong binding to the DOPC/DOPS bilayer, comprising a liquid disordered phase, with neutron reflectometry (NR) showing interaction with the bilayer's headgroup area. Conversely, negligible binding was observed with lipid bilayers in a liquid ordered phase. Notably, the influenza peptide (E4K) demonstrated slower binding kinetics with DOPC/DOPS bilayers and distinct interactions compared to gp41, as observed through QCM-D. This suggests different mechanisms of interaction with the lipid bilayers: one peptide interacts more within the headgroup region, while the other is more involved in transmembrane interactions. These findings hold implications for understanding viral fusion mechanisms and developing antimicrobials and antivirals targeting membrane interactions. The differential binding behaviours of the viral fusion peptides underscore the importance of considering membrane composition and properties in therapeutic strategy design.

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Covalent organic frameworks (COFs) are a novel family of porous crystalline materials utilized in various advanced applications. However, applying COFs as a hazardous organic acid gas sensor is substantial but still challenging. Herein, a phenylenediamine-based covalent organic framework (TPDA-TPB COF) featuring excellent crystallinity, ultrastable thermal stability, and high surface area was successfully constructed. Then, the TPDA-TPB COF-modified quartz crystal microbalance (QCM) sensor is fabricated by immobilizing the TPDA-TPB COF thin film on the gold-QCM chip. The fabricated TPDA-TPB COF-modified QCM sensor demonstrates a rapid response, excellent reproducibility, high selectivity, and sensitivity to formic gas, arising from hydrogen-bonding interactions between formic acid and the outermost layer of the TPDA-TPB COF, as determined by extensive analysis and density functional theory calculations. The basic sites of the TPDA-TPB COF, which are numerous due to its high nitrogen content, and the carboxylic acid groups present in formic acid exhibit efficient interactions. The sensitivity of the TPDA-TPB COF-modified QCM sensor was found to be 7.75 Hz ppm-1 at standard room temperature and pressure conditions, with a limit of detection (LOD) of formic acid down to 1.18 ppm, which is significantly below the workplace olfactory threshold limit of 5.0 ppm established by the Occupational Safety and Health Administration. The TPDA-TPB COF-modified QCM sensor exhibits remarkable detecting capabilities, making it highly attractive for detecting organic acid vapors in diverse applications that require superior performance.

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A fast and accurate identification of Listeria monocytogenes. A new quartz crystal microbalance (QCM) aptasensor was designed for the specific and rapid detection of L. monocytogenes. Before detection of the target bacterium from samples in the QCM aptasensor, a magnetic pre-enrichment system was used to eliminate any contaminant in the samples. The prepared magnetic system was characterized using ATR-FTIR, SEM, VSM, BET, and analytical methods. The saturation magnetization values of the Fe3O4, Fe3O4@PDA, and Fe3O4@PDA@DAPEG particles were 57.2, 40.8, and 36.4 emu/g, respectively. The same aptamer was also immobilized on the QCM crystal integrated into QCM flow cell and utilized to quantitatively detect L. monocytogenes cells from the samples. It was found that a specific aptamer-magnetic pre-concentration system efficiently captured L. monocytogenes cells in a short time (approximately 10 min). The Fe3O4@PDA@DA-PEG-Apt particles provided selective isolation of L. monocytogenes from the bacteria-spiked media up to 91.8%. The immobilized aptamer content of the magnetic particles was 5834 µg/g using 500 ng Apt/mL. The QCM aptasensor showed a very high range of analytical performance to the target bacterium from 1.0 × 102 and 1.0 × 107 CFU/mL. The limit of detection (LOD) and limit of quantitation (LOQ) were 148 and 448 CFU/mL, respectively, from the feeding of the QCM aptasensor flow cell with the eluent of the magnetic pre-concentration system. The reproducibility of the aptasensor was more than 95%. The aptasensor was very specific to L. monocytogenes compared to the other Listeria species (i.e., L. ivanovii, L. innocua, and L. seeligeri) or other tested bacteria such as Staphylococcus aureus, Escherichia coli, and Bacillus subtilis. The QCM aptasensor was regenerated with NaOH solution, and the system was reused many times.

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Research on pharmaceutical dry powders has been increasing worldwide, along with increased therapeutic strategies for an application through the pulmonary or the nasal routes. In vitro methodologies and tests that mimic the respiratory environment and the process of inhalation itself are, thus, essential. The literature frequently reports cell-based in vitro assays that involve testing the dry powders in suspension. This experimental setting is not adequate, as both the lung and the nasal cavity are devoid of abundant liquid. However, devices that permit powder insufflation over cells in culture are either scarce or technically complex and expensive, which is not feasible in early stages of research. In this context, this work proposes the development of a device that allows the delivery of dry powders onto cell surfaces, thus simulating inhalation more appropriately. Subsequently, a quartz crystal microbalance (QCM) was used to establish a technique enabling the determination of dry powder deposition profiles. Additionally, the determination of the viability of respiratory cells (A549) after the insufflation of a dry powder using the developed device was performed. In all, a prototype for dry powder insufflation was designed and developed, using 3D printing methods for its production. It allowed the homogenous dispersion of the insufflated powders over a petri dish and a QCM crystal, and a more detailed study on how dry powders disperse over the supports. The device, already protected by a patent, still requires further improvement, especially regarding the method for powder weighing and the efficiency of the insufflation process, which is being addressed. The impact of insufflation of air and of locust bean gum (LBG)-based microparticles revealed absence of cytotoxic effect, as cell viability roughly above 70 % was always determined.

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As a carcinogenic and highly neurotoxic hazardous gas, benzene vapor is particularly difficult to be distinguished in BTEX (benzene, toluene, ethylbenzene, xylene) atmosphere and be detected in low concentrations due to its chemical inertness. Herein, we develop a depth-related pore structure in Cu-TCPP-Cu to thermodynamically and kinetically enhance the adsorption of benzene vapor and realize the detection of ultralow-temperature benzene gas. We find that the in-plane π electronic nature and proper pore sizes in Cu-TCPP-Cu can selectively induce the adsorption and diffusion of BTEX. Interestingly, the theoretical calculations (including density functional theory (DFT) and grand canonical Monte Carlo (GCMC) simulations) exhibit that benzene molecules are preferred to adsorb and array as a consecutive arrangement mode in the Cu-TCPP-Cu pore, while the TEX (toluene, ethylbenzene, xylene) dominate the jumping arrangement model. The differences in distribution behaviors can allow adsorption and diffusion of more benzene molecules within limited room. Furthermore, the optimal pore-depth range (60-65 nm) of Cu-TCPP-Cu allows more exposure of active sites and hinders the gas-blocking process. The optimized sensor exhibits ultrahigh sensitivity to benzene vapor (155 Hz/µg@1 ppm), fast response time (less than 10 s), extremely low limit of detection (65 ppb), and excellent selectivity (83%). Our research thus provides a fundamental understanding to design and optimize two-dimensional metal-organic framework (MOF)-based gas sensors.

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Nucleic acid amplification reactions such as polymerase chain reaction (PCR), which uses a DNA polymerase to amplify individual double-stranded DNA fragments, are a useful technique for visualizing the presence of specific genomes. Although the fluorescent labeling method is mainly used with DNA amplification, other detection methods should be considered for further improvements, such as miniaturization and cost reduction, of reaction-monitoring devices. In this study, the quartz-crystal microbalance (QCM) method, which can measure nanogram-order masses, was applied for the real-time detection of DNA fragments in a solution with nucleic acids. This was combined with an isothermal nucleic acid amplification reaction based on the recombinase polymerase amplification (RPA) method, which allowed DNA amplification at a constant temperature. When the DNA amplification reaction was initiated on a QCM sensor plate with an immobilized primer DNA strand, a significant increase in mass was observed compared to when the primer DNA was not immobilized. QCM was shown to be sufficiently sensitive for the in situ detection of amplified DNA fragments. Combining a portable QCM device and RPA offers a sensitive point-of-care method for detecting nucleic acids.

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In this work, the development of a novel method for the detection of mercury (II) ions in wastewater using a mercury ion-imprinted polymer (IIP) combined with a quartz crystal microbalance (QCM) is described. The IIP was successfully synthesized via the polymerization of a of a novel fluorescein- and 2-aminophenol-functionalized methacrylic acid monomer, which was noted to have high binding affinity to mercury (II) ions. This polymer was subsequently coated on a QCM chip to create an IIP-QCM sensor. This sensor was established to have high selectivity and good sensitivity to mercury (II) ions, and had a limit of detection (LOD) of 14.17 ppb, a limit of quantification (LOQ) of 42.94 ppb, a signal-to-noise ratio (S/N) of 4.29, good repeatability, and a working range of 42.94 ppb to 2 ppm. The sensor was also able to analyze tap water and wastewater samples. The IIP-QCM is, therefore, promising as a highly selective, cost-effective, and rapid mercury ion sensor for applications involving the detection of mercury in wastewater.

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Dimethoate (DIM) as an organophosphorus pesticide is widely utilized especially in the cultivation of vegetables and fruits due to its killing effect on harmful insects. However, unconscious use of DIM in large amounts can also cause serious health problems. For these reasons, rapid and reliable detection of DIM from food samples is significant. In this study, a novel quartz crystal microbalance (QCM) sensor based on erbium molybdate incorporating sulfur-doped graphitic carbon nitride (EM/S-g-C3N4) and a molecularly imprinting polymer (MIP) was designed for DIM detection in apple juice samples. Firstly, an EM/S-g-C3N4 nanocomposite with high purity was prepared under hydrothermal conditions at high temperatures over a long period of time. After the modification of the EM/S-g-C3N4 nanocomposite on a QCM chip, the polymerization solution including N,N'-azobisisobutyronitrile (AIBN) as an initiator, ethylene glycol dimethacrylate (EGDMA) as a cross-linker, methacryloylamidoglutamic acid (MAGA) as a monomer, and DIM as an analyte was prepared. Then, the polymerization solution was dropped on an EM/S-g-C3N4 nanocomposite modified QCM chip and an ultraviolet polymerization process was applied for the formation of the DIM-imprinted polymers on the EM/S-g-C3N4 nanocomposite modified QCM chip. After the polymerization treatment, some characterization studies, including electrochemical, microscopic, and spectroscopic methods, were performed to illuminate the surface properties of the nanocomposite and the prepared QCM sensor. The values of the limit of quantification (LOQ) and the detection limit (LOD) of the prepared QCM sensor were as 1.0 × 10-9 M and 3.3 × 10-10 M, respectively. In addition, high selectivity, stability, reproducibility, and repeatability of the developed sensor was observed, providing highly reliable analysis results. Finally, thanks to the prepared sensor, it may be possible to detect pesticides from different food and environmental samples in the future.

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The interaction between anesthetic Isoflurane (Iso) and model-biomembrane on the water surface has been investigated using quartz crystal microbalance (QCM) and quartz crystal impedance (QCI) methods. The model-biomembranes used were dipalmitoyl phosphatidyl choline (DPPC), DPPC-palmitic acid (PA) mixture (DPPC:PA = 8:2), DPPC-Alamethicin (Al) mixture (DPPC:Al = 39:1), and DPPC-ß-Lactoglobulin (ßLG) mixture (DPPC:ßLG = 139:1) monolayers, respectively. The quartz crystal oscillator (QCO) was attached horizontally to each monolayer, and QCM and QCI measurements were performed simultaneously. It was found that Iso hydrate physisorbed on each monolayer/water interface from QCM and changed those interfacial viscosities from QCI. With an increase in Iso concentration, pure DPPC, DPPC-PA mixed, and DPPC-Al mixed monolayers showed a two-step process of Iso hydrate on both physisorption and viscosity, whereas it was a one-step for the DPPC-ßLG mixed monolayer. The viscosity change in the DPPC-ßLG mixed monolayer with the physisorption of Iso hydrate was much larger than that of other monolayers, in spite of the one-step process. From these results, the action mechanism of anesthetics and their relevance to the expression of anesthesia were discussed, based on the "release of interfacial hydrated water" hypothesis on the membrane/water interface.

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Degradation of cathode materials in lithium-ion batteries results in the presence of transition metal ions in the electrolyte, and these ions are known to play a major role in capacity fade and cell failure. Yet, while it is known that transition metal ions migrate from the metal oxide cathode and deposit on the graphite anode, their specific influence on anode reactions and structures, such as the solid electrolyte interphase (SEI), is still quite poorly understood due to the complexity in studying this interface in operational cells. In this work we combine operando electrochemical atomic force microscopy (EC-AFM), electrochemical quartz crystal microbalance (EQCM), and electrochemical impedance spectroscopy (EIS) measurements to probe the influence of a range of transition metal ions on the morphological, mechanical, chemical, and electrical properties of the SEI. By adding representative concentrations of Ni2+, Mn2+, and Co2+ ions into a commercially relevant battery electrolyte, the impacts of each on the formation and stability of the anode interface layer is revealed; all are shown to pose a threat to battery performance and stability. Mn2+, in particular, is shown to induce a thick, soft, and unstable SEI layer, which is known to cause severe degradation of batteries, while Co2+ and Ni2+ significantly impact interfacial conductivity. When transition metal ions are mixed, SEI degradation is amplified, suggesting a synergistic effect on the cell stability. Hence, by uncovering the roles these cathode degradation products play in operational batteries, we have provided a foundation upon which strategies to mitigate or eliminate these degradation products can be developed.

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Introducing ethylene glycol (EG) side chains to a conjugated polymer backbone is a well-established synthetic strategy for designing organic mixed ion-electron conductors (OMIECs). However, the impact that film swelling has on mixed conduction properties has yet to be scoped, particularly for electron-transporting (n-type) OMIECs. Here, the authors investigate the effect of the length of branched EG chains on mixed charge transport of n-type OMIECs based on a naphthalene-1,4,5,8-tetracarboxylic-diimide-bithiophene backbone. Atomic force microscopy (AFM), grazing-incidence wide-angle X-ray scattering (GIWAXS), and scanning tunneling microscopy (STM) are used to establish the similarities between the common-backbone films in dry conditions. Electrochemical quartz crystal microbalance with dissipation monitoring (EQCM-D) and in situ GIWAXS measurements reveal stark changes in film swelling properties and microstructure during electrochemical doping, depending on the side chain length. It is found that even in the loss of the crystallite content upon contact with the aqueous electrolyte, the films can effectively transport charges and that it is rather the high water content that harms the electronic interconnectivity within the OMIEC films. These results highlight the importance of controlling water uptake in the films to impede charge transport in n-type electrochemical devices.