Quartz Crystal Microbalance with Dissipation Monitoring: Enabling Real-Time Characterization of Biological Materials and Their Interactions

PubMed Central

Dixon, Matthew C.

2008-01-01

In recent years, there has been a rapid growth in the number of scientific reports in which the quartz crystal microbalance (QCM) technique has played a key role in elucidating various aspects of biological materials and their interactions. This article illustrates some key advances in the development of a special variation of this technique called quartz crystal microbalance with dissipation monitoring (QCM-D). The main feature and advantage of QCM-D, compared with the conventional QCM, is that it in addition to measuring changes in resonant frequency (Δf), a simultaneous parameter related to the energy loss or dissipation (ΔD) of the system is also measured. Δf essentially measures changes in the mass attached to the sensor surface, while ΔD measures properties related to the viscoelastic properties of the adlayer. Thus, QCM-D measures two totally independent properties of the adlayer. The focus of this review is an overview of the QCM-D technology and highlights of recent applications. Specifically, recent applications dealing with DNA, proteins, lipids, and cells will be detailed. This is not intended as a comprehensive review of all possible applications of the QCM-D technology, but rather a glimpse into a few highlighted application areas in the biomolecular field that were published in 2007. PMID:19137101

Polymer coated quartz crystal microbalance sensors for detection of volatile organic compounds in gas mixtures.

PubMed

Si, Pengchao; Mortensen, John; Komolov, Alexei; Denborg, Jens; Møller, Preben Juul

2007-08-06

By coating different conducting polymers of thiophene and its derivatives on quartz crystal microbalance (QCM) sensor surfaces, new novel QCM gas sensors have been produced in two simple ways, which could classify testing gas samples of volatile organic compounds (VOCs) gases. Principle components analysis (PCA) has been performed based on the QCM measurement results, which shows that our QCM sensors array has very good utilizing potential on sensing both polar and low-polar/nonpolar VOC gases. The sensitivity, selectivity, reproducibility and detection limit of QCM sensors have also been discussed. Quantitative variation of sensitivity response with the increasing concentration has been studied. (PLS) analysis and prediction of concentrations of single gas in mixtures have been carried out.

Utilisation of Quartz Crystal Microbalance Sensors with Dissipation (QCM-D) for a Clauss Fibrinogen Assay in Comparison with Common Coagulation Reference Methods.

PubMed

Oberfrank, Stephanie; Drechsel, Hartmut; Sinn, Stefan; Northoff, Hinnak; Gehring, Frank K

2016-02-24

The determination of fibrinogen levels is one of the most important coagulation measurements in medicine. It plays a crucial part in diagnostic and therapeutic decisions, often associated with time-critical conditions. The commonly used measurement is the Clauss fibrinogen assay (CFA) where plasma is activated by thrombin reagent and which is conducted by mechanical/turbidimetric devices. As quartz crystal microbalance sensors with dissipation (QCM-D) based devices have a small footprint, can be operated easily and allow measurements independently from sample transportation time, laboratory location, availability and opening hours, they offer a great opportunity to complement laboratory CFA measurements. Therefore, the objective of the work was to (1) transfer the CFA to the QCM-D method; (2) develop an easy, time- and cost-effective procedure and (3) compare the results with references. Different sensor coatings (donor's own plasma; gold surface) and different QCM-D parameters (frequency signal shift; its calculated turning point; dissipation signal shift) were sampled. The results demonstrate the suitability for a QCM-D-based CFA in physiological fibrinogen ranges. Results were obtained in less than 1 min and in very good agreement with a standardized reference (Merlin coagulometer). The results provide a good basis for further investigation and pave the way to a possible application of QCM-D in clinical and non-clinical routine in the medical field.

Utilisation of Quartz Crystal Microbalance Sensors with Dissipation (QCM-D) for a Clauss Fibrinogen Assay in Comparison with Common Coagulation Reference Methods

PubMed Central

Oberfrank, Stephanie; Drechsel, Hartmut; Sinn, Stefan; Northoff, Hinnak; Gehring, Frank K.

2016-01-01

The determination of fibrinogen levels is one of the most important coagulation measurements in medicine. It plays a crucial part in diagnostic and therapeutic decisions, often associated with time-critical conditions. The commonly used measurement is the Clauss fibrinogen assay (CFA) where plasma is activated by thrombin reagent and which is conducted by mechanical/turbidimetric devices. As quartz crystal microbalance sensors with dissipation (QCM-D) based devices have a small footprint, can be operated easily and allow measurements independently from sample transportation time, laboratory location, availability and opening hours, they offer a great opportunity to complement laboratory CFA measurements. Therefore, the objective of the work was to (1) transfer the CFA to the QCM-D method; (2) develop an easy, time- and cost-effective procedure and (3) compare the results with references. Different sensor coatings (donor’s own plasma; gold surface) and different QCM-D parameters (frequency signal shift; its calculated turning point; dissipation signal shift) were sampled. The results demonstrate the suitability for a QCM-D-based CFA in physiological fibrinogen ranges. Results were obtained in less than 1 min and in very good agreement with a standardized reference (Merlin coagulometer). The results provide a good basis for further investigation and pave the way to a possible application of QCM-D in clinical and non-clinical routine in the medical field. PMID:26927107

Highly sensitive quartz crystal microbalance based biosensor using Au dendrite structure

NASA Astrophysics Data System (ADS)

Asai, Naoto; Terasawa, Hideaki; Shimizu, Tomohiro; Shingubara, Shoso; Ito, Takeshi

2018-02-01

A Au dendrite structure was obtained by only electroplating under a suitable potential. A blanch like nanostructure was formed along the crystal orientation. In this study, we attempted to fabricate a Au dendrite structure on the electrode of a quartz crystal by electroplating to increase the specific surface area. We estimated the effective surface area by cyclic voltammetry (CV) and monitored the frequency shift induced by antigen-antibody interaction by the quartz crystal microbalance (QCM) method. The dendrite structure with the largest surface area was formed under -0.95 V for 5 min. In the measurement of the antigen-antibody interaction, the frequency shifts of 40, 80, and 110 Hz were obtained with the dendrite structured QCM chips formed at the above potential for 1, 1.5, and 2.0 min, respectively. The sensitivity was improved compared with that QCM chip having a flat surface electrode.

Respiratory monitoring by porphyrin modified quartz crystal microbalance sensors.

PubMed

Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

2011-01-01

A respiratory monitoring system based on a quartz crystal microbalance (QCM) sensor with a functional film was designed and investigated. Porphyrins 5,10,15,20-tetrakis-(4-sulfophenyl)-21H,23H-porphine (TSPP) and 5,10,15,20-tetrakis-(4-sulfophenyl)-21H, 23H-porphine manganese (III) chloride (MnTSPP) used as sensitive elements were assembled with a poly(diallyldimethyl ammonium chloride) (PDDA). Films were deposited on the QCM resonators using layer-by-layer method in order to develop the sensor. The developed system, in which the sensor response reflects lung movements, was able to track human respiration providing respiratory rate (RR) and respiratory pattern (RP). The sensor system was tested on healthy volunteers to compare RPs and calculate RRs. The operation principle of the proposed system is based on the fast adsorption/desorption behavior of water originated from human breath into the sensor films deposited on the QCM electrode.

A Noncontact Dibutyl Phthalate Sensor Based on a Wireless-Electrodeless QCM-D Modified with Nano-Structured Nickel Hydroxide.

PubMed

Chen, Daqi; Sun, Xiyang; Zhang, Kaihuan; Fan, Guokang; Wang, You; Li, Guang; Hu, Ruifen

2017-07-21

Dibutyl phthalate (DBP) is a widely used plasticizer which has been found to be a reproductive and developmental toxicant and ubiquitously existing in the air. A highly sensitive method for DBP monitoring in the environment is urgently needed. A DBP sensor based on a homemade wireless-electrodeless quartz crystal microbalance with dissipation (QCM-D) coated with nano-structured nickel hydroxide is presented. With the noncontact configuration, the sensing system could work at a higher resonance frequency (the 3rd overtone) and the response of the system was even more stable compared with a conventional quartz crystal microbalance (QCM). The sensor achieved a sensitivity of 7.3 Hz/ppb to DBP in a concentration range of 0.4-40 ppb and an ultra-low detection limit of 0.4 ppb of DBP has also been achieved.

Determination of isoelectric points and the role of pH for common quartz crystal microbalance sensors.

PubMed

Cuddy, Michael F; Poda, Aimee R; Brantley, Lauren N

2013-05-01

Isoelectric points (IEPs) were determined by the method of contact angle titration for five common quartz crystal microbalance (QCM) sensors. The isoelectric points range from mildly basic in the case of Al2O3 sensors (IEP = 8.7) to moderately acidic for Au (5.2) and SiO2 (3.9), to acidic for Ag (3.2) and Ti (2.9). In general, the values reported here are indicative of inherent surface oxides. A demonstration of the effect of the surface isoelectric point on the packing efficiency of thin mucin films is provided for gold and silica QCM sensors. It is determined that mucin layers on both substrates achieve a maximum and equal layer density of ∼3500 kg/m(3) at the corresponding IEP of either QCM sensor. This implies that mucin film packing is dependent upon short-range electrostatic interactions at the sensor surface.

Respiratory Monitoring by Porphyrin Modified Quartz Crystal Microbalance Sensors

PubMed Central

Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

2011-01-01

A respiratory monitoring system based on a quartz crystal microbalance (QCM) sensor with a functional film was designed and investigated. Porphyrins 5,10,15,20-tetrakis-(4-sulfophenyl)-21H,23H-porphine (TSPP) and 5,10,15,20-tetrakis-(4-sulfophenyl)-21H, 23H-porphine manganese (III) chloride (MnTSPP) used as sensitive elements were assembled with a poly(diallyldimethyl ammonium chloride) (PDDA). Films were deposited on the QCM resonators using layer-by-layer method in order to develop the sensor. The developed system, in which the sensor response reflects lung movements, was able to track human respiration providing respiratory rate (RR) and respiratory pattern (RP). The sensor system was tested on healthy volunteers to compare RPs and calculate RRs. The operation principle of the proposed system is based on the fast adsorption/desorption behavior of water originated from human breath into the sensor films deposited on the QCM electrode. PMID:22346621

A Noncontact Dibutyl Phthalate Sensor Based on a Wireless-Electrodeless QCM-D Modified with Nano-Structured Nickel Hydroxide

PubMed Central

Sun, Xiyang; Zhang, Kaihuan; Fan, Guokang; Wang, You; Li, Guang; Hu, Ruifen

2017-01-01

Dibutyl phthalate (DBP) is a widely used plasticizer which has been found to be a reproductive and developmental toxicant and ubiquitously existing in the air. A highly sensitive method for DBP monitoring in the environment is urgently needed. A DBP sensor based on a homemade wireless-electrodeless quartz crystal microbalance with dissipation (QCM-D) coated with nano-structured nickel hydroxide is presented. With the noncontact configuration, the sensing system could work at a higher resonance frequency (the 3rd overtone) and the response of the system was even more stable compared with a conventional quartz crystal microbalance (QCM). The sensor achieved a sensitivity of 7.3 Hz/ppb to DBP in a concentration range of 0.4–40 ppb and an ultra-low detection limit of 0.4 ppb of DBP has also been achieved. PMID:28753974

Small Business Innovations (Mass Microbalance)

NASA Technical Reports Server (NTRS)

1991-01-01

Femtometrics of Costa Mesa, CA, developed the Model 200-1 SAW Mass Microbalance under a NASA Small Business Innovation Research (SBIR) contract with Langley Research Center. The product is described as "the next generation of aerosol mass microbalance technology," because a new type of sensor, the Surface Acoustic Wave (SAW) piezoelectric crystal, offers mass resolution two orders of magnitude greater than the Quartz Crystal Microbalance cascade impactor (QCM) (used at Langley since 1979 for collection and measurement of aerosol particles in the upper atmosphere). The Model 200-1 SAW Mass Microbalance, which provides a 400-fold increase in mass sensitivity per unit area over the QCM, can be used for real-time particle monitoring in clean rooms, measuring chemical vapors in very low concentrations, measuring target chemicals in the stratosphere and in industry as a toxic vapor monitor.

A Study of Drop-Microstructured Surface Interactions during Dropwise Condensation with Quartz Crystal Microbalance

PubMed Central

Su, Junwei; Charmchi, Majid; Sun, Hongwei

2016-01-01

Dropwise condensation (DWC) on hydrophobic surfaces is attracting attention for its great potential in many industrial applications, such as steam power plants, water desalination, and de-icing of aerodynamic surfaces, to list a few. The direct dynamic characterization of liquid/solid interaction can significantly accelerate the progress toward a full understanding of the thermal and mass transport mechanisms during DWC processes. This work reports a novel Quartz Crystal Microbalance (QCM) based method that can quantitatively analyze the interaction between water droplets and micropillar surfaces during different condensation states such as filmwise, Wenzel, and partial Cassie states. A combined nanoimprinting lithography and chemical surface treatment approach was utilized to fabricate the micropillar based superhydrophobic and superhydrophilic surfaces on the QCM substrates. The normalized frequency shift of the QCM device together with the microscopic observation of the corresponding drop motion revealed the droplets growth and their coalescence processes and clearly demonstrated the differences between the three aforementioned condensation states. In addition, the transition between Cassie and Wenzel states was successfully captured by this method. The newly developed QCM system provides a valuable tool for the dynamic characterization of different condensation processes. PMID:27739452

Quartz Crystal Microbalance (QCM) monitor of contamination for LES-8/9

NASA Technical Reports Server (NTRS)

Lynch, J. T.

1977-01-01

A Quartz Crystal Microbalance (QCM) was used to monitor condensable contamination during the launching of two Lincoln Laboratory Experimental Satellites--LES-8 and LES-9. The QCM was installed on the dispenser truss and measured contamination by means of a frequency shift of a quartz crystal oscillator. By using a special crystal cut and a second reference quartz crystal, the sensor had extreme sensitivity and remarkable temperature independence. A 1-Hz frequency shift, which corresponds to 3.5 x 10 to the -9th power g/sq cm was resolved by the flight instrumentation.

Determination of functionalized gold nanoparticles incorporated in hydrophilic and hydrophobic microenvironments by surface modification of quartz crystal microbalance

NASA Astrophysics Data System (ADS)

Wu, Tsui-Hsun; Liao, Shu-Chuan; Chen, Ying-Fang; Huang, Yi-You; Wei, Yi-Syuan; Tu, Shu-Ju; Chen, Ko-Shao

2013-06-01

In this study, plasma deposition methods were used to immobilize Au electrode of a quartz crystal microbalance (QCM) to create different microenvironments for mass measurement of various modified Au nanoparticles (AuNPs). AuNPs were modified by 11-mercaptoundecanoic acid (MUA) and 1-decanethiol (DCT) for potential applications to drug release, protective coatings, and immunosensors. We aimed to develop a highly sensitive and reliable method to quantify the mass of various modified AuNPs. The surface of AuNPs and Au electrode was coated with polymer films, as determined by Fourier transform infrared spectroscopy and atomic force microscopy. Measurements obtained for various AuNPs and the plasma-treated surface of the Au electrode were compared with those obtained for an untreated Au electrode. According to the resonant frequency shift of QCM, a linear relationship was observed that significantly differed for AuNPs, MUA-AuNPs, and DCT-AuNPs (R2 range, 0.94-0.965, 0.934-0.972, and 0.874-0.9514, respectively). Compared to inductively coupled plasma and micro-computerized tomography, the QCM method with plasma treatment has advantages of real-time monitoring, greater sensitivity, and lower cost. Our results demonstrate that surface modifications measured by a QCM system for various modified AuNPs were reliable.

Accounting for unintended binding events in the analysis of quartz crystal microbalance kinetic data.

PubMed

Heller, Gabriella T; Zwang, Theodore J; Sarapata, Elizabeth A; Haber, Michael A; Sazinsky, Matthew H; Radunskaya, Ami E; Johal, Malkiat S

2014-05-01

Previous methods for analyzing protein-ligand binding events using the quartz crystal microbalance with dissipation monitoring (QCM-D) fail to account for unintended binding that inevitably occurs during surface measurements and obscure kinetic information. In this article, we present a system of differential equations that accounts for both reversible and irreversible unintended interactions. This model is tested on three protein-ligand systems, each of which has different features, to establish the feasibility of using the QCM-D for protein binding analysis. Based on this analysis, we were able to obtain kinetic information for the intended interaction that is consistent with those obtained in literature via bulk-phase methods. In the appendix, we include a method for decoupling these from the intended binding events and extracting relevant affinity information. Copyright © 2014 Elsevier B.V. All rights reserved.

Surface Modification Enhanced Reflection Intensity of Quartz Crystal Microbalance Sensors upon Molecular Adsorption.

PubMed

Kojima, Taisuke

2018-01-01

Molecular adsorption on a sensing surface involves molecule-substrate and molecule-molecule interactions. Combining optical systems and a quartz crystal microbalance (QCM) on the same sensing surface allows the quantification of such interactions and reveals the physicochemical properties of the adsorbed molecules. However, low sensitivity of the current reflection-based techniques compared to the QCM technique hinders the quantitative analysis of the adsorption events. Here, a layer-by-layer surface modification of a QCM sensor is studied to increase the optical sensitivity. The intermediate layers of organic-inorganic molecules and metal-metal oxide were explored on a gold (Au) surface of a QCM sensor. First, polyhedral oligomeric silsesquioxane-derivatives that served as the organic-inorganic intermediate layer were synthesized and modified on the Au-QCM surface. Meanwhile, titanium oxide, fabricated by anodic oxidation of titanium, was used as a metal-metal oxide intermediate layer on a titanium-coated QCM surface. The developed technique enabled interrogation of the molecular adsorption owing to the enhanced optical sensitivity.

An ultrasensitive micropillar-based quartz crystal microbalance device for real-time measurement of protein immobilization and protein-protein interaction.

PubMed

Su, Junwei; Esmaeilzadeh, Hamed; Zhang, Fang; Yu, Qing; Cernigliaro, George; Xu, Jin; Sun, Hongwei

2018-01-15

A new sensing device was developed to achieve ultrahigh sensitivity, by coupling polymer micropillars with a quartz crystal microbalance (QCM) substrate to form a two-degree- of-freedom resonance system (QCM-P). The sensitivity of these QCM-P devices was evaluated by measuring mass changes for both deposited gold film and adsorption of bovine serum albumin (BSA), respectively, on poly(methyl methacrylate) (PMMA) micropillar surfaces, as well as assessing ligand-analyte binding interactions between anti-human immunoglobulin G (anti-hIgG) and human immunoglobulin G (hIgG). The anti-hIgG and hIgG binding results show QCM-P achieved an eightfold improvement in sensitivity relative to conventional QCM sensors. In addition, the binding affinity obtained from the QCM-P device for anti-hIgG and hIgG proteins was found in good agreement with that measured by surface plasmon resonance (SPR) for the same binding reaction. Copyright © 2017 Elsevier B.V. All rights reserved.

Ultrasensitive quartz crystal microbalance sensors for detection of M13-Phages in liquids.

PubMed

Uttenthaler, E; Schräml, M; Mandel, J; Drost, S

2001-12-01

Quartz crystal microbalance (QCM) sensors are widely used for determining liquid properties or probing interfacial processes. For some applications the sensitivity of the QCM sensors typically used (5-20 MHz) is limited compared with other biosensor methods. In this study ultrasensitive QCM sensors with resonant frequencies from 39 to 110 MHz for measurements in the liquid phase are presented. The fundamental sensor effect of a QCM is the decrease of the resonant frequency of an oscillating quartz crystal due to the binding of mass on a coated surface during the measurement. The sensitivity of QCM sensors increases strongly with an increasing resonant frequency and, therefore, with a decreasing thickness of the sensitive area. The new kind of ultrasensitive QCM sensors used in this study is based on chemically milled shear mode quartz crystals which are etched only in the center of the blank, forming a thin quartz membrane with a thick, mechanically stable outer ring. An immunoassay using a virus specific monoclonal antibody and a M13-Phage showed an increase in the signal to noise ratio by a factor of more than 6 for 56 MHz quartz crystals compared with standard 19 MHz quartz crystals, the detection limit was improved by a factor of 200. Probing of acoustic properties of glycerol/water mixtures resulted in an increase in sensitivity, which is in very good agreement with theory. Chemically milled QCM sensors strongly improve the sensitivity in biosensing and probing of acoustic properties and, therefore, offer interesting new application fields for QCM sensors.

In-Line Measurement of Water Contents in Ethanol Using a Zeolite-Coated Quartz Crystal Microbalance

PubMed Central

Kim, Byoung Chul; Yamamoto, Takuji; Kim, Young Han

2015-01-01

A quartz crystal microbalance (QCM) was utilized to measure the water content in ethanol. For the improvement of measurement sensitivity, the QCM was modified by applying zeolite particles on the surface with poly(methyl methacrylate) (PMMA) binder. The measurement performance was examined with ethanol of 1% to 5% water content in circulation. The experimental results showed that the frequency drop of the QCM was related with the water content though there was some deviation. The sensitivity of the zeolite-coated QCM was sufficient to be implemented in water content determination, and a higher ratio of silicon to aluminum in the molecular structure of the zeolite gave better performance. The coated surface was inspected by microscopy to show the distribution of zeolite particles and PMMA spread. PMID:26516859

Material Outgassing, Identification and Deposition, MOLIDEP System

NASA Technical Reports Server (NTRS)

Scialdone, John J.; Montoya, Alex F.

2002-01-01

The outgassing tests are performed employing a modified vacuum operated Cahn analytical microbalance, identified as the MOLIDEP system. The test measures under high vacuum, the time varying Molecular mass loss of a material sample held at a chosen temperature; it Identifies the outgassing molecular components using an inline SRS 300 amu Residual Gas Analyzer (RGA) and employs a temperature controlled 10 MHz Quartz Crystal Microbalance (QCM) to measure the condensable DEPosits. Both the QCM and the RGA intercept within the conductive passage the outgassing products being evacuated by a turbomolecular pump. The continuous measurements of the mass loss, the rate of loss, the sample temperature, the rate of temperature change, the QCM temperature and the QCM recorded condensable deposits or rate of deposits are saved to an Excel spreadsheet. A separate computer controls the RGA.

Prototypes of newly conceived inorganic and biological sensors for health and environmental applications.

PubMed

Nicolini, Claudio; Adami, Manuela; Sartore, Marco; Bragazzi, Nicola Luigi; Bavastrello, Valter; Spera, Rosanna; Pechkova, Eugenia

2012-12-12

This paper describes the optimal implementation of three newly conceived sensors for both health and environmental applications, utilizing a wide range of detection methods and complex nanocomposites. The first one is inorganic and based on matrices of calcium oxide, the second is based on protein arrays and a third one is based on Langmuir-Blodgett laccase multi-layers. Special attention was paid to detecting substances significant to the environment (such as carbon dioxide) and medicine (drug administration, cancer diagnosis and prognosis) by means of amperometric, quartz crystal microbalance with frequency (QCM_F) and quartz crystal microbalance with dissipation monitoring (QCM_D) technologies. The resulting three implemented nanosensors are described here along with proofs of principle and their corresponding applications.

Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

PubMed Central

Kusakawa, You

2017-01-01

Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

Quartz crystal microbalance (QCM) as biosensor for the detecting of Escherichia coli O157:H7

NASA Astrophysics Data System (ADS)

Thanh Ngo, Vo Ke; Giang Nguyen, Dang; Phuong Uyen Nguyen, Hoang; Tran, Van Man; Nguyen, Thi Khoa My; Phat Huynh, Trong; Lam, Quang Vinh; Dat Huynh, Thanh; Truong, Thi Ngoc Lien

2014-12-01

Although Escherichia coli (E. coli) is a commensalism organism in the intestine of humans and warm-blooded animals, it can be toxic at higher density and causes diseases, especially the highly toxic E. coli O157:H7. In this paper a quartz crystal microbalance (QCM) biosensor was developed for the detection of E. coli O157:H7 bacteria. The anti-E. coli O157:H7 antibodies were immobilized on a self-assembly monolayer (SAM) modified 5 MHz AT-cut quartz crystal resonator. The SAMs were activated with 16-mercaptopropanoic acid, in the presence of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and ester N-hydroxysuccinimide (NHS). The result of changing frequency due to the adsorption of E. coli O157:H7 was measured by the QCM biosensor system designed and fabricated by ICDREC-VNUHCM. This system gave good results in the range of 102-107 CFU mL-1 E. coli O157:H7. The time of bacteria E. coli O157:H7 detection in the sample was about 50 m. Besides, QCM biosensor from SAM method was comparable to protein A method-based piezoelectric immunosensor in terms of the amount of immobilized antibodies and detection sensitivity.

Dependence of Fuel Properties During Blending of Iso-Paraffinic Kerosene and Petroleum-Derived Jet Fuel

DTIC Science & Technology

2008-11-01

36 3.4. Thermal Stability via QCM ...37 Figure 14. Diagram of the Quartz Crystal Microbalance ( QCM ) apparatus. ............................... 39 vi Figure 15. QCM profile of...F4909, F3166 and F4919 at 140°C with air headspace. .................... 41 Figure 16. QCM profile of F4909, F3602, and F4917 at 140°C with air headspace

Fabrication of a Quartz-Crystal-Microbalance/Surface-Plasmon-Resonance Hybrid Sensor and Its Use for Detection of Polymer Thin-Film Deposition and Evaluation of Moisture Sorption Phenomena

NASA Astrophysics Data System (ADS)

Shinbo, Kazunari; Ishikawa, Hiroshi; Baba, Akira; Ohdaira, Yasuo; Kato, Keizo; Kaneko, Futao

2012-03-01

We fabricated a hybrid sensor utilizing quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) spectroscopy. We confirmed its effectiveness by observing QCM frequency shifts and SPR wavelength changes for two processes: deposition of various transparent polymer thin films and moisture sorption. For thin-film deposition, the relationship between the QCM frequency and SPR wavelength was found to depend on the refractive index of the film material. For moisture sorption, the direction of SPR wavelength shift depended on the film thickness. This was estimated to be caused by film swelling and decrease in refractive index induced by moisture.

Fabrication of a Quartz-Crystal-Microbalance/Optical-Waveguide Hybrid Sensor and In situ Evaluation of Vacuum-Evaporated Lead Phthalocyanine Thin Film

NASA Astrophysics Data System (ADS)

Shinbo, Kazunari; Uno, Akihiro; Hirakawa, Ryo; Baba, Akira; Ohdaira, Yasuo; Kato, Keizo; Kaneko, Futao

2013-05-01

In this study, we fabricated a novel quartz-crystal-microbalance (QCM)/optical-waveguide hybrid sensor. An in situ observation of a lead phthalocyanine (PbPc) thin-film deposition was conducted during vacuum evaporation, and the effectiveness of the sensor was demonstrated. The film thickness was obtained from the QCM frequency, and the optical absorption of the film was observed by optical waveguide spectroscopy using part of the QCM substrate without the electrode. The film absorption depends on the polarization direction, substrate temperature and deposition rate, owing to aggregate formation. The thickness dependence of the absorption property was also investigated.

Probing the interaction between nanoparticles and lipid membranes by quartz crystal microbalance with dissipation monitoring

NASA Astrophysics Data System (ADS)

Yousefi, Nariman; Tufenkji, Nathalie

2016-12-01

There is increasing interest in using quartz crystal microbalance with dissipation monitoring (QCM-D) to investigate the interaction of nanoparticles (NPs) with model surfaces. The high sensitivity, ease of use and the ability to monitor interactions in real-time has made it a popular technique for colloid chemists, biologists, bioengineers and biophysicists. QCM-D has been recently used to probe the interaction of NPs with supported lipid bilayers (SLBs) as model cell membranes. The interaction of NPs with SLBs is highly influenced by the quality of the lipid bilayers. Unlike many surface sensitive techniques, using QCM-D, the quality of SLBs can be assessed in real-time, hence QCM-D studies on SLB-NP interactions are less prone to the artefacts arising from bilayers that are not well formed. The ease of use and commercial availability of a wide range of sensor surfaces also have made QCM-D a versatile tool for studying NP interactions with lipid bilayers. In this review, we summarize the state-of-the-art on QCM-D based techniques for probing the interactions of NPs with lipid bilayers.

SHORT COMMUNICATION: Recognition of supercooled dew in a quartz crystal microbalance dew-point sensor by slip phenomena

NASA Astrophysics Data System (ADS)

Kwon, Su-Yong; Kim, Jong-Chul; Choi, Byung-Il

2007-10-01

Distinguishing between a supercooled dew and frost below 0 °C in dew/frost-point measurements is an important and challenging problem that has not yet been completely solved. This study presents a new method for the recognition of a supercooled dew in a dew/frost-point sensor. A quartz crystal microbalance (QCM) sensor was used as a dew/frost-point sensor to detect a dew and a supercooled dew as well as frost. The slip phenomenon occurring at an interface between the water droplet and the surface of the quartz crystal resonator of the QCM sensor gives a simple and accurate way of distinguishing between a supercooled dew and frost below 0 °C. This method can give a highly accurate measurement of the dew or the frost point without misreading in the dew-point sensor at temperatures below 0 °C.

Mucoadhesion vs mucus permeability of thiolated chitosan polymers and their resulting nanoparticles using a quartz crystal microbalance with dissipation (QCM-D).

PubMed

Oh, Sejin; Borrós, Salvador

2016-11-01

The aim of this present study was to evaluate the combination properties between mucoadhesion/mucus permeability of thiolated chitosans (TC) and their resulting nanoparticles using a quartz crystal microbalance with dissipation (QCM-D). The QCM-D experiments were conducted at pH 4 or 6.8 to assess the interaction between thiolated polymers, with low (TCL), medium (TCM) and high (TCH) contents of free thiol groups, and native porcine gastric mucin (NPGM). TCL was chosen for further carriers as it showed higher permeability into the NPGM layer compared to TCM and TCH. In this study, we describe a formulation of a novel carrier comprised by positively charged TCL, negatively charged DNA and degradable oligopeptide-modified poly(β-amino ester)s (PBAEs), which were employed in order to approach for tuning particle size and surface charge of complexes. TCL/PBAE complexes with or without DNA were characterized using dynamic light scattering. Mechanism of adsorption or permeation of the TCL/PBAE/DNA complexes into the NPGM barrier was investigated with QCM-D, which is a highly sensitive technique for studying nanomechanical (viscoelastic) changes of the substrates. This work might provide that the QCM-D technique would be a promising method to monitor the dynamic behaviour between complexes and NPGM. Copyright © 2016 Elsevier B.V. All rights reserved.

Investigating calcite growth rates using a quartz crystal microbalance with dissipation (QCM-D)

NASA Astrophysics Data System (ADS)

Cao, Bo; Stack, Andrew G.; Steefel, Carl I.; DePaolo, Donald J.; Lammers, Laura N.; Hu, Yandi

2018-02-01

Calcite precipitation plays a significant role in processes such as geological carbon sequestration and toxic metal sequestration and, yet, the rates and mechanisms of calcite growth under close to equilibrium conditions are far from well understood. In this study, a quartz crystal microbalance with dissipation (QCM-D) was used for the first time to measure macroscopic calcite growth rates. Calcite seed crystals were first nucleated and grown on sensors, then growth rates of calcite seed crystals were measured in real-time under close to equilibrium conditions (saturation index, SI = log ({Ca2+}/{CO32-}/Ksp) = 0.01-0.7, where {i} represent ion activities and Ksp = 10-8.48 is the calcite thermodynamic solubility constant). At the end of the experiments, total masses of calcite crystals on sensors measured by QCM-D and inductively coupled plasma mass spectrometry (ICP-MS) were consistent, validating the QCM-D measurements. Calcite growth rates measured by QCM-D were compared with reported macroscopic growth rates measured with auto-titration, ICP-MS, and microbalance. Calcite growth rates measured by QCM-D were also compared with microscopic growth rates measured by atomic force microscopy (AFM) and with rates predicted by two process-based crystal growth models. The discrepancies in growth rates among AFM measurements and model predictions appear to mainly arise from differences in step densities, and the step velocities were consistent among the AFM measurements as well as with both model predictions. Using the predicted steady-state step velocity and the measured step densities, both models predict well the growth rates measured using QCM-D and AFM. This study provides valuable insights into the effects of reactive site densities on calcite growth rate, which may help design future growth models to predict transient-state step densities.

Quartz-Crystal Microbalance (QCM) for Public Health: An Overview of Its Applications.

PubMed

Bragazzi, Nicola Luigi; Amicizia, Daniela; Panatto, Donatella; Tramalloni, Daniela; Valle, Ivana; Gasparini, Roberto

2015-01-01

Nanobiotechnologies, from the convergence of nanotechnology and molecular biology and postgenomics medicine, play a major role in the field of public health. This overview summarizes the potentiality of piezoelectric sensors, and in particular, of quartz-crystal microbalance (QCM), a physical nanogram-sensitive device. QCM enables the rapid, real time, on-site detection of pathogens with an enormous burden in public health, such as influenza and other respiratory viruses, hepatitis B virus (HBV), and drug-resistant bacteria, among others. Further, it allows to detect food allergens, food-borne pathogens, such as Escherichia coli and Salmonella typhimurium, and food chemical contaminants, as well as water-borne microorganisms and environmental contaminants. Moreover, QCM holds promises in early cancer detection and screening of new antiblastic drugs. Applications for monitoring biohazards, for assuring homeland security, and preventing bioterrorism are also discussed. © 2015 Elsevier Inc. All rights reserved.

Preparation of a molecularly imprinted sensor based on quartz crystal microbalance for specific recognition of sialic acid in human urine.

PubMed

Qiu, Xiuzhen; Xu, Xian-Yan; Chen, Xuncai; Wu, Yiyong; Guo, Huishi

2018-05-08

A novel molecularly imprinted quartz crystal microbalance (QCM) sensor was successfully prepared for selective determination of sialic acid (SA) in human urine samples. To obtain the QCM sensor, we first modified the gold surface of the QCM chip by self-assembling of allylmercaptane to introduce polymerizable double bonds on the chip surface. Then, SA molecularly imprinted polymer (MIP) nanofilm was attached to the modified QCM chip surface. For comparison, we have also characterized the nonmodified and improved surfaces of the QCM sensor by using atomic force microscopy (AFM) and Fourier transform infrared (FTIR) spectroscopy. We then tested the selectivity and detection limit of the imprinted QCM sensor via a series of adsorption experiments. The results show a linear response in the range of 0.025-0.50 μmol L -1 for sialic acid. Moreover, the limit of detection (LOD) of the prepared imprinted QCM sensor was found to be 1.0 nmol L -1 for sialic acid, and high recovery values range from 87.6 to 108.5% with RSD < 8.7 (n = 5) for the spiked urine sample obtained. Overall, this work presents how a novel QCM sensor was developed and used to detect sialic acid in human urine samples. Graphical abstract Specific recognition of sialic acid by the MIP-QCM sensor system.

New Approach to a Practical Quartz Crystal Microbalance Sensor Utilizing an Inkjet Printing System

PubMed Central

Fuchiwaki, Yusuke; Tanaka, Masato; Makita, Yoji; Ooie, Toshihiko

2014-01-01

The present work demonstrates a valuable approach to developing quartz crystal microbalance (QCM) sensor units inexpensively for reliable determination of analytes. This QCM sensor unit is constructed by inkjet printing equipment utilizing background noise removal techniques. Inkjet printing equipment was chosen as an alternative to an injection pump in conventional flow-mode systems to facilitate the commercial applicability of these practical devices. The results demonstrate minimization of fluctuations from external influences, determination of antigen-antibody interactions in an inkjet deposition, and quantification of C-reactive protein in the range of 50–1000 ng(x000B7)mL−1. We thus demonstrate a marketable application of an inexpensive and easily available QCM sensor system. PMID:25360577

C-Axis-Oriented Hydroxyapatite Film Grown Using ZnO Buffer Layer

NASA Astrophysics Data System (ADS)

Sakoishi, Yasuhiro; Iguchi, Ryo; Nishikawa, Hiroaki; Hontsu, Shigeki; Hayami, Takashi; Kusunoki, Masanobu

2013-11-01

A method of fabricating c-axis-oriented hydroxyapatite film on a quartz crystal microbalance (QCM) sensor was investigated. ZnO was used as a template to obtain a hexagonal hydroxyapatite crystal of uniaxial orientation. The ZnO was grown as a c-axis film on a Au/quartz with the surface structure of a QCM sensor. Under optimized conditions, hydroxyapatite was deposited by pulsed laser deposition. X-ray diffraction showed the hydroxyapatite film to be oriented along the c-axis. Because Au and ZnO are applied to many devices, the anisotropic properties of hydroxyapatite may be incorporated into these devices as well as QCM sensors.

Scanning tunneling microscope-quartz crystal microbalance study of temperature gradients at an asperity contact.

PubMed

Pan, L; Krim, J

2013-01-01

Investigations of atomic-scale friction frequently involve setups where a tip and substrate are initially at different temperatures. The temperature of the sliding interface upon contact has thus become a topic of interest. A method for detecting initial tip-sample temperature differences at an asperity contact is described, which consists of a scanning tunneling microscope (STM) tip in contact with the surface electrode of a quartz crystal microbalance (QCM). The technique makes use of the fact that a QCM is extremely sensitive to abrupt changes in temperature. In order to demonstrate the technique's capabilities, QCM frequency shifts were recorded for varying initial tip-substrate temperature differences as an STM tip was brought into and out of contact. The results are interpreted within the context of a recent model for thermal heat conduction at an asperity contact, and it is concluded that the transient frequency response is attributable to small changes in temperature close to the region of contact rather than a change in the overall temperature of the QCM itself. For the assumed model parameters, the results moreover reveal substantial temperature discontinuities at the boundary between the tip and the sample, for example, on the order of 10-15 °C for initial temperature differences of 20 °C.

Study of quartz crystal microbalance NO2 sensor coated with sputtered indium tin oxide film

NASA Astrophysics Data System (ADS)

Georgieva, V.; Aleksandrova, M.; Stefanov, P.; Grechnikov, A.; Gadjanova, V.; Dilova, T.; Angelov, Ts

2014-12-01

A study of NO2 gas sorption ability of thin indium tin oxide (ITO) deposited on 16 MHz quartz crystal microbalance (QCM) is presented. ITO films are grown by RF sputtering of indium/tin target with weight proportion 95:5 in oxygen environment. The ITO films have been characterized by X-ray photoelectron spectroscopy measurements. The ITO surface composition in atomic % is defined to be: In-40.6%, Sn-4.3% and O-55%. The thickness and refractive index of the films are determined by ellipsometric method. The frequency shift of QCM-ITO is measured at different NO2 concentrations. The QCM-ITO system becomes sensitive at NO2 concentration >= 500 ppm. The sorbed mass for each concentration is calculated according the Sauerbrey equation. The results indicated that the 1.09 ng of the gas is sorbed into 150 nm thick ITO film at 500 ppm NO2 concentration. When the NO2 concentration increases 10 times the calculated loaded mass is 5.46 ng. The sorption process of the gas molecules is defined as reversible. The velocity of sorbtion /desorption processes are studied, too. The QCM coated with thin ITO films can be successfully used as gas sensors for detecting NO2 in the air at room temperature.

Scanning tunneling microscope-quartz crystal microbalance study of temperature gradients at an asperity contact

NASA Astrophysics Data System (ADS)

Pan, L.; Krim, J.

2013-01-01

Investigations of atomic-scale friction frequently involve setups where a tip and substrate are initially at different temperatures. The temperature of the sliding interface upon contact has thus become a topic of interest. A method for detecting initial tip-sample temperature differences at an asperity contact is described, which consists of a scanning tunneling microscope (STM) tip in contact with the surface electrode of a quartz crystal microbalance (QCM). The technique makes use of the fact that a QCM is extremely sensitive to abrupt changes in temperature. In order to demonstrate the technique's capabilities, QCM frequency shifts were recorded for varying initial tip-substrate temperature differences as an STM tip was brought into and out of contact. The results are interpreted within the context of a recent model for thermal heat conduction at an asperity contact, and it is concluded that the transient frequency response is attributable to small changes in temperature close to the region of contact rather than a change in the overall temperature of the QCM itself. For the assumed model parameters, the results moreover reveal substantial temperature discontinuities at the boundary between the tip and the sample, for example, on the order of 10-15 °C for initial temperature differences of 20 °C.

Sensing Properties of GO and Amine-Silica Nanoparticles Functionalized QCM Sensors for Detection of Formaldehyde

NASA Astrophysics Data System (ADS)

Wang, Zhenqiang; Yang, Mingqing; He, Junhui

2014-12-01

In the current work, graphene oxides (GO) and Amine-Functionalized Silica Nanoparticles (NH2-SNs) were used as sensing layer on quart crystal microbalance (QCM) for detection of HCHO gas. The GO and NH2-SNs functionalized QCM resonators all had a significant response to HCHO gas. The sensitivity of GO functionalized QCM resonator is 0.04 Hz/(μgṡppm), which is four times as high as that of NH2-SNs functionalized QCM resonator (0.01 Hz/(μgṡppm)). The GO functionalized QCM resonators would be of benefit in area of environmental applications.

Probing the Interaction between Nanoparticles and Lipid Membranes by Quartz Crystal Microbalance with Dissipation Monitoring

PubMed Central

Yousefi, Nariman; Tufenkji, Nathalie

2016-01-01

There is increasing interest in using quartz crystal microbalance with dissipation monitoring (QCM-D) to investigate the interaction of nanoparticles (NPs) with model surfaces. The high sensitivity, ease of use and the ability to monitor interactions in real-time has made it a popular technique for colloid chemists, biologists, bioengineers, and biophysicists. QCM-D has been recently used to probe the interaction of NPs with supported lipid bilayers (SLBs) as model cell membranes. The interaction of NPs with SLBs is highly influenced by the quality of the lipid bilayers. Unlike many surface sensitive techniques, by using QCM-D, the quality of SLBs can be assessed in real-time, hence QCM-D studies on SLB-NP interactions are less prone to the artifacts arising from bilayers that are not well formed. The ease of use and commercial availability of a wide range of sensor surfaces also have made QCM-D a versatile tool for studying NP interactions with lipid bilayers. In this review, we summarize the state-of-the-art on QCM-D based techniques for probing the interactions of NPs with lipid bilayers. PMID:27995125

Development of a Flow Injection Based High Frequency Dual Channel Quartz Crystal Microbalance

PubMed Central

Liang, Jinxing; Zhang, Jing; Zhou, Wenxiang; Ueda, Toshitsugu

2017-01-01

When the quartz crystal microbalance (QCM) is used in liquid for adsorption or desorption monitoring based bio- or chemical sensing applications, the frequency shift is not only determined by the surface mass change, but also by the change of liquid characteristics, such as density and viscosity, which are greatly affected by the liquid environmental temperature. A monolithic dual-channel QCM is designed and fabricated by arranging two QCM resonators on one single chip for cancelling the fluctuation induced by environmental factors. In actual applications, one QCM works as a specific sensor by modifying with functional membranes and the other acts as a reference, only measuring the liquid property. The dual-channel QCM is designed with an inverted-mesa structure, aiming to realize a high frequency miniaturized chip and suppress the frequency interference between the neighbored QCM resonators. The key problem of dual-channel QCMs is the interference between two channels, which is influenced by the distance of adjacent resonators. The diameter of the reference electrode has been designed into several values in order to find the optimal parameter. Experimental results demonstrated that the two QCMs could vibrate individually and the output frequency stability and drift can be greatly improved with the aid of the reference QCM. PMID:28509851

Molecular Imprinting Technology in Quartz Crystal Microbalance (QCM) Sensors.

PubMed

Emir Diltemiz, Sibel; Keçili, Rüstem; Ersöz, Arzu; Say, Rıdvan

2017-02-24

Molecularly imprinted polymers (MIPs) as artificial antibodies have received considerable scientific attention in the past years in the field of (bio)sensors since they have unique features that distinguish them from natural antibodies such as robustness, multiple binding sites, low cost, facile preparation and high stability under extreme operation conditions (higher pH and temperature values, etc.). On the other hand, the Quartz Crystal Microbalance (QCM) is an analytical tool based on the measurement of small mass changes on the sensor surface. QCM sensors are practical and convenient monitoring tools because of their specificity, sensitivity, high accuracy, stability and reproducibility. QCM devices are highly suitable for converting the recognition process achieved using MIP-based memories into a sensor signal. Therefore, the combination of a QCM and MIPs as synthetic receptors enhances the sensitivity through MIP process-based multiplexed binding sites using size, 3D-shape and chemical function having molecular memories of the prepared sensor system toward the target compound to be detected. This review aims to highlight and summarize the recent progress and studies in the field of (bio)sensor systems based on QCMs combined with molecular imprinting technology.

Study of PEG Tether Length of Pegylated-Lipid Sensing Films in QCM Odor Sensors

NASA Astrophysics Data System (ADS)

Wyszynski, Bartosz; Somboon, Pakpum; Nakamoto, Takamichi

Odor sensing system using quartz crystal microbalance (QCM) sensor array and pattern recognition technique has been for a long time an important research topic. Research of novel sensing materials for QCM odor sensors is vital for realization of artificial olfaction and related devices such as odor recorder. Herein we study quartz crystal microbalance (QCM, 20 MHz, AT-cut) sensors coated with lipopolymers with polyethylene glycol (PEG) as a tether. The tether's molecular weights were 1000, 2000 and 5000. In addition, we fabricated QCM sensors coated with PEGs of molecular weights 1000, 2000 and 4000. The fabricated sensors' properties were evaluated during experiments of exposures to vapors of alcohols, esters and acids. From the obtained results it is clear that the tether's length (molecular weight) is an important factor influencing the resulting material's sensing properties. Sensititivity patterns of the lipopolymeric sensors were clealrly different from the ones for respective polymers. The obtained sensors seem to have a good capability to discriminate among odor samples according to the functional group of an odorant.

Low-cost scalable quartz crystal microbalance array for environmental sensing

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Anazagasty, Cristain; Jacobs, Christopher B.; Hianik, Tibor; Ivanov, Ilia N.

2016-09-01

Proliferation of environmental sensors for internet of things (IoT) applications has increased the need for low-cost platforms capable of accommodating multiple sensors. Quartz crystal microbalance (QCM) crystals coated with nanometer-thin sensor films are suitable for use in high-resolution ( 1 ng) selective gas sensor applications. We demonstrate a scalable array for measuring frequency response of six QCM sensors controlled by low-cost Arduino microcontrollers and a USB multiplexer. Gas pulses and data acquisition were controlled by a LabVIEW user interface. We test the sensor array by measuring the frequency shift of crystals coated with different compositions of polymer composites based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) while films are exposed to water vapor and oxygen inside a controlled environmental chamber. Our sensor array exhibits comparable performance to that of a commercial QCM system, while enabling high-throughput 6 QCM testing for under $1,000. We use deep neural network structures to process sensor response and demonstrate that the QCM array is suitable for gas sensing, environmental monitoring, and electronic-nose applications.

170-MHz electrodeless quartz crystal microbalance biosensor: capability and limitation of higher frequency measurement.

PubMed

Ogi, Hirotsugu; Nagai, Hironao; Naga, Hironao; Fukunishi, Yuji; Hirao, Masahiko; Nishiyama, Masayoshi

2009-10-01

We develop a highly sensitive quartz crystal microbalance (QCM) biosensor with a fundamental resonance frequency of 170 MHz. A naked AT-cut quartz plate of 9.7 microm thick is set in a sensor cell. Its shear vibration is excited by the line wire, and the vibration signals are detected by the other line wire, achieving the noncontacting measurement of the resonance frequency. The mass sensitivity of the 170 MHz QCM biosensor is 15 pg/(cm2 Hz), which is better than that of a conventional 5 MHz QCM by 3 orders of magnitude. Its high sensitivity is confirmed by detecting human immunoglobulin G (hIgG) via Staphylococcus protein A immobilized nonspecifically on both surfaces of the quartz plate. The detection limit is 0.5 pM. Limitation of the high-frequency QCM measurement is then theoretically discussed with a continuum mechanics model for a plate with point masses connected by elastic springs. The result indicates that a QCM measurement will break down at frequencies one-order-of-magnitude higher than the local resonance frequency at specific binding cites.

Quartz crystal microbalance and photoacoustic measurements in dental photocuring

NASA Astrophysics Data System (ADS)

Lima, Marcenilda A.; Bastos, Ivan N.; Cella, Norberto

2016-09-01

Photocured dental resins are used extensively in restorative procedures in dentistry. Inadequate curing reduces the lifetime of the dental restoration, and consequently it is essential to precisely measure the polymerisation kinetics. In this study, two techniques, Quartz Crystal Microbalance (QCM) and Photoacoustic Spectroscopy (PAS), were used to monitor the real-time cure and to obtain the optical absorption spectra of resins, respectively. From the PAS measurements, the precise peaks of absorption were identified, and were used as the appropriate wavelength of the photocuring light in the QCM monitoring. The combined use of these techniques allows reliable determination of the duration of the phases of physical and chemical changes that occur during photocuring. Two commercial dental resins were tested, and the results confirmed the advantages of using PAS and QCM to study polymerisation kinetics.

Quartz Crystal Microbalance with Dissipation Monitoring

DTIC Science & Technology

2014-11-06

Hydroxyapatite , 10 nm, Sensors • Biotin Functionalized on Gold Sensors • His-tag Capturing Sensor QCM-D techniques provide answers about...UV/Ozone cleaner • Hydroxyapatite , 10 nm, Sensors • Biotin Functionalized on Gold Sensors • His-tag Capturing Sensor QCM-D techniques provide

Designing of MIP based QCM sensor having thymine recognition sites based on biomimicking DNA approach.

PubMed

Diltemiz, S Emir; Hür, D; Ersöz, A; Denizli, A; Say, R

2009-11-15

Quartz crystal microbalance (QCM) sensors coated with molecular imprinted polymers (MIP) have been developed for the determination of thymine. In this method, methacryloylamidoadenine (MA-Ade) have used as a new monomer and thymine template for inspiration of DNA nucleobases interaction. The thymine can be simultaneously hydrogen binding to MA-Ade and fit into the shape-selective cavities. Thus, the interaction between nucleobases has an effect on the binding ability of the QCM sensors. The binding affinity of the thymine imprinted sensors has investigated by using the Langmuir isotherm. The thymine imprinted QCM electrodes have shown homogeneous binding sites for thymine (K(a): 1.0 x 10(5)M(-1)) while heterogeneous binding sites for uracil. On the other hand, recognition selectivity of the QCM sensor based on thymine imprinted polymer toward to uracil, ssDNA and ssRNA has been reported in this work.

Piezoelectric immunochip coated with thin films of bacterial cellulose nanocrystals for dengue detection.

PubMed

Pirich, Cleverton Luiz; de Freitas, Rilton Alves; Torresi, Roberto Manuel; Picheth, Guilherme Fadel; Sierakowski, Maria Rita

2017-06-15

Low-cost piezoelectric devices, such as simple frequency monitoring quartz crystal microbalance (QCM) devices, have good clinical utility as fast diagnostic tools for the detection of several diseases. However, unspecific antigen recognition, poor molecular probe adsorption and the need for sample dilution are still common drawbacks that hinder their use in routine diagnosis. In this work, piezoelectric sensors were previously coated with thin films of bacterial cellulose nanocrystals (CN) to provide a more sensitive and adapted interface for the attachment of monoclonal immunoglobulin G (IgGNS1) and to favor specific detection of non-structural protein 1 (NS1) of dengue fever. The assembly of the immunochip surface was analyzed by atomic force microscopy (AFM) and the NS1 detection was followed by quartz crystal microbalance with (QCM-D) and without energy dissipation monitoring (QCM). The CN surface was able to immobilize 2.30±0.5mgm -2 of IgGNS1, as confirmed by AFM topography and phase images along with QCM-D. The system was able to detect the NS1 protein in serum with only 10-fold dilution in the range of 0.01-10µgmL -1 by both QCM and QCM-D. The limits of detection of the two devices were 0.1μgmL -1 for QCM-D and 0.32μgmL -1 for QCM. As a result, QCM-D and QCM apparatuses can be used to follow NS1 recognition and have good potential for more sensitive, fast and/or less expensive diagnostic assays for dengue. Copyright © 2017 Elsevier B.V. All rights reserved.

Humidity scanning quartz crystal microbalance with dissipation monitoring setup for determination of sorption-desorption isotherms and rheological changes

NASA Astrophysics Data System (ADS)

Björklund, Sebastian; Kocherbitov, Vitaly

2015-05-01

A new method to determine water sorption-desorption isotherms with high resolution in the complete range of water activities (relative humidities) is presented. The method is based on quartz crystal microbalance with dissipation monitoring (QCM-D). The QCM-D is equipped with a humidity module in which the sample film is kept in air with controlled humidity. The experimental setup allows for continuous scanning of the relative humidity from either dry to humid conditions or vice versa. The amount of water sorbed or desorbed from the sample is determined from the resonance frequencies of the coated quartz sensor, via analysis of the overtone dependence. In addition, the method allows for characterization of hydration induced changes of the rheological properties from the dissipation data, which is closely connected to the viscoelasticity of the film. The accuracy of the humidity scanning setup is confirmed in control experiments. Sorption-desorption isotherms of pig gastric mucin and lysozyme, obtained by the new method, show good agreement with previous results. Finally, we show that the deposition technique used to coat the quartz sensor influences the QCM-D data and how this issue can be used to obtain further information on the effect of hydration. In particular, we demonstrate that spin-coating represents an attractive alternative to obtain sorption-desorption isotherms, while drop-coating provides additional information on changes of the rheological properties during hydration.

Study of Asorption Kinetics of Surfactants onto Polyethersulfone Membrane Surface Using QCM-D

USDA-ARS?s Scientific Manuscript database

The adsorption kinetics of surfactants onto the crystal surface spin-coated with a thin layer of a model membrane material, polyethersulfone was monitored through measurements of frequency and dissipation shifts simultaneously using a quartz crystal microbalance with dissipation (QCM-D) device. In ...

The Quartz-Crystal Microbalance in an Undergraduate Laboratory Experiment II: Measuring Viscosity

ERIC Educational Resources Information Center

Tsionsky, Vladimir

2007-01-01

Various water-alcohol and alcohol-alcohol based experiments are used to demonstrate how the quartz-crystal microbalance (QCM) technique is used for measuring the viscosity of a system. The technique is very advantageous, as it is inexpensive and provides digital output.

Micro-balance sensor integrated with atomic layer deposition chamber

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martinson, Alex B. F.; Libera, Joseph A.; Elam, Jeffrey W.

The invention is directed to QCM measurements in monitoring ALD processes. Previously, significant barriers remain in the ALD processes and accurate execution. To turn this exclusively dedicated in situ technique into a routine characterization method, an integral QCM fixture was developed. This new design is easily implemented on a variety of ALD tools, allows rapid sample exchange, prevents backside deposition, and minimizes both the footprint and flow disturbance. Unlike previous QCM designs, the fast thermal equilibration enables tasks such as temperature-dependent studies and ex situ sample exchange, further highlighting the feasibility of this QCM design for day-to-day use. Finally, themore » in situ mapping of thin film growth rates across the ALD reactor was demonstrated in a popular commercial tool operating in both continuous and quasi-static ALD modes.« less

Molecularly imprinted polymer based quartz crystal microbalance sensor system for sensitive and label-free detection of synthetic cannabinoids in urine.

PubMed

Battal, Dilek; Akgönüllü, Semra; Yalcin, M Serkan; Yavuz, Handan; Denizli, Adil

2018-07-15

Herein, we prepared a novel quartz crystal microbalance (QCM) sensor for synthetic cannabinoids (JWH-073, JWH-073 butanoic acid, JWH-018 and JWH-018 pentanoic acid,) detection. Firstly, the synthetic cannabinoid (SCs) imprinted (MIP) and non-imprinted (NIP) nanoparticles were synthesized by mini-emulsion polymerization system. The SCs-imprinted nanoparticles were first characterized by SEM, TEM, zeta-size and FTIR-ATR analysis and then were dropped onto the gold QCM surface. The SCs-imprinted QCM sensor was characterized by an ellipsometer, contact angle, and AFM. The limit of detection was found as 0.3, 0.45, 0.4, 0.2 pg/mL JWH-018, JWH-073, JWH-018 pentanoic acid and JWH-073 butanoic acid, respectively. The selectivity of the SCs-imprinted QCM sensor was shown by using JWH-018, JWH-018 pentanoic acid, JWH-073 and JWH-073 butanoic acid. According to the results, the SCs-imprinted QCM sensors show highly selective and sensitive in a broad range of synthetic cannabinoid concentrations (0.0005-1.0 ng/mL) in both aqueous and synthetic urine solutions. Copyright © 2018 Elsevier B.V. All rights reserved.

Molecular Imprinting Technology in Quartz Crystal Microbalance (QCM) Sensors

PubMed Central

Emir Diltemiz, Sibel; Keçili, Rüstem; Ersöz, Arzu; Say, Rıdvan

2017-01-01

Molecularly imprinted polymers (MIPs) as artificial antibodies have received considerable scientific attention in the past years in the field of (bio)sensors since they have unique features that distinguish them from natural antibodies such as robustness, multiple binding sites, low cost, facile preparation and high stability under extreme operation conditions (higher pH and temperature values, etc.). On the other hand, the Quartz Crystal Microbalance (QCM) is an analytical tool based on the measurement of small mass changes on the sensor surface. QCM sensors are practical and convenient monitoring tools because of their specificity, sensitivity, high accuracy, stability and reproducibility. QCM devices are highly suitable for converting the recognition process achieved using MIP-based memories into a sensor signal. Therefore, the combination of a QCM and MIPs as synthetic receptors enhances the sensitivity through MIP process-based multiplexed binding sites using size, 3D-shape and chemical function having molecular memories of the prepared sensor system toward the target compound to be detected. This review aims to highlight and summarize the recent progress and studies in the field of (bio)sensor systems based on QCMs combined with molecular imprinting technology. PMID:28245588

Comparison of a Resonant Mirror Biosensor (IAsys) and a Quartz Crystal Microbalance (QCM) for the Study on Interaction between Paeoniae Radix 801 and Endothelin-1.

PubMed

Huang, Jiadong; Lin, Qing; Yu, Jinghua; Ge, Shenguang; Li, Jing; Yu, Min; Zhao, Zixia; Wang, Xinsheng; Zhang, Xiuming; He, Xiaorui; Yuan, Liang; Yin, Huijun; Osa, Tetsuo; Chen, Keji; Chen, Qiang

2008-12-15

A resonant mirror biosensor, IAsys, and a quartz crystal microbalance (QCM) are known independently as surface sensitive analytical devices capable of label-free and in situ bioassays. In this study, an IAsys and a QCM are employed for a new study on the action mechanism of Paeoniae Radix 801 (P. radix 801) by detecting the specific interaction between P. radix 801 and endothelin-1 (ET-1). In the experiments, ET-1 was immobilized on the surfaces of the IAsys cuvette and the QCM substrate by surface modification techniques, and then P. radix 801 solution was contacted to the cuvette and the substrate, separately. Then, the binding and interaction process between P. radix 801 and ET-1 was monitored by IAsys and QCM, respectively. The experimental results showed that P. radix 801 binds ET-1 specifically. The IAsys and QCM response curves to the ET-1 immobilization and P. radix 801 binding are similar in reaction process, but different in binding profiles, reflecting different resonation principles. Although both IAsys and QCM could detect the interaction of P. radix 801 and ET-1 with high reproducibility and reliability through optimization of the ET-1 coating, the reproducibility and reliability obtained by IAsys are better than those obtained by QCM, since the QCM frequency is more sensitive to temperature fluctuations, atmospheric changes and mechanical disturbances. However, IAsys and QCM are generally potent and reliable tools to study the interaction of P. radix 801 and ET-1, and can conclusively be applied to the action mechanism of P. radix 801.

Acoustic interference suppression of quartz crystal microbalance sensor arrays utilizing phononic crystals

NASA Astrophysics Data System (ADS)

Chen, Yung-Yu; Huang, Li-Chung; Wang, Wei-Shan; Lin, Yu-Ching; Wu, Tsung-Tsong; Sun, Jia-Hong; Esashi, Masayoshi

2013-04-01

Acoustic interference suppression of quartz crystal microbalance (QCM) sensor arrays utilizing phononic crystals is investigated in this paper. A square-lattice phononic crystal structure is designed to have a complete band gap covering the QCM's resonance frequency. The monolithic sensor array consisting of two QCMs separated by phononic crystals is fabricated by micromachining processes. As a result, 12 rows of phononic crystals with band gap boost insertion loss between the two QCMs by 20 dB and also reduce spurious modes. Accordingly, the phononic crystal is verified to be capable of suppressing the acoustic interference between adjacent QCMs in a sensor array.

Quartz crystal microbalance for the cardiac markers/antibodies binding kinetic measurements in the plasma samples

NASA Astrophysics Data System (ADS)

Agafonova, L. E.; Shumyantseva, V. V.; Archakov, A. I.

2014-06-01

The quartz crystal microbalance (QCM) was exploited for cardiac markers detection and kinetic studies of immunochemical reaction of cardiac troponin I (cTnI) and human heart fatty acid binding protein (H-FABP) with the corresponding monoclonal antibodies in undiluted plasma (serum) and standard solutions. The QCM technique allowed to dynamically monitor the kinetic differences in specific interactions and nonspecific sorption, without multiple labeling procedures and separation steps. The affinity binding process was characterized by the association (ka) and the dissociation (kd) kinetic constants and the equilibrium association (K) constant, all of which were obtained from experimental data.

Inexpensive but accurate driving circuits for quartz crystal microbalances

NASA Astrophysics Data System (ADS)

Bruschi, L.; Delfitto, G.; Mistura, G.

1999-01-01

The quartz crystal microbalance (QCM) is a common technique which finds a wide variety of applications in many different areas like adsorption, catalysis, analytical chemistry, biochemistry, etc., and more generally as a sensor in the investigation of viscoelastic films. In this article we describe some driving circuits of the quartz which we have realized and tested in our laboratory. These can be assembled with standard components which can be easily found. Their performance, in some cases, is as good as that of the much more expensive frequency modulation technique employed in very precise QCM measurements and which requires high-quality commercial radiofrequency generators and amplifiers.

Displacement-type quartz crystal microbalance immunosensing platform for ultrasensitive monitoring of small molecular toxins.

PubMed

Tang, Dianping; Zhang, Bing; Tang, Juan; Hou, Li; Chen, Guonan

2013-07-16

A novel displacement-type quartz crystal microbalance (QCM) immunosensing strategy, based on glucose and its analogue dextran for concanavalin A (ConA) binding sites, was designed for ultrasensitive monitoring of small molecular biotoxins (brevetoxin B, PbTx-2, used as a model) with signal amplification on a graphene-functionalized sensing interface. To construct such a QCM immunosensing platform, phenoxy-functionalized dextran (DexP) was initially assembled onto the surface of graphene-coated QCM probe via the π-stacking interaction, and ConA-labeled monoclonal mouse anti-PbTx-2 capture antibody was then immobilized on the DexP-modified probe by dextran-ConA binding. Gold nanoparticle heavily functionalized with glucoamylase and bovine serum albumin-PbTx-2 (PbTx-2-BSA) conjugate was employed as the trace tag. A competitive-type immunoassay format was adopted for the online monitoring of PbTx-2 between anti-PbTx-2 antibody immobilized on the QCM probe and PbTx-2-BSA labeled on the gold nanoparticle. Accompanying the gold nanoparticle, the carried glucoamylase could hydrolyze amylopectin in glucose. The produced glucose competed with dextran for ConA and displaced the ConA-streptavidin-anti-PbTx-2 complex from the QCM probe, resulting in the frequency change. Under optimal conditions, the frequency of the QCM immunosensor was indirectly proportional to the concentration of target PbTx-2 in the sample and exhibited a dynamic range from 1.0 pg·mL(-1) to 10 ng·mL(-1) with a detection limit (LOD) of 0.6 pg·mL(-1) at the 3Sblank level. Intra- and interassay coefficients of variation were below 7.5% and 9.5%, respectively. In addition, the methodology was evaluated for analysis of PbTx-2 in 15 spiked seafood samples and showed good accordance between results obtained by the displacement-type QCM immunosensor and a commercialized enzyme-linked immunosorbent assay (ELISA) method.

Alcohol vapours sensor based on thin polyaniline salt film and quartz crystal microbalance.

PubMed

Ayad, Mohamad M; Torad, Nagy L

2009-06-15

A sensor based on the quartz crystal microbalance (QCM) technique was developed for detection of a number of primary aliphatic alcohols such as ethanol, methanol, 1-propanol, and 2-propanol vapours. Detection was based on a sensitive and a thin film of polyaniline, emeraldine salt (ES), coated the QCM electrode. The frequency shifts (Delta f) of the QCM were increased due to the vapour absorption into the ES film. The values of Delta f were found to be linearly correlated with the concentrations of alcohols vapour in mg L(-1). The changes in frequency are due to the hydrophilic character of the ES and the electrostatic interaction as well as the type of the alcohol. The sensor shows a good reproducibility and reversibility. The diffusion and diffusion coefficient (D) of different alcohols vapour were determined. It was found that the sensor follows Fickian kinetics.

Adhesion of liposomes: a quartz crystal microbalance study

NASA Astrophysics Data System (ADS)

Lüthgens, Eike; Herrig, Alexander; Kastl, Katja; Steinem, Claudia; Reiss, Björn; Wegener, Joachim; Pignataro, Bruno; Janshoff, Andreas

2003-11-01

Three different systems are presented, exploring the adhesion of liposomes mediated by electrostatic and lipid-protein interactions as well as molecular recognition of ligand receptor pairs. Liposomes are frequently used to gain insight into the complicated processes involving adhesion and subsequent events such as fusion and fission mainly triggered by specific proteins. We combined liposome technology with the quartz crystal microbalance (QCM) technique as a powerful tool to study the hidden interface between the membrane and functionalized surface. Electrostatic attraction and molecular recognition were employed to bind liposomes to the functionalized quartz crystal. The QCM was used to distinguish between adsorption of vesicles and rupture due to strong adhesive forces. Intact vesicles display viscoelastic behaviour, while planar lipid bilayers as a result of vesicle rupture can be modelled by a thin rigid film. Furthermore, the adhesion of cells was modelled successfully by receptor bearing liposomes. Scanning force microscopy was used to confirm the results obtained by QCM measurements.

Microcontact imprinted quartz crystal microbalance nanosensor for protein C recognition.

PubMed

Bakhshpour, Monireh; Özgür, Erdoğan; Bereli, Nilay; Denizli, Adil

2017-03-01

Detection of protein C (PC) in human serum was performed by quartz crystal microbalance (QCM) based on molecular imprinting technique (MIP). The high-resolution and mass-sensitive QCM based sensor was integrated with high sensitivity and selectivity of the MIP technique. The PC microcontact imprinted (PC-μCIP) nanofilm was prepared on the glass surface. Then, the PC-μCIP/QCM sensor was prepared with 2-hydroxyethyl methacrylate (HEMA), ethylene glycol dimethacrylate (EGDMA) and N-methacryloyl l-histidine methylester (MAH) as the functional monomer with copper(II) ions. The polymerization was performed under UV light (100W and 365nm) for 20-25min under nitrogen atmosphere. The characterization studies of QCM sensor were done by observation using atomic force microscopy (AFM), contact angle measurements, ellipsometry and fourier transform infrared spectroscopy (FTIR). Detection of PC was investigated in a concentration range of 0.1-30μg/mL. Selectivity of PC-μCIP and PC non-imprinted/QCM (PC-non-μCIP) sensors for PC determination was investigated by using proteins namely hemoglobin (Hb), human serum albumin (HSA) and fibrinogen solutions. QCM sensor was also used for detection of PC molecules in aqueous solutions and human plasma. The detection limit was determined as 0.01μg/mL for PC analysis. The PC-μCIP/QCM sensor was used for five consecutive adsorption-desorption cycles. According to the results, the PC-μCIP/QCM sensor had obtained high selectivity and sensitivity for detection of PC molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

Unfound Associated Resonant Model and Its Impact on Response of a Quartz Crystal Microbalance in the Liquid Phase.

PubMed

Kang, Qi; Shen, Qirui; Zhang, Ping; Wang, Honghai; Sun, Yan; Shen, Dazhong

2018-02-20

Quartz crystal microbalance (QCM) is an important tool to detect in real time the mass change at the nanogram level. However, for a QCM operated in the liquid phase, the Sauerbrey equation is usually disturbed by the changes in liquid properties and the longitudinal wave effect. Herein, we report another unfound associated high-frequency resonance (HFR) model for the QCM, with the intensity 2 orders of magnitude higher than that of the fundamental peak in the liquid phase. The HFR model exhibits obvious impact on the response of QCM in the thickness-shear model (TSM), especially for overtones. The frequency of HFR peak is decreased dramatically with increasing conductivity or permittivity of the liquid phase, resulting in considerable additional frequency shifts in the TSM as baseline drift. Compared to that with a faraway HFR peak, the overlapping of HFR peak to a TSM overtone results in the frequency shifts of ±50-70 kHz with its intensity enhancement by 3 orders of magnitude in the later. The HFR behavior is explained by an equivalent circuit model including leading wire inductance, liquid inductance, and static capacitance of QCM. Taking into account the HFR model, the positive frequency shifts of the QCM at high overtones during the cell adhesion process is understandable. Combining the TSM and HFR is an effective way to improve the stability of QCM and provides more reliable information from the responses of QCM. The HFR may have potential application in chemical and biological sensors.

Chemically grafted fibronectin for use in QCM-D cell studies

PubMed Central

Sobolewski, Peter; Tomczyk, Nancy; Composto, Russell J.; Eckmann, David M.

2014-01-01

Traditionally, fibronectin has been used as a physisorbed surface coating (physFN) in cell culture experiments due to its critical role in cell adhesion. However, because the resulting layer is thick, unstable, and of unpredictable uniformity, this method of fibronectin deposition is unsuitable for some types of research, including quartz crystal microbalance (QCM) experiments involving cells. Here, we present a new method for chemical immobilization of fibronectin onto silicon oxide surfaces, including QCM crystals pre-coated with silicon oxide. We characterize these chemically coated fibronectin surfaces (chemFN) as well as physFN ones using surface ellipsometry (SE), Fourier transform infrared spectroscopy (FTIR), atomic force microscopy (AFM), and contact angle measurements. A cell culture model demonstrates that cells on chemFN and physFN surfaces exhibit similar viability, structure, adhesion and metabolism. Finally, we perform QCM experiments using cells on both surfaces which demonstrate the superior suitability of chemFN coatings for QCM research, and provide real-time QCM-D data from cells subjected to an actin depolymerizing agent. Overall, our method of chemical immobilization of fibronectin yields great potential for furthering cellular experiments in which thin, stable and uniform coatings are desirable. As QCM research with cells has been rather limited in success thus far, we anticipate that this new technique will particularly benefit this experimental system by availing it to the much broader field of cell mechanics. PMID:24657645

Application of Kevin-Voigt Model in Quantifying Whey Protein Adsorption on Polyethersulfone Using QCM-D

USDA-ARS?s Scientific Manuscript database

The study of protein adsorption on the membrane surface is of great importance to cheese-making processors that use polymeric membrane-based processes to recover whey protein from the process waste streams. Quartz crystal microbalance with dissipation (QCM-D) is a lab-scale, fast analytical techniq...

Post-flight analyses of the crystals from the M0003-14 quartz crystal microbalance experiment

NASA Technical Reports Server (NTRS)

Stuckey, W. K.; Radhakrishnan, G.; Wallace, D.

1993-01-01

Quartz Crystal Microbalances constructed by QCM Research were flown on the leading and trailing edges of LDEF as one of the sub-experiments of M0003. Response of the crystals coated with 150 A of In2O3 was recorded during the first 424 days of the mission. A second QCM with crystals coated with 150 A of ZnS was also flown but not monitored. After the flight, the QCM's were disassembled and analyzed in The Aerospace Corporation laboratories. The samples included the crystals from the leading and trailing edge samples of both types of coatings along with the reference crystals, which were inside the QCM housing. Analyses were performed by scanning electron microscopy, energy dispersive x-ray analyses, x-ray photoelectron spectroscopy, ion microprobe mass analysis, and reflectance spectroscopy in the infrared and UV/visible regions. The crystals are contaminated predominantly with silicone compounds. The contamination is higher on the leading edge than on the trailing edge and higher on the exposed crystals than on the reference crystals.

Total and Differential Sputter Yields of Boron Nitride Measured by Quartz Crystal Microbalance (Preprint)

DTIC Science & Technology

2009-08-20

Nomenclature As = QCM sensor area E = ion energy E* = characteristic energy describing the differential sputter yield profile shape Eth...We report differential and total sputter yields for several grades of BN at ion energies down to 60 eV, obtained with a QCM deposition sensor 3-7,9...personal computer with LabView is used for data logging. Detailed discussion of the QCM sensor is provided in subsection IIF. B. Definition of Angles

Quartz Crystal Microbalance Based System for High-Sensitivity Differential Sputter Yield Measurements (Preprint)

DTIC Science & Technology

2009-08-20

at low ion energies require appropriate ion sources. For example, past work using QCM sensors employed a magnetron as an ion source 32,33 . The...and for data logging. Detailed discussion of the QCM sensor is provided in Section IID. Figure 1. Schematic diagram of the experimental set-up...mass flow rate of 0.5 sccm. The PBN was biased negatively relative to ground potential. D. QCM Sensor and Temperature Control In deposition mode

Total and Differential Sputter Yields of Boron Nitride Measured by Quartz Crystal Microbalance (Preprint)

DTIC Science & Technology

2009-05-07

energies down to 60 eV, obtained with a QCM deposition sensor [5-7, 9-11]. In Section II we discuss the experimental apparatus and procedures used for...logging. Detailed discussion of the QCM sensor is provided in Section IIF. Figure 1. Left: Schematic diagram of experimental set-up. Right...above assumptions (this equation applies for both differential and total yields). F. QCM Sensor and Measurement Proceedure We use a Sigma

ASTM E 1559 method for measuring material outgassing/deposition kinetics has applications to aerospace, electronics, and semiconductor industries

NASA Technical Reports Server (NTRS)

Garrett, J. W.; Glassford, A. P. M.; Steakley, J. M.

1994-01-01

The American Society for Testing and Materials has published a new standard test method for characterizing time and temperature-dependence of material outgassing kinetics and the deposition kinetics of outgassed species on surfaces at various temperatures. This new ASTM standard, E 1559(1), uses the quartz crystal microbalance (QCM) collection measurement approach. The test method was originally developed under a program sponsored by the United States Air Force Materials Laboratory (AFML) to create a standard test method for obtaining outgassing and deposition kinetics data for spacecraft materials. Standardization by ASTM recognizes that the method has applications beyond aerospace. In particular, the method will provide data of use to the electronics, semiconductor, and high vacuum industries. In ASTM E 1559 the material sample is held in vacuum in a temperature-controlled effusion cell, while its outgassing flux impinges on several QCM's which view the orifice of the effusion cell. Sample isothermal total mass loss (TML) is measured as a function of time from the mass collected on one of the QCM's which is cooled by liquid nitrogen, and the view factor from this QCM to the cell. The amount of outgassed volatile condensable material (VCM) on surfaces at higher temperatures is measured as a function of time during the isothermal outgassing test by controlling the temperatures of the remaining QCM's to selected values. The VCM on surfaces at temperatures in between those of the collector QCM's is determined at the end of the isothermal test by heating the QCM's at a controlled rate and measuring the mass loss from the end of the QCM's as a function of time and temperature. This reevaporation of the deposit collected on the QCM's is referred to as QCM thermogravimetric analysis. Isothermal outgassing and deposition rates can be determined by differentiating the isothermal TML and VCM data, respectively, while the evaporation rates of the species can be obtained as a function of temperature by differentiating the QCM thermogravimetric analysis data.

A Quartz Crystal Microbalance dew point sensor without frequency measurement.

PubMed

Wang, Guohua; Zhang, Weishuo; Wang, Shuo; Sun, Jinglin

2014-11-01

This work deals with the design of a dew point sensor based on Quartz Crystal Microbalance (QCM) without measuring the frequency. This idea is inspired by the fact that the Colpitts oscillation circuit will stop oscillating when the QCM works in the liquid media. The quartz crystal and the electrode are designed through the finite element simulation and the stop oscillating experiment is conducted to verify the sensibility. Moreover, the measurement result is calibrated to approach the true value. At last a series of dew points at the same temperature is measured with the designed sensor. Results show that the designed dew point sensor is able to detect the dew point with the proper accuracy.

A quartz crystal microbalance dew point sensor without frequency measurement

NASA Astrophysics Data System (ADS)

Wang, Guohua; Zhang, Weishuo; Wang, Shuo; Sun, Jinglin

2014-11-01

This work deals with the design of a dew point sensor based on Quartz Crystal Microbalance (QCM) without measuring the frequency. This idea is inspired by the fact that the Colpitts oscillation circuit will stop oscillating when the QCM works in the liquid media. The quartz crystal and the electrode are designed through the finite element simulation and the stop oscillating experiment is conducted to verify the sensibility. Moreover, the measurement result is calibrated to approach the true value. At last a series of dew points at the same temperature is measured with the designed sensor. Results show that the designed dew point sensor is able to detect the dew point with the proper accuracy.

New synthesis method for 4-MAPBA monomer and using for the recognition of IgM and mannose with MIP-based QCM sensors.

PubMed

Diltemiz, Sibel Emir; Hür, Deniz; Keçili, Rüstem; Ersöz, Arzu; Say, Rıdvan

2013-03-07

Quartz crystal microbalance (QCM) sensors coated with molecularly imprinted polymers (MIP) have been developed for the recognition of immunoglobulin M (IgM) and mannose. In this method, methacryloylamidophenylboronic acid (MAPBA) was used as a monomer and mannose was used as a template. For this purpose, initially, QCM electrodes were modified with 2-propene-1-thiol to form mannose-binding regions on the QCM sensor surface. In the second step, the methacryloylamidophenylboronic acid-mannose [MAPBA-mannose], pre-organized monomer system, was prepared using the MAPBA monomer. Then, a molecularly imprinted film was coated on to the QCM electrode surface under UV light using ethylene glycol dimethacrylate (EDMA), and azobisisobutyronitrile (AIBN) as a cross-linking agent and an initiator, respectively. The mannose can be simultaneously bound to MAPBA and fitted into the shape-selective cavities. The binding affinity of the mannose-imprinted sensors was investigated using the Langmuir isotherm. The mannose-imprinted QCM electrodes have shown homogeneous binding sites for mannose (K(a): 3.3 × 10(4) M(-1)) and heterogeneous binding sites for IgM (K(a1): 1.0 × 10(4) M(-1); K(a2): 3.3 × 10(3) M(-1)).

Investigation of the interaction between liquid and micro/nanostructured surfaces during condensation with quartz crystal microbalance

NASA Astrophysics Data System (ADS)

Su, Junwei

Dropwise condensation (DWC) on hydrophobic surfaces is attracting attention for its great potential in many industrial applications, such as steam power plants, water desalination, and de-icing of aerodynamic surfaces, to list a few. The direct dynamic characterization of liquid/solid interaction can significantly accelerate the progress toward a full understanding of the thermal and mass transport mechanisms during DWC processes. The research focuses on the development of a novel acoustic-based technique for analyzing the liquid/solid interactions of different condensations on micro- and nanostructured surfaces including DWC. hi addition. the newly developed technology was demonstrated for quantitatively sensing different wetting states of liquid on rough surfaces. First, different micro/nanostructures were fabricated on the quartz crystal microbalance (QCM), which serves as acoustic sensor. Polymethyl methacrylate (PMMA) micropillars, with varying heights from 6.03 to 25.02 microm, were fabricated on a quartz crystal microbalance (QCM) substrate by thermal nanoimprinting lithography to form pillar-based QCM (QCM-P). For nanostructured QCM. a copper layer was deposited on the QCM surface and then nanostructures of copper oxide (CuO) films were formed via chemical oxidation in an alkaline solution. Then, these surfaces were treated to make them superhydrophilic or superhydrophobic using oxygen plasma treatment or with coating of 1H,1 H,2H,2H-perfluorooctyl-trichlorosilane (PFOTS). Based on the geometry of these micro/nanostructures, the relationship between the frequency responses of QCM and the wetting states of these surfaces was theoretically investigated. Different theoretical models were established to describing the frequency shift of the micro- and nanostructured QCM in different wetting states. For the microstructured surface, the cantilever based model and a two-degree-of-freedom dynamic model were applied to predict the frequency shift of the QCM-P in different wetting states, by taking advantage of the well-defined micropillar structures. For the nanostructured surface, the gravimetric term was applied for the penetrated liquid as it moves synchronously with the oscillating crystal surface. It was revealed that the penetrated wetting state (Wenzel state) causes one order of magnitude higher frequency shift of the QCM than the suspended state (Cassie state) does. For the suspended state, the equivalent liquid mass on the tips of the roughness dominates the frequency shift signal instead of the damping. A nonlinear relationship appears between the frequency shift and micropillar height for both Cassie and Wenzel wetting states, due to the vibration phase veering at the "critical height". This implied that a significant improvement of sensitivity of QCM-P over traditional QCM occurred in the suspended state, as well as in the penetrated state. Besides, the suspended state provides a much higher quality factor than penetrated state. Using the insights gained from the experimental results and modeling results, the frequency shift of the QCM was normalized to reveal the wetting state directly. Then. the QCM device together with the microscopic observation was used to probe the droplets' growth and their coalescence processes. The normalized frequency shifts of QCM devices are clearly linked to the different condensation states at a global level, which cannot be characterized by other techniques such as E-SEM and TEM. The characterization of the trapped liquid in micro/nanostructures, which is very challenging for microscopic observation, can be easily carried out by this acoustic technique. These results quantitatively demonstrated the different condensation states. In addition, the transition between the Cassie and the Wenzel states was successfully captured by this method. The newly developed QCM system provides a valuable tool for the dynamic characterization of different condensation processes.

The use of trichloroacetic acid imprinted polymer coated quartz crystal microbalance as a screening method for determination of haloacetic acids in drinking water.

PubMed

Suedee, Roongnapa; Intakong, Wimon; Dickert, Franz L

2006-08-15

An alternative screening method for haloacetic acids (HAAs) disinfection by-products in drinking water is described. The method is based on the use of piezoelectric quartz crystal microbalance (QCM) transducing system, where the electrode is coated with a trichloacetic acid-molecularly imprinted polymer (TCAA-MIP). This MIP comprises a crosslinked poly(ethyleneglycoldimethacrylate-co-4-vinylpyridine). The coated QCM is able to specifically detect the analytes in water samples in terms of the mass change in relation to acid-base interactions of the analytes with the MIP. The TCAA-MIP coated QCM showed high specificity for the determination of TCAA in aqueous solutions containing inorganic anions, but its sensitivity reduced in water samples containing hydrochloric acid due to a mass loss at the sensor surface. Cross-reactivity studies with HAA analogs (dichloro-, monochloro-, tribromo-, dibromo-, and monobromo-acetic acids) and non-structurally related TCAA molecules (acetic acid and malonic acid) indicated that recognition of the structurally related TCAA compounds by the TCAA-MIP-based QCM is due to a carboxylic acid functional group, and probably involves a combination of both size and shape selectivity. The total response time of sensor is in the order of 10min. The achieved limits of detection for HAAs (20-50mugl(-1)) are at present higher than the actual concentrations found in real-life samples, but below the guidelines for the maximum permissible levels (60mugl(-1) for mixed HAAs). Recovery studies with drinking water samples spiked with TCAA or spiked with mixtures of HAAs revealed the reproducibility and precision of the method. The present work has demonstrated that the proposed assay can be a fast, reliable and inexpensive screening method for HAA contaminants in water samples, but further refinement is required to improve the limits of detection.

Gas Dynamics, Characterization, and Calibration of Fast Flow Flight Cascade Impactor Quartz Crystal Microbalances (QCM) for Aerosol Measurements

NASA Technical Reports Server (NTRS)

Grant, J.R.; Thorpe, A. N.; James, C.; Michael, A.; Ware, M.; Senftle, F.; Smith, S.

1997-01-01

During recent high altitude flights, we have tested the aerosol section of the fast flow flight cascade impactor quartz crystal microbalance (QCM) on loan to Howard University from NASA. The aerosol mass collected during these flights was disappointingly small. Increasing the flow through the QCM did not correct the problem. It was clear that the instrument was not being operated under proper conditions for aerosol collect ion primarily because the gas dynamics is not well understood. A laboratory study was therefore undertaken using two different fast flow QCM's in an attempt to establish the gas flow characteristics of the aerosol sections and its effect on particle collection, Some tests were made at low temperatures but most of the work reported here was carried out at room temperature. The QCM is a cascade type impactor originally designed by May (1945) and later modified by Anderson (1966) and Mercer et al (1970) for chemical gas analysis. The QCM has been used extensively for collecting and sizing stratospheric aerosol particles. In this paper all flow rates are given or corrected and referred to in terms of air at STP. All of the flow meters were kept at STP. Although there have been several calibration and evaluation studies of moderate flow cascade impactors of less than or equal to 1 L/rein., there is little experimental information on the gas flow characteristics for fast flow rates greater than 1 L/rein.

Characterization of QCM sensor surfaces coated with molecularly imprinted nanoparticles.

PubMed

Reimhult, Kristina; Yoshimatsu, Keiichi; Risveden, Klas; Chen, Si; Ye, Lei; Krozer, Anatol

2008-07-15

Molecularly imprinted polymers (MIPs) are gaining great interest as tailor-made recognition materials for the development of biomimetic sensors. Various approaches have been adopted to interface MIPs with different transducers, including the use of pre-made imprinted particles and the in situ preparation of thin polymer layers directly on transducer surfaces. In this work we functionalized quartz crystal microbalance (QCM) sensor crystals by coating the sensing surfaces with pre-made molecularly imprinted nanoparticles. The nanoparticles were immobilized on the QCM transducers by physical entrapment in a thin poly(ethylene terephthalate) (PET) layer that was spin-coated on the transducer surface. By controlling the deposition conditions, it was possible to gain a high nanoparticle loading in a stable PET layer, allowing the recognition sites in nanoparticles to be easily accessed by the test analytes. In this work, different sensor surfaces were studied by micro-profilometry and atomic force microscopy and the functionality was evaluated using quartz crystal microbalance with dissipation (QCM-D). The molecular recognition capability of the sensors were also confirmed using radioligand binding analysis by testing their response to the presence of the test compounds, (R)- and (S)-propranolol in aqueous buffer.

Highly sensitive heavy metal ion detection using AlQ3 microwire functionalized QCM

NASA Astrophysics Data System (ADS)

Can, Nursel; Aǧar, Meltem; Altındal, Ahmet

2016-03-01

Tris(8-hydroxyquinoline) aluminum (Alq3) microwires was successfully synthesized for the fabrication of Alq3 microwires-coated QCM sensors to detect the heavy metal ions in aqueous solution. AT-cut quartz crystal microbalance (QCM) of 10 MHz fundamental resonance frequency having gold electrodes were used as transducers. Typical measuring cycle consisted of repeated flow of target measurands through the flow cell and subsequent washing to return the baseline. The QCM results indicated that the Alq3 microwires exhibit excellent sensitivity, stability and short response-recovery time, which are much attractive for the development of portable and highly sensitive heavy metal ion sensors in water samples.

Simultaneous monitoring of humidity and chemical changes using quartz crystal microbalance sensors modified with nano-thin films.

PubMed

Selyanchyn, Roman; Korposh, Serhiy; Wakamatsu, Shunichi; Lee, Seung-Woo

2011-01-01

Quartz crystal microbalance (QCM) electrodes modified with nano-thin films were used to develop a system for measuring significant environment changes (smoke, humidity, hazardous material release). A layer-by-layer approach was used for the deposition of sensitive coatings with a nanometer thickness on the electrode surface. The QCM electrode was modified with self-assembled alternate layers of tetrakis-(4-sulfophenyl) porphine (TSPP) (or its manganese derivative, MnTSPP) and poly(diallyldimethylammonium chloride) (PDDA). The QCM sensors, which had been reported previously for humidity sensing purposes, revealing a high possibility to recognize significant environmental changes. Identifying of the origin of environmental change is possible via differential signal analysis of the obtained data. The sensors showed different responses to humidity changes, hazardous gas (ammonia) or cigarette smoke exposure. Even qualitative analysis is not yet available; it has been shown that ventilation triggers or alarms for monitoring smoke or hazardous material release can be built using the obtained result.

1-Butyl-3-Methylimidazolium Tetrafluoroborate Film as a Highly Selective Sensing Material for Non-Invasive Detection of Acetone Using a Quartz Crystal Microbalance.

PubMed

Tao, Wenyan; Lin, Peng; Liu, Sili; Xie, Qingji; Ke, Shanming; Zeng, Xierong

2017-01-20

Breath acetone serves as a biomarker for diabetes. This article reports 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF₄]), a type of room temperature ionic liquid (RTIL), as a selective sensing material for acetone. The RTIL sensing layer was coated on a quartz crystal microbalance (QCM) for detection. The sensing mechanism is based on a decrease in viscosity and density of the [bmim][BF₄] film due to the solubilization of acetone leading to a positive frequency shift in the QCM. Acetone was detected with a linear range from 7.05 to 750 ppmv. Sensitivity and limit of detection were found to be 3.49 Hz/ppmv and 5.0 ppmv, respectively. The [bmim][BF₄]-modified QCM sensor demonstrated anti-interference ability to commonly found volatile organic compounds in breath, e.g., isoprene, 1,2-pentadiene, d -limonene, and dl -limonene. This technology is useful for applications in non-invasive early diabetic diagnosis.

1-Butyl-3-Methylimidazolium Tetrafluoroborate Film as a Highly Selective Sensing Material for Non-Invasive Detection of Acetone Using a Quartz Crystal Microbalance

PubMed Central

Tao, Wenyan; Lin, Peng; Liu, Sili; Xie, Qingji; Ke, Shanming; Zeng, Xierong

2017-01-01

Breath acetone serves as a biomarker for diabetes. This article reports 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), a type of room temperature ionic liquid (RTIL), as a selective sensing material for acetone. The RTIL sensing layer was coated on a quartz crystal microbalance (QCM) for detection. The sensing mechanism is based on a decrease in viscosity and density of the [bmim][BF4] film due to the solubilization of acetone leading to a positive frequency shift in the QCM. Acetone was detected with a linear range from 7.05 to 750 ppmv. Sensitivity and limit of detection were found to be 3.49 Hz/ppmv and 5.0 ppmv, respectively. The [bmim][BF4]-modified QCM sensor demonstrated anti-interference ability to commonly found volatile organic compounds in breath, e.g., isoprene, 1,2-pentadiene, d-limonene, and dl-limonene. This technology is useful for applications in non-invasive early diabetic diagnosis. PMID:28117697

Quartz crystal microbalance as a sensing active element for rupture scanning within frequency band.

PubMed

Dultsev, F N; Kolosovsky, E A

2011-02-14

A new method based on the use of quartz crystal microbalance (QCM) as an active sensing element is developed, optimized and tested in a model system to measure the rupture force and deduce size distribution of nanoparticles. As suggested by model predictions, the QCM is shaped as a strip. The ratio of rupture signals at the second and the third harmonics versus the geometric position of a body on QCM surface is investigated theoretically. Recommendations concerning the use of the method for measuring the nanoparticle size distribution are presented. It is shown experimentally for an ensemble of test particles with a characteristic size within 20-30 nm that the proposed method allows one to determine particle size distribution. On the basis of the position and value of the measured rupture signal, a histogram of particle size distribution and percentage of each size fraction were determined. The main merits of the bond-rupture method are its rapid response, simplicity and the ability to discriminate between specific and non-specific interactions. The method is highly sensitive with respect to mass (the sensitivity is generally dependent on the chemical nature of receptor and analyte and may reach 8×10(-14) g mm(-2)) and applicable to measuring rupture forces either for weak bonds, for example hydrogen bonds, or for strong covalent bonds (10(-11)-10(-9) N). This procedure may become a good alternative for the existing methods, such as AFM or optical methods of determining biological objects, and win a broad range of applications both in laboratory research and in biosensing for various purposes. Possible applications include medicine, diagnostics, environmental or agricultural monitoring. Copyright © 2010 Elsevier B.V. All rights reserved.

Development of a mass sensitive quartz crystal microbalance (QCM)-based DNA biosensor using a 50 MHz electronic oscillator circuit.

PubMed

García-Martinez, Gonzalo; Bustabad, Enrique Alonso; Perrot, Hubert; Gabrielli, Claude; Bucur, Bogdan; Lazerges, Mathieu; Rose, Daniel; Rodriguez-Pardo, Loreto; Fariña, Jose; Compère, Chantal; Vives, Antonio Arnau

2011-01-01

This work deals with the design of a high sensitivity DNA sequence detector using a 50 MHz quartz crystal microbalance (QCM) electronic oscillator circuit. The oscillator circuitry is based on Miller topology, which is able to work in damping media. Calibration and experimental study of frequency noise are carried out, finding that the designed sensor has a resolution of 7.1 ng/cm(2) in dynamic conditions (with circulation of liquid). Then the oscillator is proved as DNA biosensor. Results show that the system is able to detect the presence of complementary target DNAs in a solution with high selectivity and sensitivity. DNA target concentrations higher of 50 ng/mL can be detected.

The use of a quartz crystal microbalance as an analytical tool to monitor particle/surface and particle/particle interactions under dry ambient and pressurized conditions: a study using common inhaler components.

PubMed

Turner, N W; Bloxham, M; Piletsky, S A; Whitcombe, M J; Chianella, I

2016-12-19

Metered dose inhalers (MDI) and multidose powder inhalers (MPDI) are commonly used for the treatment of chronic obstructive pulmonary diseases and asthma. Currently, analytical tools to monitor particle/particle and particle/surface interaction within MDI and MPDI at the macro-scale do not exist. A simple tool capable of measuring such interactions would ultimately enable quality control of MDI and MDPI, producing remarkable benefits for the pharmaceutical industry and the users of inhalers. In this paper, we have investigated whether a quartz crystal microbalance (QCM) could become such a tool. A QCM was used to measure particle/particle and particle/surface interactions on the macroscale, by additions of small amounts of MDPI components, in the powder form into a gas stream. The subsequent interactions with materials on the surface of the QCM sensor were analyzed. Following this, the sensor was used to measure fluticasone propionate, a typical MDI active ingredient, in a pressurized gas system to assess its interactions with different surfaces under conditions mimicking the manufacturing process. In both types of experiments the QCM was capable of discriminating interactions of different components and surfaces. The results have demonstrated that the QCM is a suitable platform for monitoring macro-scale interactions and could possibly become a tool for quality control of inhalers.

Optimization of the Automated Spray Layer-by-Layer Technique for Thin Film Deposition

DTIC Science & Technology

2010-06-01

pieces. All silicon was cleaned with ethanol and Milli-Q water to hydroxylate the surface. Quartz Crystal Microbalance Si02 coated sensors (Q-sense...was deposited onto a SiO2 coated QCM crystal using the automated dipping process described earlier. Once the film was deposited, it was dried over...night, and then placed in the QCM -D device. An additional layer of PAH was deposited onto the crystal in the QCM -D chamber at a flow rate of 1pL/minute

Mercury Sorption and Desorption on Gold: A Comparative Analysis of Surface Acoustic Wave and Quartz Crystal Microbalance-Based Sensors.

PubMed

Kabir, K M Mohibul; Sabri, Ylias M; Esmaielzadeh Kandjani, Ahmad; Matthews, Glenn I; Field, Matthew; Jones, Lathe A; Nafady, Ayman; Ippolito, Samuel J; Bhargava, Suresh K

2015-08-04

Microelectromechanical sensors based on surface acoustic wave (SAW) and quartz crystal microbalance (QCM) transducers possess substantial potential as online elemental mercury (Hg(0)) vapor detectors in industrial stack effluents. In this study, a comparison of SAW- and QCM-based sensors is performed for the detection of low concentrations of Hg(0) vapor (ranging from 24 to 365 ppbv). Experimental measurements and finite element method (FEM) simulations allow the comparison of these sensors with regard to their sensitivity, sorption and desorption characteristics, and response time following Hg(0) vapor exposure at various operating temperatures ranging from 35 to 75 °C. Both of the sensors were fabricated on quartz substrates (ST and AT cut quartz for SAW and QCM devices, respectively) and employed thin gold (Au) layers as the electrodes. The SAW-based sensor exhibited up to ∼111 and ∼39 times higher response magnitudes than did the QCM-based sensor at 35 and 55 °C, respectively, when exposed to Hg(0) vapor concentrations ranging from 24 to 365 ppbv. The Hg(0) sorption and desorption calibration curves of both sensors were found to fit well with the Langmuir extension isotherm at different operating temperatures. Furthermore, the Hg(0) sorption and desorption rate demonstrated by the SAW-based sensor was found to decrease as the operating temperature increased, while the opposite trend was observed for the QCM-based sensor. However, the SAW-based sensor reached the maximum Hg(0) sorption rate faster than the QCM-based sensor regardless of operating temperature, whereas both sensors showed similar response times (t90) at various temperatures. Additionally, the sorption rate data was utilized in this study in order to obtain a faster response time from the sensor upon exposure to Hg(0) vapor. Furthermore, comparative analysis of the developed sensors' selectivity showed that the SAW-based sensor had a higher overall selectivity (90%) than did the QCM counterpart (84%) while Hg(0) vapor was measured in the presence of ammonia (NH3), humidity, and a number of volatile organic compounds at the chosen operating temperature of 55 °C.

Different experimental results for the influence of immersion angle on the resonant frequency of a quartz crystal microbalance in a liquid phase: with a comment.

PubMed

Shen, Dazhong; Kang, Qi; Li, Xiaoyu; Cai, Hongmei; Wang, Yuandong

2007-06-19

This paper presents different experimental results of the influence of an immersion angle (theta, the angle between the surface of a quartz crystal resonator and the horizon) on the resonant frequency of a quartz crystal microbalance (QCM) sensor exposed one side of its sensing surfaces to liquid. The experimental results show that the immersion angle is an added factor that may influence the frequency of the QCM sensor. This type of influence is caused by variation of the reflection conditions of the longitudinal wave between the QCM sensor and the walls of the detection cell. The frequency shifts, measured by varying theta, are related to the QCM sensor used. When a QCM sensor with a weak longitudinal wave is used, its resonant frequency is nearly independent of theta. But, if a QCM sensor with a strong longitudinal wave is employed, the immersion angle is a potential error source for the measurements performed on the QCM sensor. When the reflection conditions of the longitudinal wave are reduced, the influence of theta on the resonant frequency of the QCM sensor is negligible. The slope of the plot of frequency shifts (deltaF) versus (rho eta)(1/2), the square root of the product of solution density (rho) and viscosity (eta), may be influenced by theta in a single experiment for the QCM sensor with a strong longitudinal wave in low viscous liquids, which can however, be effectively weakened by using the averaged values of reduplicated experiments. In solutions with a large (rho eta)(1/2) region (0-55 wt% sucrose solution as an example, with rho value from 1.00 to 1.26 g cm(-3) and eta value from 0.01 to 0.22 g cm(-1) s(-1), respectively), the slope of the plot of deltaF versus (rho eta)(1/2) is independent of theta even for the QCM sensor with a strong longitudinal wave in a single experiment. The influence of theta on the resonant frequency of the QCM sensor should be taken into consideration in its applications in liquid phase.

Synthesis and humidity sensing analysis of ZnS nanowires

NASA Astrophysics Data System (ADS)

Okur, Salih; Üzar, Neslihan; Tekgüzel, Nesli; Erol, Ayşe; Çetin Arıkan, M.

2012-03-01

ZnS nanowires synthesized by the vapor-liquid-solid (VLS) method and humidity sensing properties of obtained ZnS nanowires were investigated by quartz crystal microbalance (QCM) method and electrical measurements. The synthesized nanowires were exposed to relative humidity (RH) between 22% and 97% under controlled environment. Our experimental results show that ZnS nanowires have a great potential for humidity sensing applications in room temperature operations.

Relations between Mass Change and Frequency Shift of a QCM Sensor in Contact with Viscoelastic Medium

NASA Astrophysics Data System (ADS)

Tan, Feng; Huang, Xian-He

2013-05-01

We investigate frequency shift of a quartz crystal microbalance (QCM) sensor introduced by mass effect, and properties of material of its coated viscoelastic film are discussed. The validity of the Sauerbrey relation cannot be held if the viscoelastic properties of the contacting medium are considered. When the QCM sensor with a viscoelastic film works in the gas phase, the viscoelastic properties will introduce an extra mass effect. While in the liquid phase, the missing mass effect can be observed. The experimental results demonstrate that the QCM sensor is sensitive to the viscoelastic properties of the coating film. Properties of the viscoelastic contacting medium should be considered.

Calibration of the QCM/SAW Cascade Impactor for Measurement of Ozone in the Stratosphere

NASA Technical Reports Server (NTRS)

Wright, Cassandra K.; Sims, S. C.; Peterson, C. B.; Morris, V. R.

1997-01-01

The Quartz Crystal Microbalance Surface Acoustic Wave (QCM/SAW) cascade impactor collects size-fractionated distributions of aerosols on a series of 10 MHz quartz crystals and employs SAW devices coated with chemical sensors for gas detection. Presently, we are calibrating the ER-2 certified QCM/SAW cascade impactor in the laboratory for the detection of ozone. Experiments have been performed to characterize the QCM and SAW mass loading, saturation limits, mass frequency relationships, and sensitivity. We are also characterizing sampling efficiency by measuring the loss of ozone on different materials. There are parallel experiments underway to measure the variations in the sensitivity and response of the QCM/SAW crystals as a function of temperature and pressure. Results of the work to date will be shown.

Ligand exchange and MIP-based paraoxon memories onto QCM sensor

NASA Astrophysics Data System (ADS)

Birlik Özkütük, Ebru; Emir Diltemiz, Sibel; Özalp, Elif; Uzun, Lokman; Ersöz, Arzu

2015-04-01

In this study, we have aimed to prepare quartz crystal microbalance (QCM) sensor using paraoxon-imprinted particles. Firstly, methacryloyl antipyrine (MAAP)-based metal-chelate-coordinated pre-complex has been prepared and used for paraoxon templation. Then, paraoxon-imprinted nanofilms were formed on QCM sensor after modification of the gold surfaces with allyl mercaptan. By this way, specific and selective memories, which depend on metal-chelate interactions between Eu(III) ions and template, for paraoxon molecules have been obtained on the electrode surface. QCM sensor has characterized using AFM and ellipsometer. The detection limit and the affinity constant have found to be 0.09 μM and 5.71 × 103 M-1 for MAAP-Eu paraoxon-based nanofilm, respectively. The specificity of the QCM sensor has shown using parathion as a competitor molecule.

Biomolecule-functionalized magnetic nanoparticles for flow-through quartz crystal microbalance immunoassay of aflatoxin B1.

PubMed

Wang, Li; Gan, Xian-Xue

2009-01-01

A flow-through quartz crystal microbalance (QCM) immunoassay method has been developed based on aflatoxin B(1) antibody (anti-AFB(1))-functionalized magnetic core-shell Fe(3)O(4)/SiO(2) composite nanoparticles (bionanoparticles) in this study. To construct such an assay protocol, anti-AFB(1), as a model protein, was initially covalently immobilized onto the Fe(3)O(4)/SiO(2) surface, and then the functionalized nanoparticles were attached to the surface of the QCM probe with an external magnet. The binding of target molecules onto the immobilized antibodies decreased the sensor's resonant frequency, and the frequency shift was proportional to the AFB(1) concentration in the range of 0.3-7.0 ng/ml. The regeneration of the developed immunosensor was carried out via attaching or detaching the external magnet from the detection cell. In addition, the selectivity, reproducibility, and stability of the proposed immunoassay system were acceptable. Compared with the conventional ELISAs, the proposed immunoassay system was simple and rapid without multiple labeling and separation steps. Importantly, the proposed immunoassay method could be further developed for the immobilization of other antigens or biocompounds.

Adsorption Analysis of Lactoferrin to Titanium, Stainless Steel, Zirconia, and Polymethyl Methacrylate Using the Quartz Crystal Microbalance Method

PubMed Central

Yoshida, Eiji; Hayakawa, Tohru

2016-01-01

It is postulated that biofilm formation in the oral cavity causes some oral diseases. Lactoferrin is an antibacterial protein in saliva and an important defense factor against biofilm development. We analyzed the adsorbed amount of lactoferrin and the dissociation constant (K d) of lactoferrin to the surface of different dental materials using an equilibrium analysis technique in a 27 MHz quartz crystal microbalance (QCM) measurement. Four different materials, titanium (Ti), stainless steel (SUS), zirconia (ZrO2) and polymethyl methacrylate (PMMA), were evaluated. These materials were coated onto QCM sensors and the surfaces characterized by atomic force microscopic observation, measurements of surface roughness, contact angles of water, and zeta potential. QCM measurements revealed that Ti and SUS showed a greater amount of lactoferrin adsorption than ZrO2 and PMMA. Surface roughness and zeta potential influenced the lactoferrin adsorption. On the contrary, the K d value analysis indicated that the adsorbed lactoferrin bound less tightly to the Ti and SUS surfaces than to the ZrO2 and PMMA surfaces. The hydrophobic interaction between lactoferrin and ZrO2 and PMMA is presumed to participate in better binding of lactoferrin to ZrO2 and PMMA surfaces. It was revealed that lactoferrin adsorption behavior was influenced by the characteristics of the material surface. PMID:26998486

Oxygen Plasma Effect on QCM Sensor Coated Polystyrene Film

NASA Astrophysics Data System (ADS)

Khusnah, N. F.; Sakti, S. P.; Santjojo, D. J. D. H.

2018-05-01

Hydrophobicity property of polystyrene (PS) thin film is one of the essential factors to be considered in the development of quartz crystal microbalance (QCM) biosensor using polystyrene as matrix layer. Many methods were developed to improve the immobilization rate of the biomolecule on the sensor surface without affecting the QCM essential works. Surface modification of the sensor surface aims to modify the physical and or chemical property of the surface. A straightforward method, the fast, environmentally-friendly, and low-cost solution to modify the sensor surface coated with polystyrene film is using oxygen plasma. In this experiment, the polystyrene film was spin-coated on both surface of QCM electrodes and then heated at 100 °C. The specimen is then placed for 5 min long in a chamber filled with oxygen plasma generated by 2 MHz RF-DC high-density plasma system. The relationship between DC-bias used and the changes in morphology properties of the coated film was characterized by Topography Measurement System (TMS) and Contact Angle Measurement. The electrical characteristic of QCM was also characterized using Impedance Analyzer. It was revealed that the contact angle of oxygen plasma treated film is changed and depicted the hydrophobic character. Also, there is an increasing resonance frequency of the sensor after oxygen plasma treatment indicates an etching mechanism occurs during plasma treatment.

QCM-D study of nanoparticle interactions.

PubMed

Chen, Qian; Xu, Shengming; Liu, Qingxia; Masliyah, Jacob; Xu, Zhenghe

2016-07-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been proven to be a powerful research tool to investigate in situ interactions between nanoparticles and different functionalized surfaces in liquids. QCM-D can also be used to quantitatively determine adsorption kinetics of polymers, DNA and proteins from solutions on various substrate surfaces while providing insights into conformations of adsorbed molecules. This review aims to provide a comprehensive overview on various important applications of QCM-D, focusing on deposition of nanoparticles and attachment-detachment of nanoparticles on model membranes in complex fluid systems. We will first describe the working principle of QCM-D and DLVO theory pertinent to understanding nanoparticle deposition phenomena. The interactions between different nanoparticles and functionalized surfaces for different application areas are then critically reviewed. Finally, the potential applications of QCM-D in other important fields are proposed and knowledge gaps are identified. Copyright © 2015 Elsevier B.V. All rights reserved.

Skylab electronic technological advancements

NASA Technical Reports Server (NTRS)

Hornback, G. L.

1974-01-01

The present work describes three electronic devices designed for use in the Skylab airlock module: the teleprinter system, the quartz crystal microbalance contamination monitor (QCM), and the speaker. Design considerations, operation, characteristics, and system development are described for these systems, with accompanying diagrams, graphs, and photographs. The teleprinter is a thermal dot printer used to produce hard copy messages by electrically heating print elements in contact with heat-sensitive paper. The QCM was designed to estimate contamination buildup on optical surfaces of the earth resources experiment package. A vibrating quartz crystal is used as a microbalance relating deposited mass to shifts in the crystal's resonant frequency. Audio devices provide communication between crew members and between crew and STDN, and also provide audible alarms, via the caution and warning system, of out-of-limit-conditions.

A novel assay for detecting canine parvovirus using a quartz crystal microbalance biosensor.

PubMed

Kim, Yong Kwan; Lim, Seong-In; Choi, Sarah; Cho, In-Soo; Park, Eun-Hye; An, Dong-Jun

2015-07-01

Rapid and accurate diagnosis is crucial to reduce both the shedding and clinical signs of canine parvovirus (CPV). The quartz crystal microbalance (QCM) is a new tool for measuring frequency changes associated with antigen-antibody interactions. In this study, the QCM biosensor and ProLinker™ B were used to rapidly diagnosis CPV infection. ProLinker™ B enables antibodies to be attached to a gold-coated quartz surface in a regular pattern and in the correct orientation for antigen binding. Receiver operating characteristics (ROC) curves were used to set a cut-off value using reference CPVs (two groups: one CPV-positive and one CPV-negative). The ROC curves overlapped and the point of intersection was used as the cut-off value. A QCM biosensor with a cut-off value of -205 Hz showed 95.4% (104/109) sensitivity and 98.0% (149/152) specificity when used to test 261 field fecal samples compared to PCR. In conclusion, the QCM biosensor described herein is eminently suitable for the rapid diagnosis of CPV infection with high sensitivity and specificity. Therefore, it is a promising analytical tool that will be useful for clinical diagnosis, which requires rapid and reliable analyses. Copyright © 2015 Elsevier B.V. All rights reserved.

Stability enhanced, repeatability improved Parylene-C passivated on QCM sensor for aPTT measurement.

PubMed

Yang, Yuchen; Zhang, Wei; Guo, Zhen; Zhang, Zhiqi; Zhu, Hongnan; Yan, Ruhong; Zhou, Lianqun

2017-12-15

Determination of blood clotting time is essential in monitoring therapeutic anticoagulants. In this work, Parylene-C passivated on quartz crystal microbalance (P-QCM) was developed for the activated partial thromboplastin time (aPTT) measurement. Compared with typical QCM, P-QCM possessed a hydrophobic surface and sensitive frequency response to viscoelastic variations on electrode surface. Fibrin could be adsorbed effectively, due to the hydrophobicity of the P-QCM surface. Comparing with typical QCM, the peak-to-peak value (PPV) of P-QCM was increased by 1.94% ± 0.63%, which indicated enhancement of signal-to-noise ratio. For P-QCM, the coefficient of variation (CV) of frequency decrease and aPTT were 2.58% and 1.24% separately, which demonstrated improvement of stability and reproducibility. Moreover, compared with SYSMEX CS 2000i haematology analyzer, clinical coefficient index (R 2 ) was 0.983. In conclusion, P-QCM exhibited potential for improving stability, reproducibility and linearity of piezoelectric sensors, and might be more promising for point of care testing (POCT) applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Label-Free QCM Immunosensor for the Detection of Ochratoxin A

PubMed Central

Ertekin, Özlem; Laguna, Duygu Ercan; Özen, Fehime Şeyma; Öztürk, Zafer Ziya; Öztürk, Selma

2018-01-01

Ochratoxin A (OTA) is a potent mycotoxin that poses a risk in food and feed moieties and subject to worldwide regulation. Laboratory-based analytical methods are traditionally employed for reliable OTA quantification, but these methods cannot provide rapid and on-site analysis, where biosensors fill this gap. In this study a label-free quartz crystal microbalance (QCM)-based immunosensor for the detection of OTA, which is one of the most important small molecule contaminants, was developed by direct immobilization of OTA to amine-bearing sensor surfaces using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-Hydroxysuccinimide (NHS) chemistry. The protein-free sensor surface enabled regeneration of sensor surface with 50 mM NaOH and 1% SDS up to 13 times without loss of performance, which would disrupt a protein-containing sensor surface. We developed a QCM immunosensor using the developed sensor surface with a 17.2–200 ng/mL detection range which can be used for on-site detection of feedstuffs. PMID:29641432

Label-Free QCM Immunosensor for the Detection of Ochratoxin A.

PubMed

Pirinçci, Şerife Şeyda; Ertekin, Özlem; Laguna, Duygu Ercan; Özen, Fehime Şeyma; Öztürk, Zafer Ziya; Öztürk, Selma

2018-04-11

Ochratoxin A (OTA) is a potent mycotoxin that poses a risk in food and feed moieties and subject to worldwide regulation. Laboratory-based analytical methods are traditionally employed for reliable OTA quantification, but these methods cannot provide rapid and on-site analysis, where biosensors fill this gap. In this study a label-free quartz crystal microbalance (QCM)-based immunosensor for the detection of OTA, which is one of the most important small molecule contaminants, was developed by direct immobilization of OTA to amine-bearing sensor surfaces using 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)/N-Hydroxysuccinimide (NHS) chemistry. The protein-free sensor surface enabled regeneration of sensor surface with 50 mM NaOH and 1% SDS up to 13 times without loss of performance, which would disrupt a protein-containing sensor surface. We developed a QCM immunosensor using the developed sensor surface with a 17.2-200 ng/mL detection range which can be used for on-site detection of feedstuffs.

Calibration of the QCM/SAW Cascade Impactor for Measurement of Ozone

NASA Technical Reports Server (NTRS)

Williams, Cassandra K.; Peterson, C. B.; Morris, V. R.

1997-01-01

The Quartz Crystal Microbalance Surface Acoustic Wave (QCM/SAW) cascade impactor is an instrument designed to collect size-fractionated distributions of aerosols on a series of quartz crystals and employ SAW devices coated with chemical sensors for gas detection. We are calibrating the cascade impactor in our laboratory for future deployment for in-situ experiments to measure ozone. Experiments have been performed to characterize the QCM and SAW mass loading, saturation limits, mass frequency relationships, and sensitivity. The characteristics of mass loading, saturation limits, mass-frequency relationships, sensitivity, and the loss of ozone on different materials have been quantified.

Time-resolved viscoelastic properties of self-assembling iron oxide nanocube superlattices probed by quartz crystal microbalance with dissipation monitoring.

PubMed

Kapuscinski, Martin; Agthe, Michael; Bergström, Lennart

2018-07-15

Self-assembly of nanoparticles into superlattices can be used to create hierarchically structured materials with tailored functions. We have used the surface sensitive quartz crystal microbalance with dissipation monitoring (QCM-D) technique in combination with video microscopy (VM) to obtain time-resolved information on the mass increase and rheological properties of evaporation-induced self-assembly of nanocubes. We have recorded the frequency and dissipation shifts during growth and densification of superlattices formed by self-assembly of oleic acid capped, truncated iron oxide nanocubes and analyzed the time-resolved QCM-D data using a Kelvin-Voigt viscoelastic model. We show that the nanoparticles first assemble into solvent-containing arrays dominated by a viscous response followed by a solvent-releasing step that results in the formation of rigid and well-ordered superlattices. Our findings demonstrate that QCM-D can be successfully used to follow self-assembly and assist in the design of optimized routes to produce well-ordered superlattices. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Optimizing the Mass-Specific Activity of Bilirubin Oxidase Adlayers through Combined Electrochemical Quartz Crystal Microbalance and Dual Polarization Interferometry Analyses.

PubMed

McArdle, Trevor; McNamara, Thomas P; Fei, Fan; Singh, Kulveer; Blanford, Christopher F

2015-11-18

Two surface analysis techniques, dual polarization interferometry (DPI) and analysis by an electrochemical quartz crystal microbalance with dissipation capability (E-QCM-D), were paired to find the deposition conditions that give the highest and most stable electrocatalytic activity per adsorbed mass of enzyme. Layers were formed by adsorption from buffered solutions of bilirubin oxidase from Myrothecium verrucaria at pH 6.0 to planar surfaces, under high enzyme loading (≥1 mg mL(-1)) for contact periods of up to 2 min. Both unmodified and carboxylate-functionalized gold-coated sensors showed that a deposition solution concentration of 10-25 mg mL(-1) gave the highest activity per mass of adsorbed enzyme with an effective catalytic rate constant (k(cat)) of about 60 s(-1). The densification of adsorbed layers observed by DPI correlated with reduced bioactivity observed by parallel E-QCM-D measurements. Postadsorption changes in thickness and density observed by DPI were incorporated into Kelvin-Voigt models of the QCM-D response. The modeled response matched experimental observations when the adlayer viscosity tripled after adsorption.

Polyacrylonitrile nanofiber as polar solvent N,N-dimethyl formamide sensor based on quartz crystal microbalance technique

NASA Astrophysics Data System (ADS)

Rianjanu, A.; Julian, T.; Hidayat, S. N.; Suyono, E. A.; Kusumaatmaja, A.; Triyana, K.

2018-04-01

Here, we describe an N,N-dimethyl formamide (DMF) vapour sensor fabricated by coating polyacrylonitrile (PAN) nanofiber structured on quartz crystal microbalance (QCM). The PAN nanofiber sensors with an average diameter of 225 nm to 310 nm were fabricated via electrospinning process with different mass deposition on QCM substrate. The nanostructured of PAN nanofiber offers a high specific surface area that improved the sensing performance of nanofiber sensors. Benefiting from that fine structure, and high polymer-solvent affinity between PAN and DMF, the development of DMF sensors presented good response at ambient temperature. Since there is no chemical reaction between PAN nanofiber and DMF vapour, weak physical interaction such absorption and swelling were responsible for the sensing behavior. The results are indicating that the response of PAN nanofiber sensors has more dependency on the nanofiber structure (specific surface area) rather than its mass deposition. The sensor also showed good stability after a few days sensing. These findings have significant implications for developing DMF vapour sensor based on QCM coated polymer nanofibers.

A Quartz Crystal Microbalance Immunosensor for Stem Cell Selection and Extraction

PubMed Central

Costanzo, Salvatore; Zambrano, Gerardo; Mauro, Marco; Battaglia, Raffaele; Ferrini, Gianluca; Nastri, Flavia; Pavone, Vincenzo

2017-01-01

A cost-effective immunosensor for the detection and isolation of dental pulp stem cells (DPSCs) based on a quartz crystal microbalance (QCM) has been developed. The recognition mechanism relies on anti-CD34 antibodies, DPSC-specific monoclonal antibodies that are anchored on the surface of the quartz crystals. Due to its high specificity, real time detection, and low cost, the proposed technology has a promising potential in the field of cell biology, for the simultaneous detection and sorting of stem cells from heterogeneous cell samples. The QCM surface was properly tailored through a biotinylated self-assembled monolayer (SAM). The biotin–avidin interaction was used to immobilize the biotinylated anti-CD34 antibody on the gold-coated quartz crystal. After antibody immobilization, a cellular pellet, with a mixed cell population, was analyzed; the results indicated that the developed QCM immunosensor is highly specific, being able to detect and sort only CD34+ cells. Our study suggests that the proposed technology can detect and efficiently sort any kind of cell from samples with high complexity, being simple, selective, and providing for more convenient and time-saving operations. PMID:29182568

Apparent negative mass in QCM sensors due to punctual rigid loading

NASA Astrophysics Data System (ADS)

Castro, P.; Resa, P.; Elvira, L.

2012-12-01

Quartz Crystal Microbalances (QCM) are highly sensitive piezoelectric sensors able to detect very small loads attached to them. These devices are widely employed in many applications including process control and industrial and environmental monitoring. Mass loading is usually related to frequency shift by the well-known Sauerbrey's equation, valid for thin rigid homogeneous films. However, a significant deviation from this equation can occur when the mass is not uniformly distributed over the surface. Whereas the effects of a thin film on a QCM have been thoroughly studied, there are relatively few results on punctual loads, even though particles are usually deposited randomly and non-uniformly on the resonator surface. In this work, we have studied the effect of punctual rigid loading on the resonant frequency shift of a QCM sensor, both experimentally and using finite element method (FEM). The FEM numerical analysis was done using COMSOL software, 3D modeling a linear elastic piezoelectric solid and introducing the properties of an AT-cut quartz crystal. It is shown that a punctual rigid mass deposition on the surface of a QCM sensor can lead to positive shifts of resonance frequency, contrary to Sauerbrey's equation.

A Nano-Thin Film-Based Prototype QCM Sensor Array for Monitoring Human Breath and Respiratory Patterns.

PubMed

Selyanchyn, Roman; Wakamatsu, Shunichi; Hayashi, Kenshi; Lee, Seung-Woo

2015-07-31

Quartz crystal microbalance (QCM) sensor array was developed for multi-purpose human respiration assessment. The sensor system was designed to provide feedback for human respiration. Thorough optimization of measurement conditions: air flow, temperature in the QCM chamber, frequency measurement rate, and electrode position regarding to the gas flow-was performed. As shown, acquisition of respiratory parameters (rate and respiratory pattern) could be achieved even with a single electrode used in the system. The prototype system contains eight available QCM channels that can be potentially used for selective responses to certain breath chemicals. At present, the prototype machine is ready for the assessment of respiratory functions in larger populations in order to gain statistical validation. To the best of our knowledge, the developed prototype is the only respiratory assessment system based on surface modified QCM sensors.

Dopaminergic receptor-ligand binding assays based on molecularly imprinted polymers on quartz crystal microbalance sensors.

PubMed

Naklua, Wanpen; Suedee, Roongnapa; Lieberzeit, Peter A

2016-07-15

Molecularly imprinted polymers (MIPs) have been successfully applied as selective materials for assessing the binding activity of agonist and antagonist of dopamine D1 receptor (D1R) by using quartz crystal microbalance (QCM). In this study, D1R derived from rat hypothalamus was used as a template and thus self-organized on stamps. Those were pressed into an oligomer film consisting of acrylic acid: N-vinylpyrrolidone: N,N'-(1,2-dihydroxyethylene) bis-acrylamide in a ratio of 2:3:12 spin coated onto a dual electrode QCM. Such we obtained one D1R-MIP-QCM electrode, whereas the other electrode carried the non-imprinted control polymer (NIP) that had remained untreated. Successful imprinting of D1R was confirmed by AFM. The polymer can re-incorporate D1R leading to frequency responses of 100-1200Hz in a concentration range of 5.9-47.2µM. In a further step such frequency changes proved inherently useful for examining the binding properties of test ligands to D1R. The resulting mass-sensitive measurements revealed Kd of dopamine∙HCl, haloperidol, and (+)-SCH23390 at 0.874, 25.6, and 0.004nM, respectively. These results correlate well with the values determined in radio ligand binding assays. Our experiments revealed that D1R-MIP sensors are useful for estimating the strength of ligand binding to the active single site. Therefore, we have developed a biomimetic surface imprinting strategy for QCM studies of D1R-ligand binding and presented a new method to ligand binding assay for D1R. Copyright © 2016 Elsevier B.V. All rights reserved.

Multi-wall carbon nanotubes (MWCNTs)-doped polypyrrole DNA biosensor for label-free detection of genetically modified organisms by QCM and EIS.

PubMed

Truong, Thi Ngoc Lien; Tran, Dai Lam; Vu, Thi Hong An; Tran, Vinh Hoang; Duong, Tuan Quang; Dinh, Quang Khieu; Tsukahara, Toshifumi; Lee, Young Hoon; Kim, Jong Seung

2010-01-15

In this paper, we describe DNA electrochemical detection for genetically modified organism (GMO) based on multi-wall carbon nanotubes (MWCNTs)-doped polypyrrole (PPy). DNA hybridization is studied by quartz crystal microbalance (QCM) and electrochemical impedance spectroscopy (EIS). An increase in DNA complementary target concentration results in a decrease in the faradic charge transfer resistance (R(ct)) and signifying "signal-on" behavior of MWCNTs-PPy-DNA system. QCM and EIS data indicated that the electroanalytical MWCNTs-PPy films were highly sensitive (as low as 4pM of target can be detected with QCM technique). In principle, this system can be suitable not only for DNA but also for protein biosensor construction.

A real-time comparison of mercury accumulation on noble metal thin films using gravimetric device

NASA Astrophysics Data System (ADS)

Kabir, K. M. Mohibul; Kandjani, Ahmad Esmaielzadeh; Harrison, Christopher J.; Ippolito, Samuel J.; Sabri, Ylias M.; Bhargava, Suresh K.

2016-12-01

We simultaneously compared and analyzed the mercury sorption and sensing performance of gold, silver, palladium and platinum using quartz crystal microbalance (QCM). Overall, the Au- and Ag-QCM showed superior Hg sensing performance over the Pd- and Pt-counterparts when tested toward a range of concentrations (24-365 ppbv) at various operating temperatures (35-105 °C). However, it was also found that the Hg sensing performance of each metal varied significantly with the operating temperature and is dependent on the concentration tested. For instance, the Ag-QCM exhibited 57% higher response magnitude than the Au-QCM when exposed toward 24 ppbv of Hg0 vapor at 35 °C; however, the opposite trend was observed when the same concentration of Hg0 vapor was tested at 105 °C, with Au-QCM showing 104% higher response magnitudes compared to the Ag-QCM. Moreover, the Ag-QCM showed higher response magnitudes than the Au-QCM for exposure toward 365 ppbv of Hg0 vapor regardless of the operating temperature.

Detection of trace microcystin-LR on a 20 MHz QCM sensor coated with in situ self-assembled MIPs.

PubMed

He, Hao; Zhou, Lianqun; Wang, Yi; Li, Chuanyu; Yao, Jia; Zhang, Wei; Zhang, Qingwen; Li, Mingyu; Li, Haiwen; Dong, Wen-fei

2015-01-01

A 20 MHz quartz crystal microbalance (QCM) sensor coated with in situ self-assembled molecularly imprinted polymers (MIPs) was presented for the detection of trace microcystin-LR (MC-LR) in drinking water. The sensor performance obtained using the in situ self-assembled MIPs was compared with traditionally synthesized MIPs on 20 MHz and normal 10 MHz QCM chip. The results show that the response increases by more than 60% when using the in situ self-assembly method compared using the traditionally method while the 20 MHz QCM chip provides four-fold higher response than the 10 MHz one. Therefore, the in situ self-assembled MIPs coated on a high frequency QCM chip was used in the sensor performance test to detect MC-LR in tap water. It showed a limit of detection (LOD) of 0.04 nM which is lower than the safety guideline level (1 nM MC-LR) of drinking water in China. The low sensor response to other analogs indicated the high specificity of the sensor to MC-LR. The sensor showed high stability and low signal variation less than 2.58% after regeneration. The lake water sample analysis shows the sensor is possible for practical use. The combination of the higher frequency QCM with the in situ self-assembled MIPs provides a good candidate for the detection of other small molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

A sensor of alcohol vapours based on thin polyaniline base film and quartz crystal microbalance.

PubMed

Ayad, Mohamad M; El-Hefnawey, Gad; Torad, Nagy L

2009-08-30

Thin films of polyaniline base, emeraldine base (EB), coating on the quartz crystal microbalance (QCM) electrode were used as a sensitive layer for the detection of a number of primary aliphatic alcohols such as ethanol, methanol, 2-propanol and 1-propanol vapours. The frequency shifts (Deltaf) of the QCM were increased due to the vapour adsorption into the EB film. Deltaf were found to be linearly correlated with the concentrations of alcohols vapour in part per million (ppm). The sensitivity of the sensor was found to be governed by the chemical structure of the alcohol. The sensor shows a good reproducibility and reversibility. The diffusions of different alcohols vapour were studied and the diffusion coefficients (D) were calculated. It is concluded that the diffusion of the vapours into the EB film follows Fickian kinetics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stratton, Dan; Lange, Sigrun; Kholia, Sharad

Highlights: • Microvesiculating cells record loss of mass on a Quartz Crystal Microbalance. • Using the Quartz Crystal Microbalance microvesicles are measured at 0.24 pg. • The QCM-D reveals loss in viscoelastic properties in microvesiculating cells. - Abstract: Using a Quartz Crystal Microbalance with dissipation monitoring, QCM-D (label-free system) measuring changes in resonant frequency (Δf) that equate to mass deposited on a sensor, we showed the attachment, over a 60 min period, of a monolayer of PC3 cells to the gold electrodes of the quartz crystal sensor, which had been rendered hydrophilic. That MVs were released upon BzATP stimulation ofmore » cells was confirmed by NTA analysis (average 250 nm diameter), flow cytometry, showing high phosphatidylserine exposition and by fluorescent (Annexin V Alexa Fluor® 488-positive) and electron microscopy. Over a period of 1000s (16.7 min) during which early apoptosis increased from 4% plateauing at 10% and late apoptosis rose to 2%, the Δf increased 20 Hz, thereupon remaining constant for the last 1000s of the experiment. Using the Sauerbrey equation, the loss in mass, which corresponded to the release of 2.36 × 10{sup 6} MVs, was calculated to be 23 ng. We therefore estimated the mass of an MV to be 0.24 pg. With the deposition on the QCM-D of 3.5 × 10{sup 7} MVs over 200s, the decrease in Δf (Hz) gave an estimate of 0.235 pg per MV.« less

A Review of Interface Electronic Systems for AT-cut Quartz Crystal Microbalance Applications in Liquids

PubMed Central

Arnau, Antonio

2008-01-01

From the first applications of AT-cut quartz crystals as sensors in solutions more than 20 years ago, the so-called quartz crystal microbalance (QCM) sensor is becoming into a good alternative analytical method in a great deal of applications such as biosensors, analysis of biomolecular interactions, study of bacterial adhesion at specific interfaces, pathogen and microorganism detection, study of polymer film-biomolecule or cell-substrate interactions, immunosensors and an extensive use in fluids and polymer characterization and electrochemical applications among others. The appropriate evaluation of this analytical method requires recognizing the different steps involved and to be conscious of their importance and limitations. The first step involved in a QCM system is the accurate and appropriate characterization of the sensor in relation to the specific application. The use of the piezoelectric sensor in contact with solutions strongly affects its behavior and appropriate electronic interfaces must be used for an adequate sensor characterization. Systems based on different principles and techniques have been implemented during the last 25 years. The interface selection for the specific application is important and its limitations must be known to be conscious of its suitability, and for avoiding the possible error propagation in the interpretation of results. This article presents a comprehensive overview of the different techniques used for AT-cut quartz crystal microbalance in in-solution applications, which are based on the following principles: network or impedance analyzers, decay methods, oscillators and lock-in techniques. The electronic interfaces based on oscillators and phase-locked techniques are treated in detail, with the description of different configurations, since these techniques are the most used in applications for detection of analytes in solutions, and in those where a fast sensor response is necessary. PMID:27879713

Quartz Crystal Microbalance: Aerosol Viscoelastic Measurement Calibration and Subsiquent H2O Uptake

NASA Astrophysics Data System (ADS)

Farland, D. R., Jr.; Gilles, M. K.; Harder, T.; Weis, J.; Mueller, S.

2015-12-01

Aerosol particles exposed to various atmospheric relative humidity (RH) levels exhibit hygroscopic properties which are not fully understood. Water adsorption or diffusion depends on particle viscosity in semi-solid to liquid states. This relationship between particle viscosity as a function of RH and the corresponding hygroscopic behavioral response is the purpose of this study. However, reliable techniques for viscosity quantification have been limited. A Quartz Crystal Microbalance with Dissipation (QCM-D) was used for viscosity measurements and to determine phase changes. Prior to studies on field samples, microscope immersion/viscosity standard oils, salt crystals, sugars and alpha-pinene secondary organic aerosol (SOA) surrogates are used for viscosity, RH calibrations, water uptake and phase change measurements. RH was controlled by flowing N2 gas saturated with H2O for RH's between 0-75% RH. For higher RH values, (75-100% RH range) saturated salt solutions were flowed over a gore membrane to protect the QCM sensor from direct contact with the solutions. The viscosity calibration constructed via QTools fitting software illustrates the limitations as well as the ranges of reliability of the QCM viscosity measurements. Deliquescing salt crystals of differing deliquescence relative humidity's (DRH), sugars and alpha-pinene SOA's provided insight into the detection of various phase change behaviors. Water uptake experiments performed on alpha-pinene SOA and sucrose sugar yielded significantly different frequency and dissipation responses than the deliquescing salts. Future work will apply these experimental methods and analysis on aerosol particles collected during the GoAmazon field campaign.

A Nano-Thin Film-Based Prototype QCM Sensor Array for Monitoring Human Breath and Respiratory Patterns

PubMed Central

Selyanchyn, Roman; Wakamatsu, Shunichi; Hayashi, Kenshi; Lee, Seung-Woo

2015-01-01

Quartz crystal microbalance (QCM) sensor array was developed for multi-purpose human respiration assessment. The sensor system was designed to provide feedback for human respiration. Thorough optimization of measurement conditions: air flow, temperature in the QCM chamber, frequency measurement rate, and electrode position regarding to the gas flow—was performed. As shown, acquisition of respiratory parameters (rate and respiratory pattern) could be achieved even with a single electrode used in the system. The prototype system contains eight available QCM channels that can be potentially used for selective responses to certain breath chemicals. At present, the prototype machine is ready for the assessment of respiratory functions in larger populations in order to gain statistical validation. To the best of our knowledge, the developed prototype is the only respiratory assessment system based on surface modified QCM sensors. PMID:26263994

The Nose Knows: Developing Advanced Chemical Sensors for the Remote Detection of Improvised Explosive Devices in 2030

DTIC Science & Technology

2009-04-01

noses”, High Frequency Quartz Crystal Microbalance (HF- QCM ), and fluorescent polymer based sensors . The combination of the chemical binding of molecules...nose and uses HF- QCM technology. The hand-held product consists of a sampling unit and analyzer and contains an array of sensors and coatings which...i AU/ACSC/2763/2008-09 AIR COMMAND AND STAFF COLLEGE AIR UNIVERSITY THE NOSE KNOWS: DEVELOPING ADVANCED CHEMICAL SENSORS FOR THE REMOTE

Influence of humidity on CO2 gas sensors based on polyetherimide polymer film

NASA Astrophysics Data System (ADS)

Kang, Ting; Xie, Guangzhong; Zhou, Yong; Xie, Tao; Tai, Huiling

2014-09-01

Quartz Crystal Microbalance (QCM) coated with polyetherimide (PEI) by spin coating method was applied for carbon dioxide (CO2) gas detection at room temperature in this study. The experiments were performed in dry and humid air atmospheres, and the results revealed that the prepared CO2 sensor in moisture circumstance exhibited a larger sensing response than that at dry condition. An enhanced sensing response took place for CO2 detection with the existence of water molecules. The effect of different humidity on QCM sensor performances was investigated as well in this paper. A curve, which displayed a proportional relationship between sensing response and water vapor concentration, was obtained. Moreover, the relevant sensing mechanisms were investigated.

Improved frequency/voltage converters for fast quartz crystal microbalance applications.

PubMed

Torres, R; García, J V; Arnau, A; Perrot, H; Kim, L To Thi; Gabrielli, C

2008-04-01

The monitoring of frequency changes in fast quartz crystal microbalance (QCM) applications is a real challenge in today's instrumentation. In these applications, such as ac electrogravimetry, small frequency shifts, in the order of tens of hertz, around the resonance of the sensor can occur up to a frequency modulation of 1 kHz. These frequency changes have to be monitored very accurately both in magnitude and phase. Phase-locked loop techniques can be used for obtaining a high performance frequency/voltage converter which can provide reliable measurements. Sensitivity higher than 10 mVHz, for a frequency shift resolution of 0.1 Hz, with very low distortion in tracking both the magnitude and phase of the frequency variations around the resonance frequency of the sensor are required specifications. Moreover, the resonance frequency can vary in a broad frequency range from 5 to 10 MHz in typical QCM sensors, which introduces an additional difficulty. A new frequency-voltage conversion system based on a double tuning analog-digital phase-locked loop is proposed. The reported electronic characterization and experimental results obtained with conducting polymers prove its reliability for ac-electrogravimetry measurements and, in general, for fast QCM applications.

Assembly of streptolysin O pores assessed by quartz crystal microbalance and atomic force microscopy provides evidence for the formation of anchored but incomplete oligomers.

PubMed

Stewart, Sarah E; D'Angelo, Michael E; Paintavigna, Stefania; Tabor, Rico F; Martin, Lisandra L; Bird, Phillip I

2015-01-01

Streptolysin O (SLO) is a bacterial pore forming protein that is part of the cholesterol dependent cytolysin (CDC) family. We have used quartz crystal microbalance with dissipation monitoring (QCM-D) to examine SLO membrane binding and pore formation. In this system, SLO binds tightly to cholesterol-containing membranes, and assembles into partial and complete pores confirmed by atomic force microscopy. SLO binds to the lipid bilayer at a single rate consistent with the Langmuir isotherm model of adsorption. Changes in dissipation illustrate that SLO alters the viscoelastic properties of the bilayer during pore formation, but there is no loss of material from the bilayer as reported for small membrane-penetrating peptides. SLO mutants were used to further dissect the assembly and insertion processes by QCM-D. This shows the signature of SLO in QCM-D changes when pore formation is inhibited, and that bound and inserted SLO forms can be distinguished. Furthermore a pre-pore locked SLO mutant binds reversibly to lipid, suggesting that the partially complete wtSLO forms observed by AFM are anchored to the membrane. Copyright © 2014 Elsevier B.V. All rights reserved.

Improved frequency/voltage converters for fast quartz crystal microbalance applications

NASA Astrophysics Data System (ADS)

Torres, R.; García, J. V.; Arnau, A.; Perrot, H.; Kim, L. To Thi; Gabrielli, C.

2008-04-01

The monitoring of frequency changes in fast quartz crystal microbalance (QCM) applications is a real challenge in today's instrumentation. In these applications, such as ac electrogravimetry, small frequency shifts, in the order of tens of hertz, around the resonance of the sensor can occur up to a frequency modulation of 1kHz. These frequency changes have to be monitored very accurately both in magnitude and phase. Phase-locked loop techniques can be used for obtaining a high performance frequency/voltage converter which can provide reliable measurements. Sensitivity higher than 10mV/Hz, for a frequency shift resolution of 0.1Hz, with very low distortion in tracking both the magnitude and phase of the frequency variations around the resonance frequency of the sensor are required specifications. Moreover, the resonance frequency can vary in a broad frequency range from 5to10MHz in typical QCM sensors, which introduces an additional difficulty. A new frequency-voltage conversion system based on a double tuning analog-digital phase-locked loop is proposed. The reported electronic characterization and experimental results obtained with conducting polymers prove its reliability for ac-electrogravimetry measurements and, in general, for fast QCM applications.

Water Vapor Uptake of Ultrathin Films of Biologically Derived Nanocrystals: Quantitative Assessment with Quartz Crystal Microbalance and Spectroscopic Ellipsometry.

PubMed

Niinivaara, Elina; Faustini, Marco; Tammelin, Tekla; Kontturi, Eero

2015-11-10

Despite the relevance of water interactions, explicit analysis of vapor adsorption on biologically derived surfaces is often difficult. Here, a system was introduced to study the vapor uptake on a native polysaccharide surface; namely, cellulose nanocrystal (CNC) ultrathin films were examined with a quartz crystal microbalance with dissipation monitoring (QCM-D) and spectroscopic ellipsometry (SE). A significant mass uptake of water vapor by the CNC films was detected using the QCM-D upon increasing relative humidity. In addition, thickness changes proportional to changes in relative humidity were detected using SE. Quantitative analysis of the results attained indicated that in preference to being soaked by water at the point of hydration each individual CNC in the film became enveloped by a 1 nm thick layer of adsorbed water vapor, resulting in the detected thickness response.

Characterization of N3 dye adsorption on TiO2 using quartz-crystal microbalance with dissipation monitoring

NASA Astrophysics Data System (ADS)

Wayment-Steele, Hannah K.; Johnson, Lewis E.; Dixon, Matthew C.; Johal, Malkiat S.

2013-09-01

Understanding the kinetics of dye adsorption on semiconductors is crucial for designing dye-sensitized solar cells (DSSCs) with enhanced efficiency. Harms et al. recently applied the Quartz-Crystal Microbalance with Dissipation Monitoring (QCM-D) to study in situ dye adsorption on flat TiO2 surfaces. QCM-D measures adsorption in real time and therefore allows one to determine the kinetics of the process. In this work, we characterize the adsorption of N3, a commercial RuBipy dye, using the native oxide layer of a titanium sensor to simulate the TiO2 substrate of a DSSC. We report equilibrium constants that are in agreement with previous absorbance studies of N3 adsorption, and therefore demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption.

Hydrogel based QCM aptasensor for detection of avian influenza virus.

PubMed

Wang, Ronghui; Li, Yanbin

2013-04-15

The objective of this study was to develop a quartz crystal microbalance (QCM) aptasensor based on ssDNA crosslinked polymeric hydrogel for rapid, sensitive and specific detection of avian influenza virus (AIV) H5N1. A selected aptamer with high affinity and specificity against AIV H5N1 surface protein was used, and hybridization between the aptamer and ssDNA formed the crosslinker in the polymer hydrogel. The aptamer hydrogel was immobilized on the gold surface of QCM sensor using a self-assembled monolayer method. The hydrogel remained in the state of shrink if no H5N1 virus was present in the sample because of the crosslinking between the aptamer and ssDNA in the polymer network. When it exposed to target virus, the binding reaction between the aptamer and H5N1 virus caused the dissolution of the linkage between the aptamer and ssDNA, resulting in the abrupt swelling of the hydrogel. The swollen hydrogel was monitored by the QCM sensor in terms of decreased frequency. Three polymeric hydrogels with different ratio (100:1 hydrogel I, 10:1 hydrogel II, 1:1 hydrogel III) of acrylamide and the aptamer monomer were synthesized, respectively, and then were used as the QCM sensor coating material. The results showed that the developed hydrogel QCM aptasensor was capable of detecting target H5N1 virus, and among the three developed aptamer hydrogels, hydrogel III coated QCM aptasensor achieved the highest sensitivity with the detection limit of 0.0128 HAU (HA unit). The total detection time from sampling to detection was only 30 min. In comparison with the anti-H5 antibody coated QCM immunosensor, the hydrogel QCM aptasensor lowered the detection limit and reduced the detection time. Copyright © 2012 Elsevier B.V. All rights reserved.

Performance of a flight qualified, thermoelectrically temperature controlled QCM sensor with power supply, thermal controller and signal processor

NASA Technical Reports Server (NTRS)

Wallace, D. A.

1980-01-01

A thermoelectrically temperature controlled quartz crystal microbalance (QCM) system was developed for the measurement of ion thrustor generated mercury contamination on spacecraft. Meaningful flux rate measurements dictated an accurately held sensing crystal temperature despite spacecraft surface temperature variations from -35 C to +60 C over the flight temperature range. An electronic control unit was developed with magentic amplifier transformer secondary power supply, thermal control electronics, crystal temperature analog conditioning and a multiplexed 16 bit frequency encoder.

A Study of a QCM Sensor Based on TiO₂ Nanostructures for the Detection of NO₂ and Explosives Vapours in Air.

PubMed

Procek, Marcin; Stolarczyk, Agnieszka; Pustelny, Tadeusz; Maciak, Erwin

2015-04-22

The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied.

Development of QCM Trimethylamine Sensor Based on Water Soluble Polyaniline.

PubMed

Li, Guang; Zheng, Junbao; Ma, Xingfa; Sun, Yu; Fu, Jun; Wu, Gang

2007-10-17

A rapid, sensitive, low-cost device to detect trimethylamine was presented in thispaper. The preparation of water soluble polyaniline was firstly studied. Then the polyanilinewas characterized via Fourier transform infrared spectroscopy (FTIR), UV-visiblespectroscopy and scanning electron microscopy (SEM). Based on the water solublepolyaniline film, a quartz crystal microbalance (QCM) sensor for trimethylamine detectionwas fabricated and its characteristics were examined. The sensor consisted of one quartzcrystal oscillator coated with the polyaniline film for sensing and the other one forreference. Pretreated with trimethylamine, the QCM sensor had an excellent linearsensitivity to trimethylamine. Easily recovered by N2 purgation, the response of the sensorexhibited a good repeatability. Responses of the sensor to trimethylamine, ethanol and ethylacetate were compared, and the results showed that the response was related to the polarityof the analyte vapor. Experimental result also showed that the sensitivity of the sensor wasrelatively stable within one month. The simple and feasible method to prepare and coat thepolyaniline sensing film makes it promising for mass production.

A Study of a QCM Sensor Based on TiO2 Nanostructures for the Detection of NO2 and Explosives Vapours in Air

PubMed Central

Procek, Marcin; Stolarczyk, Agnieszka; Pustelny, Tadeusz; Maciak, Erwin

2015-01-01

The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied. PMID:25912352

Multiwalled Carbon Nanotube Deposition on Model Environmental Surfaces

EPA Science Inventory

Deposition of multiwalled carbon nanotubes (MWNTs) on model environmental surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Deposition behaviors of MWNTs on positively and negatively charged surfaces were in good agreement with Der...

Low cost biosensor-based molecular differential diagnosis of α-thalassemia (Southeast Asia deletion).

PubMed

Wangmaung, Nantawan; Promptmas, Chamras; Chomean, Sirinart; Sanchomphu, Chularat; Ittarat, Wanida

2013-06-01

Thalassemias are genetic hematologic diseases which the homozygous form of α-thalassemia can cause either death in utero or shortly after birth. It is necessary to accurately identify high-risk heterozygous couples. We developed a quartz crystal microbalance (QCM) to identify the abnormal gene causing the commonly found α-thalassemia1, [Southeast Asia (SEA) deletion]. This work is an improved method of our previous study by reducing both production cost and analysis time. A silver electrode on the QCM surface was immobilized with a biotinylated probe. The α-globin gene fragment was amplified and hybridized with the probe. Hybridization was indicated by changes of quartz oscillation. Each drying step was improved by using an air pump for 30 min instead of the overnight air dry. The diagnostic potency of the silver QCM was evaluated using 70 suspected samples with microcytic hypochromic erythrocytes. The silver QCM could clearly identify samples with abnormal α-globin genes, either homozygous or heterozygous, from normal samples. Thirteen out of 70 blood samples were identified as carrier of α-thalassemia1 (SEA deletion). Results were consistent with the standard agarose gel electrophoresis. Using silver instead of gold QCM could reduce the production expense 10-fold. An air pump drying the QCM surface could reduce the analysis time from 3 days to 4 h. The silver thalassemic QCM was specific, sensitive, rapid, cheap and field applicable. It could be used as a one-step definite diagnosis of α-thalassemia1 (SEA deletion) with no need for the preliminary screening test.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anazagasty, Cristain; Hianik, Tibor; Ivanov, Ilia N

Proliferation of environmental sensors for internet of things (IoT) applications has increased the need for low-cost platforms capable of accommodating multiple sensors. Quartz crystal microbalance (QCM) crystals coated with nanometer-thin sensor films are suitable for use in high-resolution (~1 ng) selective gas sensor applications. We demonstrate a scalable array for measuring frequency response of six QCM sensors controlled by low-cost Arduino microcontrollers and a USB multiplexer. Gas pulses and data acquisition were controlled by a LabVIEW user interface. We test the sensor array by measuring the frequency shift of crystals coated with different compositions of polymer composites based on poly(3,4-ethylenedioxythiophene):polystyrenemore » sulfonate (PEDOT:PSS) while films are exposed to water vapor and oxygen inside a controlled environmental chamber. Our sensor array exhibits comparable performance to that of a commercial QCM system, while enabling high-throughput 6 QCM testing for under $1,000. We use deep neural network structures to process sensor response and demonstrate that the QCM array is suitable for gas sensing, environmental monitoring, and electronic-nose applications.« less

Amplified QCM biosensor for type IV collagenase based on collagenase-cleavage of gold nanoparticles functionalized peptide.

PubMed

Dong, Zong-Mu; Jin, Xin; Zhao, Guang-Chao

2018-05-30

The present study develops a rapid, simple and efficient method for the determination of type IV collagenase by using a specific peptide-modified quartz crystal microbalance (QCM). A small peptide (P1), contains a specific sequence (Pro-Gly) and a terminal cysteine, was synthetized and immobilized to the surface of QCM electrode via the reaction between Au and thiol of the cysteine. The peptide bond between proline and glycine can be specific hydrolyzed cleavage by type IV collagenase, which enabled the modified electrode with a high selectivity toward type IV collagenase. The cleaving process caused a frequency change of QCM to give a signal related to the concentration of type IV collagenase. The morphologies of the modified electrodes were characterized by scanning electron microscope (SEM) and the specific hydrolyzed cleavage process was monitored by QCM. When P1 was modified with gold nanoparticles (P1-Au NPs), the signal could be amplified to further enhance the sensitivity of the designed sensor due to the high-mass of the modified Au NPs. Compared the direct unamplified assay, the values obtained for the limit of detection for type IV collagenase was 0.96 ng mL -1 , yielding about 6.5 times of magnitude improvement in sensitivity. This signal enhanced peptide based QCM biosensor for type IV collagenase also showed good selectivity and sensitivity in complex matrix. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Ultrasonic on Copper Electroplating from the Non-Cyanide Alkaline Baths

NASA Astrophysics Data System (ADS)

Li, Minggang; Hu, Shuangshuang; Yang, Yejiong; Xu, Shuhan; Zhao, Xixi; Wei, Guoying

2014-06-01

Effects of the different ultrasonic powers on copper electrodeposition from non-cyanide alkaline baths by using pyrophosphate as complexing agent were investigated by different electrochemical methods. Cyclic voltammetry and current transient measurements were used to characterize the nucleation and growth mechanism. It is very obvious that the reduction potential moves to more positive one as the ultrasonic power increases. The quartz crystal microbalance (QCM) and chronoamperometric method were used to study the relationship between the mass change and the deposition time. It was found that the current efficiency of electrolyte under 0, 60, 80 and 100 W is 91.95%, 92.14%, 89.25% and 96.11%, respectively measured by QCM measurements. The surface morphology of the electrodeposited Cu films is analyzed by scanning electron microscopy (SEM). The morphology of copper films electrodeposited under the power of 60 W and 80 W presents a compact surface and the grains are fine and uniform.

Simultaneous measurement of the maximum oscillation amplitude and the transient decay time constant of the QCM reveals stiffness changes of the adlayer.

PubMed

Marxer, C Galli; Coen, M Collaud; Bissig, H; Greber, U F; Schlapbach, L

2003-10-01

Interpretation of adsorption kinetics measured with a quartz crystal microbalance (QCM) can be difficult for adlayers undergoing modification of their mechanical properties. We have studied the behavior of the oscillation amplitude, A(0), and the decay time constant, tau, of quartz during adsorption of proteins and cells, by use of a home-made QCM. We are able to measure simultaneously the frequency, f, the dissipation factor, D, the maximum amplitude, A(0), and the transient decay time constant, tau, every 300 ms in liquid, gaseous, or vacuum environments. This analysis enables adsorption and modification of liquid/mass properties to be distinguished. Moreover the surface coverage and the stiffness of the adlayer can be estimated. These improvements promise to increase the appeal of QCM methodology for any applications measuring intimate contact of a dynamic material with a solid surface.

Towards vaporized molecular discrimination: a quartz crystal microbalance (QCM) sensor system using cobalt-containing mesoporous graphitic carbon.

PubMed

Tang, Jing; Torad, Nagy L; Salunkhe, Rahul R; Yoon, Jang-Hee; Al Hossain, Md Shahriar; Dou, Shi Xue; Kim, Jung Ho; Kimura, Tatsuo; Yamauchi, Yusuke

2014-11-01

A recent study on nanoporous carbon based materials (J. Am. Chem. Soc. 2012, 134, 2864) showed that the presence of abundant graphitized sp(2) carbon species in the frameworks led to higher affinity for aromatic hydrocarbons than their aliphatic analogues. Herein, improved understanding of the sensitive and selective detection of aromatic substances by using mesoporous carbon (MPC)-based materials, combined with a quartz crystal microbalance (QCM) sensor system, was obtained. MPCs were synthesized by direct carbonization of mesoporous polymers prepared from resol through a soft templating approach with Pluronic F127. The carbon-based frameworks can be graphitized through the addition of a cobalt source to the precursor solution, according to the catalytic activity of the cobalt nanoparticles formed during the carbonization process. From the Raman data, the degree of the graphitization was clearly increased by increasing the cobalt content and elevating the carbonization temperature. From a QCM study, it was proved that the highly graphitized MPCs exhibited a higher affinity for aromatic hydrocarbons than their aliphatic analogues. By increasing the degree of graphitization in the carbon-based pore walls, the MPCs showed both larger adsorption uptake and faster sensor response towards toxic benzene and toluene vapors. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent effect on polystyrene surface roughness on top of QCM sensor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sakti, Setyawan P., E-mail: sakti@ub.ac.id; Rahmawati, Eka; Robiandi, Fadli

2016-03-11

Quartz Crystal Microbalance (QCM) has been used as a basis for many chemical sensors and biosensor. Its sensitivity to mass change which can detect a mass change on its surface down to sub ng/cm2 is one of its interesting aspects. Another interesting feature is its ability to work in liquid environment. However, there are many aspects which influence QCM sensor properties in contact with liquid. One of the aspects is surface roughness of the matrix layer where on top of it a biological sensitive layer will be immobilized. One of matrix layers in the immobilizing biological sensitive layer was polystyrene.more » Polystyrene was coated on the QCM sensor by using the spin coating method. During the coating process, polystyrene was solved using non-polar solvent. It is known that the physical and chemical properties of the solvent affect a transition process from soluble polymer becoming rigid polymer layer. In this work, we show that polystyrene solved in chloroform has a higher surface roughness compare to one solved in toluene, xylene, or tetrahydrofuran. Surface roughness of the polystyrene coating were measured using a non-contact profilometer. However, we also found that there is no difference on the electrical impedance of the QCM sensor coated with polystyrene resulted from differing solvent when the sensor was in contact with air and water. Thus, all of the mentioned solvent can be used to solve the polystyrene as a coating material for QCM sensor without affecting the electrical performance of the sensor, but the choice of the solution can be used as a simple method to control the difference roughness of the polystyrene coating.« less

Solvent effect on polystyrene surface roughness on top of QCM sensor

NASA Astrophysics Data System (ADS)

Sakti, Setyawan P.; Rahmawati, Eka; Robiandi, Fadli

2016-03-01

Quartz Crystal Microbalance (QCM) has been used as a basis for many chemical sensors and biosensor. Its sensitivity to mass change which can detect a mass change on its surface down to sub ng/cm2 is one of its interesting aspects. Another interesting feature is its ability to work in liquid environment. However, there are many aspects which influence QCM sensor properties in contact with liquid. One of the aspects is surface roughness of the matrix layer where on top of it a biological sensitive layer will be immobilized. One of matrix layers in the immobilizing biological sensitive layer was polystyrene. Polystyrene was coated on the QCM sensor by using the spin coating method. During the coating process, polystyrene was solved using non-polar solvent. It is known that the physical and chemical properties of the solvent affect a transition process from soluble polymer becoming rigid polymer layer. In this work, we show that polystyrene solved in chloroform has a higher surface roughness compare to one solved in toluene, xylene, or tetrahydrofuran. Surface roughness of the polystyrene coating were measured using a non-contact profilometer. However, we also found that there is no difference on the electrical impedance of the QCM sensor coated with polystyrene resulted from differing solvent when the sensor was in contact with air and water. Thus, all of the mentioned solvent can be used to solve the polystyrene as a coating material for QCM sensor without affecting the electrical performance of the sensor, but the choice of the solution can be used as a simple method to control the difference roughness of the polystyrene coating.

Quartz crystal microbalance detection of DNA single-base mutation based on monobase-coded cadmium tellurium nanoprobe.

PubMed

Zhang, Yuqin; Lin, Fanbo; Zhang, Youyu; Li, Haitao; Zeng, Yue; Tang, Hao; Yao, Shouzhuo

2011-01-01

A new method for the detection of point mutation in DNA based on the monobase-coded cadmium tellurium nanoprobes and the quartz crystal microbalance (QCM) technique was reported. A point mutation (single-base, adenine, thymine, cytosine, and guanine, namely, A, T, C and G, mutation in DNA strand, respectively) DNA QCM sensor was fabricated by immobilizing single-base mutation DNA modified magnetic beads onto the electrode surface with an external magnetic field near the electrode. The DNA-modified magnetic beads were obtained from the biotin-avidin affinity reaction of biotinylated DNA and streptavidin-functionalized core/shell Fe(3)O(4)/Au magnetic nanoparticles, followed by a DNA hybridization reaction. Single-base coded CdTe nanoprobes (A-CdTe, T-CdTe, C-CdTe and G-CdTe, respectively) were used as the detection probes. The mutation site in DNA was distinguished by detecting the decreases of the resonance frequency of the piezoelectric quartz crystal when the coded nanoprobe was added to the test system. This proposed detection strategy for point mutation in DNA is proved to be sensitive, simple, repeatable and low-cost, consequently, it has a great potential for single nucleotide polymorphism (SNP) detection. 2011 © The Japan Society for Analytical Chemistry

Recognition of Bread Key Odorants by Using Polymer Coated QCMs

NASA Astrophysics Data System (ADS)

Nakai, Takashi; Kouno, Shinji; Hiruma, Naoya; Shuzo, Masaki; Delaunay, Jean-Jacques; Yamada, Ichiro

Polyisobutylene (PIB) polymer and methylphenylsiloxane (25%) diphenylsiloxane (75%) copolymer (OV25) were coated on Quartz Crystal Microbalance (QCM) sensors and used in recognition of bread key odorants. Representative compounds of key roasty odorants of bread were taken as 3-acetylpyridine and benzaldehyde, and representative key fatty odorants were hexanal and (E)-2-nonenal. Both OV25- and PIB-coated QCM fabricated sensors could detect concentration as low as 0.9 ppm of 3-acetylpyridine and 1.2 ppm of (E)-2-nonenal. The sensitivity to 3-acetylpyridine of the OV25-coated QCM was about 1000 times higher than that of ethanol, the major interference compound in bread key odorant analysis. Further, the OV25-coated QCM response was 5-6 times and 2-3 times larger than that of the PIB-coated QCM when exposed to roasty odorants and to fatty odorants, respectively. The difference in sensitivity of the OV25- and PIB-coated QCMs we fabricated made possible to discriminate roasty from fatty odorants as was evidenced by the odor recognition map representing the frequency shifts of the OV25-coated QCM against the frequency shift of the PIB-coated QCM. In conclusion, we found that the combination of an OV25-coated QCM and a PIB-coated QCM was successful in discriminating roasty odorants from fatty odorants at the ppm level.

Comparative determination of two probiotics by QCM and OWLS-based immunosensors.

PubMed

Szalontai, Helga; Adányi, Nóra; Kiss, Attila

2014-09-25

The regular consumption of foods containing probiotic bacteria has beneficial physiological effects on the health and the digestion system. There is a need for novel analytical approaches for the determination of these bacteria that are faster than the classical plate counting method. For this purpose, two label-free biosensors were investigated and presented in this paper: Quartz Crystal Microbalance (QCM) and Optical Waveguide Lightmode Spectroscopy (OWLS) based direct immunosensors were developed for real-time direct detection of probiotic bacteria in fermented dairy products. Bifidobacterium bifidum O1356 and Lactobacillus acidophilus O1132 were detected by polyclonal anti-B. bifidum IgG and anti-L. acidophilus IgG immobilized on the sensors' surface. Sulfo-LC-SPDP cross linking agent was used to bind antibodies to the gold surface of the QCM's AT-cut quartz wafer. Concerning OWLS, antibodies were covalently bound to the amino groups of the silanized surface of the waveguide by glutaraldehyde. The dynamic measuring range was found between 1.0E+3 and 5.0E+5CFUmL(-1) in 100 fold diluted fermented milk products by QCM and with OWLS. Considering the current legislation of the probiotic content in probiotic products, the two developed immunosensors can be applied for rapid quantification of L. acidophilus and B. bifidum in fermented milk. These examinations offer effective alternatives to the microbiological plate counting method. Copyright © 2014 Elsevier B.V. All rights reserved.

Application of quartz crystal microbalance to study the impact of pH and ionic strength on protein-silicone oil interactions.

PubMed

Dixit, Nitin; Maloney, Kevin M; Kalonia, Devendra S

2011-06-30

In this study, we have used quartz crystal microbalance (QCM) to quantitate the adsorption of a protein on silicone oil coated surfaces as a function of protein concentration, pH and ionic strength using a 5 MHz quartz crystal. Protein adsorption isotherms were generated at different solution pH and ionic strengths. Surface saturation concentrations were selected from adsorption isotherms and used to generate adsorption profiles from pH 3.0 to 9.0, and at ionic strengths of 10 mM and 150 mM. At low ionic strength (10mM) and pH 5.0 (close to the isoelectric point of the protein), maximum adsorption of protein to the silicone oil surface was observed. At higher ionic strength (150 mM), no significant pH influence on adsorption was observed. QCM could be used as a reliable technique to study the binding of proteins to silicone oil coated surfaces. Copyright © 2011 Elsevier B.V. All rights reserved.

Wireless poly(dimethylsiloxane) quartz-crystal-microbalance biosensor chip fabricated by nanoimprint lithography for micropump integration aiming at application in lab-on-a-chip

NASA Astrophysics Data System (ADS)

Kato, Fumihito; Noguchi, Hiroyuki; Kodaka, Yukinari; Oshida, Naoya; Ogi, Hirotsugu

2018-07-01

We developed a quartz-crystal-microbalance (QCM) biosensor chip that operates wirelessly via electromagnetic waves, using poly(dimethylsiloxane) (PDMS). An AT-cut quartz oscillator (22–30 µm) is packaged in a microchannel, where it is supported by micropillars without mechanical fixing. As a result, the quartz oscillator is little affected by the thermal stress caused by the difference in the thermal expansion coefficients of the components, and the leakage of the vibration energy of the quartz oscillator is reduced. Consequently, high-frequency (∼56 MHz) measurement with a stable baseline (±∼2 ppm) is realized. We succeeded in repeatedly monitoring the binding reaction between immunoglobulin G (IgG) and Staphylococcus aureus protein A (SPA) with the quartz oscillator on which SPA molecules were immobilized nonspecifically. In addition, the affinity between SPA and IgG was calculated from the association and dissociation curves, and the usefulness of our wireless PDMS QCM biosensor was demonstrated.

Accurate dew-point measurement over a wide temperature range using a quartz crystal microbalance dew-point sensor

NASA Astrophysics Data System (ADS)

Kwon, Su-Yong; Kim, Jong-Chul; Choi, Buyng-Il

2008-11-01

Quartz crystal microbalance (QCM) dew-point sensors are based on frequency measurement, and so have fast response time, high sensitivity and high accuracy. Recently, we have reported that they have the very convenient attribute of being able to distinguish between supercooled dew and frost from a single scan through the resonant frequency of the quartz resonator as a function of the temperature. In addition to these advantages, by using three different types of heat sinks, we have developed a QCM dew/frost-point sensor with a very wide working temperature range (-90 °C to 15 °C). The temperature of the quartz surface can be obtained effectively by measuring the temperature of the quartz crystal holder and using temperature compensation curves (which showed a high level of repeatability and reproducibility). The measured dew/frost points showed very good agreement with reference values and were within ±0.1 °C over the whole temperature range.

Lipid phase behavior studied with a quartz crystal microbalance: A technique for biophysical studies with applications in screening

NASA Astrophysics Data System (ADS)

Peschel, Astrid; Langhoff, Arne; Uhl, Eva; Dathathreyan, Aruna; Haindl, Susanne; Johannsmann, Diethelm; Reviakine, Ilya

2016-11-01

Quartz crystal microbalance (QCM) is emerging as a versatile tool for studying lipid phase behavior. The technique is attractive for fundamental biophysical studies as well applications because of its simplicity, flexibility, and ability to work with very small amounts of material crucial for biomedical studies. Further progress hinges on the understanding of the mechanism, by which a surface-acoustic technique such as QCM, senses lipid phase changes. Here, we use a custom-built instrument with improved sensitivity to investigate phase behavior in solid-supported lipid systems of different geometries (adsorbed liposomes and bilayers). We show that we can detect a model anesthetic (ethanol) through its effect on the lipid phase behavior. Further, through the analysis of the overtone dependence of the phase transition parameters, we show that hydrodynamic effects are important in the case of adsorbed liposomes, and viscoelasticity is significant in supported bilayers, while layer thickness changes make up the strongest contribution in both systems.

Improving the binding efficiency of quartz crystal microbalance biosensors by applying the electrothermal effect

PubMed Central

Huang, Yao-Hung; Chang, Jeng-Shian; Chao, Sheng D.; Wu, Kuang-Chong; Huang, Long-Sun

2014-01-01

A quartz crystal microbalance (QCM) serving as a biosensor to detect the target biomolecules (analytes) often suffers from the time consuming process, especially in the case of diffusion-limited reaction. In this experimental work, we modify the reaction chamber of a conventional QCM by integrating into the multi-microelectrodes to produce electrothermal vortex flow which can efficiently drive the analytes moving toward the sensor surface, where the analytes were captured by the immobilized ligands. The microelectrodes are placed on the top surface of the chamber opposite to the sensor, which is located on the bottom of the chamber. Besides, the height of reaction chamber is reduced to assure that the suspended analytes in the fluid can be effectively drived to the sensor surface by induced electrothermal vortex flow, and also the sample costs are saved. A series of frequency shift measurements associated with the adding mass due to the specific binding of the analytes in the fluid flow and the immobilized ligands on the QCM sensor surface are performed with or without applying electrothermal effect (ETE). The experimental results show that electrothermal vortex flow does effectively accelerate the specific binding and make the frequency shift measurement more sensible. In addition, the images of the binding surfaces of the sensors with or without applying electrothermal effect are taken through the scanning electron microscopy. By comparing the images, it also clearly indicates that ETE does raise the specific binding of the analytes and ligands and efficiently improves the performance of the QCM sensor. PMID:25538808

Analyzing the Deposition of Titanium Dioxide Nanoparticles at Model Rough Mineral Surfaces Using a Quartz Crystal Microbalance with Dissipation Monitoring

NASA Astrophysics Data System (ADS)

Li, Y.; Kananizadeh, N.; Rodenhausen, K. B.; Schubert, M.; Bartelt-Hunt, S.

2015-12-01

Titanium dioxide nanoparticles (nTiO2) is the most extensively manufactured engineered materials. nTiO2 from sunscreens was found to enter sediments after released into a lake. nTiO2 may also enter the subsurface via irrigation using effluents from wastewater treatment plants. Interaction of nTiO2 with soils and sediments will largely influence their fate, transport, and ecotoxicity. Measuring the interaction between nTiO2 and natural substrates (e.g. such as sands) is particularly challenging due to highly heterogeneous and rough natural sand surfaces. In this study, an engineered controllable rough surface known as three dimensional nanostructured sculptured columnar thin films (SCTFs) has been used to mimic surface roughness. SCTFs were fabricated by glancing angle deposition (GLAD), a physical vapor deposition technique facilitated by electron beam evaporation. Interaction between nTiO2 and SCTF coated surfaces was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). In parallel, a Generalized Ellipsometry (GE) was coupled with the QCM-D to measure the deposition of nTiO2. We found that the typical QCM-D modeling approach, e.g. viscoelastic model, would largely overestimate the mass of deposited nTiO2, because the frequency drops due to particle deposition or water entrapment in rough areas were not differentiated. Here, we demonstrate a new approach to model QCM-D data for nTiO2 deposition on rough surfaces, which couples the viscoelastic model with a model of flow on the non-uniform surface.

Reversible changes in cell morphology due to cytoskeletal rearrangements measured in real-time by QCM-D.

PubMed

Tymchenko, Nina; Nilebäck, Erik; Voinova, Marina V; Gold, Julie; Kasemo, Bengt; Svedhem, Sofia

2012-12-01

The mechanical properties and responses of cells to external stimuli (including drugs) are closely connected to important phenomena such as cell spreading, motility, activity, and potentially even differentiation. Here, reversible changes in the viscoelastic properties of surface-attached fibroblasts were induced by the cytoskeleton-perturbing agent cytochalasin D, and studied in real-time by the quartz crystal microbalance with dissipation (QCM-D) technique. QCM-D is a surface sensitive technique that measures changes in (dynamically coupled) mass and viscoelastic properties close to the sensor surface, within a distance into the cell that is usually only a fraction of its size. In this work, QCM-D was combined with light microscopy to study in situ cell attachment and spreading. Overtone-dependent changes of the QCM-D responses (frequency and dissipation shifts) were first recorded, as fibroblast cells attached to protein-coated sensors in a window equipped flow module. Then, as the cell layer had stabilised, morphological changes were induced in the cells by injecting cytochalasin D. This caused changes in the QCM-D signals that were reversible in the sense that they disappeared upon removal of cytochalasin D. These results are compared to other cell QCM-D studies. Our results stress the combination of QCM-D and light microscopy to help interpret QCM-D results obtained in cell assays and thus suggests a direction to develop the QCM-D technique as an even more useful tool for real-time cell studies.

Characterization of PLD grown WO3 thin films for gas sensing

NASA Astrophysics Data System (ADS)

Boyadjiev, Stefan I.; Georgieva, Velichka; Stefan, Nicolaie; Stan, George E.; Mihailescu, Natalia; Visan, Anita; Mihailescu, Ion N.; Besleaga, Cristina; Szilágyi, Imre M.

2017-09-01

Tungsten trioxide (WO3) thin films were grown by pulsed laser deposition (PLD) with the aim to be applied in gas sensors. The films were studied by atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and profilometry. To study the gas sensing behavior of these WO3 films, they were deposited on quartz resonators and the quartz crystal microbalance (QCM) method was applied to analyze their gas sensitivity. Synthesis of tetragonal-WO3 films starting from a target with predominantly monoclinic WO3 phase was observed. The films deposited at 300 °C presented a surface topology favorable for the sorption properties, consisting of a film matrix with protruding craters/cavities. QCM prototype sensors with such films were tested for NO2 sensing. The PLD grown WO3 thin films show good sensitivity and fast reaction at room temperature, even in as-deposited state. With the presented technology, the manufacturing of QCM gas sensors is simple, fast and cost-effective, and it is also suitable for energy-effective portable equipment for on-line monitoring of environmental changes.

Bacterial Surface Glycans: Microarray and QCM Strategies for Glycophenotyping and Exploration of Recognition by Host Receptors.

PubMed

Kalograiaki, Ioanna; Campanero-Rhodes, María A; Proverbio, Davide; Euba, Begoña; Garmendia, Junkal; Aastrup, Teodor; Solís, Dolores

2018-01-01

Bacterial surfaces are decorated with a diversity of carbohydrate structures that play important roles in the bacteria-host relationships. They may offer protection against host defense mechanisms, elicit strong antigenic responses, or serve as ligands for host receptors, including lectins of the innate immune system. Binding by these lectins may trigger defense responses or, alternatively, promote attachment, thereby enhancing infection. The outcome will depend on the particular bacterial surface landscape, which may substantially differ among species and strains. In this chapter, we describe two novel methods for exploring interactions directly on the bacterial surface, based on the generation of bacterial microarrays and quartz crystal microbalance (QCM) sensor chips. Bacterial microarrays enable profiling of accessible carbohydrate structures and screening of their recognition by host receptors, also providing information on binding avidity, while the QCM approach allows determination of binding affinity and kinetics. In both cases, the chief element is the use of entire bacterial cells, so that recognition of the bacterial glycan epitopes is explored in their natural environment. © 2018 Elsevier Inc. All rights reserved.

Dew Point Calibration System Using a Quartz Crystal Sensor with a Differential Frequency Method.

PubMed

Lin, Ningning; Meng, Xiaofeng; Nie, Jing

2016-11-18

In this paper, the influence of temperature on quartz crystal microbalance (QCM) sensor response during dew point calibration is investigated. The aim is to present a compensation method to eliminate temperature impact on frequency acquisition. A new sensitive structure is proposed with double QCMs. One is kept in contact with the environment, whereas the other is not exposed to the atmosphere. There is a thermal conductivity silicone pad between each crystal and a refrigeration device to keep a uniform temperature condition. A differential frequency method is described in detail and is applied to calibrate the frequency characteristics of QCM at the dew point of -3.75 °C. It is worth noting that frequency changes of two QCMs were approximately opposite when temperature conditions were changed simultaneously. The results from continuous experiments show that the frequencies of two QCMs as the dew point moment was reached have strong consistency and high repeatability, leading to the conclusion that the sensitive structure can calibrate dew points with high reliability.

A comparative review of optical surface contamination assessment techniques

NASA Technical Reports Server (NTRS)

Heaney, James B.

1987-01-01

This paper will review the relative sensitivities and practicalities of the common surface analytical methods that are used to detect and identify unwelcome adsorbants on optical surfaces. The compared methods include visual inspection, simple reflectometry and transmissiometry, ellipsometry, infrared absorption and attenuated total reflectance spectroscopy (ATR), Auger electron spectroscopy (AES), scanning electron microscopy (SEM), secondary ion mass spectrometry (SIMS), and mass accretion determined by quartz crystal microbalance (QCM). The discussion is biased toward those methods that apply optical thin film analytical techniques to spacecraft optical contamination problems. Examples are cited from both ground based and in-orbit experiments.

Nanotribological Properties of Positively and Negatively charged nanodiamonds as additives to solutions

NASA Astrophysics Data System (ADS)

Liu, Zijian; Corley, Steven; Shenderova, Olga; Brenner, Donald; Krim, Jacqueline

2013-03-01

Nano-diamond (ND) particles are known to be beneficial for wear and friction reduction when used as additives in liquids, but the fundamental origins of the improvement in tribological properties has not been established. In order to explore this issue, we have investigated the nanotribological properties of ND coated with self-assembled monolayers (SAM) as additives to solutions, employing gold/chrome coated quartz crystal microbalances (QCM). Measurements were performed with the QCM initially immersed in deionized water. ND particles with positively and negatively charged SAM end groups were then added to the water, while the frequency and amplitude of the QCM were monitored. Negative shifts in both the QCM frequency and amplitude were observed when ND with positively charged SAM end groups were added, while positive shifts in both the QCM frequency and amplitude were observed when ND with negatively charged ND end groups were added. The results are consistent with a lubricating effect for the negatively charged ND, but were only observed for sufficiently small negative ND particle size. Experiments on QCM surfaces with differing textures and roughness are in progress, to determine the separate contributing effects of surface roughness charge-water interactions. Funding provided by NSF DMR.

Kinetics, Assembling and Conformation Control of L-Cysteine Adsorption on Pt by In Situ FTIR Spectroscopy and QCM-D.

PubMed

Cordoba de Torresi, Susana Ines; Dourado, Andre H B; Silva, Rubens A; Torresi, Roberto M; Sumodjo, Paulo T A; Arenz, Matthias

2018-06-05

A quartz crystal microbalance method with dissipation (QCM-D) and attenuated total reflection infrared (ATR-FTIRS) spectroscopy were used to study the adsorption of L-cysteine (L-Cys) on Pt. Using QCM-D, it was possible to verify that the viscoelastic properties of the adsorbed species play an important role in the adsorption, rendering Sauerbrey's equation inapplicable. The modelling of QCM-D data exposed two different processes for the adsorption reaction. The first one had an activation time and is fast, whereas the second is slow. These processes were also resolved by ATR-FTIRS identified to be water and anion adsorption preceded by L-Cys adsorption. Both techniques reveal that the degree of surface coverage is pH dependent. Spectroscopic data indicate that the conformation of L-Cys(ads) changes with pH and that the structures do not fully agree with those proposed in literature for other metallic surfaces. The assembling of the adsorbed monolayer appeared to be very fast, and it was not possible to determine or quantify this kinetics. The conformation is also controlled by applied potential, and the anion adsorption and interfacial water depends on the conformation of the adsorbed molecules. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Miniature System for Separating Aerosol Particles and Measuring Mass Concentrations

PubMed Central

Liang, Dao; Shih, Wen-Pin; Chen, Chuin-Shan; Dai, Chi-An

2010-01-01

We designed and fabricated a new sensing system which consists of two virtual impactors and two quartz-crystal microbalance (QCM) sensors for measuring particle mass concentration and size distribution. The virtual impactors utilized different inertial forces of particles in air flow to classify different particle sizes. They were designed to classify particle diameter, d, into three different ranges: d < 2.28 μm, 2.28 μm ≤ d ≤ 3.20 μm, d > 3.20 μm. The QCM sensors were coated with a hydrogel, which was found to be a reliable adhesive for capturing aerosol particles. The QCM sensor coated with hydrogel was used to measure the mass loading of particles by utilizing its characteristic of resonant frequency shift. An integrated system has been demonstrated. PMID:22319317

Development of a highly sensitive MIP based-QCM nanosensor for selective determination of cholic acid level in body fluids.

PubMed

Gültekin, Aytaç; Karanfil, Gamze; Sönmezoğlu, Savaş; Say, Rıdvan

2014-09-01

Determination of cholic acid is very important and necessary in body fluids due to its both pharmaceutical and clinical significance. In this study, a quartz crystal microbalance (QCM) nanosensor, which is imprinted cholic acid, has been developed for the assignation of cholic acid. The cholic acid selective memories have been generated on QCM electrode surface by using molecularly imprinted polymer (MIP) based on methacryloylamidohistidine-copper (II) (MAH-Cu(II)) pre-organized monomer. The cholic acid imprinted nanosensor was characterized by atomic force microscopy (AFM) and then analytical performance of the cholic acid imprinted QCM nanosensor was studied. The detection limit was found to be 0.0065μM with linear range of 0.01-1,000 μM. Moreover, the high value of Langmuir constant (b) (7.3*10(5)) obtained by Langmuir graph showed that the cholic acid imprinted nanosensor had quite strong binding sites affinity. At the last step of this procedure, cholic acid levels in body fluids were determined by the prepared imprinted QCM nanosensor. Copyright © 2014 Elsevier B.V. All rights reserved.

Resonant characteristics and sensitivity dependency on the contact surface in QCM-micropillar-based system of coupled resonator sensors

NASA Astrophysics Data System (ADS)

Kashan, M. A. M.; Kalavally, V.; Lee, H. W.; Ramakrishnan, N.

2016-05-01

We report the characteristics and sensitivity dependence over the contact surface in coupled resonating sensors (CRSs) made of high aspect ratio resonant micropillars attached to a quartz crystal microbalance (QCM). Through experiments and simulation, we observed that when the pillars of resonant heights were placed in maximum displacement regions the resonance frequency of the QCM increased following the coupled resonance characteristics, as the pillar offered elastic loading to the QCM surface. However, the same pillars when placed in relatively lower displacement regions, in spite of their resonant dimension, offered inertial loading and resulted in a decrease in QCM resonance frequency, as the displacement amplitude was insufficient to couple the vibrations from the QCM to the pillars. Accordingly, we discovered that the coupled resonance characteristics not only depend on the resonant structure dimensions but also on the contact regions in the acoustic device. Further analysis revealed that acoustic pressure at the contact surface also influences the resonance frequency characteristics and sensitivity of the CRS. To demonstrate the significance of the present finding for sensing applications, humidity sensing is considered as the example measurand. When a sensing medium made of resonant SU-8 pillars was placed in a maximum displacement region on a QCM surface, the sensitivity increased by 14 times in comparison to a resonant sensing medium placed in a lower displacement region of a QCM surface.

Transport and Retention of Colloids in Porous Media: Does Shape Really Matter?

EPA Science Inventory

The effect of particle shape on its transport and retention in porous media was evaluated by stretching carboxylate-modified fluorescent polystyrene spheres into rod shapes with aspect ratios of 2:1 and 4:1. Quartz crystal microbalance with dissipation experiments (QCM-D) were c...

Interactions of Graphene Oxide Nanomaterials with Natural Organic Matter and Metal Oxide Surfaces

EPA Science Inventory

Interactions of graphene oxide (GO) with silica surfaces were investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D). Both GO deposition and release were monitored on silica- and poly-l-lysine (PLL) coated surfaces as a function of GO concentration a...

Liquid volume measurement method for the picoliter to nanoliter volume range based on quartz crystal microbalance technology

NASA Astrophysics Data System (ADS)

Liang, Dong; Zhang, Jin; Thanikhatla Govindaiah, Muniyogeshbabu; Tanguy, Laurent; Ernst, Andreas; Zengerle, Roland; Koltay, Peter

2014-09-01

In this article, a quantitative liquid volume measurement method for the sub-nanoliter range using a quartz crystal microbalance (QCM) is described and experimentally analyzed. The primary measurement device to determine the volume of small liquid droplets is a QCM sensor coated with a surface-attached hydrogel to improve the mechanical coupling of the liquid to the sensor surface. An experimental evaluation of measured volumes in the range of 3 nl to 15 nl in normal room conditions has been performed with three identical sensors prepared with a PDMAA-1%MaBP hydrogel coating with a thickness of 1.5 µm ± 0.12 µm. A linearity of R2 more than 0.87, an average coefficient of variation (CV) within one experimental run of 5.7%, a mean absolute relative bias of 5.5%, and a sensor-to-sensor variation of 6.3% have been experimentally determined. The feasibility of this method has also been experimentally proven for the picoliter volume range down to 200 pl, with an average CV of 5.3% and a mean absolute relative bias of 6.5%. Furthermore, a stability evaluation consisting of 10 experimental series with approximately 150 measurements over the course of one week has been performed. This evaluation showed that the experimental setup, although exhibiting highly consistent performance within one measurement run, is not yet reproducible enough for long-term and repeated use because of undefined swelling and crack formation in the hydrogel layer. The low reproducibility implies a relatively high expanded uncertainty, with k = 2 according to the JCGM ‘Evaluation of Measurement Data—Guide to the Expression of Uncertainty in Measurement’ (GUM) for the total measurement method of approximately 3.82 nl when measuring a 10 nl liquid droplet. Nevertheless, the QCM method as described here contributes to significant progress beyond the state-of-the-art that might allow new opportunities for precise measurement of sub-nanoliter liquid volumes.

Semiconducting and quartz microbalance (QCM) humidity sensor properties of TiO2 by sol gel calcination method

NASA Astrophysics Data System (ADS)

Yakuphanoglu, Fahrettin

2012-06-01

Titanium dioxide (TiO2) material was synthesized using the sol gel calcination method. The structural properties of the TiO2 semiconductor were investigated by atomic force microscopy. The electrical conductivity of the TiO2 was measured as a function of temperature and TiO2 exhibits a conductivity of 2.55 × 10-6 S/m at room temperature with activation energy of 104 meV. The electrical conductivity of the TiO2 at room temperature is higher than that of nanocrystalline TiO2 (3 × 10-7 S/m) and TiO2 thin film in air (5 × 10-9 S/m) and in vacuum (8.8 × 10-10 S/m). It was found that the electrical transport mechanism of the TiO2 is controlled by thermally activated mechanism. The optical band gap of the TiO2 powder sample was determined to be 3.17 eV, which is good in agreement with the bulk TiO2 (Eg = 3.2 eV). Up to our knowledge, there is no any reported data about the band gap of TiO2 nanopowder based on the diffused reflectance calculation. Quartz crystal microbalance (QCM) TiO2 humidity sensor was prepared. The sensor indicates a large frequency change with an interaction occurred between TiO2 and humidity molecules. The sensor exhibits a good repeatability when it was exposed to the moist air of 65% RH.

Label-free detection of protein-ligand interactions by the quartz crystal microbalance.

PubMed

Janshoff, Andreas; Steinem, Claudia

2005-01-01

In recent years the quartz crystal microbalance (QCM) has been accepted as a powerful technique to monitor adsorption processes at interfaces in different chemical and biological research areas. In the last decade, the investigation of adsorption of biomolecules on functionalized surfaces turned out to be one of the paramount applications of the QCM comprising the interaction of nucleic acids, specific molecular recognition of protein-receptor couples, and antigen-antibody reactions realized in immunosensors. The advantage of the QCM technique is that it allows for a label free detection of molecules. This is a result of the fact that the frequency response of the quartz resonator is proportional to the increase in thickness of the adsorbed layer. However, in recent years it became more and more evident that quartz resonators used in fluids are more than mere mass or thickness sensors. The sensor response is also influenced by viscoelastic properties of the adhered biomaterial, surface charges of adsorbed molecules and surface roughness. These phenomena have been used to get new insights in the adhesion process of living cells and to understand their response to pharmacological substances by determining morphological changes of the cells. In this chapter we describe a protocol to explore the kinetics and thermodynamics of specific interactions of different proteins such as lectins and annexins with their ligands using receptor bearing solid supported lipid bilayers.

Highly selective detection of single-nucleotide polymorphisms using a quartz crystal microbalance biosensor based on the toehold-mediated strand displacement reaction.

PubMed

Wang, Dingzhong; Tang, Wei; Wu, Xiaojie; Wang, Xinyi; Chen, Gengjia; Chen, Qiang; Li, Na; Liu, Feng

2012-08-21

Toehold-mediated strand displacement reaction (SDR) is first introduced to develop a simple quartz crystal microbalance (QCM) biosensor without an enzyme or label at normal temperature for highly selective and sensitive detection of single-nucleotide polymorphism (SNP) in the p53 tumor suppressor gene. A hairpin capture probe with an external toehold is designed and immobilized on the gold electrode surface of QCM. A successive SDR is initiated by the target sequence hybridization with the toehold domain and ends with the unfolding of the capture probe. Finally, the open-loop capture probe hybridizes with the streptavidin-coupled reporter probe as an efficient mass amplifier to enhance the QCM signal. The proposed biosensor displays remarkable specificity to target the p53 gene fragment against single-base mutant sequences (e.g., the largest discrimination factor is 63 to C-C mismatch) and high sensitivity with the detection limit of 0.3 nM at 20 °C. As the crucial component of the fabricated biosensor for providing the high discrimination capability, the design rationale of the capture probe is further verified by fluorescence sensing and atomic force microscopy imaging. Additionally, a recovery of 84.1% is obtained when detecting the target sequence in spiked HeLa cells lysate, demonstrating the feasibility of employing this biosensor in detecting SNPs in biological samples.

The dynamics of complex formation between amylose brushes on gold and fatty acids by QCM-D.

PubMed

Cao, Zheng; Tsoufis, Theodoros; Svaldo-Lanero, Tiziana; Duwez, Anne-Sophie; Rudolf, Petra; Loos, Katja

2013-10-14

Amylose brushes were synthesized by enzymatic polymerization with glucose-1-phosphate as monomer and rabbit muscle phosphorylase b as catalyst on gold-covered surfaces of a quartz crystal microbalance. Fourier transform infrared (FT-IR) spectra confirmed the presence of the characteristic absorption peaks of amylose between 3100 cm(-1) and 3500 cm(-1). The thickness of the amylose brushes-measured by Spectroscopic Ellipsometry--can be tailored from 4 to 20 nm, depending on the reaction time. The contour length of the stretched amylose chains on gold surfaces has been evaluated by single molecule force spectroscopy, and a total chain length of about 20 nm for 16.2 nm thick amylose brushes was estimated. X-ray photoelectron spectroscopy (XPS) was employed to characterize the amylose brushes before and after the adsorption of fatty acids. The dynamics of inclusion complex formation between amylose brushes and two fatty acids (octanoic acid and myristic acid) with different chain length was investigated as a function of time using a quartz crystal microbalance with dissipation monitoring (QCM-D) immersed in the liquid phase. QCM-D signals including the frequency and dissipation shifts elucidated the effects of the fatty acid concentration, the solvent types, the chain length of the fatty acids and the thickness of the amylose brushes on the dynamics of fatty acid molecule adsorption on the amylose brush-modified sensor surfaces.

Polymer-grafted QCM chemical sensor and application to heavy metalions real time detection.

PubMed

Sartore, Luciana; Barbaglio, Marzia; Borgese, Laura; Bontempi, Elza

2011-07-20

A flow type quartz crystal microbalance (QCM) chemical sensor was developed for monitoring of heavy metal ions in aqueous solutions (that is suitable for environmental monitoring). The sensor is based upon surface chelation of the metal ions at multifunctional polymer modified gold electrodes on 9 MHz AT-cut quartz resonators, functioning as a QCM. New processes have been developed which enable to obtain surface-modified gold electrodes with high heavy metal ions complexing ability. These polymer grafted QCM sensors can selectively adsorb heavy metal ions, such as copper lead chrome and cadmium, from solution over a wide range from 0.01 to 1000 ppm concentration by complexation with functional groups in the polymers. Cations typically present in natural water did not interfere with the detection of heavy metals. X-Ray Reflectivity (XRR) and Total Reflection X-ray Fluorescence (TXRF) were carried out to characterise the unmodified and modified gold surfaces as well as to verify the possibility to selectively bond and remove metal ions.

Enhanced NH3 gas sensing properties of a QCM sensor by increasing the length of vertically orientated ZnO nanorods

NASA Astrophysics Data System (ADS)

Minh, Vu Anh; Tuan, Le Anh; Huy, Tran Quang; Hung, Vu Ngoc; Quy, Nguyen Van

2013-01-01

Vertically aligned ZnO nanorods were directly synthesised on a gold electrode of quartz crystal microbalance (QCM) by a simple low-temperature hydrothermal method for a NH3 gas sensing application. The length of vertically aligned ZnO nanorods was increased to purpose enhancement in the gas sensing response of the sensor. The length of ZnO nanorods increased with an increase in growth time. The growth time of ZnO nanorods was systematically varied in the range of 1-4 h to examine the effect of the length of the ZnO nanorods on the gas sensing properties of the fabricated sensors. The gas sensing properties of sensors with different ZnO nanorods lengths was examined at room temperature for various concentrations of NH3 (50-800 ppm) in synthetic air. Enhancement in gas sensing response by increasing the length of ZnO nanorods was observed.

Enhanced Dibutyl Phthalate Sensing Performance of a Quartz Crystal Microbalance Coated with Au-Decorated ZnO Porous Microspheres

PubMed Central

Zhang, Kaihuan; Fan, Guokang; Hu, Ruifen; Li, Guang

2015-01-01

Noble metals addition on nanostructured metal oxides is an attractive way to enhance gas sensing properties. Herein, hierarchical zinc oxide (ZnO) porous microspheres decorated with cubic gold particles (Au particles) were synthesized using a facile hydrothermal method. The as-prepared Au-decorated ZnO was then utilized as the sensing film of a gas sensor based on a quartz crystal microbalance (QCM). This fabricated sensor was applied to detect dibutyl phthalate (DBP), which is a widely used plasticizer, and its coating load was optimized. When tested at room temperature, the sensor exhibited a high sensitivity of 38.10 Hz/ppb to DBP in a low concentration range from 2 ppb to 30 ppb and the calculated theoretical detection limit is below 1 ppb. It maintains good repeatability as well as long-term stability. Compared with the undecorated ZnO based QCM, the Au-decorated one achieved a 1.62-time enhancement in sensitivity to DBP, and the selectivity was also improved. According to the experimental results, Au-functionalized ZnO porous microspheres displayed superior sensing performance towards DBP, indicating its potential use in monitoring plasticizers in the gaseous state. Moreover, Au decoration of porous metal oxide nanostructures is proved to be an effective approach for enhancing the gas sensing properties and the corresponding mechanism was investigated. PMID:26343661

DOE Office of Scientific and Technical Information (OSTI.GOV)

Björklund, Sebastian, E-mail: sebastianbjorklund@gmail.com; Kocherbitov, Vitaly; Biofilms—Research Center for Biointerfaces, Malmö University, Malmö

A new method to determine water sorption-desorption isotherms with high resolution in the complete range of water activities (relative humidities) is presented. The method is based on quartz crystal microbalance with dissipation monitoring (QCM-D). The QCM-D is equipped with a humidity module in which the sample film is kept in air with controlled humidity. The experimental setup allows for continuous scanning of the relative humidity from either dry to humid conditions or vice versa. The amount of water sorbed or desorbed from the sample is determined from the resonance frequencies of the coated quartz sensor, via analysis of the overtonemore » dependence. In addition, the method allows for characterization of hydration induced changes of the rheological properties from the dissipation data, which is closely connected to the viscoelasticity of the film. The accuracy of the humidity scanning setup is confirmed in control experiments. Sorption-desorption isotherms of pig gastric mucin and lysozyme, obtained by the new method, show good agreement with previous results. Finally, we show that the deposition technique used to coat the quartz sensor influences the QCM-D data and how this issue can be used to obtain further information on the effect of hydration. In particular, we demonstrate that spin-coating represents an attractive alternative to obtain sorption-desorption isotherms, while drop-coating provides additional information on changes of the rheological properties during hydration.« less

QCM operating in threshold mode as a gas sensor.

PubMed

Dultsev, Fedor N; Kolosovsky, Eugeny A

2009-10-20

Application of the threshold mode allowed us to use the quartz resonator (quartz crystal microbalance, QCM) as a highly sensitive gas sensor measuring the forces of the rupture of adsorbed gas components from the resonator surface oscillating with increasing amplitude. This procedure allows one to analyze different gas components using the same surface modification, just varying the rupture threshold by varying the amplitude of shear oscillations. The sensitivity of the threshold measurements is 2 to 3 orders of magnitude higher than for the gravimetric procedure. It is demonstrated that the QCM operating as an active element can be used as a gas sensor. This procedure seems to be promising in investigating the reactivity of the surface or the interactions of gaseous components with the surface containing various functional groups, thus contributing to the surface chemistry.

Real-time investigation of mannosyltransferase function of a Xylella fastidiosa recombinant GumH protein using QCM-D.

PubMed

Alves, Claudia A; Pedroso, Mariele M; de Moraes, Marcela C; Souza, Dulce H F; Cass, Quezia B; Faria, Ronaldo C

2011-05-20

Xylella fastidiosa is a gram-negative bacterium that causes serious diseases in economically important crops, including grapevine, coffee, and citrus fruits. X. fastidiosa colonizes the xylem vessels of the infected plants, thereby blocking water and nutrient transport. The genome sequence of X. fastidiosa has revealed an operon containing nine genes possibly involved in the synthesis of an exopolisaccharide (EPS) named fastidian gum that can be related with the pathogenicity of this bacterium. The α-1,3-mannosyltransferase (GumH) enzyme from X. fastidiosa is involved in fastidian gum production. GumH is responsible for the transfer of mannose from guanosine diphosphate mannose (GDP-man) to the cellobiose-pyrophosphate-polyprenol carrier lipid (CPP-Lip) during the assembly and biosynthesis of EPS. In this work, a method for real-time detection of recombinant GumH enzymatic activity was successfully developed using a Quartz Crystal Microbalance with dissipation monitoring (QCM-D). The QCM-D transducer was strategically modified with CPP-Lip by using a solid-supported lipid bilayer that makes use of a self-assembled monolayer of 1-undecanethiol. Monitoring the real-time CPP-Lip QCM-D transducer in the presence of GDP-man and GumH enzyme shows a mass increase, indicating the transfer of mannose. The real-time QCM-D determination of mannosyltransferase function was validated by a High Performance Liquid Chromatography (LC) method developed for determination of GDP produced by enzymatic reaction. LC results confirmed the activity of recombinant GumH protein, which is the first enzyme involved in the biosynthesis of the EPS from X. fastidiosa enzymatically characterized. Copyright © 2011 Elsevier Inc. All rights reserved.

Coating Characterization with the Quartz Crystal Microbalance

NASA Astrophysics Data System (ADS)

Sturdy, Lauren F.

The quartz crystal microbalance is a sensitive tool that can be used to measure the mass, modulus and phase angle of films of appropriate thicknesses. It is can be applied to systems with very varied properties, from liquid to solid, and under many different conditions. In this thesis its capabilities have been used to study the properties of several different systems of relevance to the coatings, art conservation, and rubber communities, in the process of which new techniques and tools were developed to analyze data and improve QCM data collection and experimental design. Alkyd resins, which have been used in artists' paints since the twentieth century, are the subject of the first studies. Alkyds are oil-modified polyesters. These resins are of interest because of their relatively recent use in art and how little is known of the mechanical properties in the early stages of cure. The QCM was shown to be sensitive to the curing process, changes in temperature, and mass change due to exposure to water. Kinetic studies during the first days of curing showed that the curing process can be divided into three regions. The first is dominated by solvent evaporation. In the second, oxygen absorption dominates and the mechanical properties change rapidly. The final stage extends from when the film is touch dry after about a day to years and is characterized by mass loss and continued increases in the modulus. Studying the curing at different temperatures revealed that the reactions do proceed much more rapidly at higher temperatures and an overall energy of activation was calculated for the curing process. The mechanical properties of alkyd resins containing zinc oxide, a white pigment, were studied with the QCM, nanoindentation and dynamic mechanical analysis. These measurements showed increases in the modulus with the inclusion of zinc oxide, and the QCM data showed that the second region started at earlier times as the pigment concentration was increased. Linseed oil is one of the starting materials for many alkyd resins and should cure similarly since the primary curing mechanisms are the same. It takes longer to cure than alkyds because it begins with no initial polymerization. Linseed oil was harder to study, as obtaining even films was difficult, multiple peaks at a single harmonic were observed, and the material properties during the early stages of curing led to a region where viscoelastic properties could not be calculated. To facilitate studying linseed oil, a multiple peak fitting method was developed to extract data from unusual peak shapes. With this ability, measurements at short times could be obtained despite poor film quality. Although linseed oil begins as a softer material than alkyds, its curing follows the same patterns as alkyd resins, exhibiting mass gain followed by mass loss, and sharp increases in modulus and decreases in phase angle during the early stages of curing. Having demonstrated the ability of the QCM to monitor curing, the QCM was also applied to uncrosslinked rubber systems. Rubbers, like the drying oils, contain double bonds which can react with oxygen, so first the oxidation of these materials was studied. In further studies oxidation was undesirable, so protocols were developed to limit oxidation. Measurements were made of homopolymers at different temperatures and the QCM measurements appear to be consistent with time-temperature superposition results obtained at lower frequencies. Blends of the various rubbers were studied and compared with models. The mechanical properties measured by the QCM were between the Voigt and Reuss predictions for most blends studied. Modeling the expected QCM response of layered rubbers matched the predictions of the Reuss model but not the measured values of the rubber blends, suggesting that the QCM is sensitive to different morphologies. Measurements with the QCM expanded our understanding of a variety of systems and proved to be a useful tool to measure mechanical changes during processes which are difficult to study by other methods.

Analysis of Perforin Assembly by Quartz Crystal Microbalance Reveals a Role for Cholesterol and Calcium-independent Membrane Binding.

PubMed

Stewart, Sarah E; Bird, Catherina H; Tabor, Rico F; D'Angelo, Michael E; Piantavigna, Stefania; Whisstock, James C; Trapani, Joseph A; Martin, Lisandra L; Bird, Phillip I

2015-12-25

Perforin is an essential component in the cytotoxic lymphocyte-mediated cell death pathway. The traditional view holds that perforin monomers assemble into pores in the target cell membrane via a calcium-dependent process and facilitate translocation of cytotoxic proteases into the cytoplasm to induce apoptosis. Although many studies have examined the structure and role of perforin, the mechanics of pore assembly and granzyme delivery remain unclear. Here we have employed quartz crystal microbalance with dissipation monitoring (QCM-D) to investigate binding and assembly of perforin on lipid membranes, and show that perforin monomers bind to the membrane in a cooperative manner. We also found that cholesterol influences perforin binding and activity on intact cells and model membranes. Finally, contrary to current thinking, perforin efficiently binds membranes in the absence of calcium. When calcium is added to perforin already on the membrane, the QCM-D response changes significantly, indicating that perforin becomes membranolytic only after calcium binding. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

An immuno-biosensor system based on quartz crystal microbalance for avian influenza virus detection

NASA Astrophysics Data System (ADS)

Liu, Shengping; Chen, Guoming; Zhou, Qi; Wei, Yunlong

2007-12-01

For the quick detection of Avian Influenza Virus (AIV), a biosensor based on Quartz Crystal Microbalance (QCM) was fabricated according to the specific bonding principle between antibody and antigen. Staphylococcal Protein A (SPA) was extracted from Staphylococcus and purified. Then SPA was coated on the surface of QCM for immobilizing AIV monoclonal antibodies. The use of AIV monoclonal antibody could enhance the specificity of the immuno-biosensor. A multi-channel piezoelectricity detection system for the immuno-biosensor was developed. The system can work for the quick detection of AIV antigen in the case of the entirely aqueous status owe to one special oscillating circuit designed in this work. The optimum conditions of SPA coating and AIV monoclonal antibody immobilization were investigated utilizing the multi-channel detection system. The preliminary application of the immuno-biosensor system for detection of AIV was evaluated. Results indicate that the immuno-biosensor system can detect the AIV antigens with a linear range of 3-200ng/ml. The system can accomplish the detection of AIV antigens around 40 minutes.

Electrochemistry, surface plasmon resonance, and quartz crystal microbalance: an associative study on cytochrome c adsorption on pyridine tail-group monolayers on gold.

PubMed

Paulo, Tércio de F; de Sousa, Ticyano P; de Abreu, Dieric S; Felício, Nathalie H; Bernhardt, Paul V; Lopes, Luiz G de F; Sousa, Eduardo H S; Diógenes, Izaura C N

2013-07-25

Quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and electrochemistry techniques were used to study the electron-transfer (ET) reaction of cytochrome c (Cyt c) on gold surfaces modified with thionicotinamide, thioisonicotinamide, 4-mercaptopyridine, 5-(4-pyridyl)-1,3,4-oxadiazole-2-thiol, 5-phenyl-1,3,4-oxadiazole-2-thiol, 4,4'-bipyridine, and 4,4'-dithiopyridine. The electrochemical results showed that the ET process is complex, being chiefly diffusional with steps depending on the orientation of the pyridine or phenyl tail group of the modifiers. The correlation between the electrochemical results and those acquired by SPR and QCM indicated the presence of an adlayer of Cyt c adsorbed on the thiolate SAMs. This adlayer, although being not electroactive, is essential to assess the ET reaction of Cyt c in solution. The results presented in this work are consistent with the statement (Feng, Z. Q.; Imabayashi, S.; Kakiuchi, T.; Niki, K. J. Electroanal. Chem. 1995, 394, 149-154) that the ET reaction of Cyt c can be explained in terms of the through-bond tunneling mechanism.

Quartz crystal microbalance (QCM) affinity biosensor for genetically modified organisms (GMOs) detection.

PubMed

Mannelli, Ilaria; Minunni, Maria; Tombelli, Sara; Mascini, Marco

2003-03-01

A DNA piezoelectric sensor has been developed for the detection of genetically modified organisms (GMOs). Single stranded DNA (ssDNA) probes were immobilised on the sensor surface of a quartz crystal microbalance (QCM) device and the hybridisation between the immobilised probe and the target complementary sequence in solution was monitored. The probe sequences were internal to the sequence of the 35S promoter (P) and Nos terminator (T), which are inserted sequences in the genome of GMOs regulating the transgene expression. Two different probe immobilisation procedures were applied: (a) a thiol-dextran procedure and (b) a thiol-derivatised probe and blocking thiol procedure. The system has been optimised using synthetic oligonucleotides, which were then applied to samples of plasmidic and genomic DNA isolated from the pBI121 plasmid, certified reference materials (CRM), and real samples amplified by the polymerase chain reaction (PCR). The analytical parameters of the sensor have been investigated (sensitivity, reproducibility, lifetime etc.). The results obtained showed that both immobilisation procedures enabled sensitive and specific detection of GMOs, providing a useful tool for screening analysis in food samples.

Target-triggering multiple-cycle signal amplification strategy for ultrasensitive detection of DNA based on QCM and SPR.

PubMed

Song, Weiling; Yin, Wenshuo; Sun, Wenbo; Guo, Xiaoyan; He, Peng; Yang, Xiaoyan; Zhang, Xiaoru

2018-04-24

Detection of ultralow concentrations of nucleic acid sequences is a central challenge in the early diagnosis of genetic diseases. Herein, we developed a target-triggering cascade multiple cycle amplification for ultrasensitive DNA detection using quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). It was based on the exonuclease Ⅲ (Exo Ⅲ)-assisted signal amplification and the hybridization chain reaction (HCR). The streptavidin-coated Au-NPs (Au-NPs-SA) were assembled on the HCR products as recognition element. Upon sensing of target DNA, the duplex DNA probe triggered the Exo Ⅲ cleavage process, accompanied by generating a new secondary target DNA and releasing target DNA. The released target DNA and the secondary target DNA were recycled. Simultaneously, numerous single strands were liberated and acted as the trigger of HCR to generate further signal amplification, resulting in the immobilization of abundant Au-NPs-SA on the gold substrate. The QCM sensor results were found to be comparable to that achieved using a SPR sensor platform. This method exhibited a high sensitivity toward target DNA with a detection limit of 0.70 fM. The high sensitivity and specificity make this method a great potential for detecting DNA with trace amounts in bioanalysis and clinical biomedicine. Copyright © 2018 Elsevier Inc. All rights reserved.

Synchronized cell attachment triggered by photo-activatable adhesive ligands allows QCM-based detection of early integrin binding

PubMed Central

Iturri, Jagoba; García-Fernández, Luis; Reuning, Ute; García, Andrés J.; Campo, Aránzazu del; Salierno, Marcelo J.

2015-01-01

The Quartz Crystal Microbalance with dissipation (QCM-D) technique was applied to monitor and quantify integrin-RGD recognition during the early stages of cell adhesion. Using QCM-D crystals modified with a photo-activatable RGD peptide, the time point of presentation of adhesive ligand at the surface of the QCM-D crystal could be accurately controlled. This allowed temporal resolution of early integrin-RGD binding and the subsequent cell spreading process, and their separate detection by QCM-D. The specificity of the integrin-RGD binding event was corroborated by performing the experiments in the presence of soluble cyclicRGD as a competitor, and cytochalasin D as inhibitor of cell spreading. Larger frequency change in the QCM-D signal was observed for cells with larger spread area, and for cells overexpressing integrin αvβ3 upon stable transfection. This strategy enables quantification of integrin activity which, in turn, may allow discrimination among different cell types displaying distinct integrin subtypes and expression levels thereof. On the basis of these findings, we believe the strategy can be extended to other photoactivatable ligands to characterize cell membrane receptors activity, a relevant issue for cancer diagnosis (and prognosis) as other several pathologies. PMID:25825012

Gravimetric chemical sensors based on silica-based mesoporous organic-inorganic hybrids.

PubMed

Xu, Jiaqiang; Zheng, Qi; Zhu, Yongheng; Lou, Huihui; Xiang, Qun; Cheng, Zhixuan

2014-09-01

Silica-based mesoporous organic-inorganic hybrid material modified quartz crystal microbalance (QCM) sensors have been examined for their ability to achieve highly sensitive and selective detection. Mesoporous silica SBA-15 serves as an inorganic host with large specific surface area, facilitating gas adsorption, and thus leads to highly sensitive response; while the presence of organic functional groups contributes to the greatly improved specific sensing property. In this work, we summarize our efforts in the rational design and synthesis of novel sensing materials for the detection of hazardous substances, including simulant nerve agent, organic vapor, and heavy metal ion, and develop high-performance QCM-based chemical sensors.

Investigation of a liquid-fed water resistojet plume

NASA Technical Reports Server (NTRS)

Manzella, D. H.; Carney, L. M.

1989-01-01

Measurements of mass flux and flow angle were taken throughout the forward flow region of the exhaust of a liquid-fed water resistojet using a quartz crystal microbalance (QCM). The resistojet operated at a mass flow rate of 0.1 g/s with a power input of 330 Watts. Measured values were compared to theoretical predictions obtained by employing a source flow approximation. Excellent agreement between predicted and measured mass flux values was attained; however, this agreement was highly dependent on knowledge of nozzle flow conditions. Measurements of the temperature at which the exhaust condensed on the QCM were obtained as a function of incident mass flux.

Volumetric Interpretation of Protein Adsorption: Interfacial Packing of Protein Adsorbed to Hydrophobic Surfaces from Surface-Saturating Solution Concentrations

PubMed Central

Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L.; Vogler, Erwin A.

2010-01-01

The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square-or-hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square-or-hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. PMID:21035180

Volumetric interpretation of protein adsorption: interfacial packing of protein adsorbed to hydrophobic surfaces from surface-saturating solution concentrations.

PubMed

Kao, Ping; Parhi, Purnendu; Krishnan, Anandi; Noh, Hyeran; Haider, Waseem; Tadigadapa, Srinivas; Allara, David L; Vogler, Erwin A

2011-02-01

The maximum capacity of a hydrophobic adsorbent is interpreted in terms of square or hexagonal (cubic and face-centered-cubic, FCC) interfacial packing models of adsorbed blood proteins in a way that accommodates experimental measurements by the solution-depletion method and quartz-crystal-microbalance (QCM) for the human proteins serum albumin (HSA, 66 kDa), immunoglobulin G (IgG, 160 kDa), fibrinogen (Fib, 341 kDa), and immunoglobulin M (IgM, 1000 kDa). A simple analysis shows that adsorbent capacity is capped by a fixed mass/volume (e.g. mg/mL) surface-region (interphase) concentration and not molar concentration. Nearly analytical agreement between the packing models and experiment suggests that, at surface saturation, above-mentioned proteins assemble within the interphase in a manner that approximates a well-ordered array. HSA saturates a hydrophobic adsorbent with the equivalent of a single square or hexagonally-packed layer of hydrated molecules whereas the larger proteins occupy two-or-more layers, depending on the specific protein under consideration and analytical method used to measure adsorbate mass (solution depletion or QCM). Square or hexagonal (cubic and FCC) packing models cannot be clearly distinguished by comparison to experimental data. QCM measurement of adsorbent capacity is shown to be significantly different than that measured by solution depletion for similar hydrophobic adsorbents. The underlying reason is traced to the fact that QCM measures contribution of both core protein, water of hydration, and interphase water whereas solution depletion measures only the contribution of core protein. It is further shown that thickness of the interphase directly measured by QCM systematically exceeds that inferred from solution-depletion measurements, presumably because the static model used to interpret solution depletion does not accurately capture the complexities of the viscoelastic interfacial environment probed by QCM. Copyright © 2010 Elsevier Ltd. All rights reserved.

Application of electrochemically deposited nanostructured ZnO layers on quartz crystal microbalance for NO2 detection

NASA Astrophysics Data System (ADS)

Georgieva, B.; Petrov, M.; Lovchinov, K.; Ganchev, M.; Georgieva, V.; Dimova-Malinovska, D.

2014-11-01

The research was fixed on sensing behavior of ZnO nanostructured (NS) films to NO2 concentrations in the environment. The ZnO NS layers are deposited by electrochemical method on quartz resonators with Au electrodes. The sorption properties of ZnO layers were defined by measuring the resonant frequency shift (Δf) of the QCM-ZnO structure for different NO2 concentrations. The measurements were based on the correlation between the frequency shift of the QCM and additional mass loading (Δm) on the resonator calculated using Sauerbrey equation for the AT-cut quartz plate. Frequency - Time Characteristics (FTCs) of the samples were measured as a function of different NO2 concentrations in order to define the sorption abilities of ZnO layers. The experiments were carried out on a special set up in a dynamical regime. From FTCs the response and the recovery times of the QCM-ZnO structure were measured with varying NO2. Frequency shift changed from 23 Hz to 58Hz when NO2 was varied in the range of 250ppm - 5000ppm. The process of sorption was estimated as reversible and the sorption as physical. The obtained results demonstrated that QCM covered with the electrochemically deposited nanostructured ZnO films can be used as application in NO2 sensors.

Label Free QCM Immunobiosensor for AFB1 Detection Using Monoclonal IgA Antibody as Recognition Element.

PubMed

Ertekin, Özlem; Öztürk, Selma; Öztürk, Zafer Ziya

2016-08-11

This study introduces the use of an IgA isotype aflatoxin (AF) specific monoclonal antibody for the development of a highly sensitive Quartz Crystal Microbalance (QCM) immunobiosensor for the detection of AF in inhibitory immunoassay format. The higher molecular weight of IgA antibodies proved an advantage over commonly used IgG antibodies in label free immunobiosensor measurements. IgA and IgG antibodies with similar affinity for AF were used in the comparative studies. Sensor surface was prepared by covalent immobilization of AFB1, using self assembled monolayer (SAM) formed on gold coated Quartz Crystal, with 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxy succinimide (EDC/NHS) method using a diamine linker. Nonspecific binding to the surface was decreased by minimizing the duration of EDC/NHS activation. Sensor surface was chemically blocked after AF immobilization without any need for protein blocking. This protein free sensor chip endured harsh solutions with strong ionic detergent at high pH, which is required for the regeneration of the high affinity antibody-antigen interaction. According to the obtained results, the detection range with IgA antibodies was higher than IgG antibodies in QCM immunosensor developed for AFB1.

Durable superhydrophobic carbon soot coatings for sensor applications

NASA Astrophysics Data System (ADS)

Esmeryan, K. D.; Radeva, E. I.; Avramov, I. D.

2016-01-01

A novel approach for the fabrication of durable superhydrophobic (SH) carbon soot coatings used in quartz crystal microbalance (QCM) based gas or liquid sensors is reported. The method uses modification of the carbon soot through polymerization of hexamethyldisiloxane (HMDSO) by means of glow discharge RF plasma. The surface characterization shows a fractal-like network of carbon nanoparticles with diameter of ~50 nm. These particles form islands and cavities in the nanometer range, between which the plasma polymerized hexamethyldisiloxane (PPHMDSO) embeds and binds to the carbon chains and QCM surface. Such modified surface structure retains the hydrophobic nature of the soot and enhances its robustness upon water droplet interactions. Moreover, it significantly reduces the insertion loss and dynamic resistance of the QCM compared to the commonly used carbon soot/epoxy resin approach. Furthermore, the PPHMDSO/carbon soot coating demonstrates durability and no aging after more than 40 probing cycles in water based liquid environments. In addition, the surface layer keeps its superhydrophobicity even upon thermal annealing up to 540 °C. These experiments reveal an opportunity for the development of soot based SH QCMs with improved electrical characteristics, as required for high-resolution gas or liquid measurements.

Label Free QCM Immunobiosensor for AFB1 Detection Using Monoclonal IgA Antibody as Recognition Element

PubMed Central

Ertekin, Özlem; Öztürk, Selma; Öztürk, Zafer Ziya

2016-01-01

This study introduces the use of an IgA isotype aflatoxin (AF) specific monoclonal antibody for the development of a highly sensitive Quartz Crystal Microbalance (QCM) immunobiosensor for the detection of AF in inhibitory immunoassay format. The higher molecular weight of IgA antibodies proved an advantage over commonly used IgG antibodies in label free immunobiosensor measurements. IgA and IgG antibodies with similar affinity for AF were used in the comparative studies. Sensor surface was prepared by covalent immobilization of AFB1, using self assembled monolayer (SAM) formed on gold coated Quartz Crystal, with 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide/N-hydroxy succinimide (EDC/NHS) method using a diamine linker. Nonspecific binding to the surface was decreased by minimizing the duration of EDC/NHS activation. Sensor surface was chemically blocked after AF immobilization without any need for protein blocking. This protein free sensor chip endured harsh solutions with strong ionic detergent at high pH, which is required for the regeneration of the high affinity antibody-antigen interaction. According to the obtained results, the detection range with IgA antibodies was higher than IgG antibodies in QCM immunosensor developed for AFB1. PMID:27529243

Dew Point Calibration System Using a Quartz Crystal Sensor with a Differential Frequency Method

PubMed Central

Lin, Ningning; Meng, Xiaofeng; Nie, Jing

2016-01-01

In this paper, the influence of temperature on quartz crystal microbalance (QCM) sensor response during dew point calibration is investigated. The aim is to present a compensation method to eliminate temperature impact on frequency acquisition. A new sensitive structure is proposed with double QCMs. One is kept in contact with the environment, whereas the other is not exposed to the atmosphere. There is a thermal conductivity silicone pad between each crystal and a refrigeration device to keep a uniform temperature condition. A differential frequency method is described in detail and is applied to calibrate the frequency characteristics of QCM at the dew point of −3.75 °C. It is worth noting that frequency changes of two QCMs were approximately opposite when temperature conditions were changed simultaneously. The results from continuous experiments show that the frequencies of two QCMs as the dew point moment was reached have strong consistency and high repeatability, leading to the conclusion that the sensitive structure can calibrate dew points with high reliability. PMID:27869746

A new method for the determination of vaporization enthalpies of ionic liquids at low temperatures.

PubMed

Verevkin, Sergey P; Zaitsau, Dzmitry H; Emelyanenko, Vladimir N; Heintz, Andreas

2011-11-10

A new method for the determination of vaporization enthalpies of extremely low volatile ILs has been developed using a newly constructed quartz crystal microbalance (QCM) vacuum setup. Because of the very high sensitivity of the QCM it has been possible to reduce the average temperature of the vaporization studies by approximately 100 K in comparison to other conventional techniques. The physical basis of the evaluation procedure has been developed and test measurements have been performed with the common ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C(2)mim][NTf(2)] extending the range of measuring vaporization enthalpies down to 363 K. The results obtained for [C(2)mim][NTf(2)] have been tested for thermodynamic consistency by comparison with data already available at higher temperatures. Comparison of the temperature-dependent vaporization enthalpy data taken from the literature show only acceptable agreement with the heat capacity difference of -40 J K(-1) mol(-1). The method developed in this work opens also a new way to obtain reliable values of vaporization enthalpies of thermally unstable ionic liquids.

Quartz Crystal Microbalance Operation and In Situ Calibration

NASA Technical Reports Server (NTRS)

Albyn, K. C.

2004-01-01

Quartz crystal microbalances (QCMs) are commonly used to measure the rate of deposition of molecular species on a surface. The measurement is often used to select materials with a low outgassing rate for applications where the material has a line of sight to a contamination-sensitive surface. A quantitative, in situ calibration of the balance, or balances, using a pure material for which the enthalpy of sublimation is known, is described in this Technical Memorandum. Supporting calculations for surface dwell times of deposited materials and the effusion cell Clausing factor are presented along with examples of multiple QCM measurements of outgassing from a common source.

Batch fabrication of polymer microfluidic cartridges for QCM sensor packaging by direct bonding

NASA Astrophysics Data System (ADS)

Sandström, Niklas; Zandi Shafagh, Reza; Gylfason, Kristinn B.; Haraldsson, Tommy; van der Wijngaart, Wouter

2017-12-01

Quartz crystal microbalance (QCM) sensing is an established technique commonly used in laboratory based life-science applications. However, the relatively complex, multi-part design and multi-step fabrication and assembly of state-of-the-art QCM cartridges make them unsuited for disposable applications such as point-of-care (PoC) diagnostics. In this work, we present the uncomplicated manufacturing of QCMs in polymer microfluidic cartridges. Our novel approach comprises two key innovations: the batch reaction injection molding of microfluidic parts; and the integration of the cartridge components by direct, unassisted bonding. We demonstrate molding of batches of 12 off-stoichiometry thiol-ene epoxy polymer (OSTE+) polymer parts in a single molding cycle using an adapted reaction injection molding process; and the direct bonding of the OSTE+  parts to other OSTE+  substrates, to printed circuit boards, and to QCMs. The microfluidic QCM OSTE+  cartridges were successfully evaluated in terms of liquid sealing as well as electrical properties, and the sensor performance characteristics are on par with those of a commercially available QCM biosensor cartridge. The simplified manufacturing of QCM sensors with maintained performance potentializes novel application areas, e.g. as disposable devices in a point of care setting. Moreover, our results can be extended to simplifying the fabrication of other microfluidic devices with multiple heterogeneously integrated components.

Particle Characterization for a Protein Drug Product Stored in Pre-Filled Syringes Using Micro-Flow Imaging, Archimedes, and Quartz Crystal Microbalance with Dissipation.

PubMed

Zheng, Songyan; Puri, Aastha; Li, Jinjiang; Jaiswal, Archana; Adams, Monica

2017-01-01

Micro-flow imaging (MFI) has been used for formulation development for analyzing sub-visible particles. Archimedes, a novel technique for analyzing sub-micron particles, has been considered as an orthogonal method to currently existing techniques. This study utilized these two techniques to investigate the effectiveness of polysorbate (PS-80) in mitigating the particle formation of a therapeutic protein formulation stored in silicone oil-coated pre-filled syringes. The results indicated that PS-80 prevented the formation of both protein and silicone oil particles. In the case of protein particles, PS-80 might involve in the interactions with the hydrophobic patches of protein, air bubbles, and the stressed surfaces of silicone oil-coated pre-filled syringes. Such interactions played a role in mitigating the formation of protein particles. Subsequently, quartz crystal microbalance with dissipation (QCM-D) was utilized to characterize the interactions associated with silicone oil, protein, and PS-80 in the solutions. Based on QCM-D results, we proposed that PS-80 likely formed a layer on the interior surfaces of syringes. As a result, the adsorbed PS-80 might block the leakage of silicone oil from the surfaces to solution so that the silicone oil particles were mitigated at the presence of PS-80. Overall, this study demonstrated the necessary of utilizing these three techniques cooperatively in order to better understand the interfacial role of PS-80 in mitigating the formation of protein and silicone oil particles.

Bioimprinted QCM sensors for virus detection-screening of plant sap.

PubMed

Dickert, Franz L; Hayden, Oliver; Bindeus, Roland; Mann, Karl-J; Blaas, Dieter; Waigmann, Elisabeth

2004-04-01

Surface imprinting techniques on polymer-coated quartz-crystal microbalances (QCM) have been used to detect tobacco mosaic viruses (TMV) in aqueous media. Molecularly imprinted polymers (MIP), tailor-made by self organisation of monomers around a template (TMV), were generated directly on the gold electrodes. Imprinted trenches on the polymer surface mimicking the shape and surface functionality of the virus serve as recognition sites for re-adsorption after washing out of the template. The sensors are applicable to TMV detection ranging from 100 ng mL(-1) to 1 mg mL(-1) within minutes. Furthermore, direct measurements without time-consuming sample preparation are possible in complex matrices such as tobacco plant sap.

Sol-gel TiO2 films as NO2 gas sensors

NASA Astrophysics Data System (ADS)

Georgieva, V.; Gadjanova, V.; Grechnikov, A.; Donkov, N.; Sendova-Vassileva, M.; Stefanov, P.; Kirilov, R.

2014-05-01

TiO2 films were prepared by a sol-gel technique with commercial TiO2 powder as a source material (P25 Degussa AG). After a special treatment, printing paste was prepared. The TiO2 layers were formed by means of drop-coating on Si-control wafers and on the Au-electrodes of quartz resonators. The surface morphology of the films was examined by scanning electron microscopy (SEM). Their structure was studied by Raman spectroscopy and the surface composition was determined by X-ray photoelectron spectroscopy (XPS). The layers had a grain-like surface morphology and consisted mainly of anatase TiO2 phase. The sensitivity of the TiO2 films to NO2 was assessed by the quartz crystal microbalance (QCM) technique. To this end, the films were deposited on both sides of a 16-MHz QCM. The sensing characteristic of the TiO2-QCM structure was investigated by measuring the resonant frequency shift (ΔF) of the QCM due to the mass loading caused by NO2 adsorption. The Sauerbrey equation was applied to establish the correlation between the QCM frequency changes measured after exposure to different NO2 concentrations and the mass-loading of the QCM. The experiments were carried out in a dynamic mode on a special laboratory setup with complete control of the process parameters. The TiO2 films were tested in the NO2 concentration interval from 10 ppm to 5000 ppm. It was found that a TiO2 loading of the QCM by 5.76 kHz corresponded to a system sensitive to NO2 concentrations above 250 ppm. On the basis of the frequency-time characteristics (FTCs) measured, AF at different NO2 concentrations was defined, the adsorption/desorption cycles were studied and the response and recovery times were estimated. The results obtained show that the process is reversible in the NO2 interval investigated. The results further suggested that TiO2 films prepared by a sol-gel method on a QCM can be used as a sensor element for NO2 detection.

Conformational and mechanical changes of DNA upon transcription factor binding detected by a QCM and transmission line model.

PubMed

de-Carvalho, Jorge; Rodrigues, Rogério M M; Tomé, Brigitte; Henriques, Sílvia F; Mira, Nuno P; Sá-Correia, Isabel; Ferreira, Guilherme N M

2014-04-21

A novel quartz crystal microbalance (QCM) analytical method is developed based on the transmission line model (TLM) algorithm to analyze the binding of transcription factors (TFs) to immobilized DNA oligoduplexes. The method is used to characterize the mechanical properties of biological films through the estimation of the film dynamic shear moduli, G and G, and the film thickness. Using the Saccharomyces cerevisiae transcription factor Haa1 (Haa1DBD) as a biological model two sensors were prepared by immobilizing DNA oligoduplexes, one containing the Haa1 recognition element (HRE(wt)) and another with a random sequence (HRE(neg)) used as a negative control. The immobilization of DNA oligoduplexes was followed in real time and we show that DNA strands initially adsorb with low or non-tilting, laying flat close to the surface, which then lift-off the surface leading to final film tilting angles of 62.9° and 46.7° for HRE(wt) and HRE(neg), respectively. Furthermore we show that the binding of Haa1DBD to HRE(wt) leads to a more ordered and compact film, and forces a 31.7° bending of the immobilized HRE(wt) oligoduplex. This work demonstrates the suitability of the QCM to monitor the specific binding of TFs to immobilized DNA sequences and provides an analytical methodology to study protein-DNA biophysics and kinetics.

Signal enhancement in ligand-receptor interactions using dynamic polymers at quartz crystal microbalance sensors.

PubMed

Dunér, Gunnar; Anderson, Henrik; Pei, Zhichao; Ingemarsson, Björn; Aastrup, Teodor; Ramström, Olof

2016-06-20

The signal enhancement properties of QCM sensors based on dynamic, biotinylated poly(acrylic acid) brushes has been studied in interaction studies with an anti-biotin Fab fragment. The poly(acrylic acid) sensors showed a dramatic increase in signal response with more than ten times higher signal than the carboxyl-terminated self-assembled monolayer surface.

Apparatus for particulate matter analysis

DOEpatents

Gundel, Lara A.; Apte, Michael G.; Hansen, Anthony D.; Black, Douglas R.

2007-01-30

The apparatus described herein is a miniaturized system for particle exposure assessment (MSPEA) for the quantitative measurement and qualitative identification of particulate content in gases. The present invention utilizes a quartz crystal microbalance (QCM) or other mass-sensitive temperature compensated acoustic wave resonator for mass measurement. Detectors and probes and light sources are used in combination for the qualitative determination of particulate matter.

Artificial receptors in serologic tests for the early diagnosis of dengue virus infection.

PubMed

Tai, Dar-Fu; Lin, Chung-Yin; Wu, Tzong-Zeng; Huang, Jyh-Hsiung; Shu, Pei-Yun

2006-08-01

Because of the range and nonspecificity of clinical presentations of dengue virus infections, we felt there was a need to create diagnostic tests. We used artificial receptors for the virus to develop serologic assays to detect dengue virus infection. We coated a quartz crystal microbalance (QCM) with molecularly imprinted polymers specific for nonstructural protein 1 of flavivirus. These artificial receptors were specifically created on a QCM chip by polymerization of monomers and were cross-linked in the presence of the epitope site of nonstructural protein 1. We tested serum samples from patients with confirmed cases of dengue reported to the Center for Disease Control in Taipei. Samples were diluted 100-fold; no other sample pretreatment was used. The QCM response was compared with results of monoclonal ELISA. QCM signals were >15 Hz in 18 of 21 (86%) of dengue samples and in 0 of 16 control samples. The correlation (r2) of the QCM response and the ELISA result was 0.73. Within-run and run-to-run imprecisions (CV) were 4%-28% and 10%-32%, respectively. The described assay offers a serologic technique for diagnosis of early viremia. The results illustrate the potential of well-organized polymers on the highly sensitive sensor system for diagnostic and biotechnological applications.

Highly crystallized nanometer-sized zeolite a with large Cs adsorption capability for the decontamination of water.

PubMed

Torad, Nagy L; Naito, Masanobu; Tatami, Junichi; Endo, Akira; Leo, Sin-Yen; Ishihara, Shinsuke; Wu, Kevin C-W; Wakihara, Toru; Yamauchi, Yusuke

2014-03-01

Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Specific binding of large aggregates of amphiphilic molecules to the respective antibodies.

PubMed

Nabok, Alexei; Tsargorodskaya, Anna; Holloway, Alan; Starodub, Nikolay F; Demchenko, Anna

2007-07-31

The Binding of nonylphenol to respective antibodies immobilized on solid substrates was studied with the methods of total internal reflection ellipsometry (TIRE) and QCM (quartz crystal microbalance) impedance spectroscopy. The binding reaction was proved to be highly specific having an association constant of KA=1.6x10(6) mol(-1) L and resulted in an increase in both the adsorbed layer thickness of 23 nm and the added mass of 18.3 microg/cm2 at saturation. The obtained responses of both TIRE and QCM methods are substantially higher than anticipated for the immune binding of single molecules of nonylphenol. The mechanism of binding of large aggregates of nonylphenol was suggested instead. Modeling of the micelle of amphiphilic nonylphenol molecules in aqueous solutions yielded a micelle size of about 38 nm. The mechanism of binding of large molecular aggregates to respective antibodies can be extended to other hydrophobic low-molecular-weight toxins such as T-2 mycotoxin. The formation of large molecular aggregates of nonylphenol and T-2 mycotoxin molecules on the surface was proved by the AFM study.

Preparation and characterization of ALD deposited ZnO thin films studied for gas sensors

NASA Astrophysics Data System (ADS)

Boyadjiev, S. I.; Georgieva, V.; Yordanov, R.; Raicheva, Z.; Szilágyi, I. M.

2016-11-01

Applying atomic layer deposition (ALD), very thin zinc oxide (ZnO) films were deposited on quartz resonators, and their gas sensing properties were studied using the quartz crystal microbalance (QCM) method. The gas sensing of the ZnO films to NO2 was tested in the concentration interval between 10 and 5000 ppm. On the basis of registered frequency change of the QCM, for each concentration the sorbed mass was calculated. Further characterization of the films was carried out by various techniques, i.e. by SEM-EDS, XRD, ellipsometry, and FTIR spectroscopy. Although being very thin, the films were gas sensitive to NO2 already at room temperature and could register very well as low concentrations as 100 ppm, while the sorption was fully reversible. Our results for very thin ALD ZnO films show that the described fast, simple and cost-effective technology could be implemented for producing gas sensors working at room temperature and being capable to detect in real time low concentrations of NO2.

Rapid detection of microorganisms based on active and passive modes of QCM.

PubMed

Farka, Zdeněk; Kovář, David; Skládal, Petr

2014-12-23

Label-free immunosensors are well suited for detection of microorganisms because of their fast response and reasonable sensitivity comparable to infection doses of common pathogens. Active (lever oscillator and frequency counter) and passive (impedance analyzer) modes of quartz crystal microbalance (QCM) were used and compared for rapid detection of three strains of E. coli. Different approaches for antibody immobilization were compared, the immobilization of reduced antibody using Sulfo-SMCC was most effective achieving the limit of detection (LOD) 8 × 104 CFU·mL-1 in 10 min. For the passive mode, software evaluating impedance characteristics in real-time was developed and used. Almost the same results were achieved using both active and passive modes confirming that the sensor properties are not limited by the frequency evaluation method but mainly by affinity of the antibody. Furthermore, reference measurements were done using surface plasmon resonance. Effect of condition of cells on signal was observed showing that cells ruptured by ultrasonication provided slightly higher signal changes than intact microbes.

Epitope-cavities generated by molecularly imprinted films measure the coincident response to anthrax protective antigen and its segments.

PubMed

Tai, Dar-Fu; Jhang, Ming-Hong; Chen, Guan-Yu; Wang, Sue-Chen; Lu, Kuo-Hao; Lee, Yu-Der; Liu, Hsin-Tzu

2010-03-15

A molecularly imprinted film was fabricated, in the presence of epitope-peptides, onto a quartz crystal microbalance (QCM) chip. These five peptides are known linear or conformational epitopes of the anthrax protective antigen PA(83). Imprinting resulted in an epitope-cavity with affinity for the corresponding template. With the use of a basic monomer, the binding-effect was further enhanced increasing the affinity to nanomolar levels. The affinities of the peptide to their corresponding molecularly induced polymers (MIPs) were more closely related to the molecular weight of the analyte than to the number of residues. All epitope-cavities differentiated their epitope region on the protective antigen PA(83) as well as the corresponding furin cleavage fragments PA(63) and PA(20). The QCM chip differential response to the protective antigen fragment was observed in the picomolar range, thus demonstrating a method to manipulate protein on the surface with defined orientation.

Rapid Detection of Microorganisms Based on Active and Passive Modes of QCM

PubMed Central

Farka, Zdeněk; Kovář, David; Skládal, Petr

2015-01-01

Label-free immunosensors are well suited for detection of microorganisms because of their fast response and reasonable sensitivity comparable to infection doses of common pathogens. Active (lever oscillator and frequency counter) and passive (impedance analyzer) modes of quartz crystal microbalance (QCM) were used and compared for rapid detection of three strains of E. coli. Different approaches for antibody immobilization were compared, the immobilization of reduced antibody using Sulfo‐SMCC was most effective achieving the limit of detection (LOD) 8 × 104 CFU·mL−1 in 10 min. For the passive mode, software evaluating impedance characteristics in real-time was developed and used. Almost the same results were achieved using both active and passive modes confirming that the sensor properties are not limited by the frequency evaluation method but mainly by affinity of the antibody. Furthermore, reference measurements were done using surface plasmon resonance. Effect of condition of cells on signal was observed showing that cells ruptured by ultrasonication provided slightly higher signal changes than intact microbes. PMID:25545267

A study on 2, 4, 6-trinitrotolurene (TNT) vapor detection by using a quartz crystal microbalance with 18-crown-6 ether film

NASA Astrophysics Data System (ADS)

Phetchakul, Toempong; Phuvanatai, Pavaris

2017-07-01

The application of 18-crown-6 ether film for 2, 4, 6-trinitrotolurene (TNT) vapor detection by using quartz crystal microbalance (QCM) is studied. The film is coated on the quartz electrodes as sensitive material for capture TNT molecule. The parameters that are studied are concentration and mass or thickness of film. When the explosive adheres to surface of the crystal oscillator, the weight is changed and the resonance frequency of the crystal oscillator is shifted lower. The frequency shift (Δf) relates to concentration and mass or thickness. The high concentration and mass/thickness of film enhance the TNT detection.

Polyvinylpyrrolidone/reduced graphene oxide nanocomposites thin films coated on quartz crystal microbalance for NO2 detection at room temperature

NASA Astrophysics Data System (ADS)

Huang, Junlong; Xie, Guangzhong; Zhou, Yong; Xie, Tao; Tai, HuiLing; Yang, Guangjin

2014-08-01

Polyvinylpyrrolidone (PVP)/reduced graphene oxide (RGO) nanocomposites are sprayed on quartz crystal microbalance (QCM) for NO2 sensing. The thin films are characterized by Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy (UV-VIS). The experimental results reveal that PVP/RGO sensor exhibits higher sensitivity and shorter recovery time than those of PVP. Besides, the response to 20 ppm NO2 is higher than other gases such as CO, CO2 and NH3 even at 100ppm. When the PVP/RGO sensor is exposed to these gases, the good selectivity to NO2 makes the sensor ideal for NO2 detection.

Integration of Quartz Crystal Microbalance-Dissipation and Reflection-Mode Localized Surface Plasmon Resonance Sensors for Biomacromolecular Interaction Analysis.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Cho, Nam-Joon

2016-12-20

The combination of label-free, surface-sensitive measurement techniques based on different physical principles enables detailed characterization of biomacromolecular interactions at solid-liquid interfaces. To date, most combined measurement systems have involved experimental techniques with similar probing volumes, whereas the potential of utilizing techniques with different surface sensitivities remains largely unexplored, especially for data interpretation. Herein, we report a combined measurement approach that integrates a conventional quartz crystal microbalance-dissipation (QCM-D) setup with a reflection-mode localized surface plasmon (LSPR) sensor. Using this platform, we investigate vesicle adsorption on a titanium oxide-coated sensing substrate along with the amphipathic, α-helical (AH) peptide-induced structural transformation of surface-adsorbed lipid vesicles into a supported lipid bilayer (SLB) as a model biomacromolecular interaction. While the QCM-D and LSPR signals both detected mass uptake arising from vesicle adsorption, tracking the AH peptide-induced structural transformation revealed more complex measurement responses based on the different surface sensitivities of the two techniques. In particular, the LSPR signal recorded an increase in optical mass near the sensor surface which indicated SLB formation, whereas the QCM-D signals detected a significant loss in net acoustic mass due to excess lipid and coupled solvent leaving the probing volume. Importantly, these measurement capabilities allowed us to temporally distinguish the process of SLB formation at the sensor surface from the overall structural transformation process. Looking forward, these label-free measurement capabilities to simultaneously probe adsorbates at multiple length scales will provide new insights into complex biomacromolecular interactions.

Transient kinetic studies of pH-dependent hydrolyses by exo-type carboxypeptidase P on a 27-MHz quartz crystal microbalance.

PubMed

Furusawa, Hiroyuki; Takano, Hiroki; Okahata, Yoshio

2008-02-15

pH-Dependent kinetic parameters (k(on), k(off), and k(cat)) of protein (myoglobin) hydrolyses catalyzed by exo-enzyme (carboxypeptidase P, CPP) were obtained by using a protein-immobilized quartz crystal microbalance (QCM) in acidic aqueous solutions. The formation of the enzyme-substrate (ES) complex (k(on)), the decay of the ES complex (k(off)), and the formation of the product (k(cat)) could be analyzed by transient kinetics as mass changes on the QCM plate. The Kd (k(off)/k(on)) value was different from the Michaelis constant Km calculated from (k(off) + k(cat))/k(on) due to k(cat) > k(off). The rate-determining step was the binding step (k(on), and the catalytic rate k(cat) was faster than other k(on) and k(off) values. In the range of pH 2.5-5.0, values of k(on) gradually increased with decreasing pH showing a maximum at pH 3.7, values of k(off) were independent of pH, and k(cat) increased gradually with decreasing pH. As a result, the apparent rate constant (k(cat)/Km) showed a maximum at pH 3.7 and gradually increased with decreasing pH. The optimum pH at 3.7 of k(on) is explained by the optimum binding ability of CPP to the COOH terminus of the substrate with hydrogen bonds. The increase of k(cat) at the lower pH correlated with the decrease of alpha-helix contents of the myoglobin substrate on the QCM.

High-frequency phase shift measurement greatly enhances the sensitivity of QCM immunosensors.

PubMed

March, Carmen; García, José V; Sánchez, Ángel; Arnau, Antonio; Jiménez, Yolanda; García, Pablo; Manclús, Juan J; Montoya, Ángel

2015-03-15

In spite of being widely used for in liquid biosensing applications, sensitivity improvement of conventional (5-20MHz) quartz crystal microbalance (QCM) sensors remains an unsolved challenging task. With the help of a new electronic characterization approach based on phase change measurements at a constant fixed frequency, a highly sensitive and versatile high fundamental frequency (HFF) QCM immunosensor has successfully been developed and tested for its use in pesticide (carbaryl and thiabendazole) analysis. The analytical performance of several immunosensors was compared in competitive immunoassays taking carbaryl insecticide as the model analyte. The highest sensitivity was exhibited by the 100MHz HFF-QCM carbaryl immunosensor. When results were compared with those reported for 9MHz QCM, analytical parameters clearly showed an improvement of one order of magnitude for sensitivity (estimated as the I50 value) and two orders of magnitude for the limit of detection (LOD): 30μgl(-1) vs 0.66μgL(-1)I50 value and 11μgL(-1) vs 0.14μgL(-1) LOD, for 9 and 100MHz, respectively. For the fungicide thiabendazole, I50 value was roughly the same as that previously reported for SPR under the same biochemical conditions, whereas LOD improved by a factor of 2. The analytical performance achieved by high frequency QCM immunosensors surpassed those of conventional QCM and SPR, closely approaching the most sensitive ELISAs. The developed 100MHz QCM immunosensor strongly improves sensitivity in biosensing, and therefore can be considered as a very promising new analytical tool for in liquid applications where highly sensitive detection is required. Copyright © 2014 Elsevier B.V. All rights reserved.

Characterization of thin MoO3 films formed by RF and DC-magnetron reactive sputtering for gas sensor applications

NASA Astrophysics Data System (ADS)

Yordanov, R.; Boyadjiev, S.; Georgieva, V.; Vergov, L.

2014-05-01

The present work discusses a technology for deposition and characterization of thin molybdenum oxide (MoOx, MoO3) films studied for gas sensor applications. The samples were produced by reactive radio-frequency (RF) and direct current (DC) magnetron sputtering. The composition and microstructure of the films were studied by XPS, XRD and Raman spectroscopy, the morphology, using high resolution SEM. The research was focused on the sensing properties of the sputtered thin MoO3 films. Highly sensitive gas sensors were implemented by depositing films of various thicknesses on quartz resonators. Making use of the quartz crystal microbalance (QCM) method, these sensors were capable of detecting changes in the molecular range. Prototype QCM structures with thin MoO3 films were tested for sensitivity to NH3 and NO2. Even in as-deposited state and without heating the substrates, these films showed good sensitivity. Moreover, no additional thermal treatment is necessary, which makes the production of such QCM gas sensors simple and cost-effective, as it is fully compatible with the technology for producing the initial resonator. The films are sensitive at room temperature and can register concentrations as low as 50 ppm. The sorption is fully reversible, the films are stable and capable of long-term measurements.

Measurement of the accumulation of water ice on optical components in cryogenic vacuum environments

NASA Astrophysics Data System (ADS)

Moeller, Trevor M.; Montgomery Smith, L.; Collins, Frank G.; Labello, Jesse M.; Rogers, James P.; Lowry, Heard S.; Crider, Dustin H.

2012-11-01

Standard vacuum practices mitigate the presence of water vapor and contamination inside cryogenic vacuum chambers. However, anomalies can occur in the facility that can cause the accumulation of amorphous water ice on optics and test articles. Under certain conditions, the amorphous ice on optical components shatters, which leads to a reduction in signal or failure of the component. An experiment was performed to study and measure the deposition of water (H2O) ice on optical surfaces under high-vacuum cryogenic conditions. Water was introduced into a cryogenic vacuum chamber, via a hydrated molecular sieve zeolite, through an effusion cell and impinged upon a quartz-crystal microbalance (QCM) and first-surface gold-plated mirror. A laser and photodiode setup, external to the vacuum chamber, monitored the multiple-beam interference reflectance of the ice-mirror configuration while the QCM measured the mass deposition. Data indicates that water ice, under these conditions, accumulates as a thin film on optical surfaces to thicknesses over 45 microns and can be detected and measured by nonintrusive optical methods which are based upon multiple-beam interference phenomena. The QCM validated the interference measurements. This experiment established proof-of-concept for a miniature system for monitoring ice accumulation within the chamber.

QCM and AFM Study of atomic scale polishing and roughening of surfaces exposed to nanoparticle suspensions of diamond, Al2O3 and SiO2.

NASA Astrophysics Data System (ADS)

Krim, Jacqueline; Acharya, Biplav; Chestnut, Melanie; Marek, Antonin; Shendarova, Olga; Smirnov, Alex

The addition of nanoparticles to conventional automotive lubricants is known in many cases to result in increased energy efficiency, but the atomic scale mechanisms leading to the increased efficiency are yet to be established. To explore this issue, we studied surface uptake and nanotribological properties of nanoparticle suspensions of diamond, Al2O3 and SiO2 dispersed in water and/or oil (PAO6) in real time by means of an in situ Quartz Crystal Microbalance (QCM) technique, with a focus on the impact of the suspension on the surface roughness and texture of the QCM electrode and how the results compared to macroscopic reductions in friction and increased energy efficiency for the same materials' combinations. The frequency and dissipative properties (mechanical resistance) of QCM's with both gold and nickel surface electrodes were first studied for immersed samples upon addition of the nanoparticles. Nanodiamonds resulted in an increased mechanical resistance while the addition of Al2O3 and SiO2 nanoparticles resulted in a decreased resistance, indicating a reduced resistance of the fluid to the motion of the QCM. Atomic Force Microscope (AFM) measurements were then performed on the QCM electrodes after exposure to the suspensions, to explore potential polishing and/or roughening effects. The results are closely linked to the macroscopic friction and wear attributes. Work supported by NSF.

Porphyrin-Embedded Silicate Materials for Detection of Hydrocarbon Solvents

DTIC Science & Technology

2011-01-14

Sensors 2011, 11, 886-904; doi:10.3390/s110100886 sensors ISSN 1424-8220 www.mdpi.com/journal/ sensors Article Porphyrin-Embedded Silicate...Prescribed by ANSI Std Z39-18 Sensors 2011, 11 887 1. Introduction Mesoporous silicates have been widely described in sensing...absorption spectroscopy, quartz crystal microbalance ( QCM ), and FTIR have been utilized for aromatic hydrocarbon sensing applications based on these

Optical and structural properties of protein/gold hybrid bio-nanofilms prepared by layer-by-layer method.

PubMed

Pál, Edit; Hornok, Viktória; Sebok, Dániel; Majzik, Andrea; Dékány, Imre

2010-08-01

Lysozyme/gold thin layers were prepared by layer-by-layer (LbL) self-assembly method. The build-up of the films was followed by UV-vis-absorbance spectra, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) techniques. The structural property of films was examined by X-ray diffraction (XRD) measurements, while their morphology was studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). It was found that gold nanoparticles (NPs) had cubic crystalline structure, the primary particles form aggregates in the thin layer due to the presence of lysozyme molecules. The UV-vis measurements prove change in particle size while the colour of the film changes from wine-red to blue. The layer thickness of films was determined using the above methods and the loose, porous structure of the films explains the difference in the results. The vapour adsorption property of hybrid layers was also studied by QCM using different saturated vapours and ammonia gas. The lysozyme/Au films were most sensitive for ammonia gas among the tested gases/vapours due to the strongest interaction between the functional groups of the protein. Copyright 2010 Elsevier B.V. All rights reserved.

Detection of HIT antibody dependent platelet aggregation using novel surface imprinting approach.

PubMed

Hussain, Munawar; Northoff, Hinnak; Gehring, Frank K

2016-01-15

We present a fast, robust and straightforward spin force assisted surface imprinting approach for activated platelets and demonstrate that Heparin induced thrombocytopenia (HIT) platelet aggregation can be measured by this approach. A critical and challenging step in functional assays for HIT is platelet separation from the healthy donor's platelet-rich plasma (PRP). Our approach using surface imprinted polymer (MIP) for measurements on a quartz crystal microbalance with dissipation (QCM-D) enables monitoring of platelet aggregation directly in PRP thus eliminating the challenge of platelet separation. This is the first report of platelet imprinting. We also provide proof of principle that QCM-D technology can be applied for functional measurements of HIT antibodies. Copyright © 2015 Elsevier B.V. All rights reserved.

Recognition of dengue virus protein using epitope-mediated molecularly imprinted film.

PubMed

Tai, Dar-Fu; Lin, Chung-Yin; Wu, Tzong-Zeng; Chen, Li-Kuang

2005-08-15

Molecularly imprinted film was fabricated in the presence of a pentadecapeptide onto a quartz crystal microbalance (QCM) chip. This 15-mer peptide has been known as the linear epitope of the dengue virus NS1 protein. Imprinting resulted in an increased polymer affinity toward the corresponding templates but also to the virus protein. Direct detection of the dengue virus protein was achieved quantitatively. The QCM chip response to the NS1 protein was obtained using epitope-mediated imprinting demonstrating a comparable frequency shift in chips immobilized with monoclonal antibodies. The binding effect was further enhanced and confirmed using a monoclonal antibody to form a sandwich with the MIP-NS1 protein complex on the chip. No pretreatment was required.

Study of a QCM dimethyl methylphosphonate sensor based on a ZnO-modified nanowire-structured manganese dioxide film.

PubMed

Pei, Zhifu; Ma, Xingfa; Ding, Pengfei; Zhang, Wuming; Luo, Zhiyuan; Li, Guang

2010-01-01

Sensitive, selective and fast detection of chemical warfare agents is necessary for anti-terrorism purposes. In our search for functional materials sensitive to dimethyl methylphosphonate (DMMP), a simulant of sarin and other toxic organophosphorus compounds, we found that zinc oxide (ZnO) modification potentially enhances the absorption of DMMP on a manganese dioxide (MnO(2)) surface. The adsorption behavior of DMMP was evaluated through the detection of tiny organophosphonate compounds with quartz crystal microbalance (QCM) sensors coated with ZnO-modified MnO(2) nanofibers and pure MnO(2) nanofibers. Experimental results indicated that the QCM sensor coated with ZnO-modified nanostructured MnO(2) film exhibited much higher sensitivity and better selectivity in comparison with the one coated with pure MnO(2) nanofiber film. Therefore, the DMMP sensor developed with this composite nanostructured material should possess excellent selectivity and reasonable sensitivity towards the tiny gaseous DMMP species.

Bacterial adhesion to protein-coated surfaces: An AFM and QCM-D study

NASA Astrophysics Data System (ADS)

Strauss, Joshua; Liu, Yatao; Camesano, Terri A.

2009-09-01

Bacterial adhesion to biomaterials, mineral surfaces, or other industrial surfaces is strongly controlled by the way bacteria interact with protein layers or organic matter and other biomolecules that coat the materials. Despite this knowledge, many studies of bacterial adhesion are performed under clean conditions, instead of in the presence of proteins or organic molecules. We chose fetal bovine serum (FBS) as a model protein, and prepared FBS films on quartz crystals. The thickness of the FBS layer was characterized using atomic force microscopy (AFM) imaging under liquid and quartz crystal microbalance with dissipation (QCM-D). Next, we characterized how the model biomaterial surface would interact with the nocosomial pathogen Staphylococcus epidermidis. An AFM probe was coated with S. epidermidis cells and used to probe a gold slide that had been coated with FBS or another protein, fibronectin (FN). These experiments show that AFM and QCM-D can be used in complementary ways to study the complex interactions between bacteria, proteins, and surfaces.

Study of a QCM Dimethyl Methylphosphonate Sensor Based on a ZnO-Modified Nanowire-Structured Manganese Dioxide Film

PubMed Central

Pei, Zhifu; Ma, Xingfa; Ding, Pengfei; Zhang, Wuming; Luo, Zhiyuan; Li, Guang

2010-01-01

Sensitive, selective and fast detection of chemical warfare agents is necessary for anti-terrorism purposes. In our search for functional materials sensitive to dimethyl methylphosphonate (DMMP), a simulant of sarin and other toxic organophosphorus compounds, we found that zinc oxide (ZnO) modification potentially enhances the absorption of DMMP on a manganese dioxide (MnO2) surface. The adsorption behavior of DMMP was evaluated through the detection of tiny organophosphonate compounds with quartz crystal microbalance (QCM) sensors coated with ZnO-modified MnO2 nanofibers and pure MnO2 nanofibers. Experimental results indicated that the QCM sensor coated with ZnO-modified nanostructured MnO2 film exhibited much higher sensitivity and better selectivity in comparison with the one coated with pure MnO2 nanofiber film. Therefore, the DMMP sensor developed with this composite nanostructured material should possess excellent selectivity and reasonable sensitivity towards the tiny gaseous DMMP species. PMID:22163653

Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

NASA Astrophysics Data System (ADS)

Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

2016-08-01

Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

Room-temperature sensitivity to NO2 exposure of electrochemically-deposited nanostructured ZnO layers

NASA Astrophysics Data System (ADS)

Lovchinov, K.; Petrov, M.; Ganchev, M.; Georgieva, V.; Nichev, H.; Georgieva, B.; Dimova-Malinovska, D.

2014-05-01

This paper reports studies on the sensitivity of ZnO layers to NO2 exposure. ZnO layers were fabricated by electrochemical deposition on the surface of a quartz crystal microbalance (QCM) with Au electrodes. The sensitivity was estimated using the frequency-time characteristics of the QCM. For this purpose, the resonance frequency shift was measured. The sorption process was investigated in a NO2 gas flow. The change in the resonance frequency, f of the QCM as a function of the loaded mass of NO2 was followed for a NO2 concentration of 500 ppm. Under gas exposure, the frequency decreased and reached saturation in five min. A frequency shift of 38 Hz was measured and a mass loading of 8.39 ng was calculated. The resonance frequency showed a very good recovery within two minutes after the NO2 flow was switched off. The results demonstrate that the electrodeposited nanostructured ZnO layers have a potential for application as NO2 gas sensors.

Continuous monitoring of bacterial biofilm growth using uncoated Thickness-Shear Mode resonators

NASA Astrophysics Data System (ADS)

Castro, P.; Resa, P.; Durán, C.; Maestre, J. R.; Mateo, M.; Elvira, L.

2012-12-01

Quartz Crystal Microbalances (QCM) were used to nondestructively monitor in real time the microbial growth of the bacteria Staphylococcus epidermidis (S. epidermidis) in a liquid broth. QCM, sometimes referred to as Thickness-Shear Mode (TSM) resonators, are highly sensitive sensors not only able to measure very small mass, but also non-gravimetric contributions of viscoelastic media. These devices can be used as biosensors for bacterial detection and are employed in many applications including their use in the food industry, water and environment monitoring, pharmaceutical sciences and clinical diagnosis. In this work, three strains of S. epidermidis (which differ in the ability to produce biofilm) have been continuously monitored using an array of piezoelectric TSM resonators, at 37 °C in a selective culturing media. Microbial growth was followed by measuring the changes in the crystal resonant frequency and bandwidth at several harmonics. It was shown that microbial growth can be monitored in real time using multichannel and multiparametric QCM sensors.

Determination of sorption isotherm and rheological properties of lysozyme using a high-resolution humidity scanning QCM-D technique.

PubMed

Graf, Gesche; Kocherbitov, Vitaly

2013-08-29

The high-resolution humidity scanning QCM-D technique enables investigation of hydration of soft matter films using a quartz crystal microbalance with dissipation monitoring (QCM-D) equipped with a humidity module. Based on a continuous increase of relative humidity, properties of soft matter films can be investigated depending on the water content of the surrounding atmosphere. Determination of complete water sorption isotherms is possible via analysis of the overtone dependence of the resonance frequencies. Rheological properties are monitored via measurement of the dissipation. The glass transition can be identified from the change of viscoelastic properties of the film reflected in changes of the dissipation. A high-resolution water sorption isotherm of lysozyme was measured and compared with results from water sorption calorimetry. Analysis of the rheological behavior during hydration of lysozyme films revealed the presence of two separate sharp transitions at the water activities 0.67 and 0.91, which are connected to the glass transition. In previous works, only the existence of a broad glass transition has been reported so far. Combining the QCM-D data with Raman scattering data presented earlier, a new mechanism of isothermal glass transition in lysozyme is proposed.

Resolution in QCM sensors for the viscosity and density of liquids: application to lead acid batteries.

PubMed

Cao-Paz, Ana María; Rodríguez-Pardo, Loreto; Fariña, José; Marcos-Acevedo, Jorge

2012-01-01

In battery applications, particularly in automobiles, submarines and remote communications, the state of charge (SoC) is needed in order to manage batteries efficiently. The most widely used physical parameter for this is electrolyte density. However, there is greater dependency between electrolyte viscosity and SoC than that seen for density and SoC. This paper presents a Quartz Crystal Microbalance (QCM) sensor for electrolyte density-viscosity product measurements in lead acid batteries. The sensor is calibrated in H(2)SO(4) solutions in the battery electrolyte range to obtain sensitivity, noise and resolution. Also, real-time tests of charge and discharge are conducted placing the quartz crystal inside the battery. At the same time, the present theoretical "resolution limit" to measure the square root of the density-viscosity product [Formula: see text] of a liquid medium or best resolution achievable with a QCM oscillator is determined. Findings show that the resolution limit only depends on the characteristics of the liquid to be studied and not on frequency. The QCM resolution limit for [Formula: see text] measurements worsens when the density-viscosity product of the liquid is increased, but it cannot be improved by elevating the work frequency.

Limitations in interpretation of Quartz Crystal Microbalance (QCM) beyond the rigid (Sauerbrey) to viscoelastic (lossy) transition

NASA Astrophysics Data System (ADS)

Wiener, Clinton; Weiss, Robert; White, Christopher; Vogt, Bryan

2014-03-01

Since Sauerbrey's 1959 discovery of the mass-frequency relationship in quartz, the QCM has been utilized to probe deposited mass layers. The mass to frequency (imaginary component of the impedance) relationship breaks down when the added mass is not rigidly coupled to the sensor surface and viscous dissipation of the quartz occurs. This dissipation is important in the deposition of soft materials such as polymers or biological molecules. By using a viscoelastic model for frequency and dissipation; the mass, viscosity, and shear modulus can be accurately determined. Here, we demonstrate an additional breakdown in the coupling of the imaginary component of the impedance to the mass by simultaneous QCM-D and spectroscopic ellipsometry (SE) measurements by examination of the swelling behavior of thin physically crosslinked poly-n-isopropylacrylamide films. A film swollen beyond 3 times its dry thickness shows a frequency increase (mass loss) and dissipation increases (increasing lossy film character) on cooling, but SE results show increased swelling of the film. This behavior was found to be thickness invariant for dry thicknesses of 32 nm and greater. Modeling of this QCM-D data shows non-physical results. Scaling concepts associated with this high loss limit will be discussed.

Resolution in QCM Sensors for the Viscosity and Density of Liquids: Application to Lead Acid Batteries

PubMed Central

Cao-Paz, Ana María; Rodríguez-Pardo, Loreto; Fariña, José; Marcos-Acevedo, Jorge

2012-01-01

In battery applications, particularly in automobiles, submarines and remote communications, the state of charge (SoC) is needed in order to manage batteries efficiently. The most widely used physical parameter for this is electrolyte density. However, there is greater dependency between electrolyte viscosity and SoC than that seen for density and SoC. This paper presents a Quartz Crystal Microbalance (QCM) sensor for electrolyte density-viscosity product measurements in lead acid batteries. The sensor is calibrated in H2SO4 solutions in the battery electrolyte range to obtain sensitivity, noise and resolution. Also, real-time tests of charge and discharge are conducted placing the quartz crystal inside the battery. At the same time, the present theoretical “resolution limit” to measure the square root of the density-viscosity product (ρη) of a liquid medium or best resolution achievable with a QCM oscillator is determined. Findings show that the resolution limit only depends on the characteristics of the liquid to be studied and not on frequency. The QCM resolution limit for ρη measurements worsens when the density-viscosity product of the liquid is increased, but it cannot be improved by elevating the work frequency. PMID:23112618

Application of nanomaterials in the bioanalytical detection of disease-related genes.

PubMed

Zhu, Xiaoqian; Li, Jiao; He, Hanping; Huang, Min; Zhang, Xiuhua; Wang, Shengfu

2015-12-15

In the diagnosis of genetic diseases and disorders, nanomaterials-based gene detection systems have significant advantages over conventional diagnostic systems in terms of simplicity, sensitivity, specificity, and portability. In this review, we describe the application of nanomaterials for disease-related genes detection in different methods excluding PCR-related method, such as colorimetry, fluorescence-based methods, electrochemistry, microarray methods, surface-enhanced Raman spectroscopy (SERS), quartz crystal microbalance (QCM) methods, and dynamic light scattering (DLS). The most commonly used nanomaterials are gold, silver, carbon and semiconducting nanoparticles. Various nanomaterials-based gene detection methods are introduced, their respective advantages are discussed, and selected examples are provided to illustrate the properties of these nanomaterials and their emerging applications for the detection of specific nucleic acid sequences. Copyright © 2015. Published by Elsevier B.V.

Quartz crystal microbalance biosensor for rapid detection of aerosolized microorganisms

NASA Astrophysics Data System (ADS)

Farka, Zdenĕk.; Kovár, David; Skládal, Petr

2015-05-01

Biological warfare agents (BWAs) represent the current menace of the asymmetric war. The early detection of BWAs, especially in the form of bioaerosol, is a challenging task for governments all around the world. Label-free quartz crystal microbalance (QCM) immunosensor and electrochemical immunosensor were developed and tested for rapid detection of BWA surrogate (E. coli) in the form of bioaerosol. Two immobilization strategies for the attachment of antibody were tested; the gold sensor surface was activated by cysteamine and then antibody was covalently linked either using glutaraldehyde, or the reduced antibodies were attached via Sulfo-SMCC. A portable bioaerosol chamber was constructed and used for safe manipulation with aerosolized microorganisms. The dissemination was done using a piezoelectric humidifier, distribution of bioaerosol inside the chamber was ensured using three 12-cm fans. The whole system was controlled remotely using LAN network. The disseminated microbial cells were collected and preconcentrated using the wetted-wall cyclone SASS 2300, the analysis was done using the on-line linked immunosensors. The QCM immunosensor had limit of detection 1×104 CFU·L-1 of air with analysis time 16 min, the whole experiment including dissemination and sensor surface regeneration took 40 min. In case of blank (disseminated sterile buffer), no signal change was observed. The electrochemical immunosensor was able to detect 150 CFU·L-1 of air in 20 min; also in this case, no interferences were observed. Reference measurements were done using particle counter Met One 3400 and by cultivation method on agar plates. The sensors have proved to be applicable for rapid screening of microorganisms in air.

Data analysis for lidar and quartz crystal microbalance systems

NASA Technical Reports Server (NTRS)

Kent, G. S.; Deepak, A.

1985-01-01

Results are presented of the analysis of data taken on the stratospheric aerosol, using lidar, Quartz Crystal Microbalance (QCM), and the SAGE and SAM II satellite systems. The main objective of the work reported has been to use the data, taken with the NASA-LaRC instruments to study the stratospheric effects of volcanic eruptions during the period between the launch of the SAGE and SAM II satellite systems and October 1980. Four significant volcanic eruptions, for which data are available, occurred during this period--Soufriere, Sierra Negra, Mt. St. Helens, and Ulawun. Data on these have been analyzed to determine the changes in stratospheric mass loading produced by the eruptions, and to study the dispersion of the newly injected material.

Acetylcholinesterase-reduced graphene oxide hybrid films for organophosphorus neurotoxin sensing via quartz crystal microbalance

NASA Astrophysics Data System (ADS)

Tang, Shi; Ma, Wenying; Xie, Guangzhong; Su, Yuanjie; Jiang, Yadong

2016-09-01

An acetylcholinesterase (AChE)-reduced graphene oxide (RGO) hybrid films based biosensor enabled by quartz crystal microbalance (QCM) has been developed for the detection of organophosphorus neurotoxin in gas phase at room temperature. To improve the sensing performance, RGO was used to immobilize large quantities of enzyme and provide a favorable microenvironment to maintain the enzyme activity. The experimental results reveal that the response of AChE-RGO/glutaraldehyde based sensors is about 8 times larger than that of the AChE with the sensitivity of 1.583 Hz/mg/m3. 1.0 mg amount of RGO, 5% concentration of glutaraldehyde and pH 6.8 is the optimal condition of this biosensor.

Real-time QCM-D monitoring of cancer cell death early events in a dynamic context.

PubMed

Nowacki, Laetitia; Follet, Julie; Vayssade, Muriel; Vigneron, Pascale; Rotellini, Laura; Cambay, Florian; Egles, Christophe; Rossi, Claire

2015-02-15

Since a few years, the acoustic sensing of whole cell is the focus of increasing interest for monitoring the cytoskeletal cellular response to morphological modulators. We aimed at illustrating the potentialities of the quartz crystal microbalance with dissipation (QCM-D) technique for the real-time detection of the earliest morphological changes that occur at the cell-substrate interface during programmed cell death. Human breast cancer cells (MCF-7) grown on serum protein-coated gold sensors were placed in dynamic conditions under a continuous medium flow. The mass and viscoelasticity changes of the cells were tracked by monitoring the frequency and dissipation shifts during the first 4h of cell exposure to staurosporine, a well-known apoptosis inducer. We have identified a QCM-D signature characteristic of morphological modifications and cell detachment from the sensing surface that are related to the pro-apoptotic treatment. In particular, for low staurosporine doses below 1 µM, we showed that recording the dissipation shift allows to detect an early cell response which is undetectable after the same duration by the classical analytical techniques in cell biology. Furthermore, this sensing method allows quantifying the efficiency of the drug effect in less than 4h without requiring labeling and without interfering in the system, thus preventing any loss of information. In the actual context of targeted cancer therapy development, we believe that these results bring new insights in favor of the use of the non invasive QCM-D technique for quickly probing the cancer cell sensitivity to death inducer drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

PubMed

Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

2016-08-25

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5

PubMed Central

Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

2016-01-01

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example. PMID:27585356

Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films

NASA Astrophysics Data System (ADS)

Guo, Wei; Chen, Zhi; Yang, Chengwu; Neumann, Tobias; Kübel, Christian; Wenzel, Wolfgang; Welle, Alexander; Pfleging, Wilhelm; Shekhah, Osama; Wöll, Christof; Redel, Engelbert

2016-03-01

We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00532b

Practical strategies for stable operation of HFF-QCM in continuous air flow.

PubMed

Wessels, Alexander; Klöckner, Bernhard; Siering, Carsten; Waldvogel, Siegfried R

2013-09-09

Currently there are a few fields of application using quartz crystal microbalances (QCM). Because of environmental conditions and insufficient resolution of the microbalance, chemical sensing of volatile organic compounds in an open system was as yet not possible. In this study we present strategies on how to use 195 MHz fundamental quartz resonators for a mobile sensor platform to detect airborne analytes. Commonly the use of devices with a resonant frequency of about 10 MHz is standard. By increasing the frequency to 195 MHz the frequency shift increases by a factor of almost 400. Unfortunately, such kinds of quartz crystals tend to exhibit some challenges to obtain a reasonable signal-to-noise ratio. It was possible to reduce the noise in frequency in a continuous air flow of 7.5 m/s to 0.4 Hz [i.e., σ(τ) = 2 × 10-9] by elucidating the major source of noise. The air flow in the vicinity of the quartz was analyzed to reduce turbulences. Furthermore, we found a dependency between the acceleration sensitivity and mechanical stress induced by an internal thermal gradient. By reducing this gradient, we achieved reduction of the sensitivity to acceleration by more than one decade. Hence, the resulting sensor is more robust to environmental conditions such as temperature, acceleration and air flow.

A quick responding quartz crystal microbalance sensor array based on molecular imprinted polyacrylic acids coating for selective identification of aldehydes in body odor.

PubMed

Jha, Sunil K; Hayashi, Kenshi

2015-03-01

In present work, a novel quartz crystal microbalance (QCM) sensor array has been developed for prompt identification of primary aldehydes in human body odor. Molecularly imprinted polymers (MIP) are prepared using the polyacrylic acid (PAA) polymer matrix and three organic acids (propenoic acid, hexanoic acid and octanoic acid) as template molecules, and utilized as QCM surface coating layer. The performance of MIP films is characterized by 4-element QCM sensor array (three coated with MIP layers and one with pure PAA for reference) dynamic and static responses to target aldehydes: hexanal, heptanal, and nonanal in single, binary, and tertiary mixtures at distinct concentrations. The target aldehydes were selected subsequent to characterization of body odor samples with solid phase-micro extraction gas chromatography mass spectrometer (SPME-GC-MS). The hexanoic acid and octanoic acid imprinted PAA exhibit fast response, and better sensitivity, selectivity and reproducibility than the propenoic acid, and non-imprinted PAA in array. The response time and recovery time for hexanoic acid imprinted PAA are obtained as 5 s and 12 s respectively to typical concentrations of binary and tertiary mixtures of aldehydes using the static response. Dynamic sensor array response matrix has been processed with principal component analysis (PCA) for visual, and support vector machine (SVM) classifier for quantitative identification of target odors. Aldehyde odors were identified successfully in principal component (PC) space. SVM classifier results maximum recognition rate 79% for three classes of binary odors and 83% including single, binary, and tertiary odor classes in 3-fold cross validation. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of liquid medium and surface morphology on the response of QCM during immobilization and hybridization of short oligonucleotides.

PubMed

Ha, Tai Hwan; Kim, Sunhee; Lim, Geunbae; Kim, Kwan

2004-09-15

With the goal of developing a quartz crystal microbalance (QCM)-based DNA sensor, we have conducted an in situ QCM study along with fluorescence measurements using oligonucleotides (15-mer) as a model single-stranded DNA (ss-DNA) in two different aqueous buffer solutions; the sequence of 15-mer is a part of iduronate-2-sulphate exon whose mutation is known to cause Hunter syndrome, and the 15-mer is thiolated to be immobilized on the Au-coated quartz substrate. The fluorescence data indicate that the initial immobilization as well as the subsequent hybridization with a complementary strand is hardly dependent on the kind of buffer solution. In contrast, the mass increases deducible from the decrease of QCM frequency via the Sauerbrey equation are 2.7-6.2 and 3.0-4.4 times larger than the actual mass increases, as reflected in the fluorescence measurements, for the immobilization and the subsequent hybridization processes, respectively. Such an overestimation is attributed to the trapping of solvent as well as the formation of quite a rigid hydration layer associated with the higher viscosities and/or densities of the buffer solutions. Another noteworthy observation is the excessively large frequency change that occurs when the gold electrode is deposited in advance with Au nanoparticles. This clearly illustrates that the QCM detection of DNA hybridization is also affected greatly by the surface morphology of the electrode. These enlarged signals are altogether presumed to be advantageous when using a QCM system as an in situ probing device in DNA sensors.

Environmental monitors in the Midcourse Space Experiments (MSX)

NASA Technical Reports Server (NTRS)

Uy, O. M.

1993-01-01

The Midcourse Space Experiment (MSX) is an SDIO sponsored space based sensor experiment with a full complement of optical sensors. Because of the possible deleterious effect of both molecular and particulate contamination on these sensors, a suite of environmental monitoring instruments are also being flown with the spacecraft. These instruments are the Total Pressure Sensor based on the cold-cathode gauge, a quadrupole mass spectrometer, a Bennett-type ion mass spectrometer, a cryogenic quartz crystal microbalance (QCM), four temperature-controlled QCM's, and a Xenon and Krypton Flash Lamp Experiment. These instruments have been fully space-qualified, are compact and low cost, and are possible candidate sensors for near-term planetary and atmospheric monitoring. The philosophy adopted during design and fabrication, calibration and ground testing, and modeling will be discussed .

Classification of Multiple Chinese Liquors by Means of a QCM-based E-Nose and MDS-SVM Classifier.

PubMed

Li, Qiang; Gu, Yu; Jia, Jing

2017-01-30

Chinese liquors are internationally well-known fermentative alcoholic beverages. They have unique flavors attributable to the use of various bacteria and fungi, raw materials, and production processes. Developing a novel, rapid, and reliable method to identify multiple Chinese liquors is of positive significance. This paper presents a pattern recognition system for classifying ten brands of Chinese liquors based on multidimensional scaling (MDS) and support vector machine (SVM) algorithms in a quartz crystal microbalance (QCM)-based electronic nose (e-nose) we designed. We evaluated the comprehensive performance of the MDS-SVM classifier that predicted all ten brands of Chinese liquors individually. The prediction accuracy (98.3%) showed superior performance of the MDS-SVM classifier over the back-propagation artificial neural network (BP-ANN) classifier (93.3%) and moving average-linear discriminant analysis (MA-LDA) classifier (87.6%). The MDS-SVM classifier has reasonable reliability, good fitting and prediction (generalization) performance in classification of the Chinese liquors. Taking both application of the e-nose and validation of the MDS-SVM classifier into account, we have thus created a useful method for the classification of multiple Chinese liquors.

Reusable hydroxyapatite nanocrystal sensors for protein adsorption.

PubMed

Tagaya, Motohiro; Ikoma, Toshiyuki; Hanagata, Nobutaka; Chakarov, Dinko; Kasemo, Bengt; Tanaka, Junzo

2010-08-01

The repeatability of the adsorption and removal of fibrinogen and fetal bovine serum on hydroxyapatite (HAp) nanocrystal sensors was investigated by Fourier transform infrared (FTIR) spectroscopy and quartz crystal microbalance with dissipation (QCM-D) monitoring technique. The HAp nanocrystals were coated on a gold-coated quartz sensor by electrophoretic deposition. Proteins adsorbed on the HAp sensors were removed by (i) ammonia/hydrogen peroxide mixture (APM), (ii) ultraviolet light (UV), (iii) UV/APM, (iv) APM/UV and (v) sodium dodecyl sulfate (SDS) treatments. FTIR spectra of the reused surfaces revealed that the APM and SDS treatments left peptide fragments or the proteins adsorbed on the surfaces, whereas the other methods successfully removed the proteins. The QCM-D measurements indicated that in the removal treatments, fibrinogen was slowly adsorbed in the first cycle because of the change in surface wettability revealed by contact angle measurements. The SDS treatment was not effective in removing proteins. The APM or UV treatment decreased the frequency shifts for the reused HAp sensors. The UV/APM treatment did not induce the frequency shifts but decreased the dissipation shifts. Therefore, we conclude that the APM/UV treatment is the most useful method for reproducing protein adsorption behavior on HAp sensors.

Reusable hydroxyapatite nanocrystal sensors for protein adsorption

NASA Astrophysics Data System (ADS)

Tagaya, Motohiro; Ikoma, Toshiyuki; Hanagata, Nobutaka; Chakarov, Dinko; Kasemo, Bengt; Tanaka, Junzo

2010-08-01

The repeatability of the adsorption and removal of fibrinogen and fetal bovine serum on hydroxyapatite (HAp) nanocrystal sensors was investigated by Fourier transform infrared (FTIR) spectroscopy and quartz crystal microbalance with dissipation (QCM-D) monitoring technique. The HAp nanocrystals were coated on a gold-coated quartz sensor by electrophoretic deposition. Proteins adsorbed on the HAp sensors were removed by (i) ammonia/hydrogen peroxide mixture (APM), (ii) ultraviolet light (UV), (iii) UV/APM, (iv) APM/UV and (v) sodium dodecyl sulfate (SDS) treatments. FTIR spectra of the reused surfaces revealed that the APM and SDS treatments left peptide fragments or the proteins adsorbed on the surfaces, whereas the other methods successfully removed the proteins. The QCM-D measurements indicated that in the removal treatments, fibrinogen was slowly adsorbed in the first cycle because of the change in surface wettability revealed by contact angle measurements. The SDS treatment was not effective in removing proteins. The APM or UV treatment decreased the frequency shifts for the reused HAp sensors. The UV/APM treatment did not induce the frequency shifts but decreased the dissipation shifts. Therefore, we conclude that the APM/UV treatment is the most useful method for reproducing protein adsorption behavior on HAp sensors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dylla-Spears, R.; Wong, L.; Shen, N.

Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption tomore » measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles—far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface.« less

Adsorption of silica colloids onto like-charged silica surfaces of different roughness

DOE PAGES

Dylla-Spears, R.; Wong, L.; Shen, N.; ...

2017-01-17

Particle adsorption was explored in a model optical polishing system, consisting of silica colloids and like-charged silica surfaces. The adsorption was monitored in situ under various suspension conditions, in the absence of surfactants or organic modifiers, using a quartz crystal microbalance with dissipation monitoring (QCM-D). Changes in surface coverage with particle concentration, particle size, pH, ionic strength and ionic composition were quantified by QCM-D and further characterized ex situ by atomic force microscopy (AFM). A Monte Carlo model was used to describe the kinetics of particle deposition and provide insights on scaling with particle concentration. Transitions from near-zero adsorption tomore » measurable adsorption were compared with equilibrium predictions made using the Deraguin-Verwey-Landau-Overbeek (DLVO) theory. In addition, the impact of silica surface roughness on the propensity for particle adsorption was studied on various spatial scale lengths by intentionally roughening the QCM sensor surface using polishing methods. It was found that a change in silica surface roughness at the AFM scale from 1.3 nm root-mean-square (rms) to 2.7 nm rms resulted in an increase in silica particle adsorption of 3-fold for 50-nm diameter particles and 1.3-fold for 100-nm diameter particles—far exceeding adsorption observed by altering suspension conditions alone, potentially because roughness at the proper scale reduces the total separation distance between particle and surface.« less

Nanoscale evaluation of lubricity on well-defined polymer brush surfaces using QCM-D and AFM.

PubMed

Kitano, Kazuhiko; Inoue, Yuuki; Matsuno, Ryosuke; Takai, Madoka; Ishihara, Kazuhiko

2009-11-01

For preparing a "highly lubricated biointerface", which has both excellent lubricity and biocompatibility, we investigated the factors responsible for resistance to friction during polymer grafting. We prepared poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), poly(2-hydroxyethyl methacrylate) (PHEMA), and poly(methyl methacrylate) (PMMA) brush layers with high graft density and well-controlled thickness using atom transfer radical polymerization (ATRP). We measured the water absorptivity in the polymer brush layers and the viscoelasticity of the polymer-hydrated layers using a quartz crystal microbalance with dissipation monitoring (QCM-D) measurements. The PMPC brush layer had the highest water absorptivity, while the PMPC-hydrated layer had the highest fluidity. The friction properties of the polymer brush layers were determined in air, water, and toluene by atomic force microscopy (AFM). The friction on each polymer brush decreased only when a good solvent was chosen for each polymer. In conclusion, the brush layer possessing high water absorptivity and fluidity in water contributes to reduce friction. PMPC grafting is an effective and promising method for obtaining highly lubricated biointerfaces.

Using the QCM Biosensor-Based T7 Phage Display Combined with Bioinformatics Analysis for Target Identification of Bioactive Small Molecule.

PubMed

Takakusagi, Yoichi; Takakusagi, Kaori; Sugawara, Fumio; Sakaguchi, Kengo

2018-01-01

Identification of target proteins that directly bind to bioactive small molecule is of great interest in terms of clarifying the mode of action of the small molecule as well as elucidating the biological phenomena at the molecular level. Of the experimental technologies available, T7 phage display allows comprehensive screening of small molecule-recognizing amino acid sequence from the peptide libraries displayed on the T7 phage capsid. Here, we describe the T7 phage display strategy that is combined with quartz-crystal microbalance (QCM) biosensor for affinity selection platform and bioinformatics analysis for small molecule-recognizing short peptides. This method dramatically enhances efficacy and throughput of the screening for small molecule-recognizing amino acid sequences without repeated rounds of selection. Subsequent execution of bioinformatics programs allows combinatorial and comprehensive target protein discovery of small molecules with its binding site, regardless of protein sample insolubility, instability, or inaccessibility of the fixed small molecules to internally located binding site on larger target proteins when conventional proteomics approaches are used.

Antibody-antigenic peptide interactions monitored by SPR and QCM-D. A model for SPR detection of IA-2 autoantibodies in human serum.

PubMed

Ayela, Cedric; Roquet, Francoise; Valera, Lionel; Granier, Claude; Nicu, Liviu; Pugnière, Martine

2007-06-15

This work reports on a complementary use of surface plasmon resonance (SPR) and quartz crystal microbalance with dissipation monitoring (QCM-D) technologies to study interactions between a peptide antigen and polyclonal antibodies, in an experimental format suitable for diagnostic assays of autoimmune diseases. In the chosen model, a synthetic peptide from the juxtamembrane region of IA-2 (a type 1 diabetes associated antigen) was immobilized by an optimized chemical protocol applicable to both BIACORE and QCM-D sensors. A thorough study of the peptide immobilization was performed to optimize the signal-to-noise ratio using mixed self-assembled monolayers (SAM) on a gold surface. Introduction of polyethylene glycol (EG(6)) chains into mixed SAM layers and addition of an anionic surfactant to the human serum reduced non-specific binding without modifying the viscoelasticity properties of the layer. Under our conditions, the antibody SPR detection limit was determined to be 0.2 nM in diluted human serum. This value is in agreement with the reported rank distribution of IA-2 antibodies in diabetic patient sera. Label-free and real-time technologies such as SPR and/or QCM-D could be precious tools in future diagnostic assays.

Label-Free Bioanalyte Detection from Nanometer to Micrometer Dimensions-Molecular Imprinting and QCMs †.

PubMed

Mujahid, Adnan; Mustafa, Ghulam; Dickert, Franz L

2018-06-01

Modern diagnostic tools and immunoassay protocols urges direct analyte recognition based on its intrinsic behavior without using any labeling indicator. This not only improves the detection reliability, but also reduces sample preparation time and complexity involved during labeling step. Label-free biosensor devices are capable of monitoring analyte physiochemical properties such as binding sensitivity and selectivity, affinity constants and other dynamics of molecular recognition. The interface of a typical biosensor could range from natural antibodies to synthetic receptors for example molecular imprinted polymers (MIPs). The foremost advantages of using MIPs are their high binding selectivity comparable to natural antibodies, straightforward synthesis in short time, high thermal/chemical stability and compatibility with different transducers. Quartz crystal microbalance (QCM) resonators are leading acoustic devices that are extensively used for mass-sensitive measurements. Highlight features of QCM devices include low cost fabrication, room temperature operation, and most importantly ability to monitor extremely low mass shifts, thus potentially a universal transducer. The combination of MIPs with quartz QCM has turned out as a prominent sensing system for label-free recognition of diverse bioanalytes. In this article, we shall encompass the potential applications of MIP-QCM sensors exclusively label-free recognition of bacteria and virus species as representative micro and nanosized bioanalytes.

SPM analysis of fibrinogen adsorption on solid surfaces

NASA Astrophysics Data System (ADS)

Choukourov, A.; Grinevich, A.; Saito, N.; Takai, O.

2007-09-01

The adsorption kinetics, adhesion and orientation of human fibrinogen on solid surfaces have been studied by surface probe microscopy (SPM) and quartz crystal microbalance techniques (QCM). CF 3-, NH 2-terminated organo-silane self-assembled monolayers (SAM) and OH-terminated silicon dioxide have been used as model surfaces. Furthermore, the interaction of fibrinogen with nanocomposite Ti/hydrocarbon plasma polymer films (Ti/ppCH) deposited by dc magnetron sputtering has also been studied.

Sugar nanowires based on cyclodextrin on quartz crystal microbalance for gas sensing with ultra-high sensitivity

NASA Astrophysics Data System (ADS)

Asano, Atsushi; Maeyoshi, Yuta; Watanabe, Shogo; Saeki, Akinori; Sugimoto, Masaki; Yoshikawa, Masahito; Nanto, Hidehito; Tsukuda, Satoshi; Tanaka, Shun-Ichiro; Seki, Shu

2013-03-01

Cyclodextrins (CDs), hosting selectively a wide range of guest molecules in their hydrophobic cavity, were directly fabricated into 1-dimensional nanostructures with extremely wide surface area by single particle nanofabrication technique in the present paper. The copolymers of acrylamide and mono(6-allyl)-β-CD were synthesized, and the crosslinking reaction of the polymer alloys with poly(4-bromostyrene) (PBrS) in SPNT gave nanowires on the quarts substrate with high number density of 5×109 cm-2. Quartz crystal microbalance (QCM) measurement suggested 320 fold high sensitivity for formic acid vapor adsorption in the nanowire fabricated surfaces compared with that in the thin solid film of PBrS, due to the incorporation of CD units and extremely wide surface area of the nanowires.

Immersion angle dependence of the resonant-frequency shift of the quartz crystal microbalance in a liquid: effects of longitudinal wave.

PubMed

Yoshimoto, Minoru; Kobirata, Satoshi; Aizawa, Hideo; Kurosawa, Shigeru

2007-06-19

We investigated the effects of the longitudinal wave on the immersion angle dependence of the resonant-frequency shift, deltaF, of the quartz crystal microbalance, QCM. In order to study exactly the effects, we employed the three types of cells: normal cell, cell with the glass beads and cell with sponge. The longitudinal wave exists in the normal cell. On the other hand, both the cell with the glass beads and the cell with sponge eliminate the longitudinal wave. As results, we have found that the tendencies of deltaF are the same in the three types of cells. That is, we conclude that the longitudinal wave does not have effects on the immersion angle dependence of deltaF.

A Practical Model of Quartz Crystal Microbalance in Actual Applications.

PubMed

Huang, Xianhe; Bai, Qingsong; Hu, Jianguo; Hou, Dong

2017-08-03

A practical model of quartz crystal microbalance (QCM) is presented, which considers both the Gaussian distribution characteristic of mass sensitivity and the influence of electrodes on the mass sensitivity. The equivalent mass sensitivity of 5 MHz and 10 MHz AT-cut QCMs with different sized electrodes were calculated according to this practical model. The equivalent mass sensitivity of this practical model is different from the Sauerbrey's mass sensitivity, and the error between them increases sharply as the electrode radius decreases. A series of experiments which plate rigid gold film onto QCMs were carried out and the experimental results proved this practical model is more valid and correct rather than the classical Sauerbrey equation. The practical model based on the equivalent mass sensitivity is convenient and accurate in actual measurements.

Acoustic sensors as a biophysical tool for probing cell attachment and cell/surface interactions.

PubMed

Saitakis, Michael; Gizeli, Electra

2012-02-01

Acoustic biosensors offer the possibility to analyse cell attachment and spreading. This is due to the offered speed of detection, the real-time non-invasive approach and their high sensitivity not only to mass coupling, but also to viscoelastic changes occurring close to the sensor surface. Quartz crystal microbalance (QCM) and surface acoustic wave (Love-wave) systems have been used to monitor the adhesion of animal cells to various surfaces and record the behaviour of cell layers under various conditions. The sensors detect cells mostly via their sensitivity in viscoelasticity and mechanical properties. Particularly, the QCM sensor detects cytoskeletal rearrangements caused by specific drugs affecting either actin microfilaments or microtubules. The Love-wave sensor directly measures cell/substrate bonds via acoustic damping and provides 2D kinetic and affinity parameters. Other studies have applied the QCM sensor as a diagnostic tool for leukaemia and, potentially, for chemotherapeutic agents. Acoustic sensors have also been used in the evaluation of the cytocompatibility of artificial surfaces and, in general, they have the potential to become powerful tools for even more diverse cellular analysis.

Nanofiber-net-binary structured membranes for highly sensitive detection of trace HCl gas

NASA Astrophysics Data System (ADS)

Wang, Xianfeng; Wang, Jialin; Si, Yang; Ding, Bin; Yu, Jianyong; Sun, Gang; Luo, Wenjing; Zheng, Gang

2012-11-01

This work describes the detection of trace hydrogen chloride (HCl) gas through analyses of the resonance frequency signal from quartz crystal microbalance (QCM) sensors coated with polyaniline (PANI) functionalized polyamide 6 (PA 6) (PANI-PA 6) nanofiber-net-binary (NNB) structured membranes. The PA 6 NNB substrate comprising nanofibers and spider-web-like nano-nets fabricated by a versatile electro-spinning/netting (ESN) process offered an ideal interface for the uniform PANI functionalization and enhanced sensing performance. Benefiting from the large specific surface area, high porosity, and strong adhesive force to the QCM electrode of the PANI-PA 6 NNB membranes, the developed HCl-selective sensors exhibited a rapid response, good reproducibility and stability, and low detection limit (7 ppb) at room temperature. Additionally, the PANI-PA 6 NNB sensing membranes presented visible color changes upon cycled exposure to HCl and ammonia, suggesting their potential application in the development of colorimetric sensors. The PANI-PA 6 NNB coated QCM sensors are considered to be a promising candidate for trace HCl gas detection in practical applications.

Study of calixarenes thin films as chemical sensors for the detection of explosives

NASA Astrophysics Data System (ADS)

Montmeat, P.; Veignal, F.; Methivier, C.; Pradier, C. M.; Hairault, L.

2014-02-01

Calix(n)arenes (n = 4, 6, 8) are used as sensitive coatings for Quartz Crystal Microbalance (QCM)-based chemical sensors, and specially for the detection of dinitrotoluene as a model explosive molecule. Calix(n)arenes complex organic architectures were deposited by spray on gold-coated wafer surfaces, and DNT detection tests were performed by measuring both frequency changes and IR spectra during exposure to DNT vapours. The adsorption of DNT on calixarenes surface is proved by Polarisation Modulation Infrared Reflection-Absorption Spectroscopy (PM-IRRAS) experiments, which brings a chemical characterisation of the sensing surfaces. Kinetics of interaction of DNT with the surface was measured by QCM. When deposited onto QCM, calixarenes showed an excellent sensitivity to DNT vapours; no significant effect of the size of the cage was observed. The main drawback is the poor reversibility of these sensors, possibly due to a too strong interaction of dinitrotoluene inside the cage of the calixarenes, or to a loss of the ternary structure of these molecules, which in turn induces a loss of interaction strength with host molecules.

Molecular layer deposition of alucone films using trimethylaluminum and hydroquinone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choudhury, Devika; Sarkar, Shaibal K., E-mail: shaibal.sarkar@iitb.ac.in; Mahuli, Neha

2015-01-01

A hybrid organic–inorganic polymer film grown by molecular layer deposition (MLD) is demonstrated here. Sequential exposures of trimethylaluminum [Al(CH{sub 3}){sub 3}] and hydroquinone [C{sub 6}H{sub 4}(OH){sub 2}] are used to deposit the polymeric films, which is a representative of a class of aluminum oxide polymers known as “alucones.” In-situ quartz crystal microbalance (QCM) studies are employed to determine the growth characteristics. An average growth rate of 4.1 Å per cycle at 150 °C is obtained by QCM and subsequently verified with x-ray reflectivity measurements. Surface chemistry during each MLD-half cycle is studied in depth by in-situ Fourier transform infrared (FTIR) vibrationmore » spectroscopy. Self limiting nature of the reaction is confirmed from both QCM and FTIR measurements. The conformal nature of the deposit, typical for atomic layer deposition and MLD, is verified with transmission electron microscopy imaging. Secondary ion mass spectroscopy measurements confirm the uniform elemental distribution along the depth of the films.« less

QCM-nanomagnetic beads biosensor for lead ion detection.

PubMed

Zhang, Qingli; Cui, Haixia; Xiong, Xingliang; Chen, Jun; Wang, Ying; Shen, Jia; Luo, Yiting; Chen, Longcong

2018-01-15

As lead poses a serious threat to humans even in small amounts, all kinds of lead detection sensors with high sensitivity and selectivity are being constantly improved and put forward. In this report, a novel, simple and label-free quartz crystal microbalance (QCM) biosensor is proposed for detecting lead ions (Pb 2+ ). The biosensor takes full advantage of the high specificity of GR-5 DNAzyme to Pb 2+ and the high sensitivity of QCM. In particular, nanomagnetic beads (NMBs) are used as a novel and effective mean of signal amplification in the biosensor because of their mass and their ability to enhance the inductive effect, which are very beneficial for both higher sensitivity and a lower detection limit. In practice, GR-5 DNAzyme, innovatively combined with NMBs, was modified on the gold electrode of the QCM through gold-sulfur self-assembly. When the electrode was exposed to Pb 2+ solution, DNAzyme was severed into two parts at the RNA site (rA), along with the release of NMBs, which caused a great increase in frequency shift of the QCM electrode. Finally, a perfect linear correlation between the logarithm of Pb 2+ concentration and the change in frequency was obtained from 1 pM to 50 nM, with a detection limit as low as 0.3 pM. Moreover, the biosensor shows both an average recovery of 97 ± 6% in a drinking water sample and an excellent specificity for Pb 2+ compared with other metal ions.

Influence of salt and rinsing protocol on the structure of PAH/PSS polyelectrolyte multilayers.

PubMed

Feldötö, Zsombor; Varga, Imre; Blomberg, Eva

2010-11-16

A quartz crystal microbalance (QCM) and dual polarization interferometry (DPI) have been utilized to study how the structure of poly(allylamine hydrochloride) (PAH)/poly(styrene sulfonate) (PSS) multilayers is affected by the rinsing method (i.e., the termination of polyelectrolyte adsorption). The effect of the type of counterions used in the deposition solution was also investigated, and the polyelectrolyte multilayers were formed in a 0.5 M electrolyte solution (NaCl and KBr). From the measurements, it was observed that thicker layers were obtained when using KBr in the deposition solution than when using NaCl. Three different rinsing protocols have been studied: (i) the same electrolyte solution as used during multilayer formation, (ii) pure water, and (iii) first a salt solution (0.5 M) and then pure water. When the multilayer with PAH as the outermost layer was exposed to pure water, an interesting phenomenon was discovered: a large change in the energy dissipation was measured with the QCM. This could be attributed to the swelling of the layer, and from both QCM and DPI it is obvious that only the outermost PAH layer swells (to a thickness of 25-30 nm) because of a decrease in ionic strength and hence an increase in intra- and interchain repulsion, whereas the underlying layers retain a very rigid and compact structure with a low water content. Interestingly, the outermost PAH layer seems to obtain very similar thicknesses in water independent of the electrolyte used for the multilayer buildup. Another interesting aspect was that the measured thickness with the DPI evaluated by a single-layer model did not correlate with the estimated thickness from the model calculations performed on the QCM-D data. Thus, we applied a two-layer model to evaluate the DPI data and the results were in excellent agreement with the QCM-D results. To our knowledge, this evaluation of DPI data has not been done previously.

Synthesis and binding affinity analysis of α1-2- and α1-6-O/S-linked dimannosides for the elucidation of sulfur in glycosidic bonds using quartz crystal microbalance sensors.

PubMed

Norberg, Oscar; Wu, Bin; Thota, Niranjan; Ge, Jian-Tao; Fauquet, Germain; Saur, Ann-Kathrin; Aastrup, Teodor; Dong, Hai; Yan, Mingdi; Ramström, Olof

2017-11-27

The role of sulfur in glycosidic bonds has been evaluated using quartz crystal microbalance methodology. Synthetic routes towards α1-2- and α1-6-linked dimannosides with S- or O-glycosidic bonds have been developed, and the recognition properties assessed in competition binding assays with the cognate lectin concanavalin A. Mannose-presenting QCM sensors were produced using photoinitiated, nitrene-mediated immobilization methods, and the subsequent binding study was performed in an automated flow-through instrumentation, and correlated with data from isothermal titration calorimetry. The recorded K d -values corresponded well with reported binding affinities for the O-linked dimannosides with affinities for the α1-2-linked dimannosides in the lower micromolar range. The S-linked analogs showed slightly disparate effects, where the α1-6-linked analog showed weaker affinity than the O-linked dimannoside, as well as positive apparent cooperativity, whereas the α1-2-analog displayed very similar binding compared to the O-linked structure. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ultrasensitive detection of nucleic acids and proteins using quartz crystal microbalance and surface plasmon resonance sensors based on target-triggering multiple signal amplification strategy.

PubMed

Sun, Wenbo; Song, Weiling; Guo, Xiaoyan; Wang, Zonghua

2017-07-25

In this study, quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) sensors were combined with template enhanced hybridization processes (TEHP), rolling circle amplification (RCA) and biocatalytic precipitation (BCP) for ultrasensitive detection of DNA and protein. The DNA complementary to the aptamer was released by the specific binding of the aptamer to the target protein and then hybridized with the capture probe and the assistant DNA to form a ternary "Y" junction structure. The initiation chain was generated by the template-enhanced hybridization process which leaded to the rolling circle amplification reaction, and a large number of repeating unit sequences were formed. Hybridized with the enzyme-labeled probes, the biocatalytic precipitation reaction was further carried out, resulting in a large amount of insoluble precipitates and amplifying the detection signal. Under the optimum conditions, detection limits as low as 43 aM for target DNA and 53 aM for lysozyme were achieved. In addition, this method also showed good selectivity and sensitivity in human serum. Copyright © 2017 Elsevier B.V. All rights reserved.

In Situ Real-Time Mechanical and Morphological Characterization of Electrodes for Electrochemical Energy Storage and Conversion by Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring.

PubMed

Shpigel, Netanel; Levi, Mikhael D; Sigalov, Sergey; Daikhin, Leonid; Aurbach, Doron

2018-01-16

Quartz crystal microbalance with dissipation monitoring (QCM-D) generates surface-acoustic waves in quartz crystal plates that can effectively probe the structure of films, particulate composite electrodes of complex geometry rigidly attached to quartz crystal surface on one side and contacting a gas or liquid phase on the other side. The output QCM-D characteristics consist of the resonance frequency (MHz frequency range) and resonance bandwidth measured with extra-ordinary precision of a few tenths of Hz. Depending on the electrodes stiffness/softness, QCM-D operates either as a gravimetric or complex mechanical probe of their intrinsic structure. For at least 20 years, QCM-D has been successfully used in biochemical and environmental science and technology for its ability to probe the structure of soft solvated interfaces. Practical battery and supercapacitor electrodes appear frequently as porous solids with their stiffness changing due to interactions with electrolyte solutions or as a result of ion intercalation/adsorption and long-term electrode cycling. Unfortunately, most QCM measurements with electrochemical systems are carried out based on a single (fundamental) frequency and, as such, provided that the resonance bandwidth remains constant, are suitable for only gravimetric sensing. The multiharmonic measurements have been carried out mainly on conducting/redox polymer films rather than on typical composite battery/supercapacitor electrodes. Here, we summarize the most recent publications devoted to the development of electrochemical QCM-D (EQCM-D)-based methodology for systematic characterization of mechanical properties of operating battery/supercapacitor electrodes. By varying the electrodes' composition and structure (thin/thick layers, small/large particles, binders with different mechanical properties, etc.), nature of the electrolyte solutions and charging/cycling conditions, the method is shown to be operated in different application modes. A variety of useful electrode-material properties are assessed noninvasively, in situ, and in real time frames of ion intercalation into the electrodes of interest. A detailed algorithm for the mechanical characterization of battery electrodes kept in the gas phase and immersed into the electrolyte solutions has been developed for fast recognition of stiff and viscoelastic materials in terms of EQCM-D signatures treated by the hydrodynamic and viscoelastic models. Working examples of the use of in situ hydrodynamic spectroscopy to characterize stiff rough/porous solids of complex geometry and viscoelastic characterization of soft electrodes are presented. The most demonstrative example relates to the formation of solid electrolyte interphase on Li 4 Ti 5 O 12 electrodes in the presence of different electrolyte solutions and additives: only a few cycles (an experiment during ∼30 min) were required for screening the electrolyte systems for their ability to form high-quality surface films in experimental EQCM-D cells as compared to 100 cycles (200 h cycling) in conventional coin cells. Thin/small-mass electrodes required for the EQCM-D analysis enable accelerated cycling tests for ultrafast mechanical characterization of these electrodes in different electrolyte solutions. Hence, this methodology can be easily implemented as a highly effective in situ analytical tool in the field of energy storage and conversion.

Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM.

PubMed

Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A

2016-06-30

Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity.

The robust bio-immobilization based on pulsed plasma polymerization of cyclopropylamine and glutaraldehyde coupling chemistry

NASA Astrophysics Data System (ADS)

Manakhov, Anton; Makhneva, Ekaterina; Skládal, Petr; Nečas, David; Čechal, Jan; Kalina, Lukáš; Eliáš, Marek; Zajíčková, Lenka

2016-01-01

The performance of immunosensing devices crucially depends on the methodology of antibody or antigen immobilization on the sensor surface. Hence, the stable intermediate layers capable of specific and reproducible binding of antibodies are required. Herein, we introduce the amine rich (NHx concentration of 6 at.%) layers prepared by pulsed plasma polymerization of cyclopropylamine (CPA) for functionalization of the quartz crystal microbalance (QCM) surface by the antibody specific to human serum albumin. In these layers the amine groups serve as anchor for the antibody binding. The sensitivity of QCM sensors prepared in this way surpasses the one for the previously reported sensors functionalized by the thiol-based self-assembled monolayers by the factor of 2. Our results thus show that CPA plasma polymers have a significant potential for further development of the active layers for biosensing applications.

Measurement of particulates

NASA Technical Reports Server (NTRS)

Woods, D.

1980-01-01

The size distributions of particles in the exhaust plumes from the Titan rockets launched in August and September 1977 were determined from in situ measurements made from a small sampling aircraft that flew through the plumes. Two different sampling instruments were employed, a quartz crystal microbalance (QCM) cascade impactor and a forward scattering spectrometer probe (FSSP). The QCM measured the nonvolatile component of the aerosols in the plume covering an aerodynamic size ranging from 0.05 to 25 micrometers diameter. The FSSP, flown outside the aircraft under the nose section, measured both the liquid droplets and the solid particles over a size range from 0.5 to 7.5 micrometers in diameter. The particles were counted and classified into 15 size intervals. The presence of a large number of liquid droplets in the exhaust clouds is discussed and data are plotted for each launch and compared.

Structural Analysis of the QCM Aboard the ER-2

NASA Technical Reports Server (NTRS)

Jones, Phyllis D.; Bainum, Peter M.; Xing, Guangqian

1997-01-01

As a result of recent supersonic transport (SST) studies on the effect they may have on the atmosphere, several experiments have been proposed to capture and evaluate samples of the stratosphere where SST's travel. One means to achieve this is to utilize the quartz crystal microbalance (QCM) installed aboard the ER-2, formerly the U-2 reconnaissance aircraft. The QCM is a cascade impactor designed to perform in-situ, real-time measurements of aerosols and chemical vapors at an altitude of 60,000 - 70,000 feet. The ER-2 is primarily used by NASA for Earth resources to test new sensor systems before they are placed aboard satellites. One of the main reasons the ER-2 is used for this flight experiment is its capability to fly approximately twelve miles above sea level (can reach an altitude of 78,000 feet). Because the ER-2 operates at such a high altitude, it is of special interest to scientists interested in space exploration or supersonic aircraft. Some of the experiments are designed to extract data from the atmosphere around the ER-2. For the current flight experiment, the QCM is housed in a frame that is connected to an outer pod that is attached to the fuselage of the ER-2. Due to the location of the QCM within the housing frame and the location of the pod on the ER-2, the pod and its contents are subject to structural loads. In addition to structural loads, structural vibrations are also of importance because the QCM is a frequency induced instrument. Therefore, a structural analysis of the instrument within the frame is imperative to determine if resonance and/or undesirable deformations occur.

Acoustical sensing of cardiomyocyte cluster beating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tymchenko, Nina; Kunze, Angelika; Dahlenborg, Kerstin

2013-06-14

Highlights: •An example of the application of QCM-D to live cell studies. •Detection of human pluripotent stem cell-derived cardiomyocyte cluster beating. •Clusters were studied in a thin liquid film and in a large liquid volume. •The QCM-D beating profile provides an individual fingerprint of the hPS-CMCs. -- Abstract: Spontaneously beating human pluripotent stem cell-derived cardiomyocytes clusters (CMCs) represent an excellent in vitro tool for studies of human cardiomyocyte function and for pharmacological cardiac safety assessment. Such testing typically requires highly trained operators, precision plating, or large cell quantities, and there is a demand for real-time, label-free monitoring of small cellmore » quantities, especially rare cells and tissue-like structures. Array formats based on sensing of electrical or optical properties of cells are being developed and in use by the pharmaceutical industry. A potential alternative to these techniques is represented by the quartz crystal microbalance with dissipation monitoring (QCM-D) technique, which is an acoustic surface sensitive technique that measures changes in mass and viscoelastic properties close to the sensor surface (from nm to μm). There is an increasing number of studies where QCM-D has successfully been applied to monitor properties of cells and cellular processes. In the present study, we show that spontaneous beating of CMCs on QCM-D sensors can be clearly detected, both in the frequency and the dissipation signals. Beating rates in the range of 66–168 bpm for CMCs were detected and confirmed by simultaneous light microscopy. The QCM-D beating profile was found to provide individual fingerprints of the hPS-CMCs. The presented results point towards acoustical assays for evaluation cardiotoxicity.« less

New Polymer Coatings for Chemically Selective Mass Sensors

NASA Technical Reports Server (NTRS)

Sims, S. C.; Wright, Cassandra; Cobb, J.; McCalla, T.; Revelle, R.; Morris, V. R.; Pollack, S. K.

1997-01-01

There is a current need to develop sensitive and chemically specific sensors for the detection of nitric acid for in-situ measurements in the atmosphere. Polymer coatings have been synthesized and tested for their sensitivity and selectivity to nitric acid. A primary requirement for these polymers is detectability down to the parts per trillion range. The results of studies using these polymers as coatings for quartz crystal microbalances (QCM) and surface acoustic wave (SAW) devices will be presented.

Cancer biomarker detection in serum samples using surface plasmon resonance and quartz crystal microbalance sensors with nanoparticle signal amplification.

PubMed

Uludag, Yildiz; Tothill, Ibtisam E

2012-07-17

Early detection of cancer is vital for the successful treatment of the disease. Hence, a rapid and sensitive diagnosis is essential before the cancer is spread out to the other body organs. Here we describe the development of a point-of-care immunosensor for the detection of the cancer biomarker (total prostate-specific antigen, tPSA) using surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) sensor platforms in human serum samples. K(D) of the antibody used toward PSA was calculated as 9.46 × 10(-10) M, indicating high affinity of the antibody used in developing the assay. By performing a sandwich assay using antibody-modified nanoparticles concentrations of 2.3 ng mL(-1) (Au, 20 nm) and 0.29 ng mL(-1) (8.5 pM) (Au, 40 nm) tPSA in 75% human serum were detected using the developed assay on an SPR sensor chip. The SPR sensor results were found to be comparable to that achieved using a QCM sensor platform, indicating that both systems can be applied for disease biomarkers screening. The clinical applicability of the developed immunoassay can therefore be successfully applied to patient's serum samples. This demonstrates the high potential of the developed sensor devices as platforms for clinical prostate cancer diagnosis and prognosis.

Nucleation and growth of hydroxyapatite on arc-deposited TiO2 surfaces studied by quartz crystal microbalance with dissipation

NASA Astrophysics Data System (ADS)

Lilja, Mirjam; Butt, Umer; Shen, Zhijian; Bjöörn, Dorota

2013-11-01

Understanding of nucleation and growth kinetics of biomimetically deposited hydroxyapatite (HA) on crystalline TiO2 surfaces is important with respect to the application and performance of HA as functional implant coatings. Arc-evaporation was used to deposit TiO2 coatings dominated by anatase phase, rutile phase or their mixtures. Subsequent formation of HA from phosphate buffered saline solution (PBS) was investigated in real-time using in situ quartz crystal microbalance with dissipation technique (QCM-D). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were employed to characterize the presence, morphology and crystal structure of TiO2 coatings and the formed HA. Increasing temperature of the PBS, increasing flow rate and applying a higher ion concentration in solution were found to accelerate HA nucleation process and hence affect growth kinetics. Lower PBS temperature resulted in the formation of HA coatings with flake-like morphology and increasing HA porosity. All TiO2 coatings under study enabled HA formation at body temperature, while in contrast Ti reference surfaces only supported HA nucleation and growth at elevated temperatures. QCM-D technique is a powerful tool for studying the impact of process parameters during biomimetic coating deposition on coating structure evolution in real time and provides valuable information for understanding, optimizing as well as tailoring the biomimetic HA growth processes.

Practical Strategies for Stable Operation of HFF-QCM in Continuous Air Flow

PubMed Central

Wessels, Alexander; Klöckner, Bernhard; Siering, Carsten; Waldvogel, Siegfried R.

2013-01-01

Currently there are a few fields of application using quartz crystal microbalances (QCM). Because of environmental conditions and insufficient resolution of the microbalance, chemical sensing of volatile organic compounds in an open system was as yet not possible. In this study we present strategies on how to use 195 MHz fundamental quartz resonators for a mobile sensor platform to detect airborne analytes. Commonly the use of devices with a resonant frequency of about 10 MHz is standard. By increasing the frequency to 195 MHz the frequency shift increases by a factor of almost 400. Unfortunately, such kinds of quartz crystals tend to exhibit some challenges to obtain a reasonable signal-to-noise ratio. It was possible to reduce the noise in frequency in a continuous air flow of 7.5 m/s to 0.4 Hz [i.e., σ(τ) = 2 × 10−9] by elucidating the major source of noise. The air flow in the vicinity of the quartz was analyzed to reduce turbulences. Furthermore, we found a dependency between the acceleration sensitivity and mechanical stress induced by an internal thermal gradient. By reducing this gradient, we achieved reduction of the sensitivity to acceleration by more than one decade. Hence, the resulting sensor is more robust to environmental conditions such as temperature, acceleration and air flow. PMID:24021970

Au-Interaction of Slp1 Polymers and Monolayer from Lysinibacillus sphaericus JG-B53 - QCM-D, ICP-MS and AFM as Tools for Biomolecule-metal Studies

PubMed Central

Suhr, Matthias; Raff, Johannes; Pollmann, Katrin

2016-01-01

In this publication the gold sorption behavior of surface layer (S-layer) proteins (Slp1) of Lysinibacillus sphaericus JG-B53 is described. These biomolecules arrange in paracrystalline two-dimensional arrays on surfaces, bind metals, and are thus interesting for several biotechnical applications, such as biosorptive materials for the removal or recovery of different elements from the environment and industrial processes. The deposition of Au(0) nanoparticles on S-layers, either by S-layer directed synthesis 1 or adsorption of nanoparticles, opens new possibilities for diverse sensory applications. Although numerous studies have described the biosorptive properties of S-layers 2-5, a deeper understanding of protein-protein and protein-metal interaction still remains challenging. In the following study, inductively coupled mass spectrometry (ICP-MS) was used for the detection of metal sorption by suspended S-layers. This was correlated to measurements of quartz crystal microbalance with dissipation monitoring (QCM-D), which allows the online detection of proteinaceous monolayer formation and metal deposition, and thus, a more detailed understanding on metal binding. The ICP-MS results indicated that the binding of Au(III) to the suspended S-layer polymers is pH dependent. The maximum binding of Au(III) was obtained at pH 4.0. The QCM-D investigations enabled the detection of Au(III) sorption as well as the deposition of Au(0)-NPs in real-time during the in situ experiments. Further, this method allowed studying the influence of metal binding on the protein lattice stability of Slp1. Structural properties and protein layer stability could be visualized directly after QCM-D experiment using atomic force microscopy (AFM). In conclusion, the combination of these different methods provides a deeper understanding of metal binding by bacterial S-layer proteins in suspension or as monolayers on either bacterial cells or recrystallized surfaces. PMID:26863150

A Novel Method for Preparation of Gold NanoBipyramids Using Microwave Irradiation and Its Application in Immunosensors

NASA Astrophysics Data System (ADS)

Huynh, Trong Phat; Ngo, Vo Ke Thanh; Nguyen, Dang Giang; Nguyen, Hoang Phuong Uyen; Nghiem, Quoc Dat; Lam, Quang Vinh; Huynh, Thanh Dat

2016-05-01

Gold nanobipyramids (NBPs) have attracted attention for producing smart sensing devices as diagnostic tools in biotechnological and medical applications, because they show more advantageous plasmonic properties than comparable gold nanorods. Normally, NBPs were synthesized using seed-mediated growth process at room temperature. In this report, our group describes a method for synthesising of NBPs using microwave irradiation with ascorbic acid reduction and cetyltrimethylammonium bromide + silver nitrate (AgNO3) as capping agents. The advantages of this method are a highly effective approach to fast and uniform NBPs. The product was characterized by ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscopy, and x-ray powder diffraction. As an application in quartz crystal microbalance immunosensors, NBPs is conjugated with the chloramphenicol antibodies for signal amplification to detect chloramphenicol residuals in the QCM system.

Non-gravimetric contributions to QCR sensor response.

PubMed

Lucklum, Ralf

2005-11-01

Quartz crystal resonator (QCR) sensors are commonly known as mass sensitive devices, usually called QCM (Quartz Crystal Microbalance). This constricted view should not be applied to biosensor applications. In many cases the sensor response is strongly influenced or even governed by non-gravimetric effects; the QCR sensor does not act as a microbalance. For better understanding of the sensor response as well as for sensor optimization a more general description of the sensor principle is required. The Transmission Line Model (TLM) is a powerful tool to describe the transduction scheme of QCR and other acoustic-wave based sensors. It is therefore applied to the analysis of the sensor behavior under several conditions, which can be expected in biochemical experiments. The generalization of acoustic parameters provides a concept to overcome some of the limiting assumptions of the present TLM.

An electrochemical quartz crystal microbalance study of magnesium dissolution

NASA Astrophysics Data System (ADS)

Ralston, K. D.; Thomas, S.; Williams, G.; Birbilis, N.

2016-01-01

A quartz crystal microbalance (QCM) was used in conjunction with electrochemical measurements to study dissolution of pure magnesium (Mg) sensors in dilute NaCl electrolytes. Open circuit potential and potentiodynamic polarisation experiments were conducted in 0.01 M NaCl, having pH values 3 (buffered) and 6 (unbuffered). In the pH 3 solution, the Mg sensor showed a net mass-loss during the electrochemical tests, whereas, in the unbuffered pH 6 solution Mg showed a net mass-gain, corresponding to the growth of an Mg(OH)2 film on its surface. The loss in the electrochemical efficiency of Mg dissolution due to such direct parasitic Mg(OH)2 growth has been estimated to be around 17-34%. This loss relates to the low capacities and voltage fluctuations reported during discharge of primary Mg batteries.

Water Sorption in Electron-Beam Evaporated SiO2 on QCM Crystals and Its Influence on Polymer Thin Film Hydration Measurements.

PubMed

Kushner, Douglas I; Hickner, Michael A

2017-05-30

Spectroscopic ellipsometry (SE) and quartz crystal microbalance (QCM) measurements are two critical characterization techniques routinely employed for hydration studies of polymer thin films. Water uptake by thin polymer films is an important area of study to investigate antifouling surfaces, to probe the swelling of thin water-containing ionomer films, and to conduct fundamental studies of polymer brush hydration and swelling. SiO 2 -coated QCM crystals, employed as substrates in many of these hydration studies, show porosity in the thin electron-beam (e-beam) evaporated SiO 2 layer. The water sorption into this porous SiO 2 layer requires correction of the optical and mass characterization of the hydrated polymer due to changes in the SiO 2 layer as it sorbs water. This correction is especially important when experiments on SiO 2 -coated QCM crystals are compared to measurements on Si wafers with dense native SiO 2 layers. Water adsorption filling void space during hydration in ∼200-260 nm thick SiO 2 layers deposited on a QCM crystal resulted in increased refractive index of the layer during water uptake experiments. The increased refractive index led to artificially higher polymer swelling in the optical modeling of the hydration experiments. The SiO 2 -coated QCM crystals showed between 6 and 8% void as measured by QCM and SE, accounting for 60%-85% of the measured polymer swelling in the low humidity regime (<20% RH) and 25%-40% of the polymer swelling in the high humidity regime (>70% RH) from optical modeling for 105 and 47 nm thick sulfonated polymer films. Correcting the refractive index of the SiO 2 layer for its water content resulted in polymer swelling that successfully resembled swelling measured on a silicon wafer with nonporous native oxide.

Whole-bacterium SELEX of DNA aptamers for rapid detection of E.coli O157:H7 using a QCM sensor.

PubMed

Yu, Xiaofan; Chen, Fang; Wang, Ronghui; Li, Yanbin

2018-01-20

The rapid detection of foodborne pathogens is critical to ensure food safety. The objective of this study is to select aptamers specifically bound to Escherichia coli O157:H7 using the whole-bacterium SELEX (Systematic Evolution of Ligands by Exponential Enrichment) and apply the selected aptamer to a QCM (quartz crystal microbalance) sensor for rapid and sensitive detection of target bacteria. A total of 19 rounds of selection against live E. coli O157:H7 and 6 rounds of counter selection against a mixture of Staphylococcus aureus, Listeria monocytogenes, and Salmonella Typhimurium, were performed. The aptamer pool from the last round was cloned and sequenced. One sequence S1 that appeared 16 times was characterized and a dissociation constant (K d ) of 10.30nM was obtained. Subsequently, a QCM aptasensor was developed for the rapid detection of E. coli O157:H7. The limit of detection (LOD) and the detection time of the aptasensor was determined to be 1.46×10 3 CFU/ml and 50min, respectively. This study demonstrated that the ssDNA aptamer selected by the whole-bacterium SELEX possessed higher sensitivity than previous work and the potential use of the constructed QCM aptasensor in rapid screening of foodborne pathogens. Copyright © 2017 Elsevier B.V. All rights reserved.

Oligonucleotide-functionalized gold nanoparticles-enhanced QCM-D sensor for mercury(II) ions with high sensitivity and tunable dynamic range.

PubMed

Chen, Qiang; Wu, Xiaojie; Wang, Dingzhong; Tang, Wei; Li, Na; Liu, Feng

2011-06-21

A quartz crystal microbalance with dissipation monitoring (QCM-D) sensor was developed for highly sensitive and specific detection of mercury(II) ions (Hg(2+)) with a tunable dynamic range, using oligonucleotide-functionalized gold nanoparticles (GNPs) for both frequency and dissipation amplification. The fabrication of the sensor employed a 'sandwich-type' strategy, and formation of T-Hg(2+)-T structures in linker DNA reduced the hybridization of the GNPs-tagged DNA on the gold electrode, which could be used as the molecular switch for Hg(2+) sensing. This QCM-D mercury sensor showed a linear response of 10-200 nM, with detection limits of 4 nM and 7 nM for frequency and dissipation measurements, respectively. Moreover, the dynamic range of the sensor could be tuned by simply altering the concentration of linker DNA without designing new sensors in the cases where detection of Hg(2+) at different levels is required. This sensor afforded excellent selectivity toward Hg(2+) compared with other potential coexisting metal ions. The feasibility of the sensor was demonstrated by analyzing Hg(2+)-spiked tap- and lake-water samples with satisfactory recoveries. The proposed approach extended the application of the QCM-D system in metal ions sensing, and could be adopted for the detection of other analytes when complemented with the use of functional DNA structures.

Binding affinities of NKG2D and CD94 to sialyl Lewis X-expressing N-glycans and heparin.

PubMed

Higai, Koji; Suzuki, Chiho; Imaizumi, Yuzo; Xin, Xin; Azuma, Yutaro; Matsumoto, Kojiro

2011-01-01

Lectin-like receptors natural killer group 2D (NKG2D) and CD94 on natural killer (NK) cells bind to α2,3-NeuAc-containing N-glycans and heparin/heparan sulfate (HS). Using recombinant glutathione S-transferase-fused extracellular lectin-like domains of NKG2D (rGST-NKG2Dlec) and CD94 (rGST-CD94lec), we evaluated their binding affinities (K(d)) to high sialyl Lewis X (sLeX)-expressing transferrin secreted by HepG2 cells (HepTf) and heparin-conjugated bovine serum albumin (Heparin-BSA), using quartz crystal microbalance (QCM) and enzyme immunoassay (EIA) microplate methods. K(d) values obtained by linear reciprocal plots revealed good coincidence between the two methods. K(d) values of rGST-NKG2Dlec obtained by QCM and EIA, respectively, were 1.19 and 1.11 µM for heparin-BSA >0.30 and 0.20 µM for HepTf, while those of rGST-CD94lec were 1.31 and 1.45 µM for HepTf >0.37 and 0.36 µM for heparin-BSA. These results suggested that these glycans can interact with NKG2D and CD94 to modulate NK cell-dependent cytotoxicity.

Atomic layer deposition of Cu( i ) oxide films using Cu( ii ) bis(dimethylamino-2-propoxide) and water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avila, J. R.; Peters, A. W.; Li, Zhanyong

2017-01-01

To grow fIlms of Cu2O, bis-(dimethylamino-2-propoxide)Cu(II), or Cu(dmap), is used as an atomic layer deposition precursor using only water vapor as a co-reactant. Between 110 and 175 °C, a growth rate of 0.12 ± 0.02 Å per cycle was measured using an in situ quartz crystal microbalance (QCM). X-ray photoelectron spectroscopy (XPS) confirms the growth of metal– oxide films featuring Cu(I).

Diagnostic system design for the Ion Auxiliary Propulsion System (IAPS). Flight tests of two 8 cm mercury ion

NASA Technical Reports Server (NTRS)

Hurst, E. B.; Thomas, G. Z.

1981-01-01

The mechanical, thermal, electrical design and the ground test results of four types of detectors are explained. The DSS is designed to measure the thruster efflux material deposition and S/C potential relative to the local plasma in the vicinity of two 8 cm mercury ion thrusters. The DSS consists of two quartz crystal microbalance (QCM) detectors, one potential probe, nine solar cell arrays, seven ion collectors and two electronic packages.

Colorimetric Humidity Sensors Based on Electrospun Polyamide/CoCl2 Nanofibrous Membranes.

PubMed

You, Ming-Hao; Yan, Xu; Zhang, Jun; Wang, Xiao-Xiong; He, Xiao-Xiao; Yu, Miao; Ning, Xin; Long, Yun-Ze

2017-12-01

Humidity indicators based on composite polyamide 66/cobalt chloride (PA66/CoCl 2 ) nanofibrous membranes (NFMs) were successfully fabricated by electrospinning. A series of NFMs with various weight percentage of CoCl 2 to PA66 were prepared, and their humidity sensitivity based on color changing and quartz crystal microbalance (QCM) were studied. Due to the color change property of cobalt chloride, the as-spun composite NFMs show obviously macroscopic color change from blue to pink as relative humidity (RH) increasing from 12.4 to 97.2%. Moreover, the QCM detection showed a linear dependence on the RH changing and exhibited short response/recovery time (less than 65.4 s/11 s), small hysteresis (less than 11%), good reproducibility, and stability. Owing to the above double sensitive mechanism on RH, the PA66/CoCl 2 composite NFM may show great potential applications from meticulous to coarse.

Preparation of Langmuir-Blodgett thin films of calix[6]arenes and p-tert butyl group effect on their gas sensing properties

NASA Astrophysics Data System (ADS)

Ozmen, Mustafa; Ozbek, Zikriye; Bayrakci, Mevlut; Ertul, Seref; Ersoz, Mustafa; Capan, Rifat

2015-12-01

Organic vapor sensing properties of Langmuir-Blodgett (LB) thin films of p-tert-butyl calix[6]arene and calix[6]arene, and their certain characterization are reported in this work. LB films of these calixarenes have been characterized by contact angle measurement, quartz crystal microbalance (QCM), scanning electron microscopy (SEM) and atomic force microscopy (AFM). QCM system was used for the measurement of sensor response against chloroform, benzene, toluene and ethanol vapors. Forming of stable monolayers was observed at the water surface using surface pressure-area isotherm graph. The results indicate that good quality, uniform LB films can be prepared with a transfer ratio of over 0.95. Due to the adsorption of vapors into the LB film structures; they yield a response to all vapors as of large, fast, and reproducible.

Colorimetric Humidity Sensors Based on Electrospun Polyamide/CoCl2 Nanofibrous Membranes

NASA Astrophysics Data System (ADS)

You, Ming-Hao; Yan, Xu; Zhang, Jun; Wang, Xiao-Xiong; He, Xiao-Xiao; Yu, Miao; Ning, Xin; Long, Yun-Ze

2017-05-01

Humidity indicators based on composite polyamide 66/cobalt chloride (PA66/CoCl2) nanofibrous membranes (NFMs) were successfully fabricated by electrospinning. A series of NFMs with various weight percentage of CoCl2 to PA66 were prepared, and their humidity sensitivity based on color changing and quartz crystal microbalance (QCM) were studied. Due to the color change property of cobalt chloride, the as-spun composite NFMs show obviously macroscopic color change from blue to pink as relative humidity (RH) increasing from 12.4 to 97.2%. Moreover, the QCM detection showed a linear dependence on the RH changing and exhibited short response/recovery time (less than 65.4 s/11 s), small hysteresis (less than 11%), good reproducibility, and stability. Owing to the above double sensitive mechanism on RH, the PA66/CoCl2 composite NFM may show great potential applications from meticulous to coarse.

NO2 sensing properties of amorphous silicon films

NASA Astrophysics Data System (ADS)

Georgieva, V.; Donkov, N.; Stefanov, P.; Sendova-Vassileva, M.; Grechnikov, A.; Gadjanova, V.

2012-03-01

The sensitivity to NO2 was studied of amorphous silicon thin films obtained by e-beam evaporation. The process was carried out at an operational-mode vacuum of 1.5×10-5 Torr at a deposition rate of 170 nm/min. The layer's structure was analyzed by Raman spectroscopy, while its composition was determined by X-ray photoemission spectroscopy (XPS). To estimate their sensitivity to NO2, the Si films were deposited on a 16-MHz quartz crystal microbalance (QCM) and the correlation was used between the QCM frequency variation and the mass-loading after exposure to NO2 in concentrations from 10 ppm to 5000 ppm. A considerable sensitivity of the films was found in the interval 1000 ppm - 2500 ppm NO2, leading to frequency shifts from 131 Hz to 208 Hz. The results obtained on the films' sorption properties can be applied to the development sensor elements.

Molecularly Imprinted Polymer Nanoparticles for Formaldehyde Sensing with QCM

PubMed Central

Hussain, Munawar; Kotova, Kira; Lieberzeit, Peter A.

2016-01-01

Herein, we report on molecularly imprinted polymers (MIPs) for detecting formaldehyde vapors in air streams. A copolymer thin film consisting of styrene, methacrylic acid, and ethylene glycol dimethacrylate on quartz crystal microbalance (QCM) yielded a detection limit of 500 ppb formaldehyde in dry air. Surprisingly, these MIPs showed specific behavior when tested against a range of volatile organic compounds (VOCs), such as acetaldehyde, methanol, formic acid, and dichloromethane. Despite thus being a suitable receptor in principle, the MIPs were not useful for measurements at 50% humidity due to surface saturation by water. This was overcome by introducing primary amino groups into the polymer via allyl amine and by changing the coating morphology from thin film to nanoparticles. This led to the same limit of detection (500 ppb) and selectivity as before, but at the real-life conditions of 50% relative humidity. PMID:27376287

Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D.

PubMed

Iturri, Jagoba; Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B; Toca-Herrera, José Luis

2017-01-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1 H ,1 H ,2 H ,2 H -perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved.

An analytical and experimental investigation of resistojet plumes

NASA Technical Reports Server (NTRS)

Zana, L. M.; Hoffman, D. J.; Breyley, L. R.; Serafini, J. S.

1987-01-01

As a part of the electrothermal propulsion plume research program at the NASA Lewis Research Center, efforts have been initiated to analytically and experimentally investigate the plumes of resistojet thrusters. The method of G.A. Simons for the prediction of rocket exhaust plumes is developed for the resistojet. Modifications are made to the source flow equations to account for the increased effects of the relatively large nozzle boundary layer. Additionally, preliminary mass flux measurements of a laboratory resistojet using CO2 propellant at 298 K have been obtained with a cryogenically cooled quartz crystal microbalance (QCM). There is qualitative agreement between analysis and experiment, at least in terms of the overall number density shape functions in the forward flux region.

Dynamics of human cancer cell lines monitored by electrical and acoustic fluctuation analysis.

PubMed

Tarantola, Marco; Marel, Anna-Kristina; Sunnick, Eva; Adam, Holger; Wegener, Joachim; Janshoff, Andreas

2010-03-01

Early determination of the metastatic potential of cancer cells is a crucial step for successful oncological treatment. Besides the remarkable progress in molecular genomics- or proteomics-based diagnostics, there is a great demand for in vitro biosensor devices that allow rapid and selective detection of the invasive properties of tumor cells. Here, the classical cancer cell motility in vitro assays for migration and invasion relying on Boyden chambers are compared to a real-time biosensor that analyzes the dynamic properties of adherent cells electro-acoustically with a time resolution on the order of seconds. The sensor relies on the well-established quartz crystal microbalance technique (QCM) that measures the shift in resonance frequency and damping of an oscillating quartz crystal when adsorption, desorption or changes in material properties close to the quartz surface occur. In addition, the QCM is capable of detecting the rather subtle fluctuations of the cell bodies as an indicator for their micromotility. QCM-based micromotility readings of three different cancer cell lines (HT-29, HSC-4, FaDu) are compared with the well-known electrical cell-substrate impedance sensing (ECIS) revealing collective stochastic motion that corresponds to the malignancy of the cells.

Characterization of self-assembled redox polymer and antibody molecules on thiolated gold electrodes.

PubMed

Calvo, E J; Danilowicz, C; Lagier, C M; Manrique, J; Otero, M

2004-05-15

Multilayer immobilization of antibody and redox polymer molecules on a gold electrode was achieved, as a strategy for the potential development of an amperometric immunosensor. The step-by-step assembly of antibiotin IgG on Os(bpy)(2)ClPyCH(2)NH poly(allylamine) redox polymer (PAH-Os) adsorbed on thiolated gold electrodes was proved by quartz crystal microbalance (QCM) and atomic force microscopy (AFM) experiments, confirming the electrochemical evidence. The increase of redox charge during the layer-by-layer deposition demonstrated that charge propagation within the layers is feasible. The multilayer structure proved to be effective for the molecular recognition of horseradish peroxidase-biotin conjugate (HRP-biotin), as confirmed by the QCM measurements and the electrocatalytic reduction current obtained upon H(2)O(2) addition. The catalytic current resulting from PAH-Os mediation was shown to increase with the number of assembled layers. Furthermore, the inventory of IgG molecules on the supramolecular self-assembled structure and the specific and non-specific binding of HRP-biotin conjugate were confirmed by the QCM transient studies, giving information on the kinetics of IgG deposition and HRP-biotin conjugate binding to the IgG.

Influence of surface charge on the rate, extent, and structure of adsorbed Bovine Serum Albumin to gold electrodes.

PubMed

Beykal, Burcu; Herzberg, Moshe; Oren, Yoram; Mauter, Meagan S

2015-12-15

The objective of this work is to investigate the rate, extent, and structure of amphoteric proteins with charged solid surfaces over a range of applied potentials and surface charges. We use Electrochemical Quartz Crystal Microbalance with Dissipation Monitoring (E-QCM-D) to investigate the adsorption of amphoteric Bovine Serum Albumin (BSA) to a gold electrode while systematically varying the surface charge on the adsorbate and adsorbent by manipulating pH and applied potential, respectively. We also perform cyclic voltammetry-E-QCM-D on an adsorbed layer of BSA to elucidate conformational changes in response to varied applied potentials. We confirm previous results demonstrating that increasing magnitude of applied potential on the gold electrode is positively correlated with increasing mass adsorption when the protein and the surface are oppositely charged. On the other hand, we find that the rate of BSA adsorption is not governed by simple electrostatics, but instead depends on solution pH, an observation not well documented in the literature. Cyclic voltammetry with simultaneous E-QCM-D measurements suggest that BSA protein undergoes a conformational change as the surface potential varies. Copyright © 2015 Elsevier Inc. All rights reserved.

Testing and comparison of the coating materials for immunosensors on QCM

NASA Astrophysics Data System (ADS)

Oztuna, Ali; Nazir, Hasan

2012-06-01

In immunoassay based biosensors development studies polymers, as a matrix, and thiol, amine and aldehyde derivative compounds, as a antibody linker, are to be experimented. Aim of this study is to test amine and acetate functional group containing derivatives in liquid phase in order to develop an antibody immobilization strategy for Quartz Crystal Microbalance (QCM) system. In our study, 4-aminothiophenol (4-AT), carboxylated-PVC (PVC-COOH) and aminated- PVC (PVC-NH2) compared with each other as a coating material. Surface of the coated AT-cut gold crystals were characterized with Fourier Transform Infrared spectrometry (FTIR) and Scanning Electron Microscobe (SEM) and tested in a Bacillus anthracis (GenBank: GQ375871) spores immunoassay model system. Subsequently, a series of SEM micrographs were taken again in order to investigate surface morphology and show the presence of the B. anthracis spores on the sensor surface. When experimental results and SEM images were evaluated together, it was suggested that with the synthesis of PVC like open-chained polymers, containing -NH2 and -SH functional groups, B. anthracis spore detection can be accomplished on QCM without requiring complicated immobilization procedures and expensive preliminary preparations.

Identification of trimannoside-recognizing peptide sequences from a T7 phage display screen using a QCM device.

PubMed

Nishiyama, Kazusa; Takakusagi, Yoichi; Kusayanagi, Tomoe; Matsumoto, Yuki; Habu, Shiori; Kuramochi, Kouji; Sugawara, Fumio; Sakaguchi, Kengo; Takahashi, Hideyo; Natsugari, Hideaki; Kobayashi, Susumu

2009-01-01

Here, we report on the identification of trimannoside-recognizing peptide sequences from a T7 phage display screen using a quartz-crystal microbalance (QCM) device. A trimannoside derivative that can form a self-assembled monolayer (SAM) was synthesized and used for immobilization on the gold electrode surface of a QCM sensor chip. After six sets of one-cycle affinity selection, T7 phage particles displaying PSVGLFTH (8-mer) and SVGLGLGFSTVNCF (14-mer) were found to be enriched at a rate of 17/44, 9/44, respectively, suggesting that these peptides specifically recognize trimannoside. Binding checks using the respective single T7 phage and synthetic peptide also confirmed the specific binding of these sequences to the trimannoside-SAM. Subsequent analysis revealed that these sequences correspond to part of the primary amino acid sequence found in many mannose- or hexose-related proteins. Taken together, these results demonstrate the effectiveness of our T7 phage display environment for affinity selection of binding peptides. We anticipate this screening result will also be extremely useful in the development of inhibitors or drug delivery systems targeting polysaccharides as well as further investigations into the function of carbohydrates in vivo.

Thickness Dependent Effective Viscosity of a Polymer Solution near an Interface Probed by a Quartz Crystal Microbalance with Dissipation Method

PubMed Central

Fang, Jiajie; Zhu, Tao; Sheng, Jie; Jiang, Zhongying; Ma, Yuqiang

2015-01-01

The solution viscosity near an interface, which affects the solution behavior and the molecular dynamics in the solution, differs from the bulk. This paper measured the effective viscosity of a dilute poly (ethylene glycol) (PEG) solution adjacent to a Au electrode using the quartz crystal microbalance with dissipation (QCM-D) technique. We evidenced that the effect of an adsorbed PEG layer can be ignored, and calculated the zero shear rate effective viscosity to remove attenuation of high shear frequency oscillations. By increasing the overtone n from 3 to 13, the thickness of the sensed polymer solution decreased from ~70 to 30 nm. The zero shear rate effective viscosity of the polymer solution and longest relaxation time of PEG chains within it decrease with increasing solution thickness. The change trends are independent of the relation between the apparent viscosity and shear frequency and the values of the involved parameter, suggesting that the polymer solution and polymer chains closer to a solid substrate have a greater effective viscosity and slower relaxation mode, respectively. This method can study the effect of an interface presence on behavior and phenomena relating to the effective viscosity of polymer solutions, including the dynamics of discrete polymer chains. PMID:25684747

Ribozyme-mediated signal augmentation on a mass-sensitive biosensor.

PubMed

Knudsen, Scott M; Lee, Joonhyung; Ellington, Andrew D; Savran, Cagri A

2006-12-20

Mass-based detection methods such as the quartz crystal microbalance (QCM) offer an attractive option to label-based methods; however the sensitivity is generally lower by comparison. In particular, low-molecular-weight analytes can be difficult to detect based on mass addition alone. In this communication, we present the use of effector-dependent ribozymes (aptazymes) as reagents for augmenting small ligand detection on a mass-sensitive device. Two distinct aptazymes were chosen: an L1-ligase-based aptazyme (L1-Rev), which is activated by a small peptide (MW approximately 2.4 kDa) from the HIV-1 Rev protein, and a hammerhead cleavase-based aptazyme (HH-theo3) activated by theophylline (MW = 180 Da). Aptazyme activity was observed in real time, and low-molecular-weight analyte detection has been successfully demonstrated with both aptazymes.

Non-Equilibrium Water-Glassy Polymer Dynamics

NASA Astrophysics Data System (ADS)

Davis, Eric; Minelli, Matteo; Baschetti, Marco; Sarti, Giulio; Elabd, Yossef

2012-02-01

For many applications (e.g., medical implants, packaging), an accurate assessment and fundamental understanding of the dynamics of water-glassy polymer interactions is of great interest. In this study, sorption and diffusion of pure water in several glassy polymers films, such as poly(styrene) (PS), poly(methyl methacrylate) (PMMA), poly(lactide) (PLA), were measured over a wide range of vapor activities and temperatures using several experimental techniques, including quartz spring microbalance (QSM), quartz crystal microbalance (QCM), and time-resolved Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy. Non-Fickian behavior (diffusion-relaxation phenomena) was observed by all three techniques, while FTIR-ATR spectroscopy also provides information about the distribution of the states of water and water transport mechanisms on a molecular-level. Specifically, the states of water are significantly different in PS compared to PMMA and PLA. Additionally, a purely predictive non-equilibrium lattice fluid (NELF) model was applied to predict the sorption isotherms of water in these glassy polymers.

Establishing linear solvation energy relationships between VOCs and monolayer-protected gold nanoclusters using quartz crystal microbalance.

PubMed

Li, Chi-Lin; Lu, Chia-Jung

2009-08-15

Linear solvation energy relationships (LSERs) have been recognized as a useful model for investigating the chemical forces behind the partition coefficients between vapor molecules and absorbents. This study is the first to determine the solvation properties of monolayer-protected gold nanoclusters (MPCs) with different surface ligands. The ratio of partition coefficients/MPC density (K/rho) of 18 volatile organic compounds (VOCs) for four different MPCs obtained through quartz crystal microbalance (QCM) experiments were used for the LSER model calculations. LSER modeling results indicate that all MPC surfaces showed a statistically significant (p<0.05) preference to hydrogen-bond acidic molecules. Through dipole-dipole attraction, 4-methoxythiophenol-capped MPCs can also interact with polar organics (s=1.04). Showing a unique preference for the hydrogen bond basicity of vapors (b=1.11), 2-benzothiazolethiol-capped MPCs provide evidence of an intra-molecular, proton-shift mechanism on surface of nano-gold.

Development of a high-sensitivity plasticizer sensor based on a quartz crystal microbalance modified with a nanostructured nickel hydroxide film

NASA Astrophysics Data System (ADS)

Hu, Ruifen; Zhang, Kaihuan; Fan, Guokang; Luo, Zhiyuan; Li, Guang

2015-05-01

Nanostructured nickel hydroxide (nano-Ni(OH)2) was synthesized at a low temperature without annealing. Accordingly, a plasticizer sensor based on a quartz crystal microbalance (QCM) modified with the nano-Ni(OH)2 sensing film was fabricated to detect dibutyl phthalate (DBP) and its relative film thickness was optimized. The sensor worked at room temperature and exhibited a high sensitivity of 4.91 Hz ppb-1 to DBP in a low concentration range of 5-20 ppb, and an ultra-low detection limit of 5 ppb was achieved. In addition, the sensor maintained good repeatability as well as stability shown by the experimental data. The responses to five possible interferences and four other plasticizers were also measured, which indicated the excellent selectivity of the sensor and its potential use in monitoring plasticizers in a gaseous state.

A survey of the 2001 to 2005 quartz crystal microbalance biosensor literature: applications of acoustic physics to the analysis of biomolecular interactions.

PubMed

Cooper, Matthew A; Singleton, Victoria T

2007-01-01

The widespread exploitation of biosensors in the analysis of molecular recognition has its origins in the mid-1990s following the release of commercial systems based on surface plasmon resonance (SPR). More recently, platforms based on piezoelectric acoustic sensors (principally 'bulk acoustic wave' (BAW), 'thickness shear mode' (TSM) sensors or 'quartz crystal microbalances' (QCM)), have been released that are driving the publication of a large number of papers analysing binding specificities, affinities, kinetics and conformational changes associated with a molecular recognition event. This article highlights salient theoretical and practical aspects of the technologies that underpin acoustic analysis, then reviews exemplary papers in key application areas involving small molecular weight ligands, carbohydrates, proteins, nucleic acids, viruses, bacteria, cells and lipidic and polymeric interfaces. Key differentiators between optical and acoustic sensing modalities are also reviewed. Copyright (c) 2007 John Wiley & Sons, Ltd.

Real-time Monitoring of Intermediates Reveals the Reaction Pathway in the Thiol-Disulfide Exchange between Disulfide Bond Formation Protein A (DsbA) and B (DsbB) on a Membrane-immobilized Quartz Crystal Microbalance (QCM) System*

PubMed Central

Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

2013-01-01

Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

Quartz crystal microbalance sensor using ionophore for ammonium ion detection.

PubMed

Kosaki, Yasuhiro; Takano, Kosuke; Citterio, Daniel; Suzuki, Koji; Shiratori, Seimei

2012-01-01

Ionophore-based quartz crystal microbalance (QCM) ammonium ion sensors with a detection limit for ammonium ion concentrations as low as 2.2 microM were fabricated. Ionophores are molecules, which selectively bind a particular ion. In this study, one of the known ionophores for ammonium, nonactin, was used to detect ammonium ions for environmental in-situ monitoring of aquarium water for the first time. To fabricate the sensing films, poly(vinyl chloride) was used as the matrix for the immobilization of nonactin. Furthermore, the anionic additive, tetrakis (4-chlorophenyl) borate potassium salt and the plasticizer dioctyl sebacate were used to enhance the sensor properties. The sensor allowed detecting ammonium ions not only in static solution, but also in flowing water. The sensor showed a nearly linear response with the increase of the ammonium ion concentration. The QCM resonance frequency increased with the increase of ammonium ion concentration, suggesting a decreasing weight of the sensing film. The detailed response mechanism could not be verified yet. However, from the results obtained when using a different plasticizer, nitrophenyl octyl ether, it is considered that this effect is caused by the release of water molecules. Consequently, the newly fabricated sensor detects ammonium ions by discharge of water. It shows high selectivity over potassium and sodium ions. We conclude that the newly fabricated sensor can be applied for detecting ammonium ions in aquarium water, since it allows measuring low ammonium ion concentrations. This sensor will be usable for water quality monitoring and controlling.

Precision cleaning apparatus and method

DOEpatents

Schneider, T.W.; Frye, G.C.; Martin, S.J.

1998-01-13

A precision cleaning apparatus and method are disclosed. The precision cleaning apparatus includes a cleaning monitor further comprising an acoustic wave cleaning sensor such as a quartz crystal microbalance (QCM), a flexural plate wave (FPW) sensor, a shear horizontal acoustic plate mode (SH--APM) sensor, or a shear horizontal surface acoustic wave (SH--SAW) sensor; and measurement means connectable to the sensor for measuring in-situ one or more electrical response characteristics that vary in response to removal of one or more contaminants from the sensor and a workpiece located adjacent to the sensor during cleaning. Methods are disclosed for precision cleaning of one or more contaminants from a surface of the workpiece by means of the cleaning monitor that determines a state of cleanliness and any residual contamination that may be present after cleaning; and also for determining an effectiveness of a cleaning medium for removing one or more contaminants from a workpiece. 11 figs.

Precision cleaning apparatus and method

DOEpatents

Schneider, Thomas W.; Frye, Gregory C.; Martin, Stephen J.

1998-01-01

A precision cleaning apparatus and method. The precision cleaning apparatus includes a cleaning monitor further comprising an acoustic wave cleaning sensor such as a quartz crystal microbalance (QCM), a flexural plate wave (FPW) sensor, a shear horizontal acoustic plate mode (SH--APM) sensor, or a shear horizontal surface acoustic wave (SH--SAW) sensor; and measurement means connectable to the sensor for measuring in-situ one or more electrical response characteristics that vary in response to removal of one or more contaminants from the sensor and a workpiece located adjacent to the sensor during cleaning. Methods are disclosed for precision cleaning of one or more contaminants from a surface of the workpiece by means of the cleaning monitor that determines a state of cleanliness and any residual contamination that may be present after cleaning; and also for determining an effectiveness of a cleaning medium for removing one or more contaminants from a workpiece.

Rapid development of new protein biosensors utilizing peptides obtained via phage display.

PubMed

Wu, Jun; Park, Jong Pil; Dooley, Kevin; Cropek, Donald M; West, Alan C; Banta, Scott

2011-01-01

There is a consistent demand for new biosensors for the detection of protein targets, and a systematic method for the rapid development of new sensors is needed. Here we present a platform where short unstructured peptides that bind to a desired target are selected using M13 phage display. The selected peptides are then chemically synthesized and immobilized on gold, allowing for detection of the target using electrochemical techniques such as electrochemical impedance spectroscopy (EIS). A quartz crystal microbalance (QCM) is also used as a diagnostic tool during biosensor development. We demonstrate the utility of this approach by creating a novel peptide-based electrochemical biosensor for the enzyme alanine aminotransferase (ALT), a well-known biomarker of hepatotoxicity. Biopanning of the M13 phage display library over immobilized ALT, led to the rapid identification of a new peptide (ALT5-8) with an amino acid sequence of WHWRNPDFWYLK. Phage particles expressing this peptide exhibited nanomolar affinity for immobilized ALT (K(d,app) = 85±20 nM). The newly identified ALT5-8 peptide was then chemically synthesized with a C-terminal cysteine for gold immobilization. The performance of the gold-immobilized peptides was studied with cyclic voltammetry (CV), QCM, and EIS. Using QCM, the sensitivity for ALT detection was 8.9±0.9 Hz/(µg/mL) and the limit of detection (LOD) was 60 ng/mL. Using EIS measurements, the sensitivity was 142±12 impedance percentage change %/(µg/mL) and the LOD was 92 ng/mL. In both cases, the LOD was below the typical concentration of ALT in human blood. Although both QCM and EIS produced similar LODs, EIS is preferable due to a larger linear dynamic range. Using QCM, the immobilized peptide exhibited a nanomolar dissociation constant for ALT (K(d) = 20.1±0.6 nM). These results demonstrate a simple and rapid platform for developing and assessing the performance of sensitive, peptide-based biosensors for new protein targets.

Tailoring the structure of metal oxide nanostructures towards enhanced sensing properties for environmental applications.

PubMed

Yang, Mingqing; He, Junhui

2012-02-15

The present article reviews recent works in our laboratory about the sensing properties to toxic gases using nanostructured WO(3), TiO(2), FTiO(2), and CuO functionalized quartz crystal microbalance (QCM) sensors. WO(3) and TiO(2) functionalized QCM sensors have much shorter response time than those functionalized by conventional hydrogen-bond acidic branched copolymers for detection of dimethyl methylphosphonate (DMMP). FTiO(2) functionalized QCM sensors can improve the gas sensing characteristics by shortening the response time but at the price of partial irreversibility. The sensing mechanism was examined by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Varied CuO nanostructures were synthesized by simple modulation of reaction conditions. All the as-prepared CuO was applied on QCM resonators and explored for HCN sensing. Surprisingly, responses of all the sensors to HCN were found to be in an opposite direction as compared with other common volatile substances, offering excellent selectivity for HCN detection. The sensitivity was very high, and the response and recovery were very fast. Comparison of the specific surface areas of CuO nanostructures showed that CuO of higher surface area is more sensitive than that of lower surface area, indicating that the specific surface area of these CuO nanostructures plays an important role in the sensitivity of related sensors. Based on experimental results, a sensing mechanism was proposed in which a surface redox reaction occurs between CuO and Cu(2)O on the CuO nanostructures reversibly upon contact with HCN and air, respectively. The CuO functionalized QCM sensors are considered to be a promising candidate for trace HCN gas detection in practical applications. Copyright © 2011 Elsevier Inc. All rights reserved.

Multi-Ligand-Binding Flavoprotein Dodecin as a Key Element for Reversible Surface Modification in Nano-biotechnology.

PubMed

Gutiérrez Sánchez, Cristina; Su, Qiang; Schönherr, Holger; Grininger, Martin; Nöll, Gilbert

2015-01-01

In this paper the multiple (re)programming of protein-DNA nanostructures comprising generation, deletion, and reprogramming on the same flavin-DNA-modified surface is introduced. This work is based on a systematic study of the binding affinity of the multi-ligand-binding flavoprotein dodecin on flavin-terminated DNA monolayers by surface plasmon resonance and quartz crystal microbalance with dissipation (QCM-D) measurements, surface plasmon fluorescence spectroscopy (SPFS), and dynamic AFM force spectroscopy. Depending on the flavin surface coverage, a single apododecin is captured by one or more surface-immobilized flavins. The corresponding complex binding and unbinding rate constants kon(QCM) = 7.7 × 10(3) M(-1)·s(-1) and koff(QCM) = 4.5 × 10(-3) s(-1) (Kd(QCM) = 580 nM) were determined by QCM and were found to be in agreement with values for koff determined by SPFS and force spectroscopy. Even though a single apododecin-flavin bond is relatively weak, stable dodecin monolayers were formed on flavin-DNA-modified surfaces at high flavin surface coverage due to multivalent interactions between apododecin bearing six binding pockets and the surface-bound flavin-DNA ligands. If bi- or multivalent flavin ligands are adsorbed on dodecin monolayers, stable sandwich-type surface-DNA-flavin-apododecin-flavin ligand arrays are obtained. Nevertheless, the apododecin flavin complex is easily and quantitatively disassembled by flavin reduction. Binding and release of apododecin are reversible processes, which can be carried out alternatingly several times to release one type of ligand by an external redox trigger and subsequently replace it with a different ligand. Hence the versatile concept of reprogrammable functional biointerfaces with the multi-ligand-binding flavoprotein dodecin is demonstrated.

Monitoring of integrin-mediated adhesion of human ovarian cancer cells to model protein surfaces by quartz crystal resonators: evaluation in the impedance analysis mode.

PubMed

Li, Jing; Thielemann, Christiane; Reuning, Ute; Johannsmann, Diethelm

2005-01-15

The quartz crystal microbalance (QCM) was used to monitor specific, integrin-mediated adhesion of human ovarian cancer cells to distinct extracellular matrix (ECM) proteins immobilized on gold-coated quartz crystal resonators. The QCM was operated in the impedance analysis mode, where frequency shift as well as bandwidth are accessible on a broad range of overtones. The increase in bandwidth caused by covering the quartz resonator with cells was reproducible and largely independent of overtone order, whereas the frequency shift displayed some variability. Thus the bandwidth proved to be the more robust parameter for sensing cell adhesive events. The bandwidth increased in proportion to the number of seeded cells to the quartz crystal as long as the number was below 150,000 cells/ml. Comparing the resonance parameters on different harmonics, one finds that viscoelastic modeling with homogeneous layer systems cannot reproduce the results: lateral heterogeneity has to be taken into account. The differences in adhesive strength of human ovarian cancer cells towards selected ECM proteins monitored by QCM was in good agreement with data obtained by conventional cell adhesion assays. Strong cell adhesion was observed to the ECM proteins vitronectin (VN) and fibronectin (FN), while only weak attachment occurred on laminin. In order to prove specific, integrin alphavbeta3-mediated cell adhesion to its ligands FN and VN, the cyclic integrin alphavbeta3-directed peptide c(RGDfV) was used as competitor and significantly reversed cell adhesion. Since integrin interaction with ECM proteins is dependent on the presence of bivalent cations, cell detachment was also seen after treatment of cell monolayers with the chelator ethylene-dinitro-tetra-acetic acid (EDTA). The QCM technique is a reliable method to monitor cell adsorption to ECM-pretreated surfaces in real time. It may be an alternative tool for screening specific and selective antagonists of integrin/ECM interaction.

Gas sensing properties of very thin TiO2 films prepared by atomic layer deposition (ALD)

NASA Astrophysics Data System (ADS)

Boyadjiev, S.; Georgieva, V.; Vergov, L.; Baji, Zs; Gáber, F.; Szilágyi, I. M.

2014-11-01

Very thin titanium dioxide (TiO2) films of less than 10 nm were deposited by atomic layer deposition (ALD) in order to study their gas sensing properties. Applying the quartz crystal microbalance (QCM) method, prototype structures with the TiO2 ALD deposited thin films were tested for sensitivity to NO2. Although being very thin, the films were sensitive at room temperature and could register low concentrations as 50-100 ppm. The sorption is fully reversible and the films seem to be capable to detect for long term. These initial results for very thin ALD deposited TiO2 films give a promising approach for producing gas sensors working at room temperature on a fast, simple and cost-effective technology.

Analyte induced water adsorbability in gas phase biosensors: the influence of ethinylestradiol on the water binding protein capacity.

PubMed

Snopok, Borys; Kruglenko, Ivanna

2015-05-07

An ultra-sensitive gas phase biosensor/tracer/bio-sniffer is an emerging technology platform designed to provide real-time information on air-borne analytes, or those in liquids, through classical headspace analysis. The desired bio-sniffer measures gaseous 17α- ethinylestradiol (ETED) as frequency changes on a quartz crystal microbalance (QCM), which is a result of the interactions of liquid sample components in the headspace (ETED and water) with a biorecognition layer. The latter was constructed by immobilization of polyclonal antiserum against a phenolic A-ring of estrogenic receptors through protein A. The QCM response exhibited stretched exponential kinetics of negative frequency shifts with reversible and "irreversible" components of mass uptake onto the sensor surface in static headspace conditions when exposed to water solutions of ETED over the sensor working range, from 10(-10) to 10(-17) g L(-1). It was shown that the variations in the QCM response characteristics are due to the change of the water-binding capacity of the sensing layer induced by protein transformations initiated by the binding of ETED molecules. This result is well correlated with the natural physiological function of estrogens in controlling the homeostasis of body fluids in living beings.

Multimodal biopanning of T7 phage-displayed peptides reveals angiomotin as a potential receptor of the anti-angiogenic macrolide Roxithromycin.

PubMed

Takakusagi, Kaori; Takakusagi, Yoichi; Suzuki, Takahiro; Toizaki, Aya; Suzuki, Aiko; Kawakatsu, Yaichi; Watanabe, Madoka; Saito, Yukihiro; Fukuda, Ryushi; Nakazaki, Atsuo; Kobayashi, Susumu; Sakaguchi, Kengo; Sugawara, Fumio

2015-01-27

Roxithromycin (RXM) is a semi-synthetic fourteen-membered macrolide antibiotic that shows anti-angiogenic activity in solid tumors. In the present study, we conducted biopanning of T7 phage-displayed peptides either on a 96-well formatted microplate, a flow injection-type quartz-crystal microbalance (QCM) biosensor, or a cuvette-type QCM. RXM-selected peptides of different sequence, length and number were obtained from each mode of screening. Subsequent bioinformatics analysis of the RXM-selected peptides consistently gave positive scores for the extracellular domain (E458-T596) of angiomotin (Amot), indicating that this may comprise a binding region for RXM. Bead pull down assay and QCM analysis confirmed that RXM directly interacts with Amot via the screen-guided region, which also corresponds to the binding site for the endogenous anti-angiogenic inhibitor angiostatin (Anst). Thus, multimodal biopanning of T7PD revealed that RXM binds to the extracellular domain on Amot as a common binding site with Anst, leading to inhibition of angiogenesis-dependent tumor growth and metastasis. These data might explain the molecular basis underlying the mechanism of action for the anti-angiogenic activity of RXM. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

Influence of the molecular architecture on the adsorption onto solid surfaces: comb-like polymers.

PubMed

Guzmán, Eduardo; Ortega, Francisco; Prolongo, Margarita G; Starov, Victor M; Rubio, Ramón G

2011-09-28

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.

Nanoparticle-based biologic mimetics

PubMed Central

Cliffel, David E.; Turner, Brian N.; Huffman, Brian J.

2009-01-01

Centered on solid chemistry foundations, biology and materials science have reached a crossroad where bottom-up designs of new biologically important nanomaterials are a reality. The topics discussed here present the interdisciplinary field of creating biological mimics. Specifically, this discussion focuses on mimics that are developed using various types of metal nanoparticles (particularly gold) through facile synthetic methods. These methods conjugate biologically relevant molecules, e.g., small molecules, peptides, proteins, and carbohydrates, in conformationally favorable orientations on the particle surface. These new products provide stable, safe, and effective substitutes for working with potentially hazardous biologicals for applications such as drug targeting, immunological studies, biosensor development, and biocatalysis. Many standard bioanalytical techniques can be used to characterize and validate the efficacy of these new materials, including quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and enzyme-linked immunosorbent assay (ELISA). Metal nanoparticle–based biomimetics continue to be developed as potential replacements for the native biomolecule in applications of immunoassays and catalysis. PMID:20049778

QCM gas sensor characterization of ALD-grown very thin TiO2 films

NASA Astrophysics Data System (ADS)

Boyadjiev, S.; Georgieva, V.; Vergov, L.; Szilágyi, I. M.

2018-03-01

The paper presents a technology for preparation and characterization of titanium dioxide (TiO2) thin films suitable for gas sensor applications. Applying atomic layer deposition (ALD), very thin TiO2 films were deposited on quartz resonators, and their gas sensing properties were studied using the quartz crystal microbalance (QCM) method. The TiO2 thin films were grown using Ti(iOPr)4 and water as precursors. The surface of the films was observed by scanning electron microscopy (SEM), coupled with energy dispersive X-ray analysis (EDX) used for a composition study. The research was focused on the gas-sensing properties of the films. Films of 10-nm thickness were deposited on quartz resonators with Au electrodes and the QCMs were used to build highly sensitive gas sensors, which were tested for detecting NO2. Although very thin, these ALD-grown TiO2 films were sensitive to NO2 already at room temperature and could register as low concentrations as 50 ppm, while the sorption was fully reversible, and the sensors could be fully recovered. With the technology presented, the manufacturing of gas sensors is simple, fast and cost-effective, and suitable for energy-effective portable equipment for real-time environmental monitoring of NO2.

Probing Interfacial Processes on Graphene Surface by Mass Detection

NASA Astrophysics Data System (ADS)

Kakenov, Nurbek; Kocabas, Coskun

2013-03-01

In this work we studied the mass density of graphene, probed interfacial processes on graphene surface and examined the formation of graphene oxide by mass detection. The graphene layers were synthesized by chemical vapor deposition method on copper foils and transfer-printed on a quartz crystal microbalance (QCM). The mass density of single layer graphene was measured by investigating the mechanical resonance of the QCM. Moreover, we extended the developed technique to probe the binding dynamics of proteins on the surface of graphene, were able to obtain nonspecific binding constant of BSA protein of graphene surface in aqueous solution. The time trace of resonance signal showed that the BSA molecules rapidly saturated by filling the available binding sites on graphene surface. Furthermore, we monitored oxidation of graphene surface under oxygen plasma by tracing the changes of interfacial mass of the graphene controlled by the shifts in Raman spectra. Three regimes were observed the formation of graphene oxide which increases the interfacial mass, the release of carbon dioxide and the removal of small graphene/graphene oxide flakes. Scientific and Technological Research Council of Turkey (TUBITAK) grant no. 110T304, 109T209, Marie Curie International Reintegration Grant (IRG) grant no 256458, Turkish Academy of Science (TUBA-Gebip).

Impact of surface wettability on S-layer recrystallization: a real-time characterization by QCM-D

PubMed Central

Vianna, Ana C; Moreno-Cencerrado, Alberto; Pum, Dietmar; Sleytr, Uwe B

2017-01-01

Quartz crystal microbalance with dissipation monitoring (QCM-D) has been employed to study the assembly and recrystallization kinetics of isolated SbpA bacterial surface proteins onto silicon dioxide substrates of different surface wettability. Surface modification by UV/ozone oxidation or by vapor deposition of 1H,1H,2H,2H-perfluorododecyltrichlorosilane yielded hydrophilic or hydrophobic samples, respectively. Time evolution of frequency and dissipation factors, either individually or combined as the so-called Df plots, showed a much faster formation of crystalline coatings for hydrophobic samples, characterized by a phase-transition peak at around the 70% of the total mass adsorbed. This behavior has been proven to mimic, both in terms of kinetics and film assembly steps, the recrystallization taking place on an underlying secondary cell-wall polymer (SCWP) as found in bacteria. Complementary atomic force microscopy (AFM) experiments corroborate these findings and reveal the impact on the final structure achieved. PMID:28144568

QCM Thermo-Gravimetric Analysis (QTGA) Comparisons

NASA Technical Reports Server (NTRS)

Rosecrans, Glenn; Meadows, George

2004-01-01

The ASTM E-1559 apparatus has been used for years at NASA/Goddard Space Flight Center (GSFC) to determine in situ outgassing rate information, as well as pertinent in situ TML and multiple VCM values. The apparatus also affords the opportunity to experimentally compute the evaporation rates of molecular species that are reemitted as the Quartz Crystal Microbalances (QCMs) are gradually warmed up at some controlled temperature. Typically the molecular mass that accumulates onto the test QCMs are a compilation of species that are outgassing from the sample due to their respective activation energies and the desorption processes that the sample undergoes at various tested temperatures. It has been speculated that if there is too much molecular buildup of condensed water vapor (ice) onto the QCM crystal that a significantly higher temperature would be needed to break these "ice" bonds. ASTM E-1559 data plots will be used to demonstrate the thermogravimetric effects of water and other miscible molecular species with various water/ice thicknesses and at different evaporation rates.

Round-patterned ZnO nanostructure coated with siloxane-based polymer for nerve agent detection

NASA Astrophysics Data System (ADS)

Choi, Hyun Ji; Lee, Ji Won; Jeong, Dong-Cheol; Ha, Seonggyun; Song, Changsik; Boo, Jin-Hyo

2018-01-01

The alignment of zinc oxide (ZnO) nanostructures is expected to improve device sensitivities due to large surface areas which can be utilized to capture significant quantities of gas particles. In this study, we investigated patterned ZnO nanorods modified with polystyrene monolayers synthesized directly onto a quartz crystal microbalance (QCM) cell to increase the coating surface area of the sensing material. Also, we designed and synthesized a siloxane-based polymer (S1 polymer) as a sensing material. The patterned ZnO nanorods coated with S1 polymers were fabricated and used for the detection of dimethyl methylphosphonate (DMMP). The resonance frequency of QCM was shifted due to the adsorption and desorption of a compound at the surface of the modified electrodes. We have synthesized an S1 polymer that exhibited high sensitivity to DMMP. The patterned ZnO nanorods coated with the polymer also exhibited improved sensitivity due to an enhanced surface area capable of adsorbing more DMMP vapor.

A low cost technique for synthesis of gold nanoparticles using microwave heating and its application in signal amplification for detecting Escherichia Coli O157:H7 bacteria

NASA Astrophysics Data System (ADS)

Thanh Ngo, Vo Ke; Giang Nguyen, Dang; Phat Huynh, Trong; Lam, Quang Vinh

2016-09-01

In the present work a low cost technique for preparation of gold nanoparticles (AuNPs) using microwave heating was developed. The effect of different elements (precursor reagents, irradiation time, and microwave radiation power) on the final morphology of AuNPs obtained through the microwave assisted technique has been investigated. The characterization of the samples has been carried out by transmission electron microscopy, UV-vis absorption spectroscopy, Fourier transform infrared spectroscopy, and powder x-ray diffraction. The results showed that to some extent the above-mentioned characterizations influenced the size of synthetized nanoparticles and application of microwave heating has many advantages such as low cost, rapid preparation and highly uniform particles. As an application in quartz crystal microbalance (QCM) immunosensor, AuNPs are conjugated with the Escherichia coli (E.coli) O157:H7 antibodies for signal amplification to detect E.coli O157:H7 bacteria residual in QCM system.

Immobilization of Aluminum Hydroxide Particles on Quartz Crystal Microbalance Sensors to Elucidate Antigen-Adjuvant Interaction Mechanisms in Vaccines.

PubMed

Art, Jean-François; Vander Straeten, Aurélien; Dupont-Gillain, Christine C

2018-01-16

Aluminum hydroxide (AH) salts are the most widely used adjuvants in vaccine formulation. They trigger immunogenicity from antigenic subunits that would otherwise suffer from a lack of efficiency. Previous studies focusing on antigen-AH interaction mechanisms, performed with model proteins, suggested that electrostatic interactions and phosphate-hydroxyl ligand exchanges drive protein adsorption on AH. We however recently evidenced that NaCl, used in vaccine formulation, provokes AH particle aggregation. This must be taken into account to interpret data related to protein adsorption on AH. Here, we report on the successful development and use of a stable AH-coated surface to explore the mechanisms of protein adsorption by means of ultrasensitive surface analysis tools. Bovine serum albumin (BSA) adsorption was studied at different pHs and ionic strengths (I) using quartz crystal microbalance. The results show that protein adsorption on the AH adjuvant cannot be explained solely by electrostatic interactions and ligand exchanges. Hence, a higher adsorption was observed at pH 3 compared to pH 7, although AH and BSA respectively undergo repulsive and attractive electrostatic interactions at these pH values. Almost no effect of I on adsorption was moreover noted at pH 7. These new developments and observations not only suggest that other mechanisms govern protein adsorption on AH but also offer a new platform for the study of antigen adsorption in the context of vaccine formulation. Immobilizing particles on QCM sensors also enriches the range of applications for which QCM can be exploited, especially in colloid science.

Characterizing protein-protein-interaction in high-concentration monoclonal antibody systems with the quartz crystal microbalance.

PubMed

Hartl, Josef; Peschel, Astrid; Johannsmann, Diethelm; Garidel, Patrick

2017-12-13

Making use of a quartz crystal microbalance (QCM), concentrated solutions of therapeutic antibodies were studied with respect to their behavior under shear excitation with frequencies in the MHz range. At high protein concentration and neutral pH, viscoelastic behavior was found in the sense that the storage modulus, G', was nonzero. Fits of the frequency dependence of G'(ω) and G''(ω) (G'' being the loss modulus) using the Maxwell-model produced good agreement with the experimental data. The fit parameters were the relaxation time, τ, and the shear modulus at the inverse relaxation time, G* (at the "cross-over frequency" ω C = 1/τ). The influence of two different pharmaceutical excipients (histidine and citrate) was studied at variable concentrations of the antibody and variable pH. In cases, where viscoelasticity was observed, G* was in the range of a few kPa, consistent with entropy-driven interactions. τ was small at low pH, where the antibody carries a positive charge. τ increased with increasing pH. The relaxation time τ was found to be correlated with other parameters quantifying protein-protein interactions, namely the steady shear viscosity (η), the second osmotic virial coefficient as determined with both self-interaction chromatography (B 22,SIC ) and static light scattering (B 22,SLS ), and the diffusion interaction parameter as determined with dynamic light scattering (k D ). While B 22 and k D describe protein-protein interactions in diluted samples, the QCM can be applied to concentrated solutions, thereby being sensitive to higher-order protein-protein interactions.

Rapid detection of Bacillus anthracis using monoclonal antibody functionalized QCM sensor.

PubMed

Hao, Rongzhang; Wang, Dianbing; Zhang, Xian'en; Zuo, Guomin; Wei, Hongping; Yang, Ruifu; Zhang, Zhiping; Cheng, Zhenxing; Guo, Yongchao; Cui, Zongqiang; Zhou, Yafeng

2009-01-01

Since the anthrax spore bioterrorism attacks in America in 2001, the early detection of Bacillus anthracis spores and vegetative cells has gained significant interest. At present, many polyclonal antibody-based quartz crystal microbalance (QCM) sensors have been developed to detect B. anthracis simulates. To achieve a simultaneous rapid detection of B. anthracis spores and vegetative cells, this paper presents a biosensor that utilizes an anti-B. anthracis monoclonal antibody designated to 8G3 (mAb 8G3, IgG) functionalized QCM sensor. Having compared four kinds of antibody immobilizations on Au surface, an optimized mAb 8G3 was immobilized onto the Au electrode with protein A on a mixed self-assembled monolayer (SAM) of 11-mercaptoundecanoic acid (11-MUA) and 6-mercaptohexan-1-ol (6-MHO) as adhesive layer. The detection of B. anthracis was investigated under three conditions: dip-and-dry, static addition and flow through procedure. The results indicated that the sensor yielded a distinct response to B. anthracis spores or vegetative cells but had no significant response to Bacillus thuringiensis species. The functionalized sensor recognized B. anthracis spores and vegetative cells specifically from its homophylic ones, and the limit of detection (LOD) reached 10(3)CFU or spores/ml of B. anthracis in less than 30 min. Cyclic voltammogram (CV) and scanning electronic microscopy (SEM) were performed to characterize the surface of the sensor in variable steps during the modification and after the detection. The mAb functionalized QCM biosensor will be helpful in the fabrication of a similar biosensor that may be available in anti-bioterrorism in the future.

Use of the quartz crystal microbalance to determine the monomeric friction coefficient of polyimides

NASA Technical Reports Server (NTRS)

Bechtold, Mary M.

1995-01-01

When a thin film of polymer is coated on to a quartz crystal microbalance (QCM), the QCM can be used to detect the rate of increase in weight of the polymer film as the volatile penetrant diffuses into the polymer. From this rate information the diffusion coefficient of the penetrant into the polymer can be computed. Calculations requiring this diffusion coefficient lead to values which approximate the monomeric friction coefficient of the polymer. This project has been concerned with the trial of crystal oscillating circuits suitable for driving polymer coated crystals in an atmosphere of penetrant. For these studies done at room temperature, natural rubber was used as an easily applied polymer that is readily penetrated by toluene vapors, qualities anticipated with polyimides when they are tested at T(g) in the presence of toluene. Three quartz crystal oscillator circuits were tested. The simplest circuit used +/- 5 volt dc and had a transistor to transistor logic (TTL) inverter chip that provides a 180 deg phase shift via a feed back loop. This oscillator circuit was stable but would not drive the crystal when the crystal was coated with polymer and subjected to toluene vapors. Removal of a variable resistor from this circuit increased stability but did not otherwise increase performance. Another driver circuit tested contained a two stage differential input, differential output, wide band video amplifier and also contain a feed back loop. The circuit voltage could not be varied and operated at +/- 5 volts dc; this circuit was also stable but failed to oscillate the polymer coated crystal in an atmosphere saturated with toluene vapors. The third oscillator circuit was of similar construction and relied on the same video amplifier but allowed operation with variable voltage. This circuit would drive the crystal when the crystal was submerged in liquid toluene and when the crystal was coated with polymer and immersed in toluene vapors. The frequency readings obtained when using this oscillating circuit are highly variable. This circuit requires further modification to stabilize frequency readings before its use in studies to determine the diffusion coefficient of penetrant molecules into a polymer film coated on a QCM.

Monitoring contamination due to materials outgassing by QCM-based sensors

NASA Astrophysics Data System (ADS)

Dirri, Fabrizio

2016-07-01

F. Dirri, E. Palomba, A. Longobardo, D. Biondi, A. Boccaccini, E. Zampetti, B. Saggin, D. Scaccabarozzi, A. Tortora, A. Nanni, J. Alves, A. Tighe Outgassing from spacecraft materials often occurs and degassing contaminants can degrade critical spacecraft surfaces, such as optical systems, solar panels, thermal radiators and thermal management systems. The main contaminants are the water adsorbed by cold surface, organics from spacecraft structure, electronics, insulation and thrusters firings [1]. Thus, it is fundamental to monitor these low-outgassing rates especially in a long duration mission: Quartz Crystal Microbalance (QCM) based sensors (i.e. single and double crystal configurations) are a suitable instruments to monitor step by step these degradation processes which occur in space conditions. The Contamination Assessment Microbalance (CAM) is a device aimed at monitoring in-orbit contamination of sensitive surfaces and payloads on ESA's future satellites. The device, developed by a consortium of Italian research Institutes, is based on QCM technology, previously considered by NASA and ESA experiments performed on Space Shuttle and satellite missions [2,3,4]. CAM is a low mass (200 grams for the sensor head), low volume (smaller than 5x5x5 cm3 for the sensor head) and low power consumption (less than 1.5 W) sensor. The device is composed by: 1) the Sensor Head, containing a sensing crystal (which measures the deposited contaminant mass), a reference crystal (used as frequency reference), their related Proximity Electronics (PE) and a Temperature Control System (TCS); 2) the Main Electronics Unit (MEU), which acquires the signal in output from Sensor Head unit; 3) the Harness connecting Sensor Head and MEU; 4) the User Interface (UI) to read and display the data. The device shows several improvements, i.e. possibility to measure directly the crystal temperature (with an accuracy better than 0.1°C), large measurable mass range (from 5•10-9 to 7•10-4 g/cm2), large operative temperature range (from -80°C to 130°C), temperature stability within 0.5°C and good frequency resolution of 0.1 Hz. The instruments concept and the performance evaluation, based on tests performed on the QCM based sensors (i.e. simulating an outgassing source in space conditions), are presented in this work. References : [1] Soares et al. 2003, Proc. SPIE, 09/2000; [2] Miller 1982, Report NASA TM- 82457; [3] Tighe et al. 2009, AIP Conf. Proc. 1087, 195; [4] Wood et al. 1997, AIAA 97-0841

Statistical Evaluation of Molecular Contamination During Spacecraft Thermal Vacuum Test

NASA Technical Reports Server (NTRS)

Chen, Philip; Hedgeland, Randy; Montoya, Alex; Roman-Velazquez, Juan; Dunn, Jamie; Colony, Joe; Petitto, Joseph

1998-01-01

The purpose of this paper is to evaluate the statistical molecular contamination data with a goal to improve spacecraft contamination control. The statistical data was generated in typical thermal vacuum tests at the National Aeronautics and Space Administration, Goddard Space Flight Center (GSFC). The magnitude of material outgassing was measured using a Quartz Crystal Microbalance (QCM) device during the test. A solvent rinse sample was taken at the conclusion of each test. Then detailed qualitative and quantitative measurements were obtained through chemical analyses. All data used in this study encompassed numerous spacecraft tests in recent years.

Statistical Evaluation of Molecular Contamination During Spacecraft Thermal Vacuum Test

NASA Technical Reports Server (NTRS)

Chen, Philip; Hedgeland, Randy; Montoya, Alex; Roman-Velazquez, Juan; Dunn, Jamie; Colony, Joe; Petitto, Joseph

1997-01-01

The purpose of this paper is to evaluate the statistical molecular contamination data with a goal to improve spacecraft contamination control. The statistical data was generated in typical thermal vacuum tests at the National Aeronautics and Space Administration, Goddard Space Flight Center (GSFC). The magnitude of material outgassing was measured using a Quartz Crystal Microbalance (QCM) device during the test. A solvent rinse sample was taken at the conclusion of the each test. Then detailed qualitative and quantitative measurements were obtained through chemical analyses. All data used in this study encompassed numerous spacecraft tests in recent years.

Structural Loading on the QCM/SAW Instrument Aboard the ER-2 Used for Atmospheric Testing

NASA Technical Reports Server (NTRS)

Bainum, Peter M.; Jones, Phyllis D.; Irish, Sandra M.; Xing, Guang-Qian

1998-01-01

Several experiments have been proposed to capture and evaluate samples of the atmosphere where SST's travel. One means to achieve this is to utilize the quartz crystal microbalance (QCM) / surface acoustical wave (SAW) instrument installed aboard the ER-2, formerly the U-2 reconnaissance aircraft. The QCM is a cascade impactor designed to perform in-situ, real-time measurements of aerosols and chemical vapors at an altitude of 60,000-70,000 feet. The primary use of the ER-2 is by NASA for Earth resources to test new sensor systems before being placed aboard satellites. One of the main reasons the ER-2 is used for this flight experiment is its capability to fly approximately twelve miles above the sea level (can reach an altitude of 78,000 feet). Because the ER-2 operates at such a high altitude, it is of special interest to scientists interested in space exploration or supersonic aircraft. The purpose of some of the experiments is to extinct data from the atmosphere around the ER-2. For the current CSTEA flight experiment, the housing of the QCM is in a frame that connects to an outer pod that attaches to the fuselage of the ER-2. Due to the location of the QCM within the housing frame and the location of the pod on the ER-2, the pod and its contents are subject to structural loads. In addition to structural loads, structural vibrations are also of importance because the QCM output data is based on the determination of beat frequencies between a pair of oscillators (one coated, the second uncoated, according to the chemical reaction being monitored). A structural analysis of this system can indicate whether potential resonances may exist between the (higher) structural modal frequencies and the beat frequencies. In addition undesirable deformations may result due to maximum expected static or dynamic loads during typical flight conditions. If the deformations are excessive they may adversely affect the accuracy the instrumentation output.

Characterization and application of a surface modification designed for QCM-D studies of biotinylated biomolecules.

PubMed

Nilebäck, Erik; Feuz, Laurent; Uddenberg, Hans; Valiokas, Ramūnas; Svedhem, Sofia

2011-10-15

The rapid development of surface sensitive biosensor technologies, especially towards nanoscale devices, requires increasing control of surface chemistry to provide reliable and reproducible results, but also to take full advantage of the sensing opportunities. Here, we present a surface modification strategy to allow biotinylated biomolecules to be immobilized to gold coated sensor crystals for quartz crystal microbalance with dissipation monitoring (QCM-D) sensing. The unique feature of QCM-D is its sensitivity to nanomechanical (viscoelastic) properties at the sensing interface. The surface modification was based on mixed monolayers of oligo(ethylene glycol) (OEG) disulfides, with terminal -OH or biotin groups, on gold. Mixtures containing 1% of the biotin disulfide were concluded to be the most appropriate based on the performance when streptavidin was immobilized to biotinylated sensors and the subsequent biotinylated bovine serum albumin (BSA) interaction was studied. The OEG background kept the unspecific protein binding to a minimum, even when subjected to serum solutions with a high protein concentration. Based on characterization by contact angle goniometry, ellipsometry, and infrared spectroscopy, the monolayers were shown to be well-ordered, with the OEG chains predominantly adopting a helical conformation but also partly an amorphous structure. Storage stability was concluded to depend mainly on light exposure while almost all streptavidin binding activity was retained when storing the sensors cold and dark for 8 weeks. The surface modification was also tested for repeated antibody-antigen interactions between BSA and anti-BSA (immobilized to biotinylated protein A) in QCM-D measurements lasting for >10h with intermediate basic regeneration. This proved an excellent stability of the coating and good reproducibility was obtained for 5 interaction cycles. With this kind of generic surface modification QCM-D can be used in a variety of biosensing applications to provide not only mass but also relevant information of the structural properties of adlayers. Copyright © 2011 Elsevier B.V. All rights reserved.

Development and comparative investigation of Ag-sensitive layer based SAW and QCM sensors for mercury sensing applications.

PubMed

Kabir, K M Mohibul; Sabri, Ylias M; Kandjani, Ahmad Esmaielzadeh; Ippolito, Samuel J; Bhargava, Suresh K

2016-04-21

Piezoelectric acoustic wave devices integrated with noble metal surfaces provide exciting prospects for the direct measurement of toxic gas species such as mercury (Hg) in the atmosphere. Even though gold (Au) based acoustic wave sensors have been utilized extensively for detecting Hg, the potential of using other metal surfaces such as silver (Ag) is yet to be thoroughly studied. Here, we developed Ag sensitive layer-based surface acoustic wave (SAW) and quartz crystal microbalance (QCM) sensors and focused on their comparative analysis for Hg sensing applications with parameters such as the sensor sensitivity, selectivity, adsorption/desorption isotherm and Hg diffusion into the surface thoroughly studied. The SAW sensor was fabricated with nickel (Ni) interdigitated transducer (IDT) electrodes and a Ag thin film on the delay line of the device. In the case of the QCM sensor, the electrodes were constructed of Ag thin film and simultaneously employed as a sensitive layer. Mercury sensing experiments were conducted for a range of concentrations between 24-365 ppbv without/with the presence of some common industrial interfering gas species (i.e. ammonia, acetaldehyde, ethyl mercaptan, dimethyl disulphide, methyl ethyl ketone and humidity) at various operating temperatures in the range of 35-95 °C. The SAW sensor was found to possess up to 70 times higher response magnitudes than its QCM counterpart at 35 °C while up to 30 and 23 times higher response magnitudes were observed for the SAW sensor at elevated temperatures of 75 and 95 °C, respectively. Furthermore, the SAW sensor showed good selectivity (>89%) toward Hg(0) vapor in the presence of all the interferents tested at an operating temperature of 75 °C while the QCM sensor exhibited significant cross-sensitivity when ethyl mercaptan was introduced along with Hg(0) vapor. Overall, it is indicative that Ag-based acoustic wave sensors do have great potential for Hg sensing applications, given that right operating conditions are applied.

Reflectometric measurement of n-hexane adsorption on ZnO2 nanohybrid film modified by hydrophobic gold nanoparticles

NASA Astrophysics Data System (ADS)

Sebők, Dániel; Csapó, Edit; Ábrahám, Nóra; Dékány, Imre

2015-04-01

Zinc-peroxide/poly(styrenesulfonate) nanohybrid thin films (containing 20 bilayers: [ZnO2/PSS]20, d ∼ 500 nm) were prepared using layer-by-layer (LbL) method. The thin film surface was functionalized by different surface modifying agents (silanes, alkylthiols and hydrophobized nanoparticles). Based on the experimental results of quartz crystal microbalance (QCM) and contact angle measurements (as prequalifications) the octanethiol covered gold nanoparticles (OT-AuNPs) were selected for further vapour adsorption studies. Reflectometric interference spectroscopy (RIfS) was used to measure n-hexane vapour adsorption on the original and modified nanohybrid films in a gas flow platform. The thin film provides only the principle of the measurement (by interference phenomenon), the selectivity and hydrophobicity is controlled and enhanced by surface functionalization (by dispersion interaction between the alkyl chains). The interference pattern shift (Δλ) caused by the increase of the optical thickness of the thin film due to vapour adsorption was investigated. It was found that due to the surface functionalization by hydrophobic nanoparticles the effect of water vapour adsorption decreased significantly, while for n-hexane opposite tendency was observed (the effective refractive index and thus the interference pattern shift increased drastically). The correlation between QCM technique and optical method (RIfS) was specified: linear specific adsorbed amount vs. wavelength shift calibration curves were determined in the pr = 0-0.4 relative vapour pressure range. The thin film is suitable for sensorial application (e.g. volatile organic compound/VOC sensor).

Absence of molecular slip on ultraclean and SAM-coated surfaces

NASA Astrophysics Data System (ADS)

Pye, Justin; Wood, Clay; Burton, Justin

2016-11-01

The liquid/solid boundary condition is a complex problem that is becoming increasingly important for the development of nanoscale fluidic devices. Many groups have now measured slip near an interface at nanoscale dimensions using a variety of experimental techniques. In simple systems, large slip lengths are generally measured for non-wetting liquid/solid combinations, but many conflicting measurements and interpretations remain. We have developed a novel pseudo-differential technique using a quartz crystal microbalance (QCM) to measure slip lengths on various surfaces. A drop of one liquid is grown on the QCM in the presence of a second, ambient liquid. We have isolated any anomalous boundary effects such as interfacial slip by choosing two liquids which have identical bulk effects on the QCM frequency and dissipation in the presence of no-slip. Slip lengths are -less than 2 nm- for water (relative to undecane) on all surfaces measured, including plasma cleaned gold, SiO2, and two different self assembled monolayers (SAMs), regardless of contact angle. We also find that surface cleanliness is crucial to accurately measure slip lengths. Additionally, clean glass substrates appear to have a significant adsorbed water layer and SAM surfaces show excess dissipation, possibly associated with contact line motion. In addition to investigating other liquid pairs, future work will include extending this technique to surfaces with independently controllable chemistry and roughness, both of which are known to strongly affect interfacial hydrodynamics.

Monitoring N3 dye adsorption and desorption on TiO2 surfaces: a combined QCM-D and XPS study.

PubMed

Wayment-Steele, Hannah K; Johnson, Lewis E; Tian, Fangyuan; Dixon, Matthew C; Benz, Lauren; Johal, Malkiat S

2014-06-25

Understanding the kinetics of dye adsorption and desorption on semiconductors is crucial for optimizing the performance of dye-sensitized solar cells (DSSCs). Quartz crystal microbalance with dissipation monitoring (QCM-D) measures adsorbed mass in real time, allowing determination of binding kinetics. In this work, we characterize adsorption of the common RuBipy dye N3 to the native oxide layer of a planar, sputter-coated titanium surface, simulating the TiO2 substrate of a DSSC. We report adsorption equilibrium constants consistent with prior optical measurements of N3 adsorption. Dye binding and surface integrity were also verified by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy (XPS). We further study desorption of the dye from the native oxide layer on the QCM sensors using tetrabutylammonium hydroxide (TBAOH), a commonly used industrial desorbant. We find that using TBAOH as a desorbant does not fully regenerate the surface, though little ruthenium or nitrogen is observed by XPS after desorption, suggesting that carboxyl moieties of N3 remain bound. We demonstrate the native oxide layer of a titanium sensor as a valid and readily available planar TiO2 morphology to study dye adsorption and desorption and begin to investigate the mechanism of dye desorption in DSSCs, a system that requires further study.

Electrodeless QCM-D for lipid bilayer applications.

PubMed

Kunze, Angelika; Zäch, Michael; Svedhem, Sofia; Kasemo, Bengt

2011-01-15

An electrodeless quartz crystal microbalance with dissipation monitoring (QCM-D) setup is used to monitor the formation of supported lipid bilayers (SLBs) on bare quartz crystal sensor surfaces. The kinetic behavior of the formation of a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) SLB on SiO(2) surfaces is discussed and compared for three cases: (i) a standard SiO(2) film deposited onto the gold electrode of a quartz crystal, (ii) an electrodeless quartz crystal with a sputter-coated SiO(2) film, and (iii) an uncoated electrodeless quartz crystal sensor surface. We demonstrate, supported by imaging the SLB on an uncoated electrodeless surface using atomic force microscopy (AFM), that a defect-free, completely covering bilayer is formed in all three cases. Differences in the kinetics of the SLB formation on the different sensor surfaces are attributed to differences in surface roughness. The latter assumption is supported by imaging the different surfaces using AFM. We show furthermore that electrodeless quartz crystal sensors can be used not only for the formation of neutral SLBs but also for positively and negatively charged SLBs. Based on our results we propose electrodeless QCM-D to be a valuable technique for lipid bilayer and related applications providing several advantages compared to electrode-coated surfaces like optical transparency, longer lifetime, and reduced costs. Copyright © 2010 Elsevier B.V. All rights reserved.

Nanoassembled thin film gas sensors. III. Sensitive detection of amine odors using TiO2/poly(acrylic acid) ultrathin film quartz crystal microbalance sensors.

PubMed

Lee, Seung-Woo; Takahara, Naoki; Korposh, Sergiy; Yang, Do-Hyeon; Toko, Kiyoshi; Kunitake, Toyoki

2010-03-15

Quartz crystal microbalance (QCM) gas sensors based on the alternate adsorption of TiO(2) and polyacrilic acid (PAA) were developed for the sensitive detection of amine odors. Individual TiO(2) gel layers could be regularly assembled with a thickness of approximately 0.3 nm by the gas-phase surface sol-gel process (GSSG). The thickness of the poly(acrylic acid) (PAA) layer is dependent on its molecular weight, showing different thicknesses of approximately 0.4 nm for PAA(25) (Mw 250,000) and 0.6-0.8 nm for PAA(400) (Mw 4,000,000). The QCM sensors showed a linear response to ammonia in the concentration range 0.3-15 ppm, depending on the deposition cycle of the alternate TiO(2)/PAA layer. The ammonia binding is based on the acid-base interaction to the free carboxylic acid groups of PAA and the limit of detection (LOD) of the 20-cycle TiO(2)/PAA(400) film was estimated to be 0.1 ppm when exposed to ammonia. The sensor response was very fast and stable in a wide relative humidity (rH) range of 30-70%, showing almost the same frequency changes at a given concentration of ammonia. Sensitivity to n-butylamine and ammonia was higher than to pyridine, which is owing to the difference of molecular weight and basicity of the amine analytes. The alternate TiO(2)/PAA(400) films have a highly effective ability to capture amine odors, and the ambient ammonia concentration of 15 ppm could be condensed up to approximately 20,000 ppm inside the films.

Affinity Interaction between Hexamer Peptide Ligand HWRGWV and Immunoglobulin G Studied by Quartz Crystal Microbalance and Surface Plasmon Resonance

NASA Astrophysics Data System (ADS)

Shen, Fei

Immunoglobulins (Ig), also referred to as antibodies, act as protective agents against pathogens trying to invade an organism. Human immunoglobulin G (hIgG), as the most prominent immunoglobulin presented in serum and other human fluids, has broad applications in fields like immunotherapy and clinical diagnostics. Staphylococcus aureus Protein A and Streptococcus Protein G are the most common affinity ligands for IgG purifaction and detection. However, drawbacks associated with these two protein ligands have motivated searches for alternative affinity ligands. The hexamer peptide ligand HWRGWV identified from a one-bead-one-peptide combinatorial library synthesized on chromatography resins has demonstrated high affinity and specificity to the Fc fragment of hIgG. A chromatography resin with HWRGWV can purify human IgG (hIgG) from complete minimum essential medium (cMEM) with purities and yields as high as 95%, which are comparable to using Protein A as affinity ligand (4). As a short peptide ligand, HWRGWV can be produced at relatively low costs under good manufacturing practices (GMP) conditions, it is highly robust, less immunogenic and allows for milder elution conditions for the bound antibody (3, 5). Although this short peptide ligand has exhibited promising properties for IgG capture and purification, limited information is available on the intrinsic mechanisms of affinity interaction between the peptide ligand and target protein. In this study, the affinity interaction between hIgG and peptide ligand immobilized on solid surfaces was studied by quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). Compared with previous methods employed for the peptide characterization, QCM and SPR can provide direct measurements of equilibrium adsorption isotherms and rates of adsorption, allowing a complete kinetic and thermodynamics analyses of the ligand-target interactions. New methods were developed to modify gold and silica surfaces of QCM and SPR sensors for the immobilization of peptide ligands with low nonspecific binding. The silica surface was first modified by the formation of self-assembling monolayer (SAM) of 3-amino-propyl triethoxy silane as an anchor layer. Short chains of poly(ethylene glycol) (PEG) with Fmoc-protected amino groups at one end and carboxyl groups at the other end were then coupled through the carboxyl terminal to the amino groups on the silane. The short PEG chains served as spacer arms to reduce nonspecific binding to the substrate. The gold surface was modified by a two-component SAM using mixtures of HS(CH 2)11(CH2CH2O)6NH2 and HS(CH2)11(CH2CH2O)3OH. The advantage of using a modified silica surface is its relatively higher stability than the SAM on gold during the peptide functionalization step, however the SPR sensors do not work on silica surfaces. In addition, the modification process of the gold surface is relatively simple compared with that of the silica surface. The peptide immobilization process was optimized with silica surfaces and the best conditions were applied for the immobilization on gold surfaces. The results of surface modifications and peptide immobilizations were characterized by various surface analysis techniques including, ellipsometry, contact angle goniometer, chemical force microscopy (CFM), x-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopy (ToF-SIMS). QCM and SPR results indicated that this peptide ligand HWRGWV immobilized on modified silica or gold surfaces has high affinity and specificity to hIgG binding even in a complex medium such as cMEM. Both thermodynamic and kinetic parameters of affinity interaction were obtained by the analysis of QCM and SPR data. Compared with QCM, SPR is more suitable for quantitative analysis of the protein binding, which is essential for the investigation of thermodynamics and kinetics parameters. The maximum binding capacity (4.15 mg m-2 ) and the dissociation constant (1.83 muM) derived from SPR data are both close to those obtained with chromatography techniques. The association and dissociation rate constants (0.68 m3 mol-1 s-1 and 1.24 s-1 respectively) were acquired for the first time for the affinity binding of IgG on peptide ligand HWRGWV functionalized surface. Although QCM is not as quantitative as SPR, it provides additional information on the status of the adsorbed layers. For instance, the dissipation measurement of QCM indicated that no significant denaturation of adsorbed hIgG occurred during the adsorption process. In addition, it was shown that the peptide ligand immobilized on modified silica surfaces has similar affinity and binding characteristics for IgG adsorption as on modified gold surfaces. In summary, new surface modification strategies were developed to study the affinity interaction between peptide ligands and target biomolecules. The use of Fc-specific binding peptides on QCM and SPR sensors could result in new devices for IgG concentration determination and also have promise as platforms for the development of immunosensors.

Kinetic and potential sputtering of an anorthite-like glassy thin film

DOE PAGES

Hijazi, H.; Bannister, M. E.; Meyer, H. M.; ...

2017-07-28

In this paper, we present measurements of He + and He +2 ion-induced sputtering of an anorthite-like thin film at a fixed solar wind-relevant impact energy of ~0.5 keV/amu using a quartz crystal microbalance approach (QCM) for determination of total absolute sputtering yields. He +2 ions are the most abundant multicharged ions in the solar wind, and increased sputtering by these ions in comparison to equivelocity He + ions is expected to have the biggest effect on the overall sputtering efficiency of solar wind impact on the Moon. These measurements indicate an almost 70% increase of the sputtering yield formore » doubly charged incident He ions compared to that for same velocity He + impact (14.6 amu/ion for He +2 vs. 8.7 amu/ion for He+). Using a selective sputtering model, the new QCM results presented here, together with previously published results for Ar +q ions and SRIM results for the relevant kinetic-sputtering yields, the effect due to multicharged-solar-wind-ion impact on local near-surface modification of lunar anorthite-like soil is explored. It is shown that the multicharged-solar-wind component leads to a more pronounced and significant differentiation of depleted and enriched surface elements as well as a shortening of the timescale over which such surface-compositional modifications might occur in astrophysical settings. Additionally, to validate previous and future determinations of multicharged-ion-induced sputtering enhancement for those cases where the QCM approach cannot be used, relative quadrupole mass spectrometry (QMS)-based measurements are presented for the same anorthite-like thin film as were investigated by QCM, and their suitability and limitations for charge state-enhanced yield measurements are discussed.« less

Kinetic and potential sputtering of an anorthite-like glassy thin film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hijazi, H.; Bannister, M. E.; Meyer, H. M.

In this paper, we present measurements of He + and He +2 ion-induced sputtering of an anorthite-like thin film at a fixed solar wind-relevant impact energy of ~0.5 keV/amu using a quartz crystal microbalance approach (QCM) for determination of total absolute sputtering yields. He +2 ions are the most abundant multicharged ions in the solar wind, and increased sputtering by these ions in comparison to equivelocity He + ions is expected to have the biggest effect on the overall sputtering efficiency of solar wind impact on the Moon. These measurements indicate an almost 70% increase of the sputtering yield formore » doubly charged incident He ions compared to that for same velocity He + impact (14.6 amu/ion for He +2 vs. 8.7 amu/ion for He+). Using a selective sputtering model, the new QCM results presented here, together with previously published results for Ar +q ions and SRIM results for the relevant kinetic-sputtering yields, the effect due to multicharged-solar-wind-ion impact on local near-surface modification of lunar anorthite-like soil is explored. It is shown that the multicharged-solar-wind component leads to a more pronounced and significant differentiation of depleted and enriched surface elements as well as a shortening of the timescale over which such surface-compositional modifications might occur in astrophysical settings. Additionally, to validate previous and future determinations of multicharged-ion-induced sputtering enhancement for those cases where the QCM approach cannot be used, relative quadrupole mass spectrometry (QMS)-based measurements are presented for the same anorthite-like thin film as were investigated by QCM, and their suitability and limitations for charge state-enhanced yield measurements are discussed.« less

Kinetic and potential sputtering of an anorthite-like glassy thin film

NASA Astrophysics Data System (ADS)

Hijazi, H.; Bannister, M. E.; Meyer, H. M.; Rouleau, C. M.; Meyer, F. W.

2017-07-01

In this paper, we present measurements of He+ and He+2 ion-induced sputtering of an anorthite-like thin film at a fixed solar wind-relevant impact energy of 0.5 keV/amu using a quartz crystal microbalance approach (QCM) for determination of total absolute sputtering yields. He+2 ions are the most abundant multicharged ions in the solar wind, and increased sputtering by these ions in comparison to equivelocity He+ ions is expected to have the biggest effect on the overall sputtering efficiency of solar wind impact on the Moon. Our measurements indicate an almost 70% increase of the sputtering yield for doubly charged incident He ions compared to that for same velocity He+ impact (14.6 amu/ion for He+2 vs. 8.7 amu/ion for He+). Using a selective sputtering model, the new QCM results presented here, together with previously published results for Ar+q ions and SRIM results for the relevant kinetic-sputtering yields, the effect due to multicharged-solar-wind-ion impact on local near-surface modification of lunar anorthite-like soil is explored. It is shown that the multicharged-solar-wind component leads to a more pronounced and significant differentiation of depleted and enriched surface elements as well as a shortening of the timescale over which such surface-compositional modifications might occur in astrophysical settings. In addition, to validate previous and future determinations of multicharged-ion-induced sputtering enhancement for those cases where the QCM approach cannot be used, relative quadrupole mass spectrometry (QMS)-based measurements are presented for the same anorthite-like thin film as were investigated by QCM, and their suitability and limitations for charge state-enhanced yield measurements are discussed.

DNA adsorption to and elution from silica surfaces: influence of amino acid buffers.

PubMed

Vandeventer, Peter E; Mejia, Jorge; Nadim, Ali; Johal, Malkiat S; Niemz, Angelika

2013-09-19

Solid phase extraction and purification of DNA from complex samples typically requires chaotropic salts that can inhibit downstream polymerase amplification if carried into the elution buffer. Amino acid buffers may serve as a more compatible alternative for modulating the interaction between DNA and silica surfaces. We characterized DNA binding to silica surfaces, facilitated by representative amino acid buffers, and the subsequent elution of DNA from the silica surfaces. Through bulk depletion experiments, we found that more DNA adsorbs to silica particles out of positively compared to negatively charged amino acid buffers. Additionally, the type of the silica surface greatly influences the amount of DNA adsorbed and the final elution yield. Quartz crystal microbalance experiments with dissipation monitoring (QCM-D) revealed multiphasic DNA adsorption out of stronger adsorbing conditions such as arginine, glycine, and glutamine, with DNA more rigidly bound during the early stages of the adsorption process. The DNA film adsorbed out of glutamate was more flexible and uniform throughout the adsorption process. QCM-D characterization of DNA elution from the silica surface indicates an uptake in water mass during the initial stage of DNA elution for the stronger adsorbing conditions, which suggests that for these conditions the DNA film is partly dehydrated during the prior adsorption process. Overall, several positively charged and polar neutral amino acid buffers show promise as an alternative to methods based on chaotropic salts for solid phase DNA extraction.

Surface Condensation of CO2 onto Kaolinite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Owen, Antionette T.

2014-02-11

The fundamental adsorption behavior of gaseous and supercritical carbon dioxide (CO2) onto poorly crystalline kaolinite (KGa-2) at conditions relevant to geologic sequestration has been investigated using a quartz crystal microbalance (QCM) and density functional theory (DFT) methods. The QCM data indicated linear adsorption of CO2 (0-0.3 mmol CO2/g KGa-2) onto the kaolinite surface up through the gaseous state (0.186 g/cm3). However in the supercritical region, CO2 adsorption increases dramatically, reaching a peak (0.9-1.0 mmol CO2/g KGa-2) near 0.43 g/cm3, before declining rapidly to surface adsorption values equivalent or below gaseous CO2. This adsorption profile was not observed with He ormore » N2. Comparative density functional studies of CO2 interactions with kaolinite surface models rule out CO2 intercalation and confirm that surface adsorption is favored up to approximately 0.35 g/cm3 of CO2, showing distorted T-shaped CO2-CO2 clustering, typical of supercritical CO2 aggregation over the surface as the density increases. Beyond this point, the adsorption energy gain for any additional CO2 becomes less than the CO2 interaction energy (~0.2 eV) in the supercritical medium resulting in overall desorption of CO2 from the kaolinite surface.« less

Identification of the functional groups on the surface of nanoparticles formed in photonucleation of aldehydes generated during forest fire events

NASA Astrophysics Data System (ADS)

Dultsev, Fedor N.; Mik, Ivan A.; Dubtsov, Sergei N.; Dultseva, Galina G.

2014-11-01

We describe the new procedure developed to determine the functional groups on the surface of nanoparticles formed in photonucleation of furfural, one of the aldehydes generated during forest fire events. The procedure is based on the detection of nanoparticle rupture from chemically modified surface of the quartz crystal microbalance oscillating in the thickness shear mode under voltage sweep. The rupture force is determined from the voltage at which the rupture occurs. It depends on particle mass and on the affinity of the surface functional groups of the particle to the groups that are present on the modified QCM surface. It was demonstrated with the amine modification of the surface that the nanoparticles formed in furfural photonucleation contain carbonyl and carboxyl groups. The applicability of the method for the investigation of functional groups on the surface of the nanoparticles of atmospheric aerosol is demonstrated.

Odorant binding protein based biomimetic sensors for detection of alcohols associated with Salmonella contamination in packaged beef.

PubMed

Sankaran, Sindhuja; Panigrahi, Suranjan; Mallik, Sanku

2011-03-15

Detection of food-borne bacteria present in the food products is critical to prevent the spread of infectious diseases. Intelligent quality sensors are being developed for detecting bacterial pathogens such as Salmonella in beef. One of our research thrusts was to develop novel sensing materials sensitive to specific indicator alcohols at low concentrations. Present work focuses on developing olfactory sensors mimicking insect odorant binding protein to detect alcohols in low concentrations at room temperature. A quartz crystal microbalance (QCM) based sensor in conjunction with synthetic peptide was developed to detect volatile organic compounds indicative to Salmonella contamination in packaged beef. The peptide sequence used as sensing materials was derived from the amino acids sequence of Drosophila odorant binding protein, LUSH. The sensors were used to detect alcohols: 3-methyl-1-butanol and 1-hexanol. The sensors were sensitive to alcohols with estimated lower detection limits of <5 ppm. Thus, the LUSH-derived QCM sensors exhibited potential to detect alcohols at low ppm concentrations. Copyright © 2011. Published by Elsevier B.V.

Pharmacokinetics of Chiral Dendrimer-Triamine-Coordinated Gd-MRI Contrast Agents Evaluated by in Vivo MRI and Estimated by in Vitro QCM.

PubMed

Miyake, Yuka; Ishikawa, Syungo; Kimura, Yu; Son, Aoi; Imai, Hirohiko; Matsuda, Tetsuya; Yamada, Hisatsugu; Toshimitsu, Akio; Kondo, Teruyuki

2015-12-18

Recently, we developed novel chiral dendrimer-triamine-coordinated Gd-MRI contrast agents (Gd-MRI CAs), which showed longitudinal relaxivity (r₁) values about four times higher than that of clinically used Gd-DTPA (Magnevist(®), Bayer). In our continuing study of pharmacokinetic differences derived from both the chirality and generation of Gd-MRI CAs, we found that the ability of chiral dendrimer Gd-MRI CAs to circulate within the body can be directly evaluated by in vitro MRI (7 T). In this study, the association constants (K(a)) of chiral dendrimer Gd-MRI CAs to bovine serum albumin (BSA), measured and calculated with a quartz crystal microbalance (QCM) in vitro, were found to be an extremely easy means for evaluating the body-circulation ability of chiral dendrimer Gd-MRI CAs. The K(a) values of S-isomeric dendrimer Gd-MRI CAs were generally greater than those of R-isomeric dendrimer Gd-MRI CAs, which is consistent with the results of our previous MRI study in vivo.

UV-light-assisted functionalization for sensing of light molecules

NASA Astrophysics Data System (ADS)

Funari, Riccardo; Della Ventura, Bartolomeo; Ambrosio, Antonio; Lettieri, Stefano; Maddalena, Pasqualino; Altucci, Carlo; Velotta, Raffaele

2013-05-01

An antibody immobilization technique based on the formation of thiol groups after UV irradiation of the proteins is shown to be able to orient upside antibodies on a gold electrode of a Quartz Crystal Microbalance (QCM). This greatly affects the aptitude of antibodies in recognizing small antigens thereby increasing the sensitivity of the QCM. The capability of such a procedure to orient antibodies is confirmed by the Atomic Force Microscopy (AFM) of the surface that shows different statistical distributions for the height of the detected peaks, whether the irradiation is performed or not. In particular, the distributions are Gaussian with a standard deviation smaller when irradiated antibodies are used compared to that obtained with no treated antibodies. The standard deviation reduction is explained in terms of higher order induced on the host surface resulting from the trend of irradiated antibodies to be anchored upside on the surface with their antigen binding sites free to catch recognized analytes. As a result the sensitivity of the realized biosensor is increased by even more than one order of magnitude.

Anorthite sputtering by H + and Ar q+ (q = 1-9) at solar wind velocities

DOE PAGES

Hijazi, Hussein Dib; Bannister, Mark E.; Meyer, III, Harry M.; ...

2014-10-16

Here, we report sputtering measurements of anorthite-like material, taken to be representative of soils found in the lunar highlands, impacted by singly and multicharged ions representative of the solar wind. The ions investigated include protons, as well as singly and multicharged Ar ions (as proxies for the nonreactive heavy solar wind constituents), in the charge state range +1 to +9, at fixed solar wind-relevant impact velocities of 165 and 310 km/s (0.25 keV/amu and 0.5 keV/amu). A quartz microbalance approach (QCM) for determination of total sputtering yields was used. The goal of the measurements was to determine the sputtering contributionmore » of the heavy, multicharged minority solar wind constituents in comparison to that due to the dominant H + fraction. The QCM results show a yield increase of a factor of about 80 for Ar + versus H + sputtering and an enhancement by a factor of 1.67 between Ar 9+ and Ar +, which is a clear indication of a potential sputtering effect.« less

Label-free, real-time interaction and adsorption analysis 1: surface plasmon resonance.

PubMed

Fee, Conan J

2013-01-01

A key requirement for the development of proteins for use in nanotechnology is an understanding of how individual proteins bind to other molecules as they assemble into larger structures. The introduction of labels to enable the detection of biomolecules brings the inherent risk that the labels themselves will influence the nature of biomolecular interactions. Thus, there is a need for label-free interaction and adsorption analysis. In this and the following chapter, two biosensor techniques are reviewed: surface plasmon resonance (SPR) and the quartz crystal microbalance (QCM). Both allow real-time analysis of biomolecular interactions and both are label-free. The first of these, SPR, is an optical technique that is highly sensitive to the changes in refractive index that occur with protein (or other molecule) accumulation near an illuminated gold surface. Unlike QCM ( Chapter 18 ) SPR is not affected by the water that may be associated with the adsorbed layer nor by conformational changes in the adsorbed species. SPR thus provides unique information about the interaction of a protein with its binding partners.

Pharmacokinetics of Chiral Dendrimer-Triamine-Coordinated Gd-MRI Contrast Agents Evaluated by in Vivo MRI and Estimated by in Vitro QCM

PubMed Central

Miyake, Yuka; Ishikawa, Syungo; Kimura, Yu; Son, Aoi; Imai, Hirohiko; Matsuda, Tetsuya; Yamada, Hisatsugu; Toshimitsu, Akio; Kondo, Teruyuki

2015-01-01

Recently, we developed novel chiral dendrimer-triamine-coordinated Gd-MRI contrast agents (Gd-MRI CAs), which showed longitudinal relaxivity (r1) values about four times higher than that of clinically used Gd-DTPA (Magnevist®, Bayer). In our continuing study of pharmacokinetic differences derived from both the chirality and generation of Gd-MRI CAs, we found that the ability of chiral dendrimer Gd-MRI CAs to circulate within the body can be directly evaluated by in vitro MRI (7 T). In this study, the association constants (Ka) of chiral dendrimer Gd-MRI CAs to bovine serum albumin (BSA), measured and calculated with a quartz crystal microbalance (QCM) in vitro, were found to be an extremely easy means for evaluating the body-circulation ability of chiral dendrimer Gd-MRI CAs. The Ka values of S-isomeric dendrimer Gd-MRI CAs were generally greater than those of R-isomeric dendrimer Gd-MRI CAs, which is consistent with the results of our previous MRI study in vivo. PMID:26694418

Influence of loading QCMs with electrochemically-deposited ZnO on their NO2-sensing properties

NASA Astrophysics Data System (ADS)

Georgieva, B.; Nichev, H.; Petrov, M.; Koutzarova, T.; Georgieva, V.; Dimova-Malinovska, D.

2018-03-01

This paper reports on ZnO layers’ sensitivity to NO2 exposure. ZnO layers were grown by electrochemical deposition on the surface of quartz crystal microbalances (QCMs) with Au electrodes; the sensitivity was estimated by the frequency-time characteristics (FTCs) of the QCM, namely, its resonance-frequency-shift response. The sorption process was investigated in NO2 test gas. The behavior was studied of three different sensors with ZnO layers deposited for different times – 30, 35 and 60 min. The change in the frequency, ΔF, of the QCM as a function of the loaded mass of NO2 was detected in different NO2 concentrations in the range of 250 – 5000 ppm and the value of the sorbed mass was calculated, together with the rate of the NO2 sorption and desorption. As the time of ZnO layers deposition was increased, the sorbed NO2 mass increased for all concentrations used in the experiment. This can be explained by changes in the ZnO layers’ structure with the time of deposition.

Ionic liquids: differential scanning calorimetry as a new indirect method for determination of vaporization enthalpies.

PubMed

Verevkin, Sergey P; Emel'yanenko, Vladimir N; Zaitsau, Dzmitry H; Ralys, Ricardas V; Schick, Christoph

2012-04-12

Differential scanning calorimetry (DSC) has been used to measure enthalpies of synthesis reactions of the 1-alkyl-3-methylimidazolium bromide [C(n)mim][Br] ionic liquids from 1-methylimidazole and n-alkyl bromides (with n = 4, 5, 6, 7, and 8). The optimal experimental conditions have been elaborated. Enthalpies of formation of these ionic liquids in the liquid state have been determined using the DSC results according to the Hess Law. The ideal-gas enthalpies of formation of [C(n)mim][Br] were calculated using the methods of quantum chemistry. They were used together with the DSC results to derive indirectly the enthalpies of vaporization of the ionic liquids under study. In order to validate the indirect determination, the experimental vaporization enthalpy of [C(4)mim][Br] was measured by using a quartz crystal microbalance (QCM). The combination of reaction enthalpy measurements by DSC with modern high-level first-principles calculations opens valuable indirect thermochemical options to obtain values of vaporization enthalpies of ionic liquids.

Assessing the potential of quartz crystal microbalance to estimate water vapor transfer in micrometric size cellulose particles.

PubMed

Thoury-Monbrun, Valentin; Gaucel, Sébastien; Rouessac, Vincent; Guillard, Valérie; Angellier-Coussy, Hélène

2018-06-15

This study aims at assessing the use of a quartz crystal microbalance (QCM) coupled with an adsorption system to measure water vapor transfer properties in micrometric size cellulose particles. This apparatus allows measuring successfully water vapor sorption kinetics at successive relative humidity (RH) steps on a dispersion of individual micrometric size cellulose particles (1 μg) with a total acquisition duration of the order of one hour. Apparent diffusivity and water uptake at equilibrium were estimated at each step of RH by considering two different particle geometries in mass transfer modeling, i.e. sphere or finite cylinder, based on the results obtained from image analysis. Water vapor diffusivity values varied from 2.4 × 10 -14  m 2  s -1 to 4.2 × 10 -12  m 2  s -1 over the tested RH range (0-80%) whatever the model used. A finite cylinder or spherical geometry could be used equally for diffusivity identification for a particle size aspect ratio lower than 2. Copyright © 2018 Elsevier Ltd. All rights reserved.

NCO-sP(EO-stat-PO) coatings on gold sensors--a QCM study of hemocompatibility.

PubMed

Sinn, Stefan; Eichler, Mirjam; Müller, Lothar; Bünger, Daniel; Groll, Jürgen; Ziemer, Gerhard; Rupp, Frank; Northoff, Hinnak; Geis-Gerstorfer, Jürgen; Gehring, Frank K; Wendel, Hans P

2011-01-01

The reliability of implantable blood sensors is often hampered by unspecific adsorption of plasma proteins and blood cells. This not only leads to a loss of sensor signal over time, but can also result in undesired host vs. graft reactions. Within this study we evaluated the hemocompatibility of isocyanate conjugated star shaped polytheylene oxide-polypropylene oxide co-polymers NCO-sP(EO-stat-PO) when applied to gold surfaces as an auspicious coating material for gold sputtered blood contacting sensors. Quartz crystal microbalance (QCM) sensors were coated with ultrathin NCO-sP(EO-stat-PO) films and compared with uncoated gold sensors. Protein resistance was assessed by QCM measurements with fibrinogen solution and platelet poor plasma (PPP), followed by quantification of fibrinogen adsorption. Hemocompatibility was tested by incubation with human platelet rich plasma (PRP). Thrombin antithrombin-III complex (TAT), β-thromboglobulin (β-TG) and platelet factor 4 (PF4) were used as coagulation activation markers. Furthermore, scanning electron microscopy (SEM) was used to visualize platelet adhesion to the sensor surfaces. Compared to uncoated gold sensors, NCO-sP(EO-stat-PO) coated sensors revealed significant better resistance against protein adsorption, lower TAT generation and a lower amount of adherent platelets. Moreover, coating with ultrathin NCO-sP(EO-stat-PO) films creates a cell resistant hemocompatible surface on gold that increases the chance of prolonged sensor functionality and can easily be modified with specific receptor molecules.

NCO-sP(EO-stat-PO) Coatings on Gold Sensors—a QCM Study of Hemocompatibility

PubMed Central

Sinn, Stefan; Eichler, Mirjam; Müller, Lothar; Bünger, Daniel; Groll, Jürgen; Ziemer, Gerhard; Rupp, Frank; Northoff, Hinnak; Geis-Gerstorfer, Jürgen; Gehring, Frank K.; Wendel, Hans P.

2011-01-01

The reliability of implantable blood sensors is often hampered by unspecific adsorption of plasma proteins and blood cells. This not only leads to a loss of sensor signal over time, but can also result in undesired host vs. graft reactions. Within this study we evaluated the hemocompatibility of isocyanate conjugated star shaped polytheylene oxide—polypropylene oxide co-polymers NCO-sP(EO-stat-PO) when applied to gold surfaces as an auspicious coating material for gold sputtered blood contacting sensors. Quartz crystal microbalance (QCM) sensors were coated with ultrathin NCO-sP(EO-stat-PO) films and compared with uncoated gold sensors. Protein resistance was assessed by QCM measurements with fibrinogen solution and platelet poor plasma (PPP), followed by quantification of fibrinogen adsorption. Hemocompatibility was tested by incubation with human platelet rich plasma (PRP). Thrombin antithrombin-III complex (TAT), β-thromboglobulin (β-TG) and platelet factor 4 (PF4) were used as coagulation activation markers. Furthermore, scanning electron microscopy (SEM) was used to visualize platelet adhesion to the sensor surfaces. Compared to uncoated gold sensors, NCO-sP(EO-stat-PO) coated sensors revealed significant better resistance against protein adsorption, lower TAT generation and a lower amount of adherent platelets. Moreover, coating with ultrathin NCO-sP(EO-stat-PO) films creates a cell resistant hemocompatible surface on gold that increases the chance of prolonged sensor functionality and can easily be modified with specific receptor molecules. PMID:22163899

The effects of surface aging on nanoparticle fate and transport in natural and engineered porous media

NASA Astrophysics Data System (ADS)

Mittelman, Anjuliee M.

Nanomaterials will be subjected to various surface transformations in the environment and within water and wastewater treatment systems. A comprehensive understanding of the fate and transport behavior of "aged" nanomaterials in both natural and engineered porous media is required in order to accurately quantify ecological and human health risks. This research sought to (1) evaluate the impact of ultraviolet (UV) light aging on nanoparticle transport in water-saturated porous media; and (2) assess the effects of influent water quality on silver nanoparticle retention and dissolution in ceramic water filters. Additionally, the value of quartz crystal microbalance (QCM-D) data in nanoparticle fate and transport studies was evaluated by comparing deposition behavior in complementary QCM-D and sand columns experiments. Silver (nAg) and iron oxide nanoparticles exposed to UV light were up to 50% more strongly retained in porous media compared with freshly prepared suspensions due to less negative surface charge and larger aggregate sizes. UV-aged nAg were more prone to dissolution in sand columns, resulting in effluent Ag+ concentrations as high as 1.2 mg/L. In ceramic water filters, dissolution and cation exchange processes controlled silver release into treated water. The use of acidic, high salinity, or high hardness water accelerated oxidative dissolution of the silver coating and resulted in effluent silver concentrations 5-10 times above international drinking water guidelines. Results support the recommendation for a regular filter replacement or silver re-application schedule to ensure ongoing efficacy. Taken in concert, these research findings suggest that oxidative aging of nanomaterial surfaces (either through exposure to UV light or aggressive water chemistries) will alter the fate of nanomaterials in the environment and may decrease the effective lifetime of devices which utilize nanotechnology. Corresponding QCM-D and column experiments revealed that nanoparticles were generally more mobile in QCM-D due to reduced diffusive transport of larger aggregates to the sensor surface and high primary energy barriers to deposition. While QCM-D may be used to provide qualitative data, direct comparisons of deposition rates in QCM-D with attachment rates obtained from column experiments may prove difficult due to differences in flow geometry and surface characteristics between the two systems.

DNA Adsorption to and Elution from Silica Surfaces: Influence of Amino Acid Buffers

PubMed Central

Vandeventer, Peter E.; Mejia, Jorge; Nadim, Ali; Johal, Malkiat S.; Niemz, Angelika

2014-01-01

Solid phase extraction and purification of DNA from complex samples typically requires chaotropic salts that can inhibit downstream polymerase amplification if carried into the elution buffer. Amino acid buffers may serve as a more compatible alternative for modulating the interaction between DNA and silica surfaces. We characterized DNA binding to silica surfaces, facilitated by representative amino acid buffers, and the subsequent elution of DNA from the silica surfaces. Through bulk depletion experiments, we found that more DNA adsorbs to silica particles out of positively compared to negatively charged amino acid buffers. Additionally, the type of the silica surface greatly influences the amount of DNA adsorbed, and the final elution yield. Quartz crystal microbalance experiments with dissipation monitoring (QCM-D) revealed multiphasic DNA adsorption out of stronger adsorbing conditions such as arginine, glycine, and glutamine, with DNA more rigidly bound during the early stages of the adsorption process. The DNA film adsorbed out of glutamate was more flexible and uniform throughout the adsorption process. QCM-D characterization of DNA elution from the silica surface indicates an uptake in water mass during the initial stage of DNA elution for the stronger adsorbing conditions, which suggests that for these conditions the DNA film is partly dehydrated during the prior adsorption process. Overall, several positively charged and polar neutral amino acid buffers show promise as an alternative to methods based on chaotropic salts for solid phase DNA extraction. PMID:23931415

Design of a potentially prebiotic and responsive encapsulation material for probiotic bacteria based on chitosan and sulfated β-glucan.

PubMed

Yucel Falco, Cigdem; Sotres, Javier; Rascón, Ana; Risbo, Jens; Cárdenas, Marité

2017-02-01

Chitosan and sulfated oat β-glucan are materials suitable to create a prebiotic coating for targeted delivery to gastrointestinal system, using the layer by layer technology. Quartz crystal microbalance with dissipation (QCM-D), spectroscopic ellipsometry (SE) and atomic force microscopy (AFM) were used to assess the multilayer formation capacity and characterize the resulting coatings in terms of morphology and material properties such as structure and rigidity. The coating of colloidal materials was proven, specifically on L. acidophilus bacteria as measured by changes in the bacterial suspension zeta potential. Viability of coated cells was shown using plate counting method. The coatings on solid surfaces were examined after exposure to mimics of gastrointestinal fluids and a commercially available β-glucanase. Successful build-up of multilayers was confirmed with QCM-D and SE. Zeta potential values proved the coating of cells. There was 2 log CFU/mL decrease after coating cells with four alternating layers of chitosan and sulfated β-glucan when compared to viability of uncoated cells. The coatings were partially degraded after exposure to simulated intestinal fluid and restructured as a result of β-glucanase treatment, mimicking enzymes present in the microflora of the human gut, but seemed to resist acidic gastric conditions. Therefore, coatings of chitosan and sulfated β-glucan can potentially be exploited as carriers for probiotics and delicate nutraceuticals. Copyright © 2016 Elsevier Inc. All rights reserved.

Examination of High Frequency MHz Rheology of Filled Polymer Composites and Photopolymers

NASA Astrophysics Data System (ADS)

Yeh, Chyi-Huey Joshua

The quartz crystal microbalance (QCM) is a versatile characterization tool capable of tracking changes in areal mass and high frequency MHz rheology of micron thick films. The QCM primarily consists of a single quartz disc with electrodes deposited on both sides of the disc. Due to the piezoelectric nature of quartz, introduction of an oscillating voltage near the resonance condition of the quartz disc produces a traveling shear wave that can be measured with electrical admittance analysis. This technique behaves like an acoustic reflectometer, where an induced mechanical shear wave propagates and reflects at the interfaces between material layers with differing acoustic impedances. Based on how the shear wave interacts with the interfaces, information on the material properties can be quantitatively modeled. In this dissertation, a quantitative approach of determining the magnitude and sources of error is presented, so that interpretation of viscoelastic information and areal mass changes can be performed with confidence. Specifically, the role of anharmonic coupling with harmonic modes are explored and simulated with COMSOL Multiphysics. Several case studies motivating and highlighting the utility of the QCM is presented. The fracture and thermal aging behavior of several nanofilled silicone elastomers are examined using traditional mechanical tests, such as pure shear geometry and dynamic mechanical analysis (DMA). Results can be qualitatively explained by the concept of dynamic mechanical heterogeneity, where a high mechanical contrast is desired for high fracture toughness. However, DMA results can be difficult to interpret (especially at shifted high frequencies) due to thermal rheological complexity, a characteristic commonly found in many polymer composites. This motivates the application of the QCM, where MHz viscoelastic behavior can be directly probed, providing insight on the dissipative behavior at local length scales. Investigation of polysilicate nanofillers on the high frequency viscoelastic behavior of polydimethylsiloxane (PDMS) melt is discussed. The amount of filler varied from pure PDMS to pure filler, highlighting the advantage of using an acoustic rheometer to measure properties of films exhibiting viscous to highly brittle behavior. An empirical mixing law is proposed in describing the changes in visceolasticity as a function of filler content, so that the critical filler content at the liquid to solid transition can be estimated. The liquid to solid transition is qualitatively explained by percolation rigidity of the polysilicate nanofillers. The QCM is also extended as a photorheometer, capable of measuring in situ rheology of fast radical photopolymerizations. A model acrylate system is examined as a means to demonstrate the value of the QCM and to provide context for the examination of a more interesting thiol-ene photopolymer system. Due to insensitivity of thiol-ene chemical kinetics towards oxygen inhibition during curing, the impact of oxygen incorporation on the crosslinked viscoelastic network is investigated. In addition to studying thiol-ene reactions, photoinitiated copper catalyzed alkyne azide cycloaddition is also explored. The effects of plasticization on the curing kinetics and mechanical properties are presented. Altogether, this dissertation serves to contribute to the fundamental development of the QCM as a quantitative MHz rheometer. By thoroughly presenting a quantitative approach towards error analysis and providing successful QCM case studies, the barrier of entrance for using the QCM is substantially lowered. Future researchers will be able to efficiently conduct QCM experiments and analysis at a higher level of operation. Several ideas are also briefly proposed in which the QCM can provide valuable insights and contributions.

Surface Acoustic Wave Monitor for Deposition and Analysis of Ultra-Thin Films

NASA Technical Reports Server (NTRS)

Hines, Jacqueline H. (Inventor)

2015-01-01

A surface acoustic wave (SAW) based thin film deposition monitor device and system for monitoring the deposition of ultra-thin films and nanomaterials and the analysis thereof is characterized by acoustic wave device embodiments that include differential delay line device designs, and which can optionally have integral reference devices fabricated on the same substrate as the sensing device, or on a separate device in thermal contact with the film monitoring/analysis device, in order to provide inherently temperature compensated measurements. These deposition monitor and analysis devices can include inherent temperature compensation, higher sensitivity to surface interactions than quartz crystal microbalance (QCM) devices, and the ability to operate at extreme temperatures.

Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mane, Anil U.; Letourneau, Steven; Mandia, David J.

2018-01-01

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFxmore » residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS« less

Real-time and label-free analysis of binding thermodynamics of carbohydrate-protein interactions on unfixed cancer cell surfaces using a QCM biosensor

PubMed Central

Li, Xueming; Song, Siyu; Shuai, Qi; Pei, Yihan; Aastrup, Teodor; Pei, Yuxin; Pei, Zhichao

2015-01-01

A novel approach to the study of binding thermodynamics and kinetics of carbohydrate-protein interactions on unfixed cancer cell surfaces using a quartz crystal microbalance (QCM) biosensor was developed, in which binding events take place at the cell surface, more closely mimicking a biologically relevant environment. In this study, colon adenocarcinoma cells (KM-12) and ovary adenocarcinoma cells (SKOV-3) grew on the optimized polystyrene-coated biosensor chip without fixation. The association and dissociation between the cell surface carbohydrates and a range of lectins, including WGA, Con A, UEA-I, GS-II, PNA and SBA, were monitored in real time and without label for evaluation of cell surface glycosylation. Furthermore, the thermodynamic and kinetic parameters of the interaction between lectins and cell surface glycan were studied, providing detailed information about the interactions, such as the association rate constant, dissociation rate constant, affinity constant, as well as the changes of entropy, enthalpy and Gibbs free energy. This application provides an insight into the cell surface glycosylation and the complex molecular recognition on the intact cell surface, which may have impacts on disease diagnosis and drug discovery. PMID:26369583

Electrochemical MIP-Sensors for Drugs.

PubMed

Yarman, Aysu; Kurbanoglu, Sevinc; Jetzschmann, Katharina J; Ozkan, Sibel A; Wollenberger, Ulla; Scheller, Frieder

2017-10-05

In order to replace bio-macromolecules by stable synthetic materials in separation techniques and bioanalysis biomimetic receptors and catalysts have been developed: Functional monomers are polymerized together with the target analyte and after template removal cavities are formed in the "molecularly imprinted polymer" (MIP) which resemble the active sites of antibodies and enzymes. Staring almost 80 years ago, around 1,100 papers on MIPs were published in 2016. Electropolymerization allows to deposit MIPs directly on voltammetric electrodes or chips for quartz crystal microbalance (QCM) and surface plasmon resonance (SPR). For the readout of MIPs for drugs amperometry, differential pulse voltammetry (DPV) and impedance spectroscopy (EIS) offer higher sensitivity as compared with QCM or SPR. Application of simple electrochemical devices allows both the reproducible preparation of MIP sensors, but also the sensitive signal generation. Electrochemical MIP-sensors for the whole arsenal of drugs, e.g. the most frequently used analgesics, antibiotics and anticancer drugs have been presented in literature and tested under laboratory conditions. These biomimetic sensors typically have measuring ranges covering the lower nano- up to millimolar concentration range and they are stable under extreme pH and in organic solvents like non-aqueous extracts. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

High performance nano-Ni/Graphite electrode for electro-oxidation in direct alkaline ethanol fuel cells

NASA Astrophysics Data System (ADS)

Soliman, Ahmed B.; Abdel-Samad, Hesham S.; Abdel Rehim, Sayed S.; Ahmed, Mohamed A.; Hassan, Hamdy H.

2016-09-01

Ni/Graphite electrocatalysts (Ni/G) are successfully prepared through electrodeposition of Ni from acidic (pH = 0.8) and feebly acidic (pH = 5.5) aqueous Ni (II) baths. The efficiencies of such electrodes are investigated as anodes for direct alkaline ethanol fuel cells through their ethanol electrooxidation cyclic voltammetric (CV) response in alkaline medium. A direct proportionality between the amount of the electrodeposited Ni and its CV response is found. The amounts of the deposited Ni from the two baths are recorded using the Electrochemical Quartz Crystal Microbalance (eQCM). The Ni/G electrodes prepared from the feebly acidic bath show a higher electrocatalytic response than those prepared from the acidic bath. Surface morphology of the Ni particles electrodeposited from feebly acidic bath appears in a nano-scale dimension. Various electrochemical experiments are conducted to confirm that the Ni/G ethanol electrooxidation CV response greatly depends on the pH rather than nickel ion concentration of the deposition bath. The eQCM technique is used to detect the crystalline phases of nickel as α-Ni(OH)2/γ-NiOOH and β-Ni(OH)2/β-NiOOH and their in-situ inter-transformations during the potentiodynamic polarization.

Comparison of multilayer formation between different cellulose nanofibrils and cationic polymers.

PubMed

Eronen, Paula; Laine, Janne; Ruokolainen, Janne; Osterberg, Monika

2012-05-01

The multilayer formation between polyelectrolytes of opposite charge offers possibility for creating new tailored materials. Exchanging one or both components for charged nanofibrillated cellulose (NFC) further increases the variety of achievable properties. We explored this by introducing unmodified, low charged NFC and high charged TEMPO-oxidized NFC. Systematic evaluation of the effect of both NFC charge and properties of cationic polyelectrolytes on the structure of the multilayers was performed. As the cationic component cationic NFC was compared with two different cationic polyelectrolytes, poly(dimethyldiallylammoniumchloride) and cationic starch. Quartz crystal microbalance with dissipation (QCM-D) was used to monitor the multilayer formation and AFM colloidal probe microscopy (CPM) was further applied to probe surface interactions in order to gain information about fundamental interactions and layer properties. Generally, the results verified the characteristic multilayer formation between NFC of different charge and how the properties of formed multilayers can be tuned. However, the strong nonelectrostatic affinity between cellulosic fibrils was observed. CPM measurements revealed monotonically repulsive forces, which were in good correspondence with the QCM-D observations. Significant increase in adhesive forces was detected between the swollen high charged NFC. Copyright © 2011 Elsevier Inc. All rights reserved.

Using Neutron Reflectometry to Discern the Structure of Fibrinogen Adsorption at the Stainless Steel/Aqueous Interface.

PubMed

Wood, Mary H; Browning, Kathryn L; Barker, Robert D; Clarke, Stuart M

2016-06-23

Neutron reflectometry has been successfully used to study adsorption on a stainless steel surface by means of depositing a thin steel film on silicon. The film was characterized using XPS (X-ray photoelectron spectroscopy), TOF-SIMS (time-of-flight secondary ion mass spectrometry), and GIXRD (grazing incidence X-ray diffraction), demonstrating the retention both of the austenitic phase and of the required composition for 316L stainless steel. The adsorption of fibrinogen from a physiologically-relevant solution onto the steel surface was studied using neutron reflectometry and QCM (quartz crystal microbalance) and compared to that on a deposited chromium oxide surface. It was found that the protein forms an irreversibly bound layer at low concentrations, with maximum protein concentration a distance of around 20 Å from the surface. Evidence for a further diffuse reversibly-bound layer forming at higher concentrations was also observed. Both the structure of the layer revealed by the neutron reflectometry data and the high water retention predicted by the QCM data suggest that there is a significant extent of protein unfolding upon adsorption. A lower extent of adsorption was seen on the chromium surfaces, although the adsorbed layer structures were similar, suggesting comparable adsorption mechanisms.

Tribological Properties of Nanodiamonds in Aqueous Suspensions: Effect of the Surface Charge

NASA Astrophysics Data System (ADS)

Krim, J.; Liu, Zijian; Leininger, D. A.; Kooviland, A.; Smirnov, A. I.; Shendarova, O.; Brenner, D. W.

The presence of granular nanoparticulates, be they wear particles created naturally by frictional rubbing at a geological fault line or products introduced as lubricant additives, can dramatically alter friction at solid-liquid interfaces. Given the complexity of such systems, understanding system properties at a fundamental level is particularly challenging. The Quartz Crystal Microbalance (QCM) is an ideal tool for studies of material-liquid-nanoparticulate interfaces. We have employed it here to study the uptake and nanotribological properties of positively and negatively charged 5-15 nm diameter nanodiamonds dispersed in water[1] in the both the presence and absence of a macroscopic contact with the QCM electrode. The nanodiamonds were found to impact tribological performance at both nanometer and macroscopic scales. The tribological effects were highly sensitive to the sign of the charge: negatively (positively) charged particles were more weakly (strongly) bound and reduced (increased) frictional drag at the solid-liquid interface. For the macroscopic contacts, negatively charged nanodiamonds appeared to be displaced from the contact, while the positively charged ones were not. Overall, the negatively charged nanodiamonds were more stable in an aqueous dispersion for extended time periods. Work supported by NSF and DOE.

Viscoelasticity of thin biomolecular films: a case study on nucleoporin phenylalanine-glycine repeats grafted to a histidine-tag capturing QCM-D sensor.

PubMed

Eisele, Nico B; Andersson, Fredrik I; Frey, Steffen; Richter, Ralf P

2012-08-13

Immobilization of proteins onto surfaces is useful for the controlled generation of biomolecular assemblies that can be readily characterized with in situ label-free surface-sensitive techniques. Here we analyze the performance of a quartz crystal microbalance with dissipation monitoring (QCM-D) sensor surface that enables the selective and oriented immobilization of histidine-tagged molecules for morphological and interaction studies. More specifically, we characterize monolayers of natively unfolded nucleoporin domains that are rich in phenylalanine-glycine repeats (FGRDs). An FGRD meshwork is thought to be responsible for the selectivity of macromolecular transport across the nuclear pore complex between the cytosol and the nucleus of living cells. We demonstrate that nucleoporin FGRD films can be formed on His-tag Capturing Sensors with properties comparable to a previously reported immobilization platform based on supported lipid bilayers (SLB). Approaches to extract the film thickness and viscoelastic properties in a time-resolved manner from the QCM-D response are described, with particular emphasis on the practical implementation of viscoelastic modeling and a detailed analysis of the quality and reliability of the fit. By comparing the results with theoretical predictions for the viscoelastic properties of polymer solutions and gels, and experimental data from an atomic force microscopy indentation assay, we demonstrate that detailed analysis can provide novel insight into the morphology and dynamics of FG repeat domain films. The immobilization approach is simple and versatile, and can be easily extended to other His-tagged biomolecules. The data analysis procedure should be useful for the characterization of other ultrathin biomolecular and polymer films.

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches.

PubMed

Liu, Xuyang; Chen, Gexin; Su, Chunming

2012-06-19

The deposition behavior of cerium dioxide (CeO(2)) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.

A Novel Cell-Based Hybrid Acoustic Wave Biosensor with Impedimetric Sensing Capabilities

PubMed Central

Liu, Fei; Li, Fang; Nordin, Anis Nurashikin; Voiculescu, Ioana

2013-01-01

A novel multiparametric biosensor system based on living cells will be presented. The biosensor system includes two biosensing techniques on a single device: resonant frequency measurements and electric cell-substrate impedance sensing (ECIS). The multiparametric sensor system is based on the innovative use of the upper electrode of a quartz crystal microbalance (QCM) resonator as working electrode for the ECIS technique. The QCM acoustic wave sensor consists of a thin AT-cut quartz substrate with two gold electrodes on opposite sides. For integration of the QCM with the ECIS technique a semicircular counter electrode was fabricated near the upper electrode on the same side of the quartz crystal. Bovine aortic endothelial live cells (BAECs) were successfully cultured on this hybrid biosensor. Finite element modeling of the bulk acoustic wave resonator using COMSOL simulations was performed. Simultaneous gravimetric and impedimetric measurements performed over a period of time on the same cell culture were conducted to validate the device's sensitivity. The time necessary for the BAEC cells to attach and form a compact monolayer on the biosensor was 35∼45 minutes for 1.5 × 104 cells/cm2 BAECs; 60 minutes for 2.0 × 104 cells/cm2 BAECs; 70 minutes for 3.0 × 104 cells/cm2 BAECs; and 100 minutes for 5.0 × 104 cells/cm2 BAECs. It was demonstrated that this time is the same for both gravimetric and impedimetric measurements. This hybrid biosensor will be employed in the future for water toxicity detection. PMID:23459387

Microstructure and conductivity of in-situ polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) crystals

NASA Astrophysics Data System (ADS)

Liu, Jinglin; Ouyang, Liangqi; Wu, Jinghang; Kuo, Chin-Chen; Wei, Bin; Martin, David

2013-03-01

Conjugated polymers are widely used in organic solar cells, biomedical devices, and chemical sensors. Both chemical and electrochemical methods have been developed for preparing conducting polymers, but the extent of crystalline order is usually modest. Here we synthesized highly-ordered brominated (3,4-ethylenedioxythiophene) (EDOT-Br) monomer crystals via electrochemical methods. The kinetics of the synthesis was studied with a Quartz Crystal Microbalance (QCM) and Cyclic Voltammetry (CV). The chemical structure of the EDOT-Br monomer has been confirmed by Nuclear Magnetic Resonance (NMR), Ultraviolet-Visible Spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), and Mass Spectrometry (MS). The EDOT-Br monomer crystals can be in-situ polymerized into highly ordered PEDOT conjugated polymer crystals by annealing at temperatures below the EDOT-Br melting point. The crystalline structure was studied by optical microscopy, electron microscopy and X-Ray analysis. The conductivity and electrochemical properties of both the EDOT-Br monomer and corresponding PEDOT polymer crystals were examined with electrochemical impedance spectroscopy (EIS) and CV. This work was supported by NSF, DMR- 1103027.

Detection of parathion pesticide by quartz crystal microbalance functionalized with UV-activated antibodies.

PubMed

Funari, Riccardo; Della Ventura, Bartolomeo; Schiavo, Luigi; Esposito, Rosario; Altucci, Carlo; Velotta, Raffaele

2013-07-02

Photonic immobilization technique (PIT) has been used to develop an immunosensor for the detection of parathion. An antibody solution has been activated by breaking the disulfide bridge in the triad Trp/Cys-Cys through absorption of ultrashort UV laser pulses. The free thiol groups so produced interact with gold lamina making the antibody oriented upside, that is, with its variable parts exposed to the environment, thereby greatly increasing the detection efficiency. PIT has been applied to anchor polyclonal antiparathion antibodies to the gold electrode of a Quartz Crystal Microbalance (QCM) giving rise to very high detection sensitivity once the parathion is made heavier by complexion with BSA (bovine serum albumin), this latter step only required by the mass based transducer used in this case. The comparison of the sensor response with irradiated antibodies against different analytes shows that the high degree of antibody specificity is not affected by PIT nor is it by the complexion of parathion with BSA. These results pave the way to important applications in biosensing, since the widespread occurrence of the Trp/Cys-Cys residues triads in proteins make our procedure very general and effective to detect light analytes.

Piezoelectric detection of bilirubin based on bilirubin-imprinted titania film electrode.

PubMed

Yang, Zhengpeng; Yan, Jinlong; Zhang, Chunjing

2012-02-01

A novel quartz crystal microbalance (QCM) sensor with a high selectivity and sensitivity has been developed for bilirubin determination, based on the modification of bilirubin-imprinted titania film onto a quartz crystal by molecular imprinting and surface sol-gel techniques. The performance of the developed bilirubin biosensor was evaluated and the results indicated that a sensitive bilirubin biosensor could be fabricated. The obtained bilirubin biosensor presents high-selectivity monitoring of bilirubin, better reproducibility, shorter response time (30 min), wider linear range (0.1-50 μM), and lower detection limit (0.05 μM). The analytical application of the bilirubin biosensor confirms the feasibility of bilirubin determination in serum sample. Copyright © 2011 Elsevier Inc. All rights reserved.

Liquid- and Gas-Phase Diffusion of Ferrocene in Thin Films of Metal-Organic Frameworks

PubMed Central

Zhou, Wencai; Wöll, Christof; Heinke, Lars

2015-01-01

The mass transfer of the guest molecules in nanoporous host materials, in particular in metal-organic frameworks (MOFs), is among the crucial features of their applications. By using thin surface-mounted MOF films in combination with a quartz crystal microbalance (QCM), the diffusion of ferrocene vapor and of ethanolic and hexanic ferrocene solution in HKUST-1 was investigated. For the first time, liquid- and gas-phase diffusion in MOFs was compared directly in the identical sample. The diffusion coefficients are in the same order of magnitude (~10−16 m2·s−1), whereas the diffusion coefficient of ferrocene in the empty framework is roughly 3-times smaller than in the MOF which is filled with ethanol or n-hexane.

QCM-D and ToF-SIMS Investigation to Deconvolute the Relationship between Lipid Adsorption and Orientation on Lipase Activity.

PubMed

Joyce, Paul; Kempson, Ivan; Prestidge, Clive A

2015-09-22

Quartz crystal microbalance with dissipation (QCM-D) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used to provide insights into the relationship between lipid adsorption kinetics and molecular behavior in porous silica particles of varying hydrophobicities on lipase activity. Lipase (an interfacial enzyme that cleaves ester bonds to break down lipids to fatty acids and monoglycerides) activity was controlled by loading triglycerides at different surface coverages in hydrophilic and hydrophobic porous silica particles. The rate of lipid adsorption increased 2-fold for the hydrophobic surface compared to the hydrophilic surface. However, for submonolayer lipid coverage, the hydrophilic surface enhanced lipase activity 4-fold, whereas the hydrophobic surface inhibited lipase activity 16-fold, compared to lipid droplets in water. A difference in lipid orientation for low surface coverage, evidenced by ToF-SIMS, indicated that lipid adsorbs to hydrophilic silica in a conformation promoting hydrolysis. Multilayer coverage on hydrophobic and hydrophilic surfaces was indistinguishable with ToF-SIMS analysis. Increased lipid adsorption for both substrates facilitated digestion kinetics comparable to a conventional emulsion. Improved understanding of the interfacial adsorption and orientation of lipid and its digestibility in porous silica has implications in improving the uptake of pharmaceuticals and nutrients from lipid-based delivery systems.

Adsorption of hyaluronic acid on solid supports: role of pH and surface chemistry in thin film self-assembly.

PubMed

Choi, Jae-Hyeok; Kim, Seong-Oh; Linardy, Eric; Dreaden, Erik C; Zhdanov, Vladimir P; Hammond, Paula T; Cho, Nam-Joon

2015-06-15

Owing to its biocompatibility, resistance to biofouling, and desirable physicochemical and biological properties, hyaluronic acid (HA) has been widely used to modify the surface of various materials. The role of various physicochemical factors in HA adsorption remains, however, to be clarified. Herein, we employed quartz crystal microbalance with dissipation (QCM-D) in order to investigate HA adsorption at different pH conditions onto three substrates-silicon oxide, amine-terminated self-assembled monolayer (SAM) on gold, and carboxylic acid-terminated SAM on gold. The QCM-D experiments indicated specific pH conditions where either strong or weak HA adsorption occurs. The morphology of the adsorbed HA layers was investigated by atomic force microscopy (AFM), and we identified that strong HA adsorption produced a complete, homogenous and smooth HA layer, while weak HA adsorption resulted in rough and inhomogeneous HA layers. The observed specifics of the kinetics of HA adsorption, including a short initial linear phase and subsequent long non-linear phase, were described by using a mean-field kinetic model taking HA diffusion limitations and reconfiguration in the adsorbed state into account. The findings extend the physicochemical background of design strategies for improving the use of passive HA adsorption for surface modification applications. Copyright © 2015 Elsevier Inc. All rights reserved.

Curating viscoelastic properties of icosahedral viruses, virus-based nanomaterials, and protein cages.

PubMed

Kant, Ravi; Rayaprolu, Vamseedhar; McDonald, Kaitlyn; Bothner, Brian

2018-06-01

The beauty, symmetry, and functionality of icosahedral virus capsids has attracted the attention of biologists, physicists, and mathematicians ever since they were first observed. Viruses and protein cages assemble into functional architectures in a range of sizes, shapes, and symmetries. To fulfill their biological roles, these structures must self-assemble, resist stress, and are often dynamic. The increasing use of icosahedral capsids and cages in materials science has driven the need to quantify them in terms of structural properties such as rigidity, stiffness, and viscoelasticity. In this study, we employed Quartz Crystal Microbalance with Dissipation technology (QCM-D) to characterize and compare the mechanical rigidity of different protein cages and viruses. We attempted to unveil the relationships between rigidity, radius, shell thickness, and triangulation number. We show that the rigidity and triangulation numbers are inversely related to each other and the comparison of rigidity and radius also follows the same trend. Our results suggest that subunit orientation, protein-protein interactions, and protein-nucleic acid interactions are important for the resistance to deformation of these complexes, however, the relationships are complex and need to be explored further. The QCM-D based viscoelastic measurements presented here help us elucidate these relationships and show the future prospect of this technique in the field of physical virology and nano-biotechnology.

Surface modification of poly (styrene-b-(ethylene-co-butylene)-b-styrene) elastomer and its plasma protein adsorption by QCM-D

NASA Astrophysics Data System (ADS)

Li, Rui; Jin, Jing; Sun, Yingchun

2014-05-01

Protein adsorption is a dynamic process and plays a major role in determining the hemocompatibility of biomaterials. We have obtained different poly (ethylene glycol) (PEG) graft concentrations of SEBS-g-PEG and the surface chemical compositions are confirmed by X-ray photoelectron spectroscopy (XPS). Graft concentration is defined by peak-area ratio of [C--O]/[C] on modified SEBS surface. With increasing graft concentration, water contact angles of the modified SEBS have significantly decreased. The platelet adhesion and static protein adsorption demonstrate that the hemocompatibility of copolymers films are improved effectively and SEBS-g-PEG-2 with larger graft concentration has more superior anticoagulation than that of SEBS-g-PEG-1. Moreover, we have quantitatively investigated the adsorption process of bovine serum albumin (BSA) and fibrinogen (Fib) on the surfaces of pristine SEBS and modified SEBS using quartz crystal microbalance with dissipation (QCM-D) in real time. The results indicate that the inactivated BSA on the pristine SEBS can continuously induce the subsequent Fib adsorption. The hemocompatibility of SEBS-g-PEG-2 with the graft concentration of 0.207 has excellent anti-protein property and the bio-inert BSA layer on the film can resist the subsequent Fib adsorption.

Biogenic Manganese-Oxide Mineralization is Enhanced by an Oxidative Priming Mechanism for the Multi-Copper Oxidase, MnxEFG.

PubMed

Tao, Lizhi; Simonov, Alexandr N; Romano, Christine A; Butterfield, Cristina N; Fekete, Monika; Tebo, Bradley M; Bond, Alan M; Spiccia, Leone; Martin, Lisandra L; Casey, William H

2017-01-26

In a natural geochemical cycle, manganese-oxide minerals (MnO x ) are principally formed through a microbial process, where a putative multicopper oxidase MnxG plays an essential role. Recent success in isolating the approximately 230 kDa, enzymatically active MnxEFG protein complex, has advanced our understanding of biogenic MnO x mineralization. Here, the kinetics of MnO x formation catalyzed by MnxEFG are examined using a quartz crystal microbalance (QCM), and the first electrochemical characterization of the MnxEFG complex is reported using Fourier transformed alternating current voltammetry. The voltammetric studies undertaken using near-neutral solutions (pH 7.8) establish the apparent reversible potentials for the Type 2 Cu sites in MnxEFG immobilized on a carboxy-terminated monolayer to be in the range 0.36-0.40 V versus a normal hydrogen electrode. Oxidative priming of the MnxEFG protein complex substantially enhances the enzymatic activity, as found by in situ electrochemical QCM analysis. The biogeochemical significance of this enzyme is clear, although the role of an oxidative priming of catalytic activity might be either an evolutionary advantage or an ancient relic of primordial existence. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plume mass flow and optical damage distributions for an MMH/N2O4 RCS thruster. [exhaust plume contamination of spacecraft components

NASA Technical Reports Server (NTRS)

Spisz, E. W.; Bowman, R. L.; Jack, J. R.

1973-01-01

The data obtained from two recent experiments conducted in a continuing series of experiments at the Lewis Research Center into the contamination characteristics of a 5-pound thrust MMH/N2O4 engine are presented. The primary objectives of these experiments were to establish the angular distribution of condensible exhaust products within the plume and the corresponding optical damage angular distribution of transmitting optical elements attributable to this contaminant. The plume mass flow distribution was measured by five quartz crystal microbalances (QCM's) located at the engine axis evaluation. The fifth QCM was located above the engine and 15 deg behind the nozzle exit plane. The optical damage was determined by ex-situ transmittance measurements for the wavelength range from 0.2 to 0.6 microns on 2.54 cm diameter fused silica discs also located at engine centerline elevation. Both the mass deposition and optical damage angular distributions followed the expected trend of decreasing deposition and damage as the angle between sensor or sample and the nozzle axis increased. A simple plume gas flow equation predicted the deposition distribution reasonably well for angles of up to 55 degrees. The optical damage measurements also indicated significant effects at large angles.

Interaction of Human Plasma Proteins with Thin Gelatin-Based Hydrogel Films: A QCM-D and ToF-SIMS Study

PubMed Central

2015-01-01

In the fields of surgery and regenerative medicine, it is crucial to understand the interactions of proteins with the biomaterials used as implants. Protein adsorption directly influences cell-material interactions in vivo and, as a result, regulates, for example, cell adhesion on the surface of the implant. Therefore, the development of suitable analytical techniques together with well-defined model systems allowing for the detection, characterization, and quantification of protein adsorbates is essential. In this study, a protocol for the deposition of highly stable, thin gelatin-based films on various substrates has been developed. The hydrogel films were characterized morphologically and chemically. Due to the obtained low thickness of the hydrogel layer, this setup allowed for a quantitative study on the interaction of human proteins (albumin and fibrinogen) with the hydrogel by Quartz Crystal Microbalance with Dissipation Monitoring (QCM-D). This technique enables the determination of adsorbant mass and changes in the shear modulus of the hydrogel layer upon adsorption of human proteins. Furthermore, Secondary Ion Mass Spectrometry and principal component analysis was applied to monitor the changed composition of the topmost adsorbate layer. This approach opens interesting perspectives for a sensitive screening of viscoelastic biomaterials that could be used for regenerative medicine. PMID:24956040

Gold nanospikes based microsensor as a highly accurate mercury emission monitoring system

NASA Astrophysics Data System (ADS)

Sabri, Ylias M.; Ippolito, Samuel J.; Tardio, James; Bansal, Vipul; O'Mullane, Anthony P.; Bhargava, Suresh K.

2014-10-01

Anthropogenic elemental mercury (Hg0) emission is a serious worldwide environmental problem due to the extreme toxicity of the heavy metal to humans, plants and wildlife. Development of an accurate and cheap microsensor based online monitoring system which can be integrated as part of Hg0 removal and control processes in industry is still a major challenge. Here, we demonstrate that forming Au nanospike structures directly onto the electrodes of a quartz crystal microbalance (QCM) using a novel electrochemical route results in a self-regenerating, highly robust, stable, sensitive and selective Hg0 vapor sensor. The data from a 127 day continuous test performed in the presence of volatile organic compounds and high humidity levels, showed that the sensor with an electrodeposted sensitive layer had 260% higher response magnitude, 3.4 times lower detection limit (~22 μg/m3 or ~2.46 ppbv) and higher accuracy (98% Vs 35%) over a Au control based QCM (unmodified) when exposed to a Hg0 vapor concentration of 10.55 mg/m3 at 101°C. Statistical analysis of the long term data showed that the nano-engineered Hg0 sorption sites on the developed Au nanospikes sensitive layer play a critical role in the enhanced sensitivity and selectivity of the developed sensor towards Hg0 vapor.

Adsorption, aggregation, and desorption of proteins on smectite particles.

PubMed

Kolman, Krzysztof; Makowski, Marcin M; Golriz, Ali A; Kappl, Michael; Pigłowski, Jacek; Butt, Hans-Jürgen; Kiersnowski, Adam

2014-10-07

We report on adsorption of lysozyme (LYS), ovalbumin (OVA), or ovotransferrin (OVT) on particles of a synthetic smectite (synthetic layered aluminosilicate). In our approach we used atomic force microscopy (AFM) and quartz crystal microbalance (QCM) to study the protein-smectite systems in water solutions at pH ranging from 4 to 9. The AFM provided insights into the adhesion forces of protein molecules to the smectite particles, while the QCM measurements yielded information about the amounts of the adsorbed proteins, changes in their structure, and conditions of desorption. The binding of the proteins to the smectite surface was driven mainly by electrostatic interactions, and hence properties of the adsorbed layers were controlled by pH. At high pH values a change in orientation of the adsorbed LYS molecules and a collapse or desorption of OVA layer were observed. Lowering pH to the value ≤ 4 caused LYS to desorb and swelling the adsorbed OVA. The stability of OVT-smectite complexes was found the lowest. OVT revealed a tendency to desorb from the smectite surface at all investigated pH. The minimum desorption rate was observed at pH close to the isoelectric point of the protein, which suggests that nonspecific interactions between OVT and smectite particles significantly contribute to the stability of these complexes.

Neutron Reflectometry and QCM-D Study of the Interaction of Cellulases with Films of Amorphous Cellulose

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Gang; Liu, Zelin; Murton, Jaclyn K.

2011-06-13

Improving the efficiency of enzymatic hydrolysis of cellulose is one of the key technological hurdles to reduce the cost of producing ethanol and other transportation fuels from lignocellulosic material. A better understanding of how soluble enzymes interact with insoluble cellulose will aid in the design of more efficient enzyme systems. We report a study involving neutron reflectometry (NR) and quartz crystal microbalance with dissipation monitoring (QCM-D) of the interaction of a fungal enzyme extract (T. viride) and an endoglucanse from A. niger with amorphous cellulose films. The use of amorphous cellulose is motivated by that the fact that several biomassmore » pretreatments currently under investigation disrupt the native crystalline structure of cellulose and increase the amorphous content. NR reveals the profile of water through the film at nanometer resolution and is highly sensitive to interfacial roughness, whereas QCM-D provides changes in mass and film stiffness. NR can be performed using either H₂O- or D₂O-based aqueous reservoirs. NR measurement of swelling of a cellulose film in D₂O and in H₂O revealed that D/H exchange on the cellulose chains must be taken into account when a D₂O-based reservoir is used. The results also show that cellulose films swell slightly more in D₂O than in H₂O. Regarding enzymatic digestion, at 20 °C in H₂O buffer the T. viride cocktail rapidly digested the entire film, initially roughening the surface, followed by penetration and activity throughout the bulk of the film. In contrast, over the same time period, the endoglucanase was active mainly at the surface of the film and did not increase the surface roughness.« less

Probing the roles of Ca(2+) and Mg(2+) in humic acids-induced ultrafiltration membrane fouling using an integrated approach.

PubMed

Wang, Long-Fei; He, Dong-Qin; Chen, Wei; Yu, Han-Qing

2015-09-15

Membrane fouling induced by natural organic matter (NOM) negatively affects the performance of ultrafiltration (UF) technology in producing drinking water. Divalent cation is found to be an important factor that affects the NOM-induced membrane fouling process. In this work, attenuated total reflection-Fourier transformation infrared spectroscopy (ATR-FTIR) coupled with quartz crystal microbalance (QCM), assisted by isothermal titration calorimetry (ITC), is used to explore the contribution of Mg(2+) and Ca(2+), the two abundant divalent cations in natural water, to the UF membrane fouling caused by humic acid (HA) at a molecular level. The results show that Ca(2+) exhibited superior performance in accelerating fouling compared to Mg(2+). The hydrophobic polyethersulfone (PES) membrane exhibited greater complexation with HA in the presence of Mg(2+) and Ca(2+), compared to the hydrophilic cellulose membrane, as evidenced by the more intense polysaccharide C-O, aromatic C=C and carboxylic C=O bands in the FTIR spectra. The QCM and ITC measurements provide quantitative evidence to support that Ca(2+) was more effective than Mg(2+) in binding with HA and accumulating foulants on the membrane surfaces. The higher charge neutralization capacity and more favorable binding ability of Ca(2+) were found to be responsible for its greater contribution to the NOM-induced membrane fouling than Mg(2+). This work offers a new insight into the mechanism of cation-mediated NOM-induced membrane fouling process, and demonstrates that such an integrated ATR-FTIR/QCM/ITC approach could be a useful tool to explore other complicated interaction processes in natural and engineered environments. Copyright © 2015 Elsevier Ltd. All rights reserved.

Gelation Mechanisms and Characterization of Electrochemically Generated Protein Films at Metal Interfaces

NASA Astrophysics Data System (ADS)

Martin, Elizabeth J.

Although the electrochemical behavior of metals used in orthopedic implants has been studied extensively, the material interactions with proteins during corrosion processes remains poorly understood. Some studies suggest that metal-protein interactions accelerate corrosion, while others suggest that proteins protect the material from degradation. Corrosion of implant materials is a major concern due to the metal ion release that can sometimes cause adverse local tissue reactions and ultimately, failure of the implant. The initial purpose of this research was therefore to study the corrosion behavior of CoCrMo, an alloy commonly used in hip replacements, with a quartz crystal microbalance (QCM) in physiologically relevant media. The QCM enables in situ characterization of surface changes accompanying corrosion and is sensitive to viscoelastic effects at its surface. Results of QCM studies in proteinaceous media showed film deposition on the alloy surface under electrochemical conditions that otherwise produced mass loss if proteins were not present in the electrolyte. Additional studies on pure Co, Cr, and Mo demonstrated that the protein films also form on Mo surfaces after a release of molybdate ions, suggesting that these ions are essential for film formation. The electrochemically generated protein films are reminiscent of carbonaceous films that form on implant surfaces in vivo, therefore a second goal of the research was to delineate mechanisms that cause the films to form. In the second stage of this research, electrochemical QCM tests were conducted on models of the CoCrMo system consisting of Cr electrodes in proteinaceous or polymeric media containing dissolved molybdate ions. Studies indicated that films can be generated through electrochemical processes so long as both amine functional groups and molybdate ions are present in the electrolyte solution. These results suggest that the films form due to an ionic cross-linking reaction between the positively charged amine groups in the proteins and the negatively charged molybdate ions. Results also indicated that film generation is controlled by the potential at the electrode surface. Numerical analysis on the model systems suggest that a drop in the local pH at the corroding electrode surface may influence film generation, but a critical concentration of molybdate-amine cross-links must be exceeded for gels to form. A final goal of this research was to develop a technique to characterize the viscoelastic properties of polymer films in liquid media using the QCM as a high-frequency rheometer. The work showed that by measuring frequency and dissipation shifts at multiple harmonics of the QCM resonant frequency, the viscoelastic phase angle, density-modulus product, and areal mass of a film submersed in liquid can be quantified in situ. The method was successfully applied to characterize the electrochemically generated protein films. Results implied that the films are composed of a weakly cross-linked network with properties similar to concentrated albumin solutions containing 40 wt% protein. The analysis technique can be extended to characterize any polymer film in a liquid environment, with applications including adsorption, self-assembly, or cell-substrate interactions.

A new setup for experimental investigations of solar wind sputtering

NASA Astrophysics Data System (ADS)

Szabo, Paul S.; Berger, Bernhard M.; Chiba, Rimpei; Stadlmayr, Reinhard; Aumayr, Friedrich

2017-04-01

The surfaces of Mercury and Moon are not shielded by a thick atmosphere and therefore they are exposed to bombardment by charged particles, ultraviolet photons and micrometeorites. These influences lead to an alteration and erosion of the surface, and the emitted atoms and molecules form a thin atmosphere, an exosphere, around these celestial bodies [1]. The composition of these exospheres is connected to the surface composition and has been subject to flyby measurements by satellites. Model calculations which include the erosion mechanisms can be used as a method of comparison for such exosphere measurements and allow conclusions about the surface composition. Surface sputtering induced by solar wind ions hereby represents a major contribution to the erosion of the surfaces of Mercury and Moon [1]. However, the experimental database for sputtering of respective analogue materials by solar wind ions, which would be necessary for exact modelling of the space weathering process, is still in its early stages. Sputtering experiments have been performed at TU Wien during the past years using a quartz crystal microbalance (QCM) technique [2]. Target material is deposited on the quartz surface as a thin layer and the quartz's resonance frequency is measured under ion bombardment. The sputter yield can then be calculated from the frequency change and the ion current [2]. In order to remove the restrictions of a thin layer QCM target and simplify experiments with composite targets, a new QCM catcher setup was developed. In the new design, the QCM is placed beside the target holder and acts as a catcher for material that is sputtered from the target surface. By comparing the catcher signal to reference measurements and SDTrimSP simulations [3], the target sputter yield can be determined. In order to test the setup, we have performed experiments with a Au-coated QCM target under 2 keV Ar+ bombardment so that both the mass changes at the target and at the catcher could be obtained simultaneously. The results coincide very well with SDTrimSP predictions showing the feasibility of the new design [4]. Furthermore, Fe-coated QCM targets with different surface roughness were investigated in the new setup. The surface roughness represents a key factor for the solar wind induced erosion of planetary or lunar rocks. It has a strong influence on the absolute sputtering yield as well as on the spatial distribution of sputtered particles and was therefore investigated. As a next step, sputtering experiments with Mercury or Moon analogues will be conducted. Knowledge gained in the course of this research will enhance the understanding of surface sputtering by solar wind ions and used to improve theoretical models of the Mercury's and Moon's exosphere formation. References: [1] E. Kallio, et al., Planetary and Space Science, 56, 1506 (2008). [2] G. Hayderer, et al., Review of Scientific Instruments, 70, 3696 (1999). [3] A. Mutzke, R. Schneider, W. Eckstein, R. Dohmen, SDTrimSP: Version 5.00, IPP Report, 12/8, (2011). [4] B. M. Berger, P. S. Szabo, R. Stadlmayr, F. Aumayr, Nucl. Instrum. Meth. Phys. Res. B, doi: 10.1016/j.nimb.2016.11.039

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

Atomic Layer Deposition of MnS: Phase Control and Electrochemical Applications

DOE PAGES

Riha, Shannon C.; Koegel, Alexandra A.; Meng, Xiangbo; ...

2016-01-19

Manganese sulfide (MnS) thin films were synthesized via atomic layer deposition (ALD) using gaseous manganese bis(ethylcyclopentadienyl) and hydrogen sulfide as precursors. At deposition temperatures ≤150 °C phase-pure r-MnS thin films were deposited, while at temperatures >150 °C, a mixed phase, consisting of both r- and a-MnS resulted. In situ quartz crystal microbalance (QCM) studies validate the self-limiting behavior of both ALD half-reactions and, combined with quadrupole mass spectrometry (QMS) allow the derivation of a self-consistent reaction mechanism. Lastly, MnS thin films were deposited on copper foil and tested as a Li-ion battery anode. The MnS coin cells showed exceptional cyclemore » stability and near-theoretical capacity.« less

A Remarkably Simple Class of Imidazolium-Based Lipids and Their Biological Properties.

PubMed

Wang, Da; Richter, Christian; Rühling, Andreas; Drücker, Patrick; Siegmund, Daniel; Metzler-Nolte, Nils; Glorius, Frank; Galla, Hans-Joachim

2015-10-19

A series of imidazolium salts bearing two alkyl chains in the backbone of the imidazolium core were synthesized, resembling the structure of lipids. Their antibacterial activity and cytotoxicity were evaluated using Gram-positive and Gram-negative bacteria and eukaryotic cell lines including tumor cells. It is shown that the length of alkyl chains in the backbone is vital for the antibiofilm activities of these lipid-mimicking components. In addition to their biological activity, their surface activity and their membrane interactions are shown by film balance and quartz crystal microbalance (QCM) measurements. The structure-activity relationship indicates that the distinctive chemical structure contributes considerably to the biological activities of this novel class of lipids. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of casein and poly-l-arginine multilayer films

NASA Astrophysics Data System (ADS)

Szyk-Warszyńska, Lilianna; Kilan, Katarzyna; Socha, Robert P.

2014-06-01

Thin films containing casein appear to be a promising material for coatings used in the medical area to promote biomineralization. alfa- and beta-casein and poly-L-arginine multilayer films were formed by the layer-by layer technique and their thickness and mass were analyzed by ellipsometry and quartz crystal microbalance with dissipation monitoring (QCM-D). We investigated the effect of the type of casein used for the film formation and of the polyethyleneimine anchoring layer on the thickness and mass of adsorbed films. The analysis of the mass of films during their post-treatment with the solutions of various ionic strength and pH provided the information concerning films stability, while the XPS elemental analysis confirmed binding of calcium ions by the casein embedded in the multilayers.

Degradable Polymer with Protein Resistance in a Marine Environment.

PubMed

Ma, Jielin; Ma, Chunfeng; Zhang, Guangzhao

2015-06-16

Protein resistance is the central issue in marine antibiofouling. We have prepared poly(ε-caprolactone) (PCL)-based polyurethane with 2-(dimethylamino) ethyl methacrylate (DEM) as pendant groups by a combination of the thiol-ene click reaction and the condensation reaction. By the use of quartz crystal microbalance with dissipation (QCM-D) and surface plasmon resonance (SPR), we have investigated the adsorption of fibrinogen, bovine serum albumin (BSA), and lysozyme on the polymer surface. The polymer exhibits protein resistance in seawater but not in fresh water because DEM pendant groups carry net neutral charges in the former. The evaluation of antibacterial adhesion of the polymer by using Micrococcus luteus demonstrates that the polymer can effectively inhibit the settlement of marine bacteria. Our studies also show that the polymer is degradable in marine environments.

Probing adsorption of polyacrylamide-based polymers on anisotropic Basal planes of kaolinite using quartz crystal microbalance.

PubMed

Alagha, Lana; Wang, Shengqun; Yan, Lujie; Xu, Zhenghe; Masliyah, Jacob

2013-03-26

Quartz crystal microbalance with dissipation (QCM-D) was applied to investigate the adsorption characteristics of polyacrylamide-based polymers (PAMs) on anisotropic basal planes of kaolinite. Kaolinite basal planes were differentiated by depositing kaolinite nanoparticles (KNPs) on silica and alumina sensors in solutions of controlled pH values. Adsorption of an in-house synthesized organic-inorganic Al(OH)3-PAM (Al-PAM) as an example of cationic hybrid PAM and a commercially available partially hydrolyzed polyacrylamide (MF1011) as an example of anionic PAM was studied. Cationic Al-PAM was found to adsorb irreversibly and preferentially on tetrahedral silica basal planes of kaolinite. In contrast, anionic MF1011 adsorbed strongly on aluminum-hydroxy basal planes, while its adsorption on tetrahedral silica basal planes was weak and reversible. Adsorption study revealed that both electrostatic attraction and hydrogen-bonding mechanisms contribute to adsorption of PAMs on kaolinite. The adsorbed Al-PAM layer was able to release trapped water overtime and became more compact, while MF1011 film became more dissipative as backbones stretched out from kaolinite surface with minimal overlapping. Experimental results obtained from this study provide clear insights into the phenomenon that governs flocculation-based solid-liquid separation processes using multicomponent flocculants of anionic and cationic nature.

In situ reaction mechanism studies on the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O and Ti(O{sup i}Pr){sub 3}[MeC(N{sup i}Pr){sub 2}]-D{sub 2}O atomic layer deposition processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tomczak, Yoann, E-mail: yoann.tomczak@helsinki.fi; Knapas, Kjell; Leskelä, Markku

2014-01-15

Reaction mechanisms in the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O and Ti(O{sup i}Pr){sub 3}[MeC(N{sup i}Pr){sub 2}] [also written Ti(O{sup i}Pr){sub 3}(N{sup i}Pr-Me-amd)]-D{sub 2}O atomic layer deposition processes were studied in situ with quartz crystal microbalance (QCM) and quadrupole mass spectrometry (QMS) at 275 °C. For the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2}-D{sub 2}O process, both QCM and QMS results indicated adsorption of the Ti(NMe{sub 2}){sub 2}(O{sup i}Pr){sub 2} molecule through an exchange of at least one of its –NMe{sub 2} ligands with surface hydroxyl groups. Regarding the Ti(O{sup i}Pr){sub 3}(N{sup i}Pr-Me-amd)-D{sub 2}O process, a mismatch between the QCM and QMS results revealedmore » more complex reactions: the decomposition of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand is suggested by the shape of the QCM data and the intensity of the QMS signals belonging to fragments of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand. A simple calculation model associating the growth rate per cycle of a crystalline film and the surface area taken by the ligands remaining after saturation was also used to support the decomposition of the [MeC(N{sup i}Pr){sub 2}] [also written (N{sup i}Pr-Me-amd)] ligand. The observed high growth rate is incompatible with the whole [MeC(N{sup i}Pr){sub 2}] (also written [N{sup i}Pr-Me-amd)] ligand remaining on the surface.« less

Partitioning of Alkali Metal Salts and Boric Acid from Aqueous Phase into the Polyamide Active Layers of Reverse Osmosis Membranes.

PubMed

Wang, Jingbo; Kingsbury, Ryan S; Perry, Lamar A; Coronell, Orlando

2017-02-21

The partition coefficient of solutes into the polyamide active layer of reverse osmosis (RO) membranes is one of the three membrane properties (together with solute diffusion coefficient and active layer thickness) that determine solute permeation. However, no well-established method exists to measure solute partition coefficients into polyamide active layers. Further, the few studies that measured partition coefficients for inorganic salts report values significantly higher than one (∼3-8), which is contrary to expectations from Donnan theory and the observed high rejection of salts. As such, we developed a benchtop method to determine solute partition coefficients into the polyamide active layers of RO membranes. The method uses a quartz crystal microbalance (QCM) to measure the change in the mass of the active layer caused by the uptake of the partitioned solutes. The method was evaluated using several inorganic salts (alkali metal salts of chloride) and a weak acid of common concern in water desalination (boric acid). All partition coefficients were found to be lower than 1, in general agreement with expectations from Donnan theory. Results reported in this study advance the fundamental understanding of contaminant transport through RO membranes, and can be used in future studies to decouple the contributions of contaminant partitioning and diffusion to contaminant permeation.

Conformal Nanocoatings with Uniform and Controllable Thickness on Microstructured Surfaces: A General Assembly Route.

PubMed

Hou, Yi; Wang, Zhen; Cai, Chao; Hao, Xi; Li, Dongdong; Zhao, Ning; Zhao, Yiping; Chen, Li; Ma, Hongwei; Xu, Jian

2018-02-01

Assembling nanoparticles (NPs) on various surfaces are intensively investigated for the construction of functional nanocoatings; however, it is still a challenge to fabricate conformal nanocoatings uniformly on surfaces having micro- or nanostructures. Herein, it is demonstrated that the negatively charged SiO 2 NPs and the positively charged silicon coupling agent can be assembled layer-by-layer on the microstructures based on the combination of electrostatic interaction and condensation reaction. Conformal nanocoatings with controllable thickness are formed on the microstructured surfaces with different compositions and morphologies. The formation mechanism is confirmed by using quartz crystal microbalance with dissipation (QCM-D) to study the assembly process in real time. The universality of this method is illustrated by using other reactive building blocks with opposite charge to build up the conformal nanocoatings. Application in the preparation of antireflective nanocoatings on nonplanar optical materials is demonstrated. This simple, versatile, and scalable strategy for the preparation of conformal nanocoatings is promising for practical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A quantified dosing ALD reactor with in-situ diagnostics for surface chemistry studies

NASA Astrophysics Data System (ADS)

Larrabee, Thomas J.

A specialized atomic layer deposition (ALD) reactor has been constructed to serve as an instrument to simultaneously study the surface chemistry of the ALD process, and perform ALD as is conventionally done in continuum flow of inert gas. This reactor is uniquely useful to gain insight into the ALD process because of the combination of its precise, controllable, and quantified dosing/microdosing capability; its in-situ quadrupole mass spectrometer for gas composition analysis; its pair of highly-sensitive in-situ quartz crystal microbalances (QCMs); and its complete spectrum of pressures and operating conditions --- from viscous to molecular flow regimes. Control of the dose is achieved independently of the conditions by allowing a reactant gas to fill a fixed volume and measured pressure, which is held at a controlled temperature, and subsequently dosed into the system by computer controlled pneumatic valves. Absolute reactant exposure to the substrate and QCMs is unambiguously calculated from the molecular impingement flux, and its relationship to dose size is established, allowing means for easily intentionally reproducing specific exposures. Methods for understanding atomic layer growth and adsorption phenomena, including the precursor sticking probability, dynamics of molecular impingement, size of dose, and other operating variables are for the first time quantitatively related to surface reaction rates by mass balance. Extensive characterization of the QCM as a measurement tool for adsorption under realistic ALD conditions has been examined, emphasizing the state-of-the-art and importance of QCM system features required. Finally, the importance of dose-quantification and microdosing has been contextualized in view of the ALD literature, underscoring the significance of more precise condition specification in establishing a better basis for reactor and reactant comparison.

Sugar acetates as CO2-philes: molecular interactions and structure aspects from absorption measurement using quartz crystal microbalance.

PubMed

Ma, Shao-Ling; Wu, You-Ting; Hurrey, Michael L; Wallen, Scott L; Grant, Christine S

2010-03-25

Sugar acetates, recognized as attractive CO(2)-philic compounds, have potential uses as pharmaceutical excipients, controlled release agents, and surfactants for microemulsion systems in CO(2)-based processes. This study focuses on the quantitative examination of absorption of high pressure CO(2) into these sugar derivatives using quartz crystal microbalance (QCM) as a detector. In addition to the absorption measurement, the QCM is initially found to be able to detect the CO(2)-induced deliquescence of sugar acetates, and the CO(2) pressure at which the deliquescence happens depends on several influencing factors such as the temperature and thickness of the film. The CO(2) absorption in alpha-D-glucose pentaacetate (Ac-alpha-GLU) is revealed to be of an order of magnitude larger in comparison with its anomer Ac-beta-GLU, whereas alpha-D-galactose pentaacetate (Ac-alpha-GAL) absorbs CO(2) less than Ac-alpha-GLU due to the steric-hindrance between the acetyl groups on the anomeric and C4 carbons, implying the significant importance of the molecular structure and configuration of sugar acetates on the absorption. The effects of molecular size and acetyl number of sugar acetates on the CO(2) absorption are evaluated and the results indicate that the conformation and packing of crystalline sugar acetate as well as the accessibility of the acetyls are also vital for the absorption of CO(2). It is additionally found that a CO(2)-induced change in the structure from a crystalline system to an amorphous system results in an order of magnitude increase in CO(2) absorption. Further investigation illustrates the interaction strength between sugar acetates and CO(2) by calculating the thermodynamic parameters such as Henry's law constant, enthalpy and entropy of dissolution from the determined CO(2) absorption. Experiments and calculations demonstrate that sugar acetates exhibit high CO(2) absorption, as at least comparable to ionic liquids. Since the ionic liquids have potential uses in the separation of acidic gases, it is evident from this study that sugar acetates could be used as possible materials for CO(2) separation.

Caracterisation de nanofilms polymeriques deposes par plasma froid : Stabilite et proprietes mecaniques

NASA Astrophysics Data System (ADS)

Barrette, Jeremie

The current project is inscribed in the research axis on bioactive coatings of Dr. Sophie Lerouge's Laboratoire de Biomatériaux endovasculaires (LBeV). The aim of our work was to extract mechanical properties of a new plasma polymer called L-PPE :N (developed to enhance healing around stent-graft) and determine the effect of various experimental parameters on the stability behavior of our thin films (hundred nanometer thick coatings). Subsidiary to these goals, we also had in mind to test whether usual methods for characterizing polymers and films were applicable on our cold-plasma deposited material. Properties concerned by our endeavor included Young's modulus, hardness, storage and loss modulus, resistance to tearing, ultimate strain and aqueous stability under different temperature and pH for films of varying ratio of gases and thicknesses. Apparatus and work hypothesis used to succeed in our characterization work included, but was not limited to: a quartz crystal dissipative microbalance (QCM-D), a nanoindenter, an ellipsometer, and a tensile testing bench specifically designed for microscopic observation. Hypothesis attached to these methods are that each of these will work as intended for the characterization of our material. Furthermore, we also need to consider the properties of our film as constant throughout its volume (surface-wise for QCM-D analysis and thickness-wise for nanoindentation). QCM-D results allowed us to determine the best compromise of deposition gas ratio R=NH3/C2H4 of L-PPE:N for our biomedical application to be 0.75, from a stability and bioactivity point of view. Starting from that information, we submitted ratio 0.75 films to temperature, thickness and pH essays to make sure they could handle every situation we could need to put them through. Nanoindentation essays have helped us finding reduced modulus and hardness of 8.0 and 0.4 GPa for the 2 µm coating and 10.4 and 0.5 GPa for the 200 nm film, respectively. These values are greater than other biomaterials currently in use, and similar to other cold plasma materials. Further improvements to this work include, at this point of the L-PPE:N development, to start studying the impact of conventional sterilization methods on the stability, mechanical and biological properties of our film, and to submit our coating to a testing bench designed specifically to mimic the insertion and deployment of a stent-graft, in order to verify the structural integrity of the film afterwards.

Adsorption effectiveness of β-lactoglobulin onto gold surface determined by quartz crystal microbalance.

PubMed

Jachimska, B; Świątek, S; Loch, J I; Lewiński, K; Luxbacher, T

2018-06-01

Bovine β-lactoglobulin (LGB) is a transport protein that can bind to its structure hydrophobic bioactive molecules. Due to the lack of toxicity, high stability and pH-dependent molecular binding mechanism, lactoglobulin can be used as a carrier of sparingly soluble drugs. Dynamic light scattering has confirmed LGB's tendency to create oligomeric forms. The hydrodynamic diameter of LGB molecules varies from 4 nm to 6 nm in the pH range of 2-10 and ionic strength I = 0.001-0.15 M, which corresponds to the presence of mono or dimeric LGB forms. The LGB zeta potential varies from 26.5 mV to -33.3 mV for I = 0.01 M and from 13.3 mV to -16 mV for I = 0.15 M in the pH range of 2-10. The isoelectric point is at pH 4.8. As a result of strong surface charge compensation, the maximum effective ionization degree of the LGB molecule is 35% for ionic strength I = 0.01 M and 22% for I = 0.15 M. The effectiveness of adsorption is linked with the properties of the protein, as well as those of the adsorption surface. The functionalization of gold surfaces with β-lactoglobulin (LGB) was studied using a quartz crystal microbalance with energy dissipation monitoring (QCM-D). The effectiveness of LGB adsorption correlates strongly with a charge of gold surface and the zeta potential of the molecule. The greatest value of the adsorbed mass was observed in the pH range in which LGB has a positive zeta potential values, below pH 4.8. This observation shows that electrostatic interactions play a dominant role in LGB adsorption on gold surfaces. Based on the adsorbed mass, protein orientation on gold surfaces was determined. The preferential side-on orientation of LGB molecules observed in the adsorption layer is consistent with the direction of the molecule dipole momentum determined by molecular dynamics simulations of the protein (MD). The use of the QCM-D method also allowed us to determine the effectiveness of adsorption of LGB on gold surface. Knowing the mechanism of LGB adsorption is significant importance for determining the optimum conditions for immobilizing this protein on solid surfaces. As β-lactoglobulin is a protein that binds various ligands, the binding properties of immobilized β-lactoglobulin can be used to design controlled protein structures for biomedical applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Assembly of RNA nanostructures on supported lipid bilayers

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Michanek, Agnes; Jaeger, Luc; Rabe, Michael; Chworos, Arkadiusz; Höök, Fredrik; Nylander, Tommy; Sparr, Emma

2014-12-01

The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces.The assembly of nucleic acid nanostructures with controlled size and shape has large impact in the fields of nanotechnology, nanomedicine and synthetic biology. The directed arrangement of nano-structures at interfaces is important for many applications. In spite of this, the use of laterally mobile lipid bilayers to control RNA three-dimensional nanostructure formation on surfaces remains largely unexplored. Here, we direct the self-assembly of RNA building blocks into three-dimensional structures of RNA on fluid lipid bilayers composed of cationic 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or mixtures of zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC) and cationic sphingosine. We demonstrate the stepwise supramolecular assembly of discrete building blocks through specific and selective RNA-RNA interactions, based on results from quartz crystal microbalance with dissipation (QCM-D), ellipsometry, fluorescence recovery after photobleaching (FRAP) and total internal reflection fluorescence microscopy (TIRF) experiments. The assembly can be controlled to give a densely packed single layer of RNA polyhedrons at the fluid lipid bilayer surface. We show that assembly of the 3D structure can be modulated by sequence specific interactions, surface charge and changes in the salt composition and concentration. In addition, the tertiary structure of the RNA polyhedron can be controllably switched from an extended structure to one that is dense and compact. The versatile approach to building up three-dimensional structures of RNA does not require modification of the surface or the RNA molecules, and can be used as a bottom-up means of nanofabrication of functionalized bio-mimicking surfaces. Electronic supplementary information (ESI) available: Table with sequences of tRNA units used in this study; schematic structures of the RNA polyhedron and its building blocks; gel electrophoresis characterization of the RNA polyhedron and squares; AFM characterization of RNA tectosquare; schematic structures of RNA-9 and RNA-10 and their association with lipid bilayers; QCM-D frequency and dissipation data (as function of time) for adsorption of RNA polyhedrons, RNA squares and RNA9-10 TIRF images of RNA with Gelstar after photobleaching with analysis; Correlation plot in change of shear viscosity for TS3 and TO3-4 models for the stoichiometry of TS; QCM-D dissipation data for the sequential experiment in Fig. 5a; QCM-D and for the assembly of building blocks at the bilayer scaffold at varying bulk concentrations; QCM-D of adsorption of TS3. See DOI: 10.1039/c4nr05968a

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes.

PubMed

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-06

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO 2 , NO, H 2 O, as well as the related fragments during the O 2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO 2 during the complex surface chemical reaction of the ligand and O 2 plasma were monitored using the QCM. The remote PEALD ZrO 2 /zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10 -5  g/m 2 /day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10-5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Lipopolysaccharide Density and Structure Govern the Extent and Distance of Nanoparticle Interaction with Actual and Model Bacterial Outer Membranes

DOE PAGES

Jacobson, Kurt H.; Gunsolus, Ian L.; Kuech, Thomas R.; ...

2015-07-24

We report that design of nanomedicines and nanoparticle-based antimicrobial and antifouling formulations, and assessment of the potential implications of nanoparticle release into the environment require understanding nanoparticle interaction with bacterial surfaces. Here we demonstrate electrostatically driven association of functionalized nanoparticles with lipopolysaccharides of Gram-negative bacterial outer membranes and find that lipopolysaccharide structure influences the extent and location of binding relative to the lipid-solution interface. By manipulating the lipopolysaccharide content in Shewanella oneidensis outer membranes, we observed electrostatically driven interaction of cationic gold nanoparticles with the lipopolysaccharide-containing leaflet. We probed this interaction by quartz crystal microbalance with dissipation monitoring (QCM-D) andmore » second harmonic generation (SHG) using solid-supported lipopolysaccharide-containing bilayers. Association of cationic nanoparticles increased with lipopolysaccharide content, while no association of anionic nanoparticles was observed. The harmonic-dependence of QCM-D measurements suggested that a population of the cationic nanoparticles was held at a distance from the outer leaflet-solution interface of bilayers containing smooth lipopolysaccharides (those bearing a long O-polysaccharide). Additionally, smooth lipopolysaccharides held the bulk of the associated cationic particles outside of the interfacial zone probed by SHG. Lastly, our results demonstrate that positively charged nanoparticles are more likely to interact with Gram-negative bacteria than are negatively charged particles, and this interaction occurs primarily through lipopolysaccharides.« less

Adsorption and conformational modification of fibronectin and fibrinogen adsorbed on hydroxyapatite. A QCM-D study.

PubMed

Fernández-Montes Moraleda, Belén; San Román, Julio; Rodríguez-Lorenzo, Luís M

2016-10-01

Hydroxyapatite is a bioactive ceramic frequently used for bone engineering/replacement. One of the parameters that influence the biological response to implanted materials is the conformation of the first adsorbed protein layer. In this work, the adsorption and conformational changes of two fibroid serum proteins; fibronectin and fibrinogen adsorbed onto four different hydroxyapatite powders are studied with a Quartz Crystal Microbalance with Dissipation (QCM-D). Each of the calcined apatites adsorbs less protein than their corresponding synthesized samples. Adsorption on synthesized samples yields always an extended conformation whereas a reorganization of the layer is observed for the calcined samples. Fg acquires a "Side on" conformation in all the samples at the beginning of the experiment except for one of the synthesized samples where an "End-on" conformation is obtained during the whole experiment. The Extended conformation is the active conformation for Fn. This conformation is favored by apatites with large specific surface area (SSA) and on highly concentrated media. Apatite surface features should be considered in the selection or design of materials for bone regeneration, since it is possible to control the conformation mode of attachment of Fn and Fg by an appropriate selection of them. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2585-2594, 2016. © 2016 Wiley Periodicals, Inc.

Directed synthesis of bio-inorganic vanadium oxide composites using genetically modified filamentous phage

NASA Astrophysics Data System (ADS)

Mueller, Michael; Baik, Seungyun; Jeon, Hojeong; Kim, Yuchan; Kim, Jungtae; Kim, Young Jun

2015-05-01

The growth of crystalline vanadium oxide using a filamentous bacteriophage template was investigated using sequential incubation in a V2O5 precursor. Using the genetic modification of the bacteriophage, we displayed two cysteines that constrained the RSTB-1 peptide on the major coat protein P8, resulting in vanadium oxide crystallization. The phage-driven vanadium oxide crystals with different topologies, microstructures, photodegradation and vanadium oxide composites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), quartz microbalance and dissipation (QCM-D) and X-ray photoelectron spectroscopy (XPS). Non-specific electrostatic attraction between a wild-type phage (wt-phage) and vanadium cations in the V2O5 precursor caused phage agglomeration and fiber formation along the length of the viral scaffold. As a result, the addition of recombinant phage (re-phage) in V2O5 precursors formed heterogeneous structures, which led to efficient condensation of vanadium oxide crystal formation in lines, shown by QCM-D analysis. Furthermore, re-phage/VxOx composites showed significantly enhanced photodegradation activities compared with the synthesized wt-phage-V2O5 composite under illumination. This study demonstrates that peptide-mediated vanadium oxide mineralization is governed by a complicated interplay of peptide sequence, local structure, kinetics and the presence of a mineralizing aid, such as the two cysteine-constrained peptides on the phage surface, and has potential for use in nanotechnology applications.

Gold nanospikes based microsensor as a highly accurate mercury emission monitoring system

PubMed Central

Sabri, Ylias M.; Ippolito, Samuel J.; Tardio, James; Bansal, Vipul; O'Mullane, Anthony P.; Bhargava, Suresh K.

2014-01-01

Anthropogenic elemental mercury (Hg0) emission is a serious worldwide environmental problem due to the extreme toxicity of the heavy metal to humans, plants and wildlife. Development of an accurate and cheap microsensor based online monitoring system which can be integrated as part of Hg0 removal and control processes in industry is still a major challenge. Here, we demonstrate that forming Au nanospike structures directly onto the electrodes of a quartz crystal microbalance (QCM) using a novel electrochemical route results in a self-regenerating, highly robust, stable, sensitive and selective Hg0 vapor sensor. The data from a 127 day continuous test performed in the presence of volatile organic compounds and high humidity levels, showed that the sensor with an electrodeposted sensitive layer had 260% higher response magnitude, 3.4 times lower detection limit (~22 μg/m3 or ~2.46 ppbv) and higher accuracy (98% Vs 35%) over a Au control based QCM (unmodified) when exposed to a Hg0 vapor concentration of 10.55 mg/m3 at 101°C. Statistical analysis of the long term data showed that the nano-engineered Hg0 sorption sites on the developed Au nanospikes sensitive layer play a critical role in the enhanced sensitivity and selectivity of the developed sensor towards Hg0 vapor. PMID:25338965

Sensing specific adhesion of liposomal and micellar systems with attached carbohydrate recognition structures at lectin surfaces.

PubMed

Hildebrand, Annegret; Schaedlich, Anita; Rothe, Ulrich; Neubert, Reinhard H H

2002-05-15

A quartz crystal microbalance was used to investigate the adsorption behavior of liposomes and mixed micelles with attached carbohydrate recognition structures at lectin-coated quartz plates. With a self-assembly technique, the quartz was coated with the lectin Concanavalin A. In a first attempt, liposomes of natural soybean PC as well as synthetic POPC, containing 10% reactive N-Glut-PE each, were decorated with a mannopyranoside recognition structure to investigate the specific adsorption at the lectin-coated quartz surface in dependence on the concentration. In a second model, the bile salt sodium cholate was introduced to solubilize the mannopyranoside-modified liposomes and to transform them into mannopyranoside-modified binary mixed micelles. The adsorption of these micelles was further investigated. In a third approach, the adsorption behavior of mannopyranoside-modified ternary mixed bile salt-phosphatidylcholine-fatty acid micelles was characterized with sodium laurate, palmitate, and oleate as fatty acids. The micelles with oleate showed only a small frequency decrease, whereas the micelles with laurate and palmitate induced higher frequency changes. A dependence on the alkyl chain length could be detected. While the adsorption of liposomes containing recognition structures at QCM surfaces is nowadays well-established, the QCM detection of the adsorption of mixed bile salt micelles, transformed from these liposomes by solubilization, is a novel and very promising field for the development of innovative colloidal drug delivery systems.

Controlled Immobilization Strategies to Probe Short Hyaluronan-Protein Interactions

NASA Astrophysics Data System (ADS)

Minsky, Burcu Baykal; Antoni, Christiane H.; Boehm, Heike

2016-02-01

Well-controlled grafting of small hyaluronan oligosaccharides (sHA) enables novel approaches to investigate biological processes such as angiogenesis, immune reactions and cancer metastasis. We develop two strategies for covalent attachment of sHA, a fast high-density adsorption and a two-layer system that allows tuning the density and mode of immobilization. We monitored the sHA adlayer formation and subsequent macromolecular interactions by label-free quartz crystal microbalance with dissipation (QCM-D). The modified surfaces are inert to unspecific protein adsorption, and yet retain the specific binding capacity of sHA. Thus they are an ideal tool to study the interactions of hyaluronan-binding proteins and short hyaluronan molecules as demonstrated by the specific recognition of LYVE-1 and aggrecan. Both hyaladherins recognize sHA and the binding is independent to the presence of the reducing end.

Mapping a disordered portion of the Brz2001-binding site on a plant monooxygenase, DWARF4, using a quartz-crystal microbalance biosensor-based T7 phage display.

PubMed

Takakusagi, Yoichi; Manita, Daisuke; Kusayanagi, Tomoe; Izaguirre-Carbonell, Jesus; Takakusagi, Kaori; Kuramochi, Kouji; Iwabata, Kazuki; Kanai, Yoshihiro; Sakaguchi, Kengo; Sugawara, Fumio

2013-04-01

In small-molecule/protein interaction studies, technical difficulties such as low solubility of small molecules or low abundance of protein samples often restrict the progress of research. Here, we describe a quartz-crystal microbalance (QCM) biosensor-based T7 phage display in combination use with a receptor-ligand contacts (RELIC) bioinformatics server for application in a plant Brz2001/DWARF4 system. Brz2001 is a brassinosteroid biosynthesis inhibitor in the less-soluble triazole series of compounds that targets DWARF4, a cytochrome P450 (Cyp450) monooxygenase containing heme and iron. Using a Brz2001 derivative that has higher solubility in 70% EtOH and forms a self-assembled monolayer on gold electrode, we selected 34 Brz2001-recognizing peptides from a 15-mer T7 phage-displayed random peptide library using a total of four sets of one-cycle biopanning. The RELIC/MOTIF program revealed continuous and discontinuous short motifs conserved within the 34 Brz2001-selected 15-mer peptide sequences, indicating the increase of information content for Brz2001 recognition. Furthermore, an analysis of similarity between the 34 peptides and the amino-acid sequence of DWARF4 using the RELIC/MATCH program generated a similarity plot and a cluster diagram of the amino-acid sequence. Both of these data highlighted an internally located disordered portion of a catalytic site on DWARF4, indicating that this portion is essential for Brz2001 recognition. A similar trend was also noted by an analysis using another 26 Brz2001-selected peptides, and not observed using the 27 gold electrode-recognizing control peptides, demonstrating the reproducibility and specificity of this method. Thus, this affinity-based strategy enables high-throughput detection of the small-molecule-recognizing portion on the target protein, which overcomes technical difficulties such as sample solubility or preparation that occur when conventional methods are used.

Interface architecture between TiO2/perovskite, perovskite/hole transport layer, and perovskite grain boundary(Conference Presentation)

NASA Astrophysics Data System (ADS)

Hayase, Shuzi; Hirotani, Daisuke; Moriya, Masahiro; Ogomi, Yuhei; Shen, Qing; Yoshino, Kenji; Toyoda, Taro

2016-09-01

In order to examine the interface structure of TiO2/perovskite layer, quartz crystal microbalance sensor (QCM) was used. On the QCM sensor, TiO2 layer was fabricated and the PbI2 solution in Dimethylformamide (DMF) was passed on the QCM sensor to estimate the adsorption density of the PbI2 on the titania2. The amount of PbI2 adsorption on TiO2 surface increased as the adsorption time and leveled off at a certain time. PbI2 still remained even after the solvent only (DMF) was passed on the TiO2 layer on QCM (namely rinsing with DMF), suggesting that the PbI2 was tightly bonded on the TiO2 surface. The bonding structure was found to be Ti-O-Pb linkage by XPS analysis. We concluded that the Ti-OH on the surface of TiO2 reacts with I-Pb-I to form Ti-O-Pb-I and HI (Fig.1 B). The surface trap density was measured by thermally stimulated current (TSC) method. Before the PbI2 passivation, the trap density of TiO2 was 1019 cm3. The trap density decreased to 1016/cm3 after the PbI2 passivation, suggesting that the TiO2 surface trap was passivated with I-Pb-I. The passivation density was tuned by the concentration of PbI2 in DMF, by which TiO2 layer was passivated. Perovskite solar cells were fabricated on the passivated TiO2 layer with various PbI2 passivation densities by one step process (mixture of PbI2 + MAI in DMF). It was found that Jsc increased with an increase in the Ti-O-Pb density. We concluded that the interface between TiO2 and perovskite layer has passivation structure consisting of Ti-O-Pb-I which decreases the trap density of the interfaces and supresses charge recombination. The effect of Cl anion on high efficiency is still controversial when perovskite layer is prepared by one step method from the mixture of MAI and PbCl2. It was found that adsorption density of PbCl2 on TiO2 surface was much higher than that of PbI2 from the experiment using QCM sensor. After the surface was washed with DMF, Cl and Pb were detected. These results suggest that the TiO2 surface was much more passivated by PbCl2 than by PbI2. This may explain partially the high efficiency when the perovskite layer was fabricated by one step process consisting of MAI and PbCl2 solution. We also observed that the crystal size increased with an increase in the amount of Cl anion which of course one of the explanation of the high efficiency. The interface of hole transport layer/perovskite layer, and between perovskite layer /perovskite layer (grain boundary) was passivated with organic amines. The passivation was also effective for increasing Voc and Jsc. This was explained by the results of transient absorption spectroscopy that the charge recombination time between hole transport payer/perovskite layer increased from 0.3 μsec to 60 μsec.

Polyglycerol based coatings to reduce non-specific protein adsorption in sample vials and on SPR sensors.

PubMed

Becherer, Tobias; Grunewald, Christian; Engelschalt, Vivienne; Multhaup, Gerhard; Risse, Thomas; Haag, Rainer

2015-03-31

Coatings based on dendritic polyglycerol (dPG) were investigated for their use to control nonspecific protein adsorption in an assay targeted to analyze concentrations of a specific protein. We demonstrate that coating of the sample vial with dPG can significantly increase the recovery of an antibody after incubation. First, we determine the concentration dependent loss of an antibody due to nonspecific adsorption to glass via quartz crystal microbalance (QCM). Complementary to the QCM measurements, we applied the same antibody as analyte in an surface plasmon resonance (SPR) assay to determine the loss of analyte due to nonspecific adsorption to the sample vial. For this purpose, we used two different coatings based on dPG. For the first coating, which served as a matrix for the SPR sensor, carboxyl groups were incorporated into dPG as well as a dithiolane moiety enabling covalent immobilization to the gold sensor surface. This SPR-matrix exhibited excellent protein resistant properties and allowed the immobilization of amyloid peptides via amide bond formation. The second coating which was intended to prevent nonspecific adsorption to glass vials comprised a silyl moiety that allowed covalent grafting to glass. For demonstrating the impact of the vial coating on the accuracy of an SPR assay, we immobilized amyloid beta (Aβ) 1-40 and used an anti-Aβ 1-40 antibody as analyte. Alternate injection of analyte into the flow cell of the SPR device from uncoated and coated vials, respectively gave us the relative signal loss (1-RUuncoated/RUcoated) caused by the nonspecific adsorption. We found that the relative signal loss increases with decreasing analyte concentration. The SPR data correlate well with concentration dependent non-specific adsorption experiments of the analyte to glass surfaces performed with QCM. Our measurements show that rendering both the sample vial and the sensor surface is crucial for accurate results in protein assays. Copyright © 2015 Elsevier B.V. All rights reserved.

Molecularly Imprinted Sol-Gel-Based QCM Sensor Arrays for the Detection and Recognition of Volatile Aldehydes.

PubMed

Liu, Chuanjun; Wyszynski, Bartosz; Yatabe, Rui; Hayashi, Kenshi; Toko, Kiyoshi

2017-02-16

The detection and recognition of metabolically derived aldehydes, which have been identified as important products of oxidative stress and biomarkers of cancers; are considered as an effective approach for early cancer detection as well as health status monitoring. Quartz crystal microbalance (QCM) sensor arrays based on molecularly imprinted sol-gel (MISG) materials were developed in this work for highly sensitive detection and highly selective recognition of typical aldehyde vapors including hexanal (HAL); nonanal (NAL) and bezaldehyde (BAL). The MISGs were prepared by a sol-gel procedure using two matrix precursors: tetraethyl orthosilicate (TEOS) and tetrabutoxytitanium (TBOT). Aminopropyltriethoxysilane (APT); diethylaminopropyltrimethoxysilane (EAP) and trimethoxy-phenylsilane (TMP) were added as functional monomers to adjust the imprinting effect of the matrix. Hexanoic acid (HA); nonanoic acid (NA) and benzoic acid (BA) were used as psuedotemplates in view of their analogous structure to the target molecules as well as the strong hydrogen-bonding interaction with the matrix. Totally 13 types of MISGs with different components were prepared and coated on QCM electrodes by spin coating. Their sensing characters towards the three aldehyde vapors with different concentrations were investigated qualitatively. The results demonstrated that the response of individual sensors to each target strongly depended on the matrix precursors; functional monomers and template molecules. An optimization of the 13 MISG materials was carried out based on statistical analysis such as principle component analysis (PCA); multivariate analysis of covariance (MANCOVA) and hierarchical cluster analysis (HCA). The optimized sensor array consisting of five channels showed a high discrimination ability on the aldehyde vapors; which was confirmed by quantitative comparison with a randomly selected array. It was suggested that both the molecularly imprinting (MIP) effect and the matrix effect contributed to the sensitivity and selectivity of the optimized sensor array. The developed MISGs were expected to be promising materials for the detection and recognition of volatile aldehydes contained in exhaled breath or human body odor.

Molecularly Imprinted Sol-Gel-Based QCM Sensor Arrays for the Detection and Recognition of Volatile Aldehydes

PubMed Central

Liu, Chuanjun; Wyszynski, Bartosz; Yatabe, Rui; Hayashi, Kenshi; Toko, Kiyoshi

2017-01-01

The detection and recognition of metabolically derived aldehydes, which have been identified as important products of oxidative stress and biomarkers of cancers; are considered as an effective approach for early cancer detection as well as health status monitoring. Quartz crystal microbalance (QCM) sensor arrays based on molecularly imprinted sol-gel (MISG) materials were developed in this work for highly sensitive detection and highly selective recognition of typical aldehyde vapors including hexanal (HAL); nonanal (NAL) and bezaldehyde (BAL). The MISGs were prepared by a sol-gel procedure using two matrix precursors: tetraethyl orthosilicate (TEOS) and tetrabutoxytitanium (TBOT). Aminopropyltriethoxysilane (APT); diethylaminopropyltrimethoxysilane (EAP) and trimethoxy-phenylsilane (TMP) were added as functional monomers to adjust the imprinting effect of the matrix. Hexanoic acid (HA); nonanoic acid (NA) and benzoic acid (BA) were used as psuedotemplates in view of their analogous structure to the target molecules as well as the strong hydrogen-bonding interaction with the matrix. Totally 13 types of MISGs with different components were prepared and coated on QCM electrodes by spin coating. Their sensing characters towards the three aldehyde vapors with different concentrations were investigated qualitatively. The results demonstrated that the response of individual sensors to each target strongly depended on the matrix precursors; functional monomers and template molecules. An optimization of the 13 MISG materials was carried out based on statistical analysis such as principle component analysis (PCA); multivariate analysis of covariance (MANCOVA) and hierarchical cluster analysis (HCA). The optimized sensor array consisting of five channels showed a high discrimination ability on the aldehyde vapors; which was confirmed by quantitative comparison with a randomly selected array. It was suggested that both the molecularly imprinting (MIP) effect and the matrix effect contributed to the sensitivity and selectivity of the optimized sensor array. The developed MISGs were expected to be promising materials for the detection and recognition of volatile aldehydes contained in exhaled breath or human body odor. PMID:28212347

Acoustic-wave sensor for ambient monitoring of a photoresist-stripping agent

DOEpatents

Pfeifer, K.B.; Hoyt, A.E.; Frye, G.C.

1998-08-18

The acoustic-wave sensor is disclosed. The acoustic-wave sensor is designed for ambient or vapor-phase monitoring of a photoresist-stripping agent such as N-methylpyrrolidinone (NMP), ethoxyethylpropionate (EEP) or the like. The acoustic-wave sensor comprises an acoustic-wave device such as a surface-acoustic-wave (SAW) device, a flexural-plate-wave (FPW) device, an acoustic-plate-mode (APM) device, or a thickness-shear-mode (TSM) device (also termed a quartz crystal microbalance or QCM) having a sensing region on a surface thereof. The sensing region includes a sensing film for sorbing a quantity of the photoresist-stripping agent, thereby altering or shifting a frequency of oscillation of an acoustic wave propagating through the sensing region for indicating an ambient concentration of the agent. According to preferred embodiments of the invention, the acoustic-wave device is a SAW device; and the sensing film comprises poly(vinylacetate), poly(N-vinylpyrrolidinone), or poly(vinylphenol). 3 figs.

Acoustic-wave sensor for ambient monitoring of a photoresist-stripping agent

DOEpatents

Pfeifer, Kent B.; Hoyt, Andrea E.; Frye, Gregory C.

1998-01-01

The acoustic-wave sensor. The acoustic-wave sensor is designed for ambient or vapor-phase monitoring of a photoresist-stripping agent such as N-methylpyrrolidinone (NMP), ethoxyethylpropionate (EEP) or the like. The acoustic-wave sensor comprises an acoustic-wave device such as a surface-acoustic-wave (SAW) device, a flexural-plate-wave (FPW) device, an acoustic-plate-mode (APM) device, or a thickness-shear-mode (TSM) device (also termed a quartz crystal microbalance or QCM) having a sensing region on a surface thereof. The sensing region includes a sensing film for sorbing a quantity of the photoresist-stripping agent, thereby altering or shifting a frequency of oscillation of an acoustic wave propagating through the sensing region for indicating an ambient concentration of the agent. According to preferred embodiments of the invention, the acoustic-wave device is a SAW device; and the sensing film comprises poly(vinylacetate), poly(N-vinylpyrrolidinone), or poly(vinylphenol).

Pollen-imprinted polyurethanes for QCM allergen sensors.

PubMed

Jenik, Michael; Seifner, Alexandra; Lieberzeit, Peter; Dickert, Franz L

2009-05-01

Molecularly imprinted polymers for detecting plant pollen were designed as artificial recognition materials for quartz crystal microbalances in the gaseous phase. Imprints of birch (diameter, 25 mum) and nettle (diameter, 15 mum) pollen can be generated by polydimethylsiloxane stamping technique as proven by atomic force microscopy. If pollen grains are able to access the cavities and thus are incorporated, the resulting sensors display Sauerbrey-like negative frequency shifts. Non-Sauerbrey behaviour can be observed as soon as pollen is prevented from entering the selective hollows: this results in grain mobility on the electrode surface leading to frequency increases. Access to the cavities is determined by the diameter ratio between pollen grains and imprints as can be revealed during cross-selectivity measurements of nettle and birch pollen imprinted layers. When the amount of pollen grains on the electrode surface exceeds the number of available imprints, the excess particles move freely, resulting in positive, non-Sauerbrey frequency shifts.

Design considerations of Miller oscillators for high-sensitivity QCM sensors in damping media.

PubMed

Rodriguez-Pardo, Loreto; Fariña, Jose; Gabrielli, Claude; Perrot, Hubert; Brendel, Remi

2007-10-01

In this paper, a new contribution to the design of quartz crystal oscillators for high-sensitivity microbalance sensors used in liquid media is presented. The oscillation condition for a Miller configuration was studied to work in a wide dynamic range of the resonator losses. The equations relating the values of the active and passive components with the maximum supported damping and mass were obtained. Also, the conditions to obtain a stable frequency according to the resonator damping (R(Q)), the static capacity (Cp) and the filter frequency (f(F)) were found. Under these conditions, the circuit oscillation frequency will be proportional to the resonant series frequency and does not depend on the previous parameters (R(Q), f(F), and Cp). If these conditions cannot be satisfied, the expression of the oscillation frequency is given and the discrimination of these effects is obtained through resonator frequency measurements.

Adhesion of Blood Plasma Proteins and Platelet-rich Plasma on l-Valine-Based Poly(ester urea).

PubMed

Childers, Erin P; Peterson, Gregory I; Ellenberger, Alex B; Domino, Karen; Seifert, Gabrielle V; Becker, Matthew L

2016-10-10

The competitive absorption of blood plasma components including fibrinogen (FG), bovine serum albumin (BSA), and platelet-rich plasma (PRP) on l-valine-based poly(ester urea) (PEU) surfaces were investigated. Using four different PEU polymers, possessing compositionally dependent trends in thermal, mechanical, and critical surface tension measurements, water uptake studies were carried out to determine in vitro behavior of the materials. Quartz crystal microbalance (QCM) measurements were used to quantify the adsorption characteristics of PRP onto PEU thin films by coating the surfaces initially with FG or BSA. Pretreatment of the PEU surfaces with FG inhibited the adsorption of PRP and BSA decreased the absorption 4-fold. In vitro studies demonstrated that cells cultured on l-valine-based PEU thin films allowed attachment and spreading of rat aortic cells. These measurements will be critical toward efforts to use this new class of materials in blood-contacting biomaterials applications.

Photoresponsive peptide azobenzene conjugates that specifically interact with platinum surfaces

NASA Astrophysics Data System (ADS)

Dinçer, S.; Tamerler, C.; Sarıkaya, M.; Pişkin, E.

2008-05-01

The aim of this study is to prepare photoresponsive peptide-azobenzene compounds which interacts with platinum surfaces specifically, in order to create smart surfaces for further novel applications in design of smart biosensors and array platforms. Here, a water-soluble azobenzene molecule, 4-hydroxyazo benzene,4-sulfonic acid was synthesized by diazo coupling reaction. A platinum-specific peptide, originally selected by a phage display technique was chemically synthesized/purchased, and conjugated with the azobenzene compound activated with carbonyldiimidazole. Both azobenzene and its conjugate were characterized (including photoresponsive properties) by FTIR, NMR, and UV-spectrophotometer. The yield of conjugation reaction estimated by ninhydrin assay was about 65%. Peptide incorporation did not restrict the light-sensitivity of azobenzene. Adsorption of both the peptide and its azobenzene conjugate was followed by Quartz Crystal Microbalance (QCM) system. The kinetic evaluations exhibited that both molecules interact platinum surfaces, quite rapidly and strongly.

A gravimetric analysis of protein-oligosaccharide interactions.

PubMed

Rudd, T; Gallagher, J T; Ron, D; Nichols, R J; Fernig, D G

2003-04-01

Interactions between an immobilized, heparin-derived octasaccharide and growth factors have been observed using a quartz crystal microbalance-dissipation (QCM-D). This device can measure the amount of growth factors binding to the octasaccharide surface and also the change of dissipation of the surface. Dissipation is a measure of how the adhered material 'damps' the surface vibrations. The octasaccharides were anchored through their reducing ends by the intermediary of the alkanethiol molecule, which covalently binds to the crystal surface through the thiol group. As expected, heparin sulphate binding growth factors bound to the octasaccharide, but the change in mass of growth factor bound per unit change in dissipation is different for the different growth factors. Suggesting that the structures of the various growth factor-octasaccharide complexes are different, therefore, indicates that the change in dissipation can give insights into the structure, orientation and packing of the oligosaccharide-growth factor complexes.

Plasma deposited polymers as gas sensitive films

NASA Astrophysics Data System (ADS)

Radeva, E.; Georgieva, V.; Lazarov, J.; Vergov, L.; Donkov, N.

2012-03-01

The possibility is presented of producing thin plasma polymers with desired properties by using nanofillers. Composite films are synthesized from a mixture of hexamethyldisiloxane (HMDSO) and detonation nanodiamond particles (DNDs). The chemical structure of the composite consists of DNDs distributed in the polymer matrix. The effect of DNDs on the humidity and ammonia sorptive properties of the polymers obtained is studied by measuring the mass changes as a result of gas sorption by using a quartz crystal microbalance (QCM). The results show that, in view of building a sensing element for measuring humidity, ammonia or other gases, it is possible to maximize the sensor sensitivity to a certain gas by using an appropriate concentration of DNDs in HMDSO. Thus, a high degree of sensor sensitivity, together with short response time and minimum hysteresis, can be achieved. Composites of plasma-polymerized HMDSO with DNDs can be used as gas sensitive layers for the development of quartz resonator sensors.

Liquid in a tube oscillating along its axis

NASA Astrophysics Data System (ADS)

Zhdanov, Vladimir P.; Kasemo, Bengt

2015-06-01

The Quartz Crystal Microbalance with Dissipation (QCM-D) sensing technique has become widely used to study various supported thin films and adsorption of biological macromolecules, nanoparticles, aggregates, and cells. Such sensing, based on tracking shear oscillations of a piezoelectric crystal, can be employed in situations which are far beyond conventional ones. For example, one can deposit tubes on the surface of a sensor, orient them along the direction of the sensor surface oscillations, and study liquid oscillations inside the oscillating tubes. Herein, we illustrate and classify theoretically the regimes of liquid oscillations in this case. In particular, we identify and scrutinize the transition from the regime with appreciable gradients along the radial coordinate, which are qualitatively similar to those near the oscillating flat interface, to the regime where the liquid oscillates nearly coherently in the whole tube. The results are not only of relevance for the specific case of nanotubes but also for studies of certain mesoporous samples.

Interaction of bovine serum albumin protein with self assembled monolayer of mercaptoundecanoic acid

NASA Astrophysics Data System (ADS)

Poonia, Monika; Agarwal, Hitesh; Manjuladevi, V.; Gupta, R. K.

2016-05-01

Detection of proteins and other biomolecules in liquid phase is the essence for the design of a biosensor. The sensitivity of a sensor can be enhanced by the appropriate functionalization of the sensing area so as to establish the molecular specific interaction. In the present work, we have studied the interaction of bovine serum albumin (BSA) protein with a chemically functionalized surface using a quartz crystal microbalance (QCM). The gold-coated quartz crystals (AT-cut/5 MHz) were functionalized by forming self-assembled monolayer (SAM) of 11-Mercaptoundecanoic acid (MUA). The adsorption characteristics of BSA onto SAM of MUA on quartz crystal are reported. BSA showed the highest affinity for SAM of MUA as compared to pure gold surface. The SAM of MUA provides carboxylated surface which enhances not only the adsorption of the BSA protein but also a very stable BSA-MUA complex in the liquid phase.

QCM gas phase detection with ceramic materials--VOCs and oil vapors.

PubMed

Latif, Usman; Rohrer, Andreas; Lieberzeit, Peter A; Dickert, Franz L

2011-06-01

Titanate sol-gel layers imprinted with carbonic acids were used as sensitive layers on quartz crystal microbalance. These functionalized ceramics enable us detection of volatile organic compounds such as ethanol, n-propanol, n-butanol, n-hexane, n-heptane, n-/iso-octane, and n-decane. Variation of the precursors (i.e., tetrabutoxy titanium, tetrapropoxy titanium, tetraethoxy titanium) allows us to tune the sensitivity of the material by a factor of 7. Sensitivity as a function of precursors leads to selective inclusion of n-butanol vapors down to 1 ppm. The selectivity of materials is optimized to differentiate between isomers, e.g., n- and iso-octane. The results can be rationalized by correlating the sensor effects of hydrocarbons with the Wiener index. A mass-sensitive sensor based on titanate layer was also developed for monitoring emanation of degraded engine oil. Heating the sensor by a meander avoids vapor condensation. Thus, a continuously working oil quality sensor was designed.

Imparting biomolecules to a metal-organic framework material by controlled DNA tetrahedron encapsulation

PubMed Central

Jia, Yongmei; Wei, Benmei; Duan, Ruixue; Zhang, Ying; Wang, Boya; Hakeem, Abdul; Liu, Nannan; Ou, Xiaowen; Xu, Shaofang; Chen, Zhifei; Lou, Xiaoding; Xia, Fan

2014-01-01

Recently, the incorporation of biomolecules in Metal-organic frameworks (MOFs) attracts many attentions because of controlling the functions, properties and stability of trapped molecules. Although there are few reports on protein/MOFs composites and their applications, none of DNA/MOFs composite is reported, as far as we know. Here, we report a new composite material which is self-assembled from 3D DNA (guest) and pre-synthesized MOFs (host) by electrostatic interactions and hydrophilic interactions in a well-dispersed fashion. Its biophysical characterization is well analyzed by fluorescence spectroscopy, quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). This new composite material keeps 3D DNA nanostructure more stable than only 3D DNA nanostructure in DI water at room temperature, and stores amounts of genetic information. It will make DNA as a guest for MOFs and MOFs become a new platform for the development of DNA nanotechnology. PMID:25090047

Water transport and clustering behavior in homopolymer and graft copolymer polylactide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, An; Koo, Donghun; Theryo, Grayce

2015-02-19

Polylactide is a bio-based and biodegradable polymer well-known for its renewable origins. Water sorption and clustering behavior in both a homopolymer polylactide and a graft copolymer of polylactide was studied using the quartz crystal microbalance/heat conduction calorimetry (QCM/HCC) technique. The graft copolymer, poly(1,5-cyclooctadiene-co-5-norbornene-2-methanol-graft-D,L-lactide), contained polylactide chains (95 wt.%) grafted onto a hydrophobic rubbery backbone (5 wt.%). Clustering is an important phenomenon in the study of water transport properties in polymers since the presence of water clusters can affect the water diffusivity. The HCC method using the thermal power signals and Van't Hoff's law were both employed to estimate the watermore » sorption enthalpy. Sorption enthalpy of water in both polymers was determined to be approximately -40 kJ/mol for all water activity levels. Zimm-Lundberg analysis showed that water clusters start to form at a water activity of 0.4. The engaged species induced clustering (ENSIC) model was used to curve fit sorption isotherms and showed that the affinity among water molecules is higher than that between water molecules and polymer chains. All the methods used indicate that clustering of water molecules exists in both polymers.« less

Comparison of Extruded and Sonicated Vesicles for Planar Bilayer Self-Assembly

PubMed Central

Cho, Nam-Joon; Hwang, Lisa Y.; Solandt, Johan J.R.; Frank, Curtis W.

2013-01-01

Lipid vesicles are an important class of biomaterials that have a wide range of applications, including drug delivery, cosmetic formulations and model membrane platforms on solid supports. Depending on the application, properties of a vesicle population such as size distribution, charge and permeability need to be optimized. Preparation methods such as mechanical extrusion and sonication play a key role in controlling these properties, and yet the effects of vesicle preparation method on vesicular properties and integrity (e.g., shape, size, distribution and tension) remain incompletely understood. In this study, we prepared vesicles composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) lipid by either extrusion or sonication, and investigated the effects on vesicle size distribution over time as well as the concomitant effects on the self-assembly of solid-supported planar lipid bilayers. Dynamic light scattering (DLS), quartz crystal microbalance with dissipation (QCM-D) monitoring, fluorescence recovery after photobleaching (FRAP) and atomic force microscopy (AFM) experiments were performed to characterize vesicles in solution as well as their interactions with silicon oxide substrates. Collectively, the data support that sonicated vesicles offer more robust control over the self-assembly of homogenous planar lipid bilayers, whereas extruded vesicles are vulnerable to aging and must be used soon after preparation. PMID:28811437

The molecular adsorption-type endotoxin detection system using immobilized ɛ-polylysine

NASA Astrophysics Data System (ADS)

Ooe, Katsutoshi; Tsuji, Akihito; Nishishita, Naoki; Hirano, Yoshiaki

2007-12-01

Hemodialysis for chronic renal failure is the most popular treatment method with artificial organs. However, hemodialysis patients must continue the treatment throughout their life, the results of long term extracorporeal dialysis, those patients develop the various complications and diseases, for example, dialysis amyloidosis etc. Dialysis amyloidosis is one of the refractory complications, and endotoxin is thought to be the most likely cause of it, recently. Endotoxin is one of the major cell wall components of gram-negative bacteria, and it has various biological activities. In addition, it is known that a mount of endotoxin exists in living environment, and medicine is often contaminated with endotoxin. When contaminated dialyzing fluids are used to hemodialysis, above-mentioned dialysis amyloidosis is developed. Therefore, it is important that the detection and removal of endotoxin from dialyzing fluids. Until now, the measurement methods using Limulus Amebosyte Lysate (LAL) reagent were carried out as the tests for the presence of endtoxin. However, these methods include several different varieties of measurement techniques. The following are examples of them, gelatinization method, turbidimetric assay method, colorimetric assay method and fluoroscopic method. However, these techniques needed 30-60 minutes for the measurement. From these facts, they are not able to use as a "real-time endotoxin detector". The detection of endotoxin has needed to carry out immediately, for that reason, a new detection method is desired. In this research, we focused attention to adsorption reaction between ɛ-polylysine and endotoxin. ɛ-polylysine has the structure of straight chain molecule composed by 25-30 residues made by lysine, and it is used as an antimicrobial agent, moreover, cellulose beads with immobilized ɛ-polylysine is used as the barrier filter for endotoxin removal. The endotoxin is adsorbed to immobilized ɛ-polylysine, as the result of this reaction, the mass incrementation is occurred, and the existence of endtoxin can be detected immediately, by using of Quartz Crystal Microbalance (QCM). In this report, the immobilization of ɛ-polylysine onto the Au and Si substrate and its adsorptive activity are described. We use X-ray Photoelectron Spectroscopy (XPS) to confirm the ɛ-polylysine immobilization, and the adsorptive activity of immobilized ɛ-polylysine is measured by AFM and QCM. This molecular adsorption type endotoxin sensor aims to the realization of "real-time endotoxin detection system".

Use of a small overpotential approximation to analyze Geobacter sulfurreducens biofilm impedance

NASA Astrophysics Data System (ADS)

Babauta, Jerome T.; Beyenal, Haluk

2017-07-01

The electrochemical impedance of Geobacter sulfurreducens biofilms reflects the extracellular electron transfer mechanisms determining the rate of current output. Binned into two characteristic parameters, conductance and capacitance, biofilm impedance has received significant attention. The goal of this study was to evaluate a small overpotential approximation for extracellular electron transfer in G. sulfurreducens biofilms. Our motivation was to determine whether conductance over biofilm growth behaved linearly with respect to limiting current. Biofilm impedance was tracked during growth using electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (eQCM). We showed that normalization of the biofilm impedance is useful for characterizing the changes during growth. When the conductance and capacitance were compared to the biofilm current, we found that: 1) conductance had a linear response and 2) constant phase elements (CPE) had a saturating response that coincided with the limiting current. We provided a framework using a simple iV relationship that predicted the conductance-current slope to be 9.57 V-1. CPEs showed more variability across biofilm replicates than conductance values. Although G. sulfurreducens biofilms were used here, other electrochemically active biofilms exhibiting catalytic waves could be studied using the same methods.

Investigation of a sterilization system using active oxygen species generated by ultraviolet irradiation.

PubMed

Yoshino, Kiyoshi; Matsumoto, Hiroyuki; Iwasaki, Tatsuyuki; Kinoshita, Shinobu; Noda, Kazutoshi; Oya, Kei; Iwamori, Satoru

2015-01-01

We have been investigating an advanced sterilization system that employs active oxygen species (AOS). We designed the sterilization equipment, including an evacuation system, which generates AOS from pure oxygen gas using ultraviolet irradiation, in order to study the conditions necessary for sterilization in the system's chamber. Using Geobachillus stearothermophilus spores (10(6) CFU) in a sterile bag as a biological indicator (BI) in the chamber of the AOS sterilization apparatus, we examined the viability of the BI as a function of exposure time, assessing the role of the decompression level in the sterilization performance. We found that the survival curves showed exponential reduction, and that the decompression level did not exert a significant influence on the survival curve. Subsequently, we investigated the sterilization effect as influenced by the spatial and environmental temperature variation throughout the chamber, and found that the sterilization effect varied with position, due to the varying environmental temperature in the respective areas. We confirmed that temperature is one of the most important factors influencing sterilization in the chamber, and estimated the temperature effect on the distribution of atomic oxygen concentration, using the quartz crystal microbalance (QCM) method with fluorocarbon thin film prepared by radio frequency sputtering.

Surface Acoustic Wave (SAW) Resonators for Monitoring Conditioning Film Formation

PubMed Central

Hohmann, Siegfried; Kögel, Svea; Brunner, Yvonne; Schmieg, Barbara; Ewald, Christina; Kirschhöfer, Frank; Brenner-Weiß, Gerald; Länge, Kerstin

2015-01-01

We propose surface acoustic wave (SAW) resonators as a complementary tool for conditioning film monitoring. Conditioning films are formed by adsorption of inorganic and organic substances on a substrate the moment this substrate comes into contact with a liquid phase. In the case of implant insertion, for instance, initial protein adsorption is required to start wound healing, but it will also trigger immune reactions leading to inflammatory responses. The control of the initial protein adsorption would allow to promote the healing process and to suppress adverse immune reactions. Methods to investigate these adsorption processes are available, but it remains difficult to translate measurement results into actual protein binding events. Biosensor transducers allow user-friendly investigation of protein adsorption on different surfaces. The combination of several transduction principles leads to complementary results, allowing a more comprehensive characterization of the adsorbing layer. We introduce SAW resonators as a novel complementary tool for time-resolved conditioning film monitoring. SAW resonators were coated with polymers. The adsorption of the plasma proteins human serum albumin (HSA) and fibrinogen onto the polymer-coated surfaces were monitored. Frequency results were compared with quartz crystal microbalance (QCM) sensor measurements, which confirmed the suitability of the SAW resonators for this application. PMID:26007735

New pattern recognition system in the e-nose for Chinese spirit identification

NASA Astrophysics Data System (ADS)

Hui, Zeng; Qiang, Li; Yu, Gu

2016-02-01

This paper presents a new pattern recognition system for Chinese spirit identification by using the polymer quartz piezoelectric crystal sensor based e-nose. The sensors are designed based on quartz crystal microbalance (QCM) principle, and they could capture different vibration frequency signal values for Chinese spirit identification. For each sensor in an 8-channel sensor array, seven characteristic values of the original vibration frequency signal values, i.e., average value (A), root-mean-square value (RMS), shape factor value (Sf), crest factor value (Cf), impulse factor value (If), clearance factor value (CLf), kurtosis factor value (Kv) are first extracted. Then the dimension of the characteristic values is reduced by the principle components analysis (PCA) method. Finally the back propagation (BP) neutral network algorithm is used to recognize Chinese spirits. The experimental results show that the recognition rate of six kinds of Chinese spirits is 93.33% and our proposed new pattern recognition system can identify Chinese spirits effectively. Project supported by the National High Technology Research and Development Program of China (Grant No. 2013AA030901) and the Fundamental Research Funds for the Central Universities, China (Grant No. FRF-TP-14-120A2).

A self-assembled monolayer-based piezoelectric immunosensor for rapid detection of Escherichia coli O157:H7.

PubMed

Su, Xiao-Li; Li, Yanbin

2004-01-15

A piezoelectric immunosensor was developed for rapid detection of Escherichia coli O157:H7. It was based on the immobilization of affinity-purified antibodies onto a monolayer of 16-mercaptohexadecanoic acid (MHDA), a long-chain carboxylic acid-terminating alkanethiol, self-assembled on an AT-cut quartz crystal's Au electrode surface with N-hydroxysuccinimide (NHS) ester as a reactive intermediate. The binding of target bacteria onto the immobilized antibodies decreased the sensor's resonant frequency, and the frequency shift was correlated to the bacterial concentration. The stepwise assembly of the immunosensor was characterized by means of both quartz crystal microbalance (QCM) and cyclic voltammetry techniques. Three analytical procedures, namely immersion, dip-and-dry and flow-through methods, were investigated. The immunosensor could detect the target bacteria in a range of 10(3)-10(8)CFU/ml within 30-50 min, and the sensor-to-sensor reproducibility obtained at 10(3) and 10(5) colony-forming units (CFU)/ml was 18 and 11% R.S.D., respectively. The proposed sensor was comparable to Protein A-based piezoelectric immunosensor in terms of the amount of immobilized antibodies and detection sensitivity.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

PubMed Central

Chen, Zheng; Wang, Haoran; Wang, Xiao; Chen, Ping; Liu, Yunfei; Zhao, Hongyu; Zhao, Yi; Duan, Yu

2017-01-01

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10−5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime. PMID:28059160

Effect of film morphology on oxygen and water interaction with copper phthalocyanine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Nicholas; Gredig, Thomas; Ivanov, Ilia N

2016-01-01

Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25 C, 150 C, and 250 C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. Mass loading by O2 was enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200 C CuPc transition which allows higher O2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales ofmore » < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O2/H2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold, which is consistent with findings of other studies.« less

Effect of film morphology on oxygen and water interaction with copper phthalocyanine

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Miller, Nicholas; Gredig, Thomas; Ivanov, Ilia N.

2016-09-01

Copper phthalocyanine (CuPc) films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. Mass loading by O2 was enhanced by a factor of 5 in films deposited at 250°C, possibly due to the 200°C CuPc α->β transition which allows higher O2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales < 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O2/H2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold, which is consistent with findings of other studies.

Morphology-defined interaction of copper phthalocyanine with O2/H2O

NASA Astrophysics Data System (ADS)

Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; Gredig, Thomas; Ivanov, Ilia N.

2016-10-01

Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but interaction with ambient gas/vapor may lead to changes in its electronic properties and limit OPV device lifetimes. CuPc films of thickness 25 and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. We measured electrical resistance and film mass in situ during exposure to controlled pulses of O2 and H2O vapor. CuPc films deposited at 250°C showed a factor of 5 higher uptake of O2 as detected by a quartz crystal microbalance (QCM), possibly due to the formation of β-CuPc at T>200°C which allows higher O2 mobility between stacked molecules. While weight-based measurements stabilize after ˜10 min of gas exposure, resistance response stabilizes over times >1 h, suggesting that mass change occurs by rapid adsorption at active surface sites whereas resistive response is dominated by slow diffusion of adsorbates into the bulk film. The 25 nm films exhibit higher resistive response than 100 nm films after an hour of O2/H2O exposure due to fast analyte diffusion down to the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O2/H2O molecules on gold.

Ordered adsorption of coagulation factor XII on negatively charged polymer surfaces probed by sum frequency generation vibrational spectroscopy.

PubMed

Chen, Xiaoyun; Wang, Jie; Paszti, Zoltan; Wang, Fulin; Schrauben, Joel N; Tarabara, Volodymyr V; Schmaier, Alvin H; Chen, Zhan

2007-05-01

Electrostatic interactions between negatively charged polymer surfaces and factor XII (FXII), a blood coagulation factor, were investigated by sum frequency generation (SFG) vibrational spectroscopy, supplemented by several analytical techniques including attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), quartz crystal microbalance (QCM), zeta-potential measurement, and chromogenic assay. A series of sulfonated polystyrenes (sPS) with different sulfonation levels were synthesized as model surfaces with different surface charge densities. SFG spectra collected from FXII adsorbed onto PS and sPS surfaces with different surface charge densities showed remarkable differences in spectral features and especially in spectral intensity. Chromogenic assay experiments showed that highly charged sPS surfaces induced FXII autoactivation. ATR-FTIR and QCM results indicated that adsorption amounts on the PS and sPS surfaces were similar even though the surface charge densities were different. No significant conformational change was observed from FXII adsorbed onto surfaces studied. Using theoretical calculations, the possible contribution from the third-order nonlinear optical effect induced by the surface electric field was evaluated, and it was found to be unable to yield the SFG signal enhancement observed. Therefore it was concluded that the adsorbed FXII orientation and ordering were the main reasons for the remarkable SFG amide I signal increase on sPS surfaces. These investigations indicate that negatively charged surfaces facilitate or induce FXII autoactivation on the molecular level by imposing specific orientation and ordering on the adsorbed protein molecules.

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

Construction of Compact Polyelectrolyte Multilayers Inspired by Marine Mussel: Effects of Salt Concentration and pH As Observed by QCM-D and AFM.

PubMed

Wang, Weina; Xu, Yisheng; Backes, Sebastian; Li, Ang; Micciulla, Samantha; Kayitmazer, A Basak; Li, Li; Guo, Xuhong; von Klitzing, Regine

2016-04-12

Biomimetic multilayers based on layer-by-layer (LbL) assembly were prepared as functional films with compact structure by incorporating the mussel-inspired catechol cross-linking. Dopamine-modified poly(acrylic acid) (PAADopa) was synthesized as a polyanion to offer electrostatic interaction with the prelayer polyethylenimine (PEI) and consecutively cross-linked by zinc to generate compact multilayers with tunable physicochemical properties. In situ layer-by-layer growth and cross-linking were monitored by a quartz crystal microbalance with dissipation (QCM-D) to reveal the kinetics of the process and the influence of Dopa chemistry. Addition of Dopa enhanced the mass adsorption and led to the formation of a more compact structure. An increase of ionic strength induced an increase in mass adsorption in the Dopa-cross-linked multilayers. This is a universal approach for coating of various surfaces such as Au, SiO2, Ti, and Al2O3. Roughness observed by AFM in both wet and dry conditions was compared to confirm the compact morphology of Dopa-cross-linked multilayers. Because of the pH sensitivity of Dopa moiety, metal-chelated Dopa groups can be turned into softer structure at higher pH as revealed by reduction of Young's modulus determined by MFP-3D AFM. A deeper insight into the growth and mechanical properties of Dopa-cross-linked polyelectrolyte multilayers was addressed in the present study. This allows a better control of these systems for bioapplications.

Orientating lipase molecules through surface chemical control for enhanced activity: A QCM-D and ToF-SIMS investigation.

PubMed

Joyce, Paul; Kempson, Ivan; Prestidge, Clive A

2016-06-01

Bio-active materials consisting of lipase encapsulated within porous silica particles were engineered to control the adsorption kinetics and molecular orientation of lipase, which play critical roles in the digestion kinetics of triglycerides. The adsorption kinetics of Candida antartica lipase A (CalA) was monitored using quartz crystal microbalance with dissipation (QCM-D) and controlled by altering the hydrophobicity of a silica binding support. The extent of adsorption was 2-fold greater when CalA was adsorbed onto hydrophobic silica compared to hydrophilic silica. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) fragmentation patterns, in conjunction with multivariate statistics, demonstrated enhanced exposure of the lipase's catalytic domain, specifically the histidine group responsible for activity, when CalA was adsorbed on hydrophilic silica. Consequently, lipid digestion kinetics were enhanced when CalA was loaded in hydrophilic porous silica particles, i.e., a 2-fold increase in the pseudo-first-order rate constant for digestion when compared to free lipase. In contrast, digestion kinetics were inhibited when CalA was hosted in hydrophobic porous silica, i.e., a 5-fold decrease in pseudo-first-order rate constant for digestion when compared to free lipase. These findings provide valuable insights into the mechanism of lipase action which can be exploited to develop smarter food and drug delivery systems consisting of porous lipid-based materials. Copyright © 2016 Elsevier B.V. All rights reserved.

Measuring water adsorption on mineral surfaces in air, CO2, and supercritical CO2 with a quartz-crystal microbalance

NASA Astrophysics Data System (ADS)

Bryan, C. R.; Wells, R. K.; Burton, P. D.; Heath, J. E.; Dewers, T. A.; Wang, Y.

2011-12-01

Carbon sequestration via underground storage in geologic formations is a proposed approach for reducing industrial CO2 emissions. However, current models for carbon injection and long-term storage of supercritical CO2 (scCO2) do not consider the development and stability of adsorbed water films at the scCO2-hydrophilic mineral interface. The thickness and properties of the water films control the surface tension and wettability of the mineral surface, and on the core scale, affect rock permeability, saturation, and capillary properties. The film thickness is strongly dependent upon the activity of water in the supercritical fluid, which will change as initially anhydrous scCO2 absorbs water from formation brine. As described in a companion paper by the coauthors, the thickness of the adsorbed water layer is controlled by the disjoining pressure; structural and van der Waals components dominate at low water activity, while electrostatic forces become more important with increasing film thickness (higher water activities). As scCO2 water activity and water layer thickness increase, concomitant changes in mineral surface properties and reservoir/caprock hydrologic properties will affect the mobility of the aqueous phase and of scCO2. Moreover, the development of a water layer may be critical to mineral dissolution reactions in scCO2. Here, we describe the use of a quartz-crystal microbalance (QCM) to monitor adsorption of water by mineral surfaces. QCMs utilize a piezoelectrically-stimulated quartz wafer to measure adsorbed or deposited mass via changes in vibrational frequency. When used to measure the mass of adsorbed liquid films, the frequency response of the crystal must be corrected for the viscoelastic, rather than elastic, response of the adsorbed layer. Results are presented for adsorption to silica in N2 and CO2 at one bar, and in scCO2. Additional data are presented for water uptake by clays deposited on a QCM wafer. In this case, water uptake occurs by the combined processes of interlayer cation hydration, surface adsorption, and capillary condensation. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the DOE Sandia LDRD Program.

Formation of positively charged gold nanoparticle monolayers on silica sensors.

PubMed

Oćwieja, Magdalena; Maciejewska-Prończuk, Julia; Adamczyk, Zbigniew; Roman, Maciej

2017-09-01

Formation of positively charged gold nanoparticle monolayers on the Si/SiO 2 was studied under in situ conditions using quartz microbalance (QCM). The gold nanoparticles were synthesized in a chemical reduction method using sodium borohydride as reducing agent. Cysteamine hydrochloride was applied to generate a positive surface charge of nanoparticles. The micrographs obtained from transmission electron microscopy (TEM) revealed that the average size of nanoparticles was equal to 12±3nm. The stability of nanoparticle suspensions under controlled pH and ionic strength was determined by dynamic light scattering (DLS). The electrophoretic mobility measurements showed that the zeta potential of nanoparticles was positive, decreasing with ionic strength and pH from 56mV at pH 4.2 and I=10 -4 M to 22mV at pH 8.3 and I=3×10 -3 M. The surface enhanced Raman spectroscopy (SERS) confirmed chemisorption of cysteamine on nanoparticles and the contribution of amine moieties in the generation of nanoparticle charge. The influence of suspension concentration, ionic strength and flow rate on the kinetics of nanoparticle deposition on the sensors was quantitatively determined. It was confirmed that the deposition for the low coverage regime is governed by the bulk mass transfer that results in a linear increase of the coverage with time. The significant increase in the maximum coverage of gold monolayers with ionic strength was interpreted as due to the decreasing range of the electrostatic interactions among deposited particles. Moreover, the hydratation of formed monolayers, their structure and the stability were determined by the comparison of the QCM results with those obtained by AFM and SEM. The experimental data were adequately interpreted in terms of the extended random sequential adsorption (eRSA) model that considers the bulk and surface transfer steps in a rigorous way. The obtained results are useful for a facile fabrication of gold nanoparticle-based biosensors capable to bind target molecules via available amine moieties. Copyright © 2017 Elsevier Inc. All rights reserved.

Mechanism underlying bioinertness of self-assembled monolayers of oligo(ethyleneglycol)-terminated alkanethiols on gold: protein adsorption, platelet adhesion, and surface forces.

PubMed

Hayashi, Tomohiro; Tanaka, Yusaku; Koide, Yuki; Tanaka, Masaru; Hara, Masahiko

2012-08-07

The mechanism underlying the bioinertness of the self-assembled monolayers of oligo(ethylene glycol)-terminated alkanethiol (OEG-SAM) was investigated with protein adsorption experiments, platelet adhesion tests, and surface force measurements with an atomic force microscope (AFM). In this work, we performed systematic analysis with SAMs having various terminal groups (-OEG, -OH, -COOH, -NH(2), and -CH(3)). The results of the protein adsorption experiment by the quartz crystal microbalance (QCM) method suggested that having one EG unit and the neutrality of total charges of the terminal groups are essential for protein-resistance. In particular, QCM with energy dissipation analyses indicated that proteins absorb onto the OEG-SAM via a very weak interaction compared with other SAMs. Contrary to the protein resistance, at least three EG units as well as the charge neutrality of the SAM are found to be required for anti-platelet adhesion. When the identical SAMs were formed on both AFM probe and substrate, our force measurements revealed that only the OEG-SAMs possessing more than two EG units showed strong repulsion in the range of 4 to 6 nm. In addition, we found that the SAMs with other terminal groups did not exhibit such repulsion. The repulsion between OEG-SAMs was always observed independent of solution conditions [NaCl concentration (between 0 and 1 M) and pH (between 3 and 11)] and was not observed in solution mixed with ethanol, which disrupts the three-dimensional network of the water molecules. We therefore concluded that the repulsion originated from structured interfacial water molecules. Considering the correlation between the above results, we propose that the layer of the structured interfacial water with a thickness of 2 to 3 nm (half of the range of the repulsion observed in the surface force measurements) plays an important role in deterring proteins and platelets from adsorption or adhesion.

Solvent-assisted lipid bilayer formation on silicon dioxide and gold.

PubMed

Tabaei, Seyed R; Choi, Jae-Hyeok; Haw Zan, Goh; Zhdanov, Vladimir P; Cho, Nam-Joon

2014-09-02

Planar lipid bilayers on solid supports mimic the fundamental structure of biological membranes and can be investigated using a wide range of surface-sensitive techniques. Despite these advantages, planar bilayer fabrication is challenging, and there are no simple universal methods to form such bilayers on diverse material substrates. One of the novel methods recently proposed and proven to form a planar bilayer on silicon dioxide involves lipid deposition in organic solvent and solvent exchange to influence the phase of adsorbed lipids. To scrutinize the specifics of this solvent-assisted lipid bilayer (SALB) formation method and clarify the limits of its applicability, we have developed a simplified, continuous solvent-exchange version to form planar bilayers on silicon dioxide, gold, and alkanethiol-coated gold (in the latter case, a lipid monolayer is formed to yield a hybrid bilayer) and varied the type of organic solvent and rate of solvent exchange. By tracking the SALB formation process with simultaneous quartz crystal microbalance-dissipation (QCM-D) and ellipsometry, it was determined that the acoustic, optical, and hydration masses along with the acoustic and optical thicknesses, measured at the end of the process, are comparable to those observed by employing conventional fabrication methods (e.g., vesicle fusion). As shown by QCM-D measurements, the obtained planar bilayers are highly resistant to protein adsorption, and several, but not all, water-miscible organic solvents could be successfully used in the SALB procedure, with isopropanol yielding particularly high-quality bilayers. In addition, fluorescence recovery after photobleaching (FRAP) measurements demonstrated that the coefficient of lateral lipid diffusion in the fabricated bilayers corresponds to that measured earlier in the planar bilayers formed by vesicle fusion. With increasing rate of solvent exchange, it was also observed that the bilayer became incomplete and a phenomenological model was developed in order to explain this feature. The results obtained allowed us to clarify and discriminate likely steps of the SALB formation process as well as determine the corresponding influence of organic solvent type and flow conditions on these steps. Taken together, the findings demonstrate that the SALB formation method can be adapted to a continuous solvent-exchange procedure that is technically minimal, quick, and efficient to form planar bilayers on solid supports.

Controlling drug delivery kinetics from mesoporous titania thin films by pore size and surface energy.

PubMed

Karlsson, Johan; Atefyekta, Saba; Andersson, Martin

2015-01-01

The osseointegration capacity of bone-anchoring implants can be improved by the use of drugs that are administrated by an inbuilt drug delivery system. However, to attain superior control of drug delivery and to have the ability to administer drugs of varying size, including proteins, further material development of drug carriers is needed. Mesoporous materials have shown great potential in drug delivery applications to provide and maintain a drug concentration within the therapeutic window for the desired period of time. Moreover, drug delivery from coatings consisting of mesoporous titania has shown to be promising to improve healing of bone-anchoring implants. Here we report on how the delivery of an osteoporosis drug, alendronate, can be controlled by altering pore size and surface energy of mesoporous titania thin films. The pore size was varied from 3.4 nm to 7.2 nm by the use of different structure-directing templates and addition of a swelling agent. The surface energy was also altered by grafting dimethylsilane to the pore walls. The drug uptake and release profiles were monitored in situ using quartz crystal microbalance with dissipation (QCM-D) and it was shown that both pore size and surface energy had a profound effect on both the adsorption and release kinetics of alendronate. The QCM-D data provided evidence that the drug delivery from mesoporous titania films is controlled by a binding-diffusion mechanism. The yielded knowledge of release kinetics is crucial in order to improve the in vivo tissue response associated to therapeutic treatments.

Quartz crystal microbalance (QCM) with immobilized protein receptors: comparison of response to ligand binding for direct protein immobilization and protein attachment via disulfide linker.

PubMed

Baltus, Ruth E; Carmon, Kendra S; Luck, Linda A

2007-03-27

Results from an investigation of the frequency response resulting from ligand binding for a genetically engineered hormone-binding domain of the alpha-estrogen receptor immobilized to a piezoelectric quartz crystal are reported. Two different approaches were used to attach a genetically altered receptor to the gold electrode on the quartz surface: (1) the mutant receptor containing a single solvent-exposed cysteine was directly attached to the crystal via a sulfur to gold covalent bond, forming a self-assembled protein monolayer, and (2) the N-terminal histidine-tagged end was utilized to attach the receptor via a 3,3-dithiobis[N-(5-amino-5-carboxypentyl)propionamide-N',N'-diacetic acid] linker complexed with nickel. Previous studies have shown that these engineered constructs bind 17beta-estradiol and are fully functional. Exposure of the receptor directly attached to the piezoelectric crystal to the known ligand 17beta-estradiol resulted in a measurable frequency response, consistent with a change in conformation of the receptor with ligand binding. However, no response was observed when the receptor immobilized via the linker was exposed to the same ligand. The presence of the linker between the quartz surface and the protein receptor does not allow the crystal to sense the conformational change in the receptor that occurs with ligand binding. These results illustrate that the immobilization strategy used to bind the receptor to the sensor platform is key to eliciting an appropriate response from this biosensor. This study has important implications for the development of QCM-based sensors using protein receptors.

Quantitative Comparison of Protein Adsorption and Conformational Changes on Dielectric-Coated Nanoplasmonic Sensing Arrays.

PubMed

Ferhan, Abdul Rahim; Jackman, Joshua A; Sut, Tun Naw; Cho, Nam-Joon

2018-04-22

Nanoplasmonic sensors are a popular, surface-sensitive measurement tool to investigate biomacromolecular interactions at solid-liquid interfaces, opening the door to a wide range of applications. In addition to high surface sensitivity, nanoplasmonic sensors have versatile surface chemistry options as plasmonic metal nanoparticles can be coated with thin dielectric layers. Within this scope, nanoplasmonic sensors have demonstrated promise for tracking protein adsorption and substrate-induced conformational changes on oxide film-coated arrays, although existing studies have been limited to single substrates. Herein, we investigated human serum albumin (HSA) adsorption onto silica- and titania-coated arrays of plasmonic gold nanodisks by localized surface plasmon resonance (LSPR) measurements and established an analytical framework to compare responses across multiple substrates with different sensitivities. While similar responses were recorded on the two substrates for HSA adsorption under physiologically-relevant ionic strength conditions, distinct substrate-specific behavior was observed at lower ionic strength conditions. With decreasing ionic strength, larger measurement responses occurred for HSA adsorption onto silica surfaces, whereas HSA adsorption onto titania surfaces occurred independently of ionic strength condition. Complementary quartz crystal microbalance-dissipation (QCM-D) measurements were also performed, and the trend in adsorption behavior was similar. Of note, the magnitudes of the ionic strength-dependent LSPR and QCM-D measurement responses varied, and are discussed with respect to the measurement principle and surface sensitivity of each technique. Taken together, our findings demonstrate how the high surface sensitivity of nanoplasmonic sensors can be applied to quantitatively characterize protein adsorption across multiple surfaces, and outline broadly-applicable measurement strategies for biointerfacial science applications.

MEMS for medical technology applications

NASA Astrophysics Data System (ADS)

Frisk, Thomas; Roxhed, Niclas; Stemme, Göran

2007-01-01

This paper gives an in-depth description of two recent projects at the Royal Institute of Technology (KTH) which utilize MEMS and microsystem technology for realization of components intended for specific applications in medical technology and diagnostic instrumentation. By novel use of the DRIE fabrication technology we have developed side-opened out-of-plane silicon microneedles intended for use in transdermal drug delivery applications. The side opening reduces clogging probability during penetration into the skin and increases the up-take area of the liquid in the tissue. These microneedles offer about 200µm deep and pain-free skin penetration. We have been able to combine the microneedle chip with an electrically and heat controlled liquid actuator device where expandable microspheres are used to push doses of drug liquids into the skin. The entire unit is made of low cost materials in the form of a square one cm-sized patch. Finally, the design, fabrication and evaluation of an integrated miniaturized Quartz Crystal Microbalance (QCM) based "electronic nose" microsystem for detection of narcotics is described. The work integrates a novel environment-to-chip sample interface with the sensor element. The choice of multifunctional materials and the geometric features of a four-component microsystem allow a functional integration of a QCM crystal, electrical contacts, fluidic contacts and a sample interface in a single system with minimal assembly effort, a potential for low-cost manufacturing, and a few orders of magnitude reduced in system size (12*12*4 mm 3) and weight compared to commercially available instruments. The sensor chip was successfully used it for the detection of 200 ng of narcotics sample.

Differential solute gas response in ionic-liquid-based QCM arrays: elucidating design factors responsible for discriminative explosive gas sensing.

PubMed

Rehman, Abdul; Hamilton, Andrew; Chung, Alfred; Baker, Gary A; Wang, Zhe; Zeng, Xiangqun

2011-10-15

An eight-sensor array coupling a chemoselective room-temperature ionic liquid (RTIL) with quartz crystal microbalance (QCM) transduction is presented in this work in order to demonstrate the power of this approach in differentiating closely related analytes in sensory devices. The underlying mechanism behind the specific sensory response was explored by (i) studying mass loading and viscoelasticity effects of the sensing layers, predominantly through variation in damping impedance, the combination of which determines the sensitivity; (ii) creation of a solvation model based on Abraham's solvation descriptors which reveals the fact that polarizability and lipophilicity are the main factors influencing the dissolution of gas analytes into the RTILs; and (iii) determination of enthalpy and entropy values for the studied interactions and comparison via a simulation model, which is also effective for pattern discrimination, in order to establish a foundation for the analytical scientist as well as inspiration for synthetic pathways and innovative research into next-generation sensory approaches. The reported sensors displayed an excellent sensitivity with detection limit of <0.2%, fast response and recovery, and a workable temperature range of 27-55 °C and even higher. Linear discriminant analysis (LDA) showed a discrimination accuracy of 86-92% for nitromethane and 1-ethyl-2-nitrobenzene, 71% for different mixtures of nitromethane, and 100% for these analytes when thermodynamic parameters were used as input data. We envisage applications to detecting other nitroaromatics and security-related gas targets, and high-temperature or real-time situations where manual access is restricted, opening up new horizons in chemical sensing. © 2011 American Chemical Society

Role of bovine serum albumin and humic acid in the interaction between SiO2 nanoparticles and model cell membranes.

PubMed

Wei, Xiaoran; Qu, Xiaolei; Ding, Lei; Hu, Jingtian; Jiang, Wei

2016-12-01

Silica nanoparticles (SiO 2 NPs) can cause health hazard after their release into the environment. Adsorption of natural organic matter and biomolecules on SiO 2 NPs alters their surface properties and cytotoxicity. In this study, SiO 2 NPs were treated by bovine serum albumin (BSA) and humic acid (HA) to study their effects on the integrity and fluidity of model cell membranes. Giant and small unilamellar vesicles (GUVs and SUVs) were prepared as model cell membranes in order to avoid the interference of cellular activities. The microscopic observation revealed that the BSA/HA treated (BSA-/HA-) SiO 2 NPs took more time to disrupt membrane than untreated-SiO 2 NPs, because BSA/HA adsorption covered the surface SiOH/SiO - groups and weakened the interaction between NPs and phospholipids. The deposition of SiO 2 NPs on membrane was monitored by a quartz crystal microbalance with dissipation (QCM-D). Untreated- and HA-SiO 2 NPs quickly disrupted the SUV layer on QCM-D sensor; BSA-SiO 2 NPs attached on the membranes but only caused slow vesicle disruption. Untreated-, BSA- and HA-SiO 2 NPs all caused the gelation of the positively-charged membrane, which was evaluated by the generalized polarity values. HA-SiO 2 NPs caused most serious gelation, and BSA-SiO 2 NPs caused the least. Our results demonstrate that the protein adsorption on SiO 2 NPs decreases the NP-induced membrane damage. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interfacial interactions between calcined hydroxyapatite nanocrystals and substrates.

PubMed

Okada, Masahiro; Furukawa, Keiko; Serizawa, Takeshi; Yanagisawa, Yoshihiko; Tanaka, Hidekazu; Kawai, Tomoji; Furuzono, Tsutomu

2009-06-02

Interfacial interactions between calcined hydroxyapatite (HAp) nanocrystals and surface-modified substrates were investigated by measuring adsorption behavior and adhesion strength with a quartz crystal microbalance (QCM) and a contact-mode atomic force microscope (AFM), respectively. The goal was to develop better control of HAp-nanocrystal coatings on biomedical materials. HAp nanocrystals with rodlike or spherical morphology were prepared by a wet chemical process followed by calcination at 800 degrees C with an antisintering agent to prevent the formation of sintered polycrystals. The substrate surface was modified by chemical reaction with a low-molecular-weight compound, or graft polymerization with a functional monomer. QCM measurement showed that the rodlike HAp nanocrystals adsorbed preferentially onto anionic COOH-modified substrates compared to cationic NH2- or hydrophobic CH3-modified substrates. On the other hand, the spherical nanocrystals adsorbed onto NH2- and COOH-modified substrates, which indicates that the surface properties of the HAp nanocrystals determined their adsorption behavior. The adhesion strength, which was estimated from the force required to move the nanocrystal in contact-mode AFM, on a COOH-grafted substrate prepared by graft polymerization was almost 9 times larger than that on a COOH-modified substrate prepared by chemical reaction with a low-molecular-weight compound, indicating that the long-chain polymer grafted on the substrate mitigated the surface roughness mismatch between the nanocrystal and the substrate. The adhesion strength of the nanocrystal bonded covalently by the coupling reaction to a Si(OCH3)-grafted substrate prepared by graft polymerization was approximately 1.5 times larger than that when adsorbed on the COOH-grafted substrate.

Glucose monitoring using a polymer brush modified polypropylene hollow fiber-based hydraulic flow sensor.

PubMed

Fortin, Nicolas; Klok, Harm-Anton

2015-03-04

Tight regulation of blood glucose levels of diabetic patients requires durable and robust continuous glucose sensing schemes. This manuscript reports the fabrication of ultrathin, phenylboronic acid (PBA) functionalized polymer brushes that swell upon glucose binding and which were integrated as the sensing interface in a new polypropylene hollow fiber (PPHF)-based hydraulic flow glucose sensor prototype. The polymer brushes were prepared via surface-initiated atom transfer radical polymerization of sodium methacrylate followed by postpolymerization modification with 3-aminophenyl boronic acid. In a first series of experiments, the glucose-response of PBA-functionalized poly(methacrylic acid) (PMAA) brushes grafted from planar silicon surfaces was investigated by quartz crystal microbalance with dissipation (QCM-D) and atomic force microscopy (AFM) experiments. The QCM-D experiments revealed a more or less linear change of the frequency shift for glucose concentrations up to ∼10 mM and demonstrated that glucose binding was completely reversible for up to seven switching cycles. The AFM experiments indicated that glucose binding was accompanied by an increase in the film thickness of the PBA functionalized PMAA brushes. The PBA functionalized PMAA brushes were subsequently grafted from the surface of PPHF membranes. The hydraulic permeability of these porous fibers depends on the thickness and swelling of the PMAA brush coating. PBA functionalized brush-coated PPHFs showed a decrease in flux upon exposure to glucose, which is consistent with swelling of the brush coating. Because they avoid the use of enzymes and do not rely on an electrochemical transduction scheme, these PPHF-based hydraulic flow sensors could represent an interesting alternative class of continuous glucose sensors.

Formation and composition of adsorbates on hydrophobic carbon surfaces from aqueous laccase-maltodextrin mixture suspension

NASA Astrophysics Data System (ADS)

Corrales Ureña, Yendry Regina; Lisboa-Filho, Paulo Noronha; Szardenings, Michael; Gätjen, Linda; Noeske, Paul-Ludwig Michael; Rischka, Klaus

2016-11-01

A robust procedure for the surface bio-functionalization of carbon surfaces was developed. It consists on the modification of carbon materials in contact with an aqueous suspension of the enzyme laccase from Trametes versicolor and the lyophilization agent maltodextrin, with the pH value adjusted close to the isoelectric point of the enzyme. We report in-situ investigations applying Quartz Crystal Microbalance with Dissipation (QCM-D) for carbon-coated sensor surfaces and, moreover, ex-situ measurements with static contact angle measurements, X-ray Photoelectron Spectroscopy (XPS) and Scanning Force Microscopy (SFM) for smooth Highly Oriented Pyrolytic Graphite (HOPG) substrates, for contact times between the enzyme formulation and the carbon material surface ranging from 20 s to 24 h. QCM-D studies reveals the formation of rigid layer of biomaterial, a few nanometers thin, which shows a strongly improved wettability of the substrate surface upon contact angle measurements. Following spectroscopic characterization, these layers are composed of mixtures of laccase and maltodextrin. The formation of these adsorbates is attributed to attractive interactions between laccase, the maltodextrin-based lyophilization agent and the hydrophobic carbon surfaces; a short-term contact between the aqueous laccase mixture suspension and HOPG surfaces is shown to merely result in de-wetting patterns influencing the results of contact angle measurements. The new enzyme-based surface modification of carbon-based materials is suggested to be applicable for the improvement of not only the wettability of low energy substrate surfaces with fluid formulations like coatings or adhesives, but also their adhesion in contact with hardened polymers.

Evaluation of different micro/nanobeads used as amplifiers in QCM immunosensor for more sensitive detection of E. coli O157:H7.

PubMed

Jiang, Xuesong; Wang, Ronghui; Wang, Yun; Su, Xiaoli; Ying, Yibin; Wang, Jianping; Li, Yanbin

2011-11-15

Micro/nanobeads with different materials (magnetic, silica and polymer) and different sizes (diameters from 30nm to 970nm) were investigated for their use as amplifiers in a quartz crystal microbalance (QCM) immunosensor for more sensitive detection of Escherichia coli O157:H7. The micro/nanobeads were conjugated with anti-E. coli antibodies. E. coli O157:H7 cells were first captured by the first antibody immobilized on the electrode surface, and then micro/nanobeads labeled secondary antibodies attached to the cells, and finally the complexes of antibody-E. coli-antibody modified beads were formed. The results showed that antibody-labeled beads lead to signal amplification in both the change in frequency (ΔF) and the change in resistance (ΔR). Since the penetration depth of the oscillation-induced shear-waves for a ∼8MHz crystal is limited to 200nm, the interpretation of how the signal is amplified by the adsorbed particles was represented in terms of the coupled-oscillator theory. The amplification is not sensed in terms of increase in mass on the sensor surface. Amplification is sensed as a change in bacterial resonance frequency when the spheres adsorb to the bacteria. The change in the values of ΔF caused by different micro/nanobeads (amplifiers) attaching on target bacterial cells is indicative of the ratio between the resonance frequency of the absorbed bacterial-particle complex (ω(s)), and the resonance frequency of the crystal (ω). Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of hydration of sugar groups on adsorption of Quillaja bark saponin at air/water and Si/water interfaces.

PubMed

Wojciechowski, Kamil; Orczyk, Marta; Marcinkowski, Kuba; Kobiela, Tomasz; Trapp, Marcus; Gutberlet, Thomas; Geue, Thomas

2014-05-01

Adsorption of a natural glycoside surfactant Quillaja bark saponin ("QBS", Sigma Aldrich 84510) was studied at the air/water and Si/water interfaces using a combination of surface pressure (SP), surface dilatational rheology, neutron reflectivity (NR), Infra-Red Attenuated Total Reflection Spectroscopy (IR ATR) and Quartz Crystal Microbalance (QCM). The adsorbed layers formed at the air/water interface are predominantly elastic, with the dilatational surface storage modulus reaching the maximum value of E'=184 mN/m. The NR results point to a strong hydration of the adsorbed layers (about 65% hydration, corresponding to about 60 molecules of water per one QBS molecule), most likely related to the presence of multiple sugar groups constituting the glycone part of the QBS molecules. With a layer thickness of 19 Å, the adsorbed amount obtained from NR seems largely underestimated in comparison to the value obtained from the surface tension isotherm. While this high extent of hydration does not prevent formation of dense and highly elastic layers at the air-water surface, QBS adsorption at the Si/water interface is much weaker. The adsorption isotherm of QBS on Si obtained from the QCM study reflects much lower affinity of highly hydrated and negatively charged saponin molecules to the Si/water interface. We postulate that at the air/water interface, QBS adsorbs through the triterpene aglycone moiety. In contrast, weak hydrogen bonding between the glycone part and the surface silanol groups of Si is responsible for QBS adsorption on more polar Si/water interface. Copyright © 2014 Elsevier B.V. All rights reserved.

Nanoparticle-based immunosensor with apoferritin templated metallic phosphate label for quantification of phosphorylated acetylcholinesterase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Dan; Chen, Aiqiong; Xie, Yunying

2011-05-15

A new sandwich-like electrochemical immunosensor has been developed for quantification of organophosphorylated acetylcholinesterase (OP-AChE), an exposure biomarker of organophosphate pesticides and nerve agents. Zirconia nanoparticles (ZrO2 NPs) were anchored on a screen printed electrode (SPE) to preferably capture OP-AChE adducts by metal chelation with phospho-moieties, which was selectively recognized by lead phosphate-apoferritin labeled anti-AChE antibody (LPA-anti-AChE). The sandwich-like immunoreactions were performed among ZrO2 NPs, OP-AChE and LPA-anti-AChE to form ZrO2/OP-AChE/LPA-anti-AChE complex and the released lead ions were detected on a disposable SPE. The binding affinity was investigated by both square wave voltammetry (SWV) and quartz crystal microbalance (QCM) measurements. Themore » proposed immunosensor yielded a linear response current over a broad OP-AChE concentrations range from 0.05 nM to 10 nM, with detection limit of 0.02 nM, which has enough sensitivity for monitoring of low-dose exposure to OPs. This method avoids the drawback of unavailability of commercial OP-specific antibody as well as amplifies detection signal by using apoferritin encoded metallic phosphate nanoparticle tags. This nanoparticle-based immunosensor offers a new method for rapid, sensitive, selective and inexpensive quantification of phosphorylated adducts for monitoring of OP pesticides and nerve agents exposures.« less

Preparation and characterization of PTFE coating in new polymer quartz piezoelectric crystal sensor for testing liquor products

NASA Astrophysics Data System (ADS)

Gu, Yu; Li, Qiang

2015-07-01

A new method was developed based on the electron beam vacuum dispersion (EBVD) technology to prepare the PTFE polymer coating of the new polymer quartz piezoelectric crystal sensor for testing liquor products. The new method was applied in the new EBVD equipment which we designed. A real-time system monitoring the polymer coating’s thickness was designed for the new EBVD equipment according to the quartz crystal microbalance (QCM) principle, playing an important role in preparing stable and uniform PTFE polymer coatings of the same thickness. 30 pieces of PTFE polymer coatings on the surface of the quartz crystal basis were prepared with the PTFE polymer ultrafine powder (purity ≥ 99.99%) as the starting material. We obtained 30 pieces of new PTFE polymer sensors. By using scanning electron microscopy (SEM), the structure of the PTFE polymer coating’s column clusters was studied. One sample from the 30 pieces of new PTFE polymer sensors was analysed by SEM in four scales, i.e., 400×, 1000×, 10000×, and 25000×. It was shown that under the condition of high bias voltage and low bias current, uniformly PTFE polymer coating could be achieved, which indicates that the new EBVD equipment is suitable for mass production of stable and uniform polymer coating. Project supported by the National High Technology Research and Development Program of China (Grant No. 2013AA030901).

Ionic Strength, Surface Charge, and Packing Density Effects on the Properties of Peptide Self-Assembled Monolayers.

PubMed

Leo, Norman; Liu, Juan; Archbold, Ian; Tang, Yongan; Zeng, Xiangqun

2017-02-28

The various environmental parameters of packing density, ionic strength, and solution charge were examined for their effects on the properties of the immobilized peptide mimotope CH19 (CGSGSGSQLGPYELWELSH) that binds with the therapeutic antibody Trastuzumab (Herceptin) on a gold substrate. The immobilization of CH19 onto gold was examined with a quartz crystal microbalance (QCM). The QCM data showed the presence of intermolecular interactions resulting in the increase of viscoelastic properties of the peptide self-assembled monolayer (SAM). The CH19 SAM was diluted with CS7 (CGSGSGS) to decrease the packing density as CH19/CS7. The packing density and ionic strength parameters were evaluated by atomic force microscopy (AFM), ellipsometry, and QCM. AFM and ellipsometry showed a distinct conformational difference between CH19 and CH19/CS7, indicating a relationship between packing density and conformational state of the immobilized peptide. The CH19 SAM thickness was 40 Å with a rough topology, while the CH19/CS7 SAM thickness was 20 Å with a smooth topology. The affinity studies showed that the affinity of CH19 and CH19/CS7 to Trastuzumab were both on the order of 10 7 M -1 in undiluted PBS buffer, while the dilution of the buffer by 1000× increased both SAMs affinities to Trastuzumab to the order of 10 15 M -2 and changed the binding behavior from noncooperative to cooperative binding. This indicated that ionic strength had a more pronounced effect on binding properties of the CH19 SAM than packing density. Electrochemical impedance spectroscopy (EIS) was conducted on the CH19/CS7 SAM, which showed an increase in impedance after each EIS measurement cycle. Cyclic voltammetry on the CH19/CS7 SAM decreased impedance to near initial values. The impact of the packing density, buffer ionic strength, and local charge perturbation of the peptide SAM properties was interpreted based on the titratable sites in CH19 that could participate in the proton transfer and water equilibrium.

Real-Time Observation of Atomic Layer Deposition Inhibition: Metal Oxide Growth on Self-Assembled Alkanethiols

DOE PAGES

Avila, Jason R.; DeMarco, Erica J.; Emery, Jonathan D.; ...

2014-07-21

Through in-situ quartz crystal microbalance (QCM) monitoring we resolve the growth of a self-assembled monolayer (SAM) and subsequent metal oxide deposition with high resolution. Here, we introduce the fitting of mass deposited during each atomic layer deposition (ALD) cycle to an analytical island-growth model that enables quantification of growth inhibition, nucleation density, and the uninhibited ALD growth rate. A long-chain alkanethiol was self-assembled as a monolayer on gold-coated quartz crystals in order to investigate its effectiveness as a barrier to ALD. Compared to solution-loading, vapor-loading is observed to produce a SAM with equal or greater inhibition-ability in minutes vs. days.more » The metal oxide growth temperature and the choice of precursor also significantly affect the nucleation density, which ranges from 0.001 to 1 sites/nm 2. Finally, we observe a minimum 100 cycle inhibition of an oxide ALD process, ZnO, under moderately optimized conditions.« less

30 s Response Time of K+ Ion-Selective Hydrogels Functionalized with 18-Crown-6 Ether Based on QCM Sensor.

PubMed

Zhang, Zhenxiao; Dou, Qian; Gao, Hongkai; Bai, Bing; Zhang, Yongmei; Hu, Debo; Yetisen, Ali K; Butt, Haider; Yang, Xiaoxia; Li, Congju; Dai, Qing

2018-03-01

Potassium detection is critical in monitoring imbalances in electrolytes and physiological status. The development of rapid and robust potassium sensors is desirable in clinical chemistry and point-of-care applications. In this study, composite supramolecular hydrogels are investigated: polyethylene glycol methacrylate and acrylamide copolymer (P(PEGMA-co-AM)) are functionalized with 18-crown-6 ether by employing surface initiated polymerization. Real-time potassium ion monitoring is realized by combining these compounds with quartz crystal microbalance. The device demonstrates a rapid response time of ≈30 s and a concentration detection range from 0.5 to 7.0 × 10 -3 m. These hydrogels also exhibit high reusability and K + ion selectivity relative to other cations in biofluids such as Na + , NH 4 + , Mg 2+ , and Ca 2+ . These results provide a new approach for sensing alkali metal ions using P(PEGMA-co-AM) hydrogels. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lignin-based polyoxyethylene ether enhanced enzymatic hydrolysis of lignocelluloses by dispersing cellulase aggregates.

PubMed

Lin, Xuliang; Qiu, Xueqing; Yuan, Long; Li, Zihao; Lou, Hongming; Zhou, Mingsong; Yang, Dongjie

2015-06-01

Water-soluble lignin-based polyoxyethylene ether (EHL-PEG), prepared from enzymatic hydrolysis lignin (EHL) and polyethylene glycol (PEG1000), was used to improve enzymatic hydrolysis efficiency of corn stover. The glucose yield of corn stover at 72h was increased from 16.7% to 70.1% by EHL-PEG, while increase in yield with PEG4600 alone was 52.3%. With the increase of lignin content, EHL-PEG improved enzymatic hydrolysis of microcrystalline cellulose more obvious than PEG4600. EHL-PEG could reduce at least 88% of the adsorption of cellulase on the lignin film measured by quartz crystal microbalance with dissipation monitoring (QCM-D), while reduction with PEG4600 was 43%. Cellulase aggregated at 1220nm in acetate buffer analyzed by dynamic light scattering. EHL-PEG dispersed cellulase aggregates and formed smaller aggregates with cellulase, thereby, reduced significantly nonproductive adsorption of cellulase on lignin and enhanced enzymatic hydrolysis of lignocelluloses. Copyright © 2015 Elsevier Ltd. All rights reserved.

Immobilization effects on the photocatalytic activity of CdS quantum Dots-Horseradish peroxidase hybrid nanomaterials.

PubMed

Iñarritu, Iker; Torres, Eduardo; Topete, Antonio; Campos-Terán, José

2017-11-15

The potential use of hybrid nanomaterials based on inorganic optically active nanoparticles known as quantum dots (QDs) and horseradish peroxidase (HRP) has been proposed by several authors as light-controllable nanocatalyzers, moreover, the immobilization within or over silica based supports represents an advantage over bulk-dispersed systems. However, the implications of the immobilization of such hybrid photoactivatable catalyzing systems have not been clarified with detail. Here, we present a thorough study of the functional photoactive efficiency and recycling of immobilized CdS QDs and HRP systems with different configurations, immobilized over silanized silica quartz crystal microbalance (QCM) sensors, allowing an accurate measure of the immobilized mass of each component and its correlation with the initial reaction rate of conversion of Amplex Red (AR) to resorufin. As well, the conversion efficiency is compared between the different systems and also to non-immobilized QD-HRP complexed systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Chitosan adsorption on nanofibrillated cellulose with different aldehyde content and interaction with phosphate buffered saline.

PubMed

Ondaral, Sedat; Çelik, Elif; Kurtuluş, Orçun Çağlar; Aşıkuzun, Elif; Yakın, İsmail

2018-04-15

The chitosan adsorption on films prepared using nanofibrillated cellulose (NFC) with different content of aldehyde group was studied by means of Quartz Crystal Microbalance with Dissipation (QCM-D). Results showed that frequency change (Δf) was higher when the chitosan adsorbed on NFC film consisting more aldehyde group indicating the higher adsorption. The (Δf) and dissipation (ΔD) factors completely changed during adsorption of chitosan pre-treated with acetic acid: Δf increased and ΔD decreased, oppositely to un-treated chitosan adsorption. After acid treatment, molecular weight and crystallinity index of chitosan decreased addition to change in chemical structure. It was found that more phosphate buffered saline (PBS), as a model liquid for wound exudate, adsorbed to acid treated chitosan-NFC film, especially to film having more aldehyde groups. Comparing with bare NFC film, chitosan-NFC films adsorbed less PBS because chitosan crosslinked the NFC network and blocked the functional groups of NFC and thus, preventing swelling film. Copyright © 2017 Elsevier Ltd. All rights reserved.

Nafion as Cosurfactant: Solubilization of Nafion in Water in the Presence of Pluronics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kelarakis, Antonios; Giannelis, Emmanuel P.

2011-01-18

Incorporation of Nafion to aqueous solutions of Pluronics adversely impacts micellization due to extensive Nafion/copolymer interactions. Light scattering and zeta potential measurements provide evidence for the formation of sizable and stable Nafion/copolymer complexes, in expense of the neat copolymer micelles. At high copolymer concentrations, the overall interaction diagram of Nafion/copolymer reflects the competitive action of the release of packing constraints due to micellar destabilization induced by Nafion on one hand and the gelator nature of the Nafion on the other. Measurements using a quartz crystal microbalance (QCM-D) show that aqueous solutions of Pluronics (even at very low concentration) can dissolvemore » the Nafion coating on the crystal resonator, while typical low molecular weight ionic surfactants fail to induce similar effects. These studies demonstrate that complexation with this class of copolymers is a facile route to impart dispersibility to Nafion in aqueous environments that otherwise can be achieved through tedious and harsh treatments.« less

Reconstitution of a nanomachine driving the assembly of proteins into bacterial outer membranes

NASA Astrophysics Data System (ADS)

Shen, Hsin-Hui; Leyton, Denisse L.; Shiota, Takuya; Belousoff, Matthew J.; Noinaj, Nicholas; Lu, Jingxiong; Holt, Stephen A.; Tan, Khershing; Selkrig, Joel; Webb, Chaille T.; Buchanan, Susan K.; Martin, Lisandra L.; Lithgow, Trevor

2014-10-01

In biological membranes, various protein secretion devices function as nanomachines, and measuring the internal movements of their component parts is a major technological challenge. The translocation and assembly module (TAM) is a nanomachine required for virulence of bacterial pathogens. We have reconstituted a membrane containing the TAM onto a gold surface for characterization by quartz crystal microbalance with dissipation (QCM-D) and magnetic contrast neutron reflectrometry (MCNR). The MCNR studies provided structural resolution down to 1 Å, enabling accurate measurement of protein domains projecting from the membrane layer. Here we show that dynamic movements within the TamA component of the TAM are initiated in the presence of a substrate protein, Ag43, and that these movements recapitulate an initial stage in membrane protein assembly. The reconstituted system provides a powerful new means to study molecular movements in biological membranes, and the technology is widely applicable to studying the dynamics of diverse cellular nanomachines.

Production of Silicon Oxide like Thin Films by the Use of Atmospheric Plasma Torch

NASA Astrophysics Data System (ADS)

Ozono, E. M.; Fachini, E. R.; Silva, M. L. P.; Ruchko, L. F.; Galvão, R. M. O.

2015-03-01

The advantages of HMDS (hexamethyldisilazane) APT-plasma films for sensor applications were explored producing films in a three-turn copper coil APT equipment. HMDS was introduced into the argon plasma at four different conditions. Additional flux of oxygen could modulate the presence of organic components in the film, the composition varying from pure inorganic oxides to organo-silane polymers. Oxygen promoted deposition rates as high as 900 nm/min on silicon, acrylic or piezoelectric quartz crystal substrates. Films with a clustered morphology and refractive index of 1.45 were obtained, mainly due to a silicon oxide structure. Raman spectroscopy and XPS data showed the presence of CHn and amorphous carbon in the inorganic matrix. The films were sensitive to the humidity of the air. The adsorptive capabilities of outstanding films were tested in a Quartz Crystal Microbalance (QCM). The results support that those films can be a useful and simple alternative for the development of sensors.

Electrostatic immobilization of antimicrobial peptides on polyethylenimine and their antibacterial effect against Staphylococcus epidermidis.

PubMed

Hernandez-Montelongo, J; Corrales Ureña, Y R; Machado, D; Lancelloti, M; Pinheiro, M P; Rischka, K; Lisboa-Filho, P N; Cotta, M A

2018-04-01

Staphylococcus epidermidis is a gram-positive bacterium, and one of the most prevalent causes of nosocomial infections due to its strong ability to form biofilms on catheters and surgical implants. Here we explore the antimicrobial properties of Tet-124 peptides, which are part of the innate defense against different multicellular organisms in nature. Two different Tet-124 peptides were immobilized on a polyethylenimine (PEI) film to determine their impact on the antimicrobial properties: KLWWMIRRW (Tet-124), which contains only natural amino acids, and KLWWMIRRWG-(F-Br)-G (F-Br = 4-Bromophenylalanine), a modified Tet-124 sequence with the addition of an unnatural amino acid. The immobilization was obtained as a result of the electrostatic interaction between PEI amino groups and the C-terminal carboxylic groups of tryptophan and glycine amino acids of Tet-124 and Tet-124-Br peptides, respectively. The process was monitored and studied by water contact angle, Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Quartz Crystal Microbalance with Dissipation (QCM-D) measurements. The antibacterial effect of our samples against S. epidermis was evaluated by the spread plate counting method, and cytotoxicity was tested using fibroblast cultures. Our results indicate the feasibility to immobilize electrostatically both Tet-124 peptides for biomedical applications. Copyright © 2018 Elsevier B.V. All rights reserved.

Study on dissolution behavior of polymer-bound and polymer-blended photo-acid generator (PAG) resists

NASA Astrophysics Data System (ADS)

Yamamoto, Hiroki; Kozawa, Takahiro; Tagawa, Seiichi

2013-03-01

The requirements for the next generation resist materials are so challenging that it is indispensable for feasibility of EUV lithography to grasp basic chemistry of resist matrices in all stage of resist processes. Under such circumstances, it is very important to know dissolution characteristics of the resist film into alkaline developer though the dissolution of exposed area of resist films in alkaline developer to form a pattern is a complex reactive process. In this study, the influence of EUV and KrF exposure on the dissolution behavior of polymer bound PAG and polymer blended PAG was studied in detail using quartz crystal microbalance (QCM) methods. The difference in swelling formation between KrF and EUV exposure was observed. It is likely that difference of reaction mechanism induces the difference of these swelling. Also, it is observed that the swelling of polymer-bound PAG is less than that of polymer blended PAG in both KrF and EUV exposure. This result indicates that polymer-bound PAG suppresses swelling very well and showed an excellent performance. Actually, the developed polymer bound-PAG resist showed an excellent performance (half pitch 50 nm line and space pattern). Thus, polymer bound PAG is one of the promising candidate for 16 nm EUV resist.

Design and Validation of a 150 MHz HFFQCM Sensor for Bio-Sensing Applications

PubMed Central

Fernández, Román; García, Pablo; García, María; Jiménez, Yolanda; Arnau, Antonio

2017-01-01

Acoustic wave resonators have become suitable devices for a broad range of sensing applications due to their sensitivity, low cost, and integration capability, which are all factors that meet the requirements for the resonators to be used as sensing elements for portable point of care (PoC) platforms. In this work, the design, characterization, and validation of a 150 MHz high fundamental frequency quartz crystal microbalance (HFF-QCM) sensor for bio-sensing applications are introduced. Finite element method (FEM) simulations of the proposed design are in good agreement with the electrical characterization of the manufactured resonators. The sensor is also validated for bio-sensing applications. For this purpose, a specific sensor cell was designed and manufactured that addresses the critical requirements associated with this type of sensor and application. Due to the small sensing area and the sensor’s fragility, these requirements include a low-volume flow chamber in the nanoliter range, and a system approach that provides the appropriate pressure control for assuring liquid confinement while maintaining the integrity of the sensor with a good base line stability and easy sensor replacement. The sensor characteristics make it suitable for consideration as the elemental part of a sensor matrix in a multichannel platform for point of care applications. PMID:28885551

Delayed condensation and frost formation on superhydrophobic carbon soot coatings by controlling the presence of hydrophilic active sites

NASA Astrophysics Data System (ADS)

Esmeryan, Karekin D.; Castano, Carlos E.; Mohammadi, Reza; Lazarov, Yuliyan; Radeva, Ekaterina I.

2018-02-01

Condensation frosting is an undesired natural phenomenon that could be impeded efficiently using appropriate wettability and morphologically patterned surfaces. The icephobic properties of carbon soot and the fabrication scalability of its synthesis method are a good foundation for anti-frosting applications; however, the fundamentals of frost growth and spreading on sooted surfaces have not been examined yet. In this study, we investigate the anti-frosting performance of three groups of superhydrophobic soot coatings by means of 16 MHz quartz crystal microbalances (QCMs). The analysis of the real-time sensor signal of each soot coated QCM pattern shows that frost formation and its propagation velocity depend on the quantity of oxygen functionalities and structural defects in the material. In turn, the reduction of both parameters shifts the onset of frost growth to temperatures below  -20 °C, whereas the interdroplet ice bridging is slowed by a factor of four. Moreover, high-resolution scanning electron micrographs of the samples imply delamination upon defrosting of the soot with spherical-like morphology via polar interactions driven mechanism. These results reveal an opportunity for control of frost incipiency on sooted surfaces by adjusting the synthesis conditions and depositing soot coatings with as low as possible content of hydrophilic active sites.

Interfacial Interaction between Transmembrane Ocular Mucins and Adhesive Polymers and Dendrimers Analyzed by Surface Plasmon Resonance

PubMed Central

Noiray, M.; Briand, E.; Woodward, A. M.; Argüeso, P.; Molina Martínez, I. T.; Herrero-Vanrell, R.; Ponchel, G.

2013-01-01

Purpose Development of the first in vitro method based on biosensor chip technology designed for probing the interfacial interaction phenomena between transmembrane ocular mucins and adhesive polymers and dendrimers intended for ophthalmic administration. Methods The surface plasmon resonance (SPR) technique was used. A transmembrane ocular mucin surface was prepared on the chip surface and characterized by QCM-D (Quartz Crystal Microbalance with Dissipation) and XPS (X-ray photoelectron spectroscopy). The mucoadhesive molecules tested were: hyaluronic acid (HA), carboxymethyl cellulose (CMC), hydroxypropylmethyl cellulose (HPMC), chitosan (Ch) and polyamidoamine dendrimers (PAMAM). Results While Ch originated interfacial interaction with ocular transmembrane mucins, for HA, CMC and HPMC, chain interdiffusion seemed to be mandatory for bioadherence at the concentrations used in ophthalmic clinical practise. Interestingly, PAMAM dendrimers developed permanent interfacial interactions with transmembrane ocular mucins whatever their surface chemical groups, showing a relevant importance of co-operative effect of these multivalent systems. Polymers developed interfacial interactions with ocular membrane-associated mucins in the following order: Ch(1 %) > G4PAMAM-NH2(2 %) = G4PAMAM-OH(2 %) > G3.5PAMAM-COOH(2 %)≫ CMC(0.5 %) = HA(0.2 %) = HPMC(0.3 %). Conclusions The method proposed is useful to discern between the mucin-polymer chemical interactions at molecular scale. Results reinforce the usefulness of chitosan and den-drimers as polymers able to increase the retention time of drugs on the ocular surface and hence their bioavailability. PMID:22565639

Fabrication of ultrathin MIL-96(Al) films and study of CO2 adsorption/desorption processes using quartz crystal microbalance.

PubMed

Andrés, Miguel A; Benzaqui, M; Serre, C; Steunou, N; Gascón, I

2018-06-01

This contribution reports the fabrication and characterization of ultrathin films of nanoparticles of the water stable microporous Al tricarboxylate metal organic framework MIL-96(Al). The preparation of MOF dispersions in chloroform has been optimized to obtain dense monolayer films of good quality, without nanoparticle agglomeration, at the air-water interface that can be deposited onto solid substrates of different nature without any previous substrate functionalization. The MOF studied shows great interest for CO 2 capture because it presents Al 3+ Lewis centers and hydroxyl groups that strongly interact with CO 2 molecules. A comparative CO 2 adsorption study on drop-cast, Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) films using a Quartz Crystal Microbalance-based setup (QCM) has revealed that the CO 2 uptake depends strongly on the film fabrication procedure and the storage conditions. Noteworthy the CO 2 adsorption capacity of LB films is increased by 30% using a simple and green treatment (immersion of the film into water during 12 h just after film preparation). Finally, the stability of LB MOF monolayers upon several CO 2 adsorption/desorption cycles has been demonstrated, showing that CO 2 can be easily desorbed from the films at 303 K by flowing an inert gas (He). These results show that MOF LB monolayers can be of great interest for the development of MOF-based devices that require the use of very small MOF quantities, especially gas sensors. Copyright © 2018 Elsevier Inc. All rights reserved.

Anesthetic level prediction using a QCM based E-nose.

PubMed

Saraoğlu, H M; Ozmen, A; Ebeoğlu, M A

2008-06-01

Anesthetic level measurement is a real time process. This paper presents a new method to measure anesthesia level in surgery rooms at hospitals using a QCM based E-Nose. The E-Nose system contains an array of eight different coated QCM sensors. In this work, the best linear reacting sensor is selected from the array and used in the experiments. Then, the sensor response time was observed about 15 min using classic method, which is impractical for on-line anesthetic level detection during a surgery. Later, the sensor transition data is analyzed to reach a decision earlier than the classical method. As a result, it is found out that the slope of transition data gives valuable information to predict the anesthetic level. With this new method, we achieved to find correct anesthetic levels within 100 s.

Transport, motility, biofilm forming potential and survival of Bacillus subtilis exposed to cold temperature and freeze-thaw.

PubMed

Asadishad, Bahareh; Olsson, Adam L J; Dusane, Devendra H; Ghoshal, Subhasis; Tufenkji, Nathalie

2014-07-01

In cold climate regions, microorganisms in upper layers of soil are subject to low temperatures and repeated freeze-thaw (FT) conditions during the winter. We studied the effects of cold temperature and FT cycles on the viability and survival strategies (namely motility and biofilm formation) of the common soil bacterium and model pathogen Bacillus subtilis. We also examined the effect of FT on the transport behavior of B. subtilis at two solution ionic strengths (IS: 10 and 100 mM) in quartz sand packed columns. Finally, to study the mechanical properties of the bacteria-surface bond, a quartz crystal microbalance with dissipation monitoring (QCM-D) was used to monitor changes in bond stiffness when B. subtilis attached to a quartz substrate (model sand surface) under different environmental conditions. We observed that increasing the number of FT cycles decreased bacterial viability and that B. subtilis survived for longer time periods in higher IS solution. FT treatment decreased bacterial swimming motility and the transcription of flagellin encoding genes. Although FT exposure had no significant effect on the bacterial growth rate, it substantially decreased B. subtilis biofilm formation and correspondingly decreased the transcription of matrix production genes in higher IS solution. As demonstrated with QCM-D, the bond stiffness between B. subtilis and the quartz surface decreased after FT. Moreover, column transport studies showed higher bacterial retention onto sand grains after exposure to FT. This investigation demonstrates how temperature variations around the freezing point in upper layers of soil can influence key bacterial properties and behavior, including survival and subsequent transport. Copyright © 2014 Elsevier Ltd. All rights reserved.

The role of alginate in Pseudomonas aeruginosa EPS adherence, viscoelastic properties and cell attachment.

PubMed

Orgad, Oded; Oren, Yoram; Walker, Sharon L; Herzberg, Moshe

2011-08-01

Among various functions, extracellular polymeric substances (EPS) provide microbial biofilms with mechanical stability and affect initial cell attachment, the first stage in the biofilm formation process. The role of alginate, an abundant polysaccharide in Pseudomonas aeruginosa biofilms, in the viscoelastic properties and adhesion kinetics of EPS was analyzed using a quartz crystal microbalance with dissipation (QCM-D) monitoring technology. EPS was extracted from two P. aeruginosa biofilms, a wild type strain, PAO1, and a mucoid strain, PAOmucA22 that over-expresses alginate production. The higher alginate content in the EPS originating from the mucoid biofilms was clearly shown to increase both the rate and the extent of attachment of the EPS, as well as the layer's thickness. Also, the presence of calcium and elevated ionic strength increased the thickness of the EPS layer. Dynamic light scattering (DLS) showed that the presence of calcium and elevated ionic strength induced intermolecular attractive interactions in the mucoid EPS molecules. For the wild type EPS, in the presence of calcium, an elevated shift in the distribution of the diffusion coefficients was observed with DLS due to a more compacted conformation of the EPS molecules. Moreover, the alginate over-expression effect on EPS adherence was compared to the effect of alginate over-expression on P. aeruginosa cell attachment. In a parallel plate flow cell, under similar hydraulic and aquatic conditions as those applied for the EPS adsorption tests in the QCM-D flow cell, reduced adherence of the mucoid strain was clearly observed compared to the wild type isogenic bacteria. The results suggest that alginate contributes to steric hindrance and shielding of cell surface features and adhesins that are known to promote cell attachment. © 2011 Taylor & Francis

Viscoelastic properties of cationic starch adsorbed on quartz studied by QCM-D.

PubMed

Tammelin, Tekla; Merta, Juha; Johansson, Leena-Sisko; Stenius, Per

2004-12-07

The adsorption and viscoelastic properties of layers of a cationic polyelectrolyte (cationic starch, CS, with 2-hydroxy-3-trimethylammoniumchloride as the substituent) adsorbed from aqueous solutions (pH 7.5, added NaCl 0, 1, 100, and 500 mM) on silica were studied with a quartz crystal microbalance with dissipation (QCM-D). Three different starches were investigated (weight-average molecular weights M(w) approximately 8.7 x 10(5) and 4.5 x 10(5) with degree of substitution DS = 0.75 and M(w) approximately 8.8 x 10(5) with DS = 0.2). At low ionic strength, the adsorbed layers are thin and rigid and the amount adsorbed can be calculated using the Sauerbrey equation. When the ionic strength is increased, significant changes take place in the amount of adsorbed CS and the viscoelasticity of the adsorbed layer. These changes were analyzed assuming that the layer can be described as a Voigt element on a rigid surface in contact with purely viscous solvent. It was found that CS with low charge density forms a thicker and more mobile layer with higher viscosity and elasticity than CS with high charge density. The polymers adsorbed on the silica even when the ionic strength was so high that electrostatic interactions were effectively screened. At this high ionic strength, it was possible to study the effect of molecular weight and molecular weight distribution of the CS on the properties of the adsorbed film. Increasing the molecular weight of CS resulted in a larger hydrodynamic thickness. CS with a narrow molecular weight distribution formed a more compact and rigid layer than broadly distributed CS, presumably due to the better packing of the molecules.

Fibronectin and bovine serum albumin adsorption and conformational dynamics on inherently conducting polymers: a QCM-D study.

PubMed

Molino, Paul J; Higgins, Michael J; Innis, Peter C; Kapsa, Robert M I; Wallace, Gordon G

2012-06-05

Quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to characterize the adsorption of the model proteins, bovine serum albumin (BSA) and fibronectin (FN), to polypyrrole doped with dextran sulfate (PPy-DS) as a function of DS loading and surface roughness. BSA adsorption was greater on surfaces of increased roughness and was above what could be explained by the increase in surface area alone. Furthermore, the additional mass adsorbed on the rough films was concomitant with an increase in the rigidity of the protein layer. Analysis of the dynamic viscoelastic properties of the protein adlayer reveal BSA adsorption on the rough films occurs in two phases: (1) arrival and initial adsorption of protein to the polymer surface and (2) postadsorption molecular rearrangement to a more dehydrated and compact conformation that facilitates further recruitment of protein to the polymer interface, likely forming a multilayer. In contrast, FN adsorption was independent of surface roughness. However, films prepared from solutions containing the highest concentration of DS (20 mg/mL) demonstrated both an increase in adsorbed mass and adlayer viscoelasticity. This is attributed to the higher DS loading in the conducting polymer film resulting in presentation of a more hydrated molecular structure indicative of a more unfolded and bioactive conformation. Modulating the redox state of the PPy-DS polymers was shown to modify both the adsorbed mass and viscoelastic nature of FN adlayers. An oxidizing potential increased both the total adsorbed mass and the adlayer viscoelasticity. Our findings demonstrate that modification of polymer physicochemical and redox condition alters the nature of protein-polymer interaction, a process that may be exploited to tailor the bioactivity of protein through which interactions with cells and tissues may be controlled.

Vibration analysis of a new polymer quartz piezoelectric crystal sensor for detecting characteristic materials of volatility liquid

NASA Astrophysics Data System (ADS)

Gu, Yu; Li, Qiang; Xu, Bao-Jun; Zhao, Zhe

2014-01-01

We present a new polymer quartz piezoelectric crystal sensor that takes a quartz piezoelectric crystal as the basal material and a nanometer nonmetallic polymer thin film as the surface coating based on the principle of quartz crystal microbalance (QCM). The new sensor can be used to detect the characteristic materials of a volatile liquid. A mechanical model of the new sensor was built, whose structure was a thin circle plate composing of polytef/quartz piezoelectric/polytef. The mechanical model had a diameter of 8 mm and a thickness of 170 μm. The vibration state of the model was simulated by software ANSYS after the physical parameters and the boundary condition of the new sensor were set. According to the results of experiments, we set up a frequency range from 9.995850 MHz to 9.997225 MHz, 17 kinds of frequencies and modes of vibration were obtained within this range. We found a special frequency fsp of 9.996358 MHz. When the resonant frequency of the new sensor's mechanical model reached the special frequency, a special phenomenon occurred. In this case, the amplitude of the center point O on the mechanical model reached the maximum value. At the same time, the minimum absolute difference between the simulated frequency based on the ANSYS software and the experimental measured stable frequency was reached. The research showed that the design of the new polymer quartz piezoelectric crystal sensor perfectly conforms to the principle of QCM. A special frequency value fsp was found and subsequently became one of the most important parameters in the new sensor design.

A comparative study of the nanoscale and macroscale tribological attributes of alumina and stainless steel surfaces immersed in aqueous suspensions of positively or negatively charged nanodiamonds

PubMed Central

Curtis, Colin K; Marek, Antonin; Smirnov, Alex I

2017-01-01

This article reports a comparative study of the nanoscale and macroscale tribological attributes of alumina and stainless steel surfaces immersed in aqueous suspensions of positively (hydroxylated) or negatively (carboxylated) charged nanodiamonds (ND). Immersion in −ND suspensions resulted in a decrease in the macroscopic friction coefficients to values in the range 0.05–0.1 for both stainless steel and alumina, while +ND suspensions yielded an increase in friction for stainless steel contacts but little to no increase for alumina contacts. Quartz crystal microbalance (QCM), atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements were employed to assess nanoparticle uptake, surface polishing, and resistance to solid–liquid interfacial shear motion. The QCM studies revealed abrupt changes to the surfaces of both alumina and stainless steel upon injection of –ND into the surrounding water environment that are consistent with strong attachment of NDs and/or chemical changes to the surfaces. AFM images of the surfaces indicated slight increases in the surface roughness upon an exposure to both +ND and −ND suspensions. A suggested mechanism for these observations is that carboxylated −NDs from aqueous suspensions are forming robust lubricious deposits on stainless and alumina surfaces that enable gliding of the surfaces through the −ND suspensions with relatively low resistance to shear. In contrast, +ND suspensions are failing to improve tribological performance for either of the surfaces and may have abraded existing protective boundary layers in the case of stainless steel contacts. This study therefore reveals atomic scale details associated with systems that exhibit starkly different macroscale tribological properties, enabling future efforts to predict and design complex lubricant interfaces. PMID:29046852

Morphology-defined interaction of copper phthalocyanine with O 2/H 2O

DOE PAGES

Muckley, Eric S.; Miller, Nicholas; Jacobs, Christopher B.; ...

2016-11-01

Copper phthalocyanine (CuPc) is an important hole transport layer for organic photovoltaics (OPVs), but its interaction with ambient gas/vapor may lead to changes in electronic properties of the material which subsequently limits the lifetime of OPV devices. CuPc films of thickness 25 nm and 100 nm were grown by thermal sublimation at 25°C, 150°C, and 250°C in order to vary morphology. Using a source-measure unit and a quartz crystal microbalance (QCM), we measured changes in electrical resistance and film mass in situ during exposure to controlled pulses of O 2 and H 2O vapor. Mass loading by O 2 wasmore » enhanced by a factor of 5 in films deposited at 250 C, possibly due to the ~200° C CuPc -> transition which allows higher O 2 mobility between stacked molecules. While gas/vapor sorption occurred over timescales of < 10 minutes, resistance change occurred over timescales > 1 hour, suggesting that mass change occurs by rapid adsorption at active surface sites, whereas resistive response is dominated by slow diffusion of adsorbates into the film bulk. Resistive response generally increases with film deposition temperature due to increased porosity associated with larger crystalline domains. The 25 nm thick films exhibit higher resistive response than 100 nm thick films after an hour of O 2/H 2O exposure due to the smaller analyte diffusion length required for reaching the film/electrode interface. We found evidence of decoupling of CuPc from the gold-coated QCM crystal due to preferential adsorption of O 2/H 2O molecules on gold, which is consistent with findings of other studies.« less

Water Adsorption Isotherms on Fly Ash from Several Sources.

PubMed

Navea, Juan G; Richmond, Emily; Stortini, Talia; Greenspan, Jillian

2017-10-03

In this study, horizontal attenuated total reflection (HATR) Fourier-transform infrared (FT-IR) spectroscopy was combined with quartz crystal microbalance (QCM) gravimetry to investigate the adsorption isotherms of water on fly ash, a byproduct of coal combustion in power plants. Because of composition variability with the source region, water uptake was studied at room temperature as a function of relative humidity (RH) on fly ash from several regions: United States, India, The Netherlands, and Germany. The FT-IR spectra show water features growth as a function of RH, with water absorbing on the particle surface in both an ordered (ice-like) and a disordered (liquid-like) structure. The QCM data was modeled using the Brunauer, Emmett, and Teller (BET) adsorption isotherm model. The BET model was found to describe the data well over the entire range of RH, showing that water uptake on fly ash takes place mostly on the surface of the particle, even for poorly combusted samples. In addition, the source region and power-plant efficiency play important roles in the water uptake and ice nucleation (IN) ability of fly ash. The difference in the observed water uptake and IN behavior between the four samples and mullite (3Al 2 O 3 ·2SiO 2 ), the aluminosilicate main component of fly ash, is attributed to differences in composition and the density of OH binding sites on the surface of each sample. A discussion is presented on the RH required to reach monolayer coverage on each sample as well as a comparison between surface sites of fly ash samples and enthalpies of adsorption of water between the samples and mullite.

Annexin-A6 presents two modes of association with phospholipid membranes. A combined QCM-D, AFM and cryo-TEM study.

PubMed

Buzhynskyy, Nikolay; Golczak, Marcin; Lai-Kee-Him, Joséphine; Lambert, Olivier; Tessier, Béatrice; Gounou, Céline; Bérat, Rémi; Simon, Anne; Granier, Thierry; Chevalier, Jean-Marc; Mazères, Serge; Bandorowicz-Pikula, Joanna; Pikula, Slawomir; Brisson, Alain R

2009-10-01

Annexins are soluble proteins that bind to biological membranes in a Ca(2+)-dependent manner. Annexin-A6 (AnxA6) is unique in the annexin family as it consists of the repeat of two annexin core modules, while all other annexins consist of a single module. AnxA6 has been proposed to participate in various membrane-related processes, including endocytosis and exocytosis, yet the molecular mechanism of association of AnxA6 with biological membranes, especially its ability to aggregate membranes, is still unclear. To address this question, we studied the association of AnxA6 with model phospholipid membranes by combining the techniques of quartz crystal microbalance with dissipation monitoring (QCM-D), (cryo-) transmission electron microscopy (TEM) and atomic force microscopy (AFM). The properties of membrane binding and membrane aggregation of AnxA6 were compared to two reference systems, annexin A5 (AnxA5), which is the annexin prototype, and a chimerical AnxA5-dimer molecule, which is able to aggregate two membranes in a symmetrical manner. We show that AnxA6 presents two modes of association with lipid membranes depending on Ca(2+)-concentration. At low Ca(2+)-concentration ( approximately 60-150microM), AnxA6 binds to membranes via its two coplanar annexin modules and is not able to associate two separate membranes. At high Ca(2+)-concentration ( approximately 2mM), AnxA6 molecules are able to bind two adjacent phospholipid membranes and present a conformation similar to the AnxA6 3D crystallographic structure. Possible biological implications of these novel membrane-binding properties of AnxA6 are discussed.

Engineered biomarkers for leprosy diagnosis using labeled and label-free analysis.

PubMed

de Santana, Juliana F; da Silva, Mariângela R B; Picheth, Guilherme F; Yamanaka, Isabel B; Fogaça, Rafaela L; Thomaz-Soccol, Vanete; Machado-de-Avila, Ricardo A; Chávez-Olórtegui, Carlos; Sierakowski, Maria Rita; de Freitas, Rilton Alves; Alvarenga, Larissa M; de Moura, Juliana

2018-09-01

The biotechnological evolution towards the development of antigens to detect leprosy has been progressing. However, the identification of leprosy in paucibacillary patients, based solely on the antigen-antibody interaction still remains a challenge. The complexity of clinical manifestations requires innovative approaches to improve the sensitivity of assays to detect leprosy before the onset of symptoms, thus avoiding disabilities and contributing, indirectly, to reduce transmission. In this study, the strategies employed for early leprosy diagnosis were: i. using a phage-displayed mimotope (APDDPAWQNIFNLRR) which mimics an immunodominant sequence (PPNDPAWQRNDPILQ) of an antigen of Mycobacterium leprae known as Ag85B; ii. engineering the mimotope by adding a C-terminal flexible spacer (SGSG-C); iii. conjugating the mimotope to a carrier protein to provide better exposure to antibodies; iv. amplifying the signal using biotin-streptavidin detection system in an ELISA; and v. coating the optimized mimotope on a quartz crystal microbalance (QCM) sensor for label-free biosensing. The ELISA sensitivity increased up to 91.7% irrespective of the immunological profile of the 132 patients assayed. By using comparative modeling, the M. tuberculosis Ag85B was employed as a template to ascertain which features make the mimotope a good antigen in terms of its specificity. For the first time, a sensitive QCM-based immunosensor to detect anti M. leprae antibodies in human serum was used. M. leprae antibodies could also be detected in the sera of paucibacillary patients; thus, the use of a mimotope-derived synthetic peptide as bait for antibodies in a novel analytical label-free immunoassay for leprosy diagnosis exhibits great potential. Copyright © 2018 Elsevier B.V. All rights reserved.

A 3D CFD Simulation and Analysis of Flow-Induced Forces on Polymer Piezoelectric Sensors in a Chinese Liquors Identification E-Nose.

PubMed

Gu, Yu; Wang, Yang-Fu; Li, Qiang; Liu, Zu-Wu

2016-10-20

Chinese liquors can be classified according to their flavor types. Accurate identification of Chinese liquor flavors is not always possible through professional sommeliers' subjective assessment. A novel polymer piezoelectric sensor electric nose (e-nose) can be applied to distinguish Chinese liquors because of its excellent ability in imitating human senses by using sensor arrays and pattern recognition systems. The sensor, based on the quartz crystal microbalance (QCM) principle is comprised of a quartz piezoelectric crystal plate sandwiched between two specific gas-sensitive polymer coatings. Chinese liquors are identified by obtaining the resonance frequency value changes of each sensor using the e-nose. However, the QCM principle failed to completely account for a particular phenomenon: we found that the resonance frequency values fluctuated in the stable state. For better understanding the phenomenon, a 3D Computational Fluid Dynamics (CFD) simulation using the finite volume method is employed to study the influence of the flow-induced forces to the resonance frequency fluctuation of each sensor in the sensor box. A dedicated procedure was developed for modeling the flow of volatile gas from Chinese liquors in a realistic scenario to give reasonably good results with fair accuracy. The flow-induced forces on the sensors are displayed from the perspective of their spatial-temporal and probability density distributions. To evaluate the influence of the fluctuation of the flow-induced forces on each sensor and ensure the serviceability of the e-nose, the standard deviation of resonance frequency value (SD F ) and the standard deviation of resultant forces (SD Fy ) in y-direction (F y ) are compared. Results show that the fluctuations of F y are bound up with the resonance frequency values fluctuations. To ensure that the sensor's resonance frequency values are steady and only fluctuate slightly, in order to improve the identification accuracy of Chinese liquors using the e-nose, the sensors in the sensor box should be in the proper place, i.e., where the fluctuations of the flow-induced forces is relatively small. This plays a significant reference role in determining the optimum design of the e-nose for accurately identifying Chinese liquors.

Influence of spacer length on heparin coupling efficiency and fibrinogen adsorption of modified titanium surfaces

PubMed Central

Tebbe, David; Thull, Roger; Gbureck, Uwe

2007-01-01

Background Chemical bonding of the drug onto surfaces by means of spacer molecules is accompanied with a reduction of the biological activity of the drug due to a constricted mobility since normally only short spacer molecule like aminopropyltrimethoxysilane (APMS) are used for drug coupling. This work aimed to study covalent attachment of heparin to titanium(oxide) surfaces by varying the length of the silane coupling agent, which should affect the biological potency of the drug due to a higher mobility with longer spacer chains. Methods Covalent attachment of heparin to titanium metal and TiO2 powder was carried out using the coupling agents 3-(Trimethoxysilyl)-propylamine (APMS), N- [3-(Trimethoxysilyl)propyl]ethylenediamine (Diamino-APMS) and N1- [3-(Trimethoxy-silyl)-propyl]diethylenetriamine (Triamino-APMS). The amount of bound coupling agent and heparin was quantified photometrically by the ninhydrin reaction and the tolidine-blue test. The biological potency of heparin was determined photometrically by the chromogenic substrate Chromozym TH and fibrinogen adsorption to the modified surfaces was researched using the QCM-D (Quartz Crystal Microbalance with Dissipation Monitoring) technique. Results Zeta-potential measurements confirmed the successful coupling reaction; the potential of the unmodified anatase surface (approx. -26 mV) shifted into the positive range (> + 40 mV) after silanisation. Binding of heparin results in a strongly negatively charged surface with zeta-potentials of approx. -39 mV. The retaining biological activity of heparin was highest for the spacer molecule Triamino-APMS. QCM-D measurements showed a lower viscosity for adsorbed fibrinogen films on heparinised surfaces by means of Triamino-APMS. Conclusion The remaining activity of heparin was found to be highest for the covalent attachment with Triamino-APMS as coupling agent due to the long chain of this spacer molecule and therefore the highest mobility of the drug. Furthermore, the adsorption of fibrinogen on the differently heparinised surfaces in real time demonstrated that with longer spacer chains the ΔD/Δf ratios became higher, which is also associated with better biocompatible properties of the substrates in contact with a biosystem. PMID:17640335

A new method for wideband characterization of resonator-based sensing platforms

NASA Astrophysics Data System (ADS)

Munir, Farasat; Wathen, Adam; Hunt, William D.

2011-03-01

A new approach to the electronic instrumentation for extracting data from resonator-based sensing devices (e.g., microelectromechanical, piezoelectric, electrochemical, and acoustic) is suggested and demonstrated here. Traditionally, oscillator-based circuitry is employed to monitor shift in the resonance frequency of the resonator. These circuits give a single point measurement at the frequency where the oscillation criterion is met. However, the resonator response itself is broadband and contains much more information than a single point measurement. Here, we present a method for the broadband characterization of a resonator using white noise as an excitation signal. The resonator is used in a two-port filter configuration, and the resonator output is subjected to frequency spectrum analysis. The result is a wideband spectral map analogous to the magnitude of the S21 parameters of a conventional filter. Compared to other sources for broadband excitation (e.g., frequency chirp, multisine, or narrow time domain pulse), the white noise source requires no design of the input signal and is readily available for very wide bandwidths (1 MHz-3 GHz). Moreover, it offers simplicity in circuit design as it does not require precise impedance matching; whereas such requirements are very strict for oscillator-based circuit systems, and can be difficult to fulfill. This results in a measurement system that does not require calibration, which is a significant advantage over oscillator circuits. Simulation results are first presented for verification of the proposed system, followed by measurement results with a prototype implementation. A 434 MHz surface acoustic wave (SAW) resonator and a 5 MHz quartz crystal microbalance (QCM) are measured using the proposed method, and the results are compared to measurements taken by a conventional bench-top network analyzer. Maximum relative differences in the measured resonance frequencies of the SAW and QCM resonators are 0.0004% and 0.002%, respectively. The ability to track a changing sensor response is demonstrated by inducing temperature variations and measuring resonance frequency simultaneously using the proposed technique in parallel with a network analyzer. The relative difference between the two measurements is about 5.53 ppm, highlighting the impressive accuracy of the proposed system. Using commercially available digital signal processors (DSPs), we believe that this technique can be implemented as a system-on-a-chip solution resulting in a very low cost, easy to use, portable, and customizable sensing system. In addition, given the simplicity of the signal and circuit design, and its immunity to other common interface concerns (injection locking, oscillator interference, and drift, etc.), this method is better suited to accommodating array-based systems.

Building a Three-Dimensional Nano-Bio Interface for Aptasensing: An Analytical Methodology Based on Steric Hindrance Initiated Signal Amplification Effect.

PubMed

Du, Xiaojiao; Jiang, Ding; Hao, Nan; Qian, Jing; Dai, Liming; Zhou, Lei; Hu, Jianping; Wang, Kun

2016-10-04

The development of novel detection methodologies in electrochemiluminescence (ECL) aptasensor fields with simplicity and ultrasensitivity is essential for constructing biosensing architectures. Herein, a facile, specific, and sensitive methodology was developed unprecedentedly for quantitative detection of microcystin-LR (MC-LR) based on three-dimensional boron and nitrogen codoped graphene hydrogels (BN-GHs) assisted steric hindrance amplifying effect between the aptamer and target analytes. The recognition reaction was monitored by quartz crystal microbalance (QCM) to validate the possible steric hindrance effect. First, the BN-GHs were synthesized via self-assembled hydrothermal method and then applied as the Ru(bpy) 3 2+ immobilization platform for further loading the biomolecule aptamers due to their nanoporous structure and large specific surface area. Interestingly, we discovered for the first time that, without the aid of conventional double-stranded DNA configuration, such three-dimensional nanomaterials can directly amplify the steric hindrance effect between the aptamer and target analytes to a detectable level, and this facile methodology could be for an exquisite assay. With the MC-LR as a model, this novel ECL biosensor showed a high sensitivity and a wide linear range. This strategy supplies a simple and versatile platform for specific and sensitive determination of a wide range of aptamer-related targets, implying that three-dimensional nanomaterials would play a crucial role in engineering and developing novel detection methodologies for ECL aptasensing fields.