Optical Quartz Crystal Microbalance (OQCM) for Dual-Mode Analysis

Label-free biosensors allow for real-time measurements of the target molecule, providing valuable kinetic data about the unperturbed biological system. Yet, they generally rely on a single transduction mechanism that reflects a single aspect of a system. In order to have a more complete understanding of the system, many aspects of the system need to be examined simultaneously. An integrated multi-mode label-free sensor capable of providing consistent and complementary information about multiple aspects of a system is highly desirable for biomedical research. Currently there are some hybrid sensors utilizing the optical and quartz crystal microbalance (QCM) techniques to measure both the optical and mechanical properties of a system. However, those hybrid sensors have some shortcomings in implementation and performance that limit their applicability. In this research, we developed Optical Quartz Crystal Microbalance (OQCM) sensors - hybrid sensors utilizing the same techniques for simultaneously measuring both optical and mechanical properties, which also address these shortcomings. Two OQCM structures were designed, fabricated and explored. The first structure is an interferometric OQCM sensor (I-OQCM) with a multilayer planar optical structure. The interference between reflections at the interfaces between layers generates an interference pattern in the optical spectrum that shifts upon accumulation of additional films on the structure. The second structure is a plasmonically-enhanced grating OQCM sensor (PEG-OQCM). The theory and simulation analyses indicate that the PEG-OQCM can achieve near zero bulk refractive index sensitivity by optimizing the incidence angle. Simulation results show that at an incident angle of 47 degrees, the bulk RI sensitivity becomes near zero around bulk RI = 1.33. Experimental results for vapor deposition, water and biosensing (solution of streptavidin) match well with the simulation results. With this PEG-OQCM structure, an optical linewidth of 25 nm was obtained in air, 15 nm in water – up to 6 times narrower than that of SPR/LSPR (50-100 nm in water). The OQCMs were characterized separately to demonstrate the operation in each mode for each structure, and tests were performed to show biosensing capability. Dual-mode tests were conducted for both the I-OQCM and PEG-OQCM to show the capability of simultaneous measurement of both optical and mechanical properties and responses of a system. The test results validate the simulation analyses and correlation between the optical and mechanical responses that would provide corroborating information for more reliable, robust cross-examination/confirmation for the evaluation of test systems. The OQCM-A sensor with 3 single I-OQCM sensors on a single wafer was also designed, fabricated. Each I-OQCM sensor can be characterized independently of the others. Mechanical response tests performed on the OQCM-A indicate that each sensor responds independently of the other sensors and the cross-talk between on adjacent sensors is negligible.PHDElectrical EngineeringUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttps://deepblue.lib.umich.edu/bitstream/2027.42/143989/1/zvzhang_1.pd

New kind of polymer materials based on selected complexing star-shaped polyethers

In today’s analytical trends, there is an ever-increasing importance of polymeric materials for low molecular weight compounds including amines and drugs because they can act as carriers or capture amines or drugs. The use of this type of materials will allow the development of modern materials for the chromatographic column beds and the substrates of selective sensors. Moreover, these kinds of materials could be used as a drug carrier. Therefore, the aim of this study is presenting the synthesis and complexing properties of star-shaped oxiranes as a new sensor for the selective complexation of low molecular weight compounds. Propylene oxide and selected oxirane monomers with carbazolyl in the substituent were selected as the monomers in this case and tetrahydrofuran as its solvent. The obtained polymer structures were characterized using the MALDI-TOF. It was found that in the initiation step potassium hydride deprotonates the monomer molecule and takes also part in the nucleophilic substitution. The resulting polymeric material preferably cross-linked with selected di-oxiranes (1,2,7,8-diepoksyoktan in respect ratio 3:1 according to active center) was then used as a stationary phase in the column and thin layer chromatography for amine separation and identification. Sorption ability of the resulting deposits was determined using a quartz microbalance (QCMB). The study was carried out in stationary mode and flow cells to simulate actual operating phase conditions. Based on changes in electrode vibration frequency, the maximum amount of adsorbed analyte and the best conditions for its sorption were determined

Laboratory demonstration model: Active cleaning technique device

The technique which utilizes exposure to a plasma to remove contaminants from a surface was incorporated into a laboratory model which demonstrates active cleaning by both plasma cleaning and ion sputtering modes of operation. The development phase is reported and includes discussion of the plasma tube configuration, device design, and performance tests. A general description of the active cleaning device is provided which includes information on the main power/plasma discharge sensors, and the power, gas supply, and ion accelerator systems. Development of the active cleaning species at high vacuum conditions is described and results indicate that plasma cleaning occurs in the region of a visible plume which extends from the end of the plasma tube. Recommendations are made for research to determine the plasma cleaning mechanism and the plasma species responsible for the cleaning, as well limitations on the type of contaminants that can be removed

In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors.

Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors.A.C.F., J.M.G. and C.P.G. acknowledge the Sims Scholarship (A.C.F.), EPSRC (through the Supergen consortium for J.M.G.) and the EU ERC (through an Advanced Fellowship to C.P.G.) for financial support. P.S. and W.-Y.T. acknowledge support from the European Research Council (ERC, Advanced Grant, ERC-2011-AdG, Project 291543–IONACES). P.S. also acknowledges financial support from the Chair ‘Embedded Multi-Functional Nanomaterials’ from the Airbus Group Foundation. A.C.F. and J.M.G. thank the NanoDTC Cambridge for travel funding.This is the author accepted manuscript. The final version is available from NPG at http://www.nature.com/nmat/journal/vaop/ncurrent/full/nmat4318.html#abstract.

Reversible intercalation of methyl viologen as a dicationic charge carrier in aqueous batteries.

The interactions between charge carriers and electrode structures represent one of the most important considerations in the search for new energy storage devices. Currently, ionic bonding dominates the battery chemistry. Here we report the reversible insertion of a large molecular dication, methyl viologen, into the crystal structure of an aromatic solid electrode, 3,4,9,10-perylenetetracarboxylic dianhydride. This is the largest insertion charge carrier when non-solvated ever reported for batteries; surprisingly, the kinetic properties of the (de)insertion of methyl viologen are excellent with 60% of capacity retained when the current rate is increased from 100 mA g-1 to 2000 mA g-1. Characterization reveals that the insertion of methyl viologen causes phase transformation of the organic host, and embodies guest-host chemical bonding. First-principles density functional theory calculations suggest strong guest-host interaction beyond the pure ionic bonding, where a large extent of covalency may exist. This study extends the boundary of battery chemistry to large molecular ions as charge carriers and also highlights the electrochemical assembly of a supramolecular system

Design and Validation of a 150 MHz HFFQCM Sensor for Bio-Sensing Applications

[EN] 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.This work was funded by the European Commission Horizon 2020 Programme under Grant Agreement number ICT-28-2015/687785-LIQBIOPSENS (Reliable Liquid Biopsy technology for early detection of colorectal cancer).Fernández Díaz, R.; García Molla, P.; García, M.; García Narbón, JV.; Jiménez Jiménez, Y.; Arnau Vives, A. (2017). Design and Validation of a 150 MHz HFFQCM Sensor for Bio-Sensing Applications. Sensors. 17(9):1-13. https://doi.org/10.3390/s17092057S113179Soper, S. 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