Molecular Design of Intercalation-Based Sensors. 2. Sensing of Carbon Dioxide in Functionalized Thin Films of Copper Octanediylbis(phosphonate)

Abstract

Self-assembled thin films of layered copper alkanediylbis-(phosphonates) retain the amine-specific intercalation chemistry of the corresponding microcrystalline solids. Aliphatic and aromatic amines bind in a 1:1 ratio to coordinatively unsaturated copper ions in anhydrous Cu 2 (O 3 P(CH 2 ) 8 PO 3 ); and by selecting an amine with an appropriate functional tail group, a chemically and sterically well-defined interlamellar binding site for CO 2 is created. Powder X-ray diffraction, Fourier transform infrared spectroscopy, and solid-state NMR experiments were used to study the intercalation of 3-aminopropanol, (3-aminopropyl)methyldihydroxysilane, and p-xylylenediamine, and their reversible reaction with CO 2 to form carbonates and carbamates, respectively. By growing these films on the electrodes of a quartz crystal microbalance device, a sensor can be fabricated for monitoring CO 2 in gas streams at concentrations of 0.5-19% (v/v). A Henrian response (frequency change directly proportional to CO 2 partial pressure) was observed, and the time required for equilibration of these devices with CO 2 , using 5-layer films, was 3-4 min. Effective diffusion coefficients for CO 2 in the films were determined using a dualtransport model and were found to be in the range (6-9) × 10 -9 cm 2 /s.

Syntheses, characterization and electrical property of a new silver diphosphonate with zeolite-like framework and three-dimensional silver interactions: [Ag4(O3PCH2CH2PO3)]

“…Metal organodiphosphonates as new hybrid inorganic-organic materials have attracted a great deal of research interest in the past 10 years, due to many applications as small molecular sensors [1,2], adsorption [3] and catalyst [4]. Particularly, metal organodiphosphonates are very important in preparing meso/microporous materials [5][6][7][8][9] because the open frameworks can be adjusted through modifying lengths and shapes of the organic units.…”

Piezoelectric Inkjet Printing of Biomimetic Inks for Reactive Surfaces

“…The multiple print cycles over larger areas were necessary to produce highly reactive multilayer films, increasing the quantity of accessible surface amines. Arrington et al have used micro‐contact printing in conjunction with atomic force microscopy to show that repetitive dendrimer stamping increases the amount of deposited dendrimer in the form of 3D frameworks of cross‐linked amines in air 20, 21. This cross linking enables the amines to act as an adhesive layer on a substrate while providing a highly functionalized surface essential for silica precipitation.…”

Application of Nanoparticles in Quartz Crystal Microbalance Biosensors

“…The combined measurements of frequency shift and changes in the dissipation factor and resonant resistance have been termed, QCM-D and QCM-R, respectively [17]. With the combined mass and viscosity-density effects, QCM can be applied for bio/chemical sensing by coating with a chemically or biologically sensitive film to sense very small amount of adsorbed gases such as volatile organic compounds (VOCs) [18] [19] and environmental pollutants [20]- [22] and liquid phase biochemicals. A quartz crystal microbalance (QCM) measures a mass per unit area by measuring the change in frequency of a quartz crystal resonator.…”