Preparation of Polymer Nanoparticles by Ring Opening Metathesis Polymerization in Aqueous Dispersed Systems with Water-Soluble Ruthenium-based Catalyst

Ring opening metathesis polymerization (ROMP) is a variant of olefin metathesis used to polymerize strained cyclic olefins. Ruthenium-based Grubbs’ catalysts are widely used in ROMP to produce industrially important products. While highly efficient in organic solvents such as dichloromethane and toluene, these hydrophobic catalysts are not typically applied in aqueous systems. With the advancements in emulsion and miniemulsion polymerization, it is promising to conduct ROMP in an aqueous dispersed phase to generate well-defined latex nanoparticles while improving heat transfer and reducing the use of volatile organic solvents (VOCs). Herein I report the efforts made using a PEGylated ruthenium alkylidene as the catalyst to initiate ROMP in an oil-in-water miniemulsion. 1H NMR revealed that the synthesized PEGylated catalyst was stable and reactive in water. Using 1,5-cyclooctadiene (COD) as monomer, we showed the highly efficient catalyst yielded colloidally stable polymer latexes with ~ 100% conversion at room temperature. Kinetic studies demonstrated first-order kinetics with good livingness as confirmed by the shift of gel permeation chromatography (GPC) traces. Depending on the surfactants used, the particle sizes ranged from 100 to 300 nm with monomodal distributions. The more strained cyclic olefin norbornene (NB) could also be efficiently polymerized with a PEGylated ruthenium alkylidene in miniemulsion to full conversion and with minimal coagulum formation.

Chemical Sensing Using a Polymer Coated Long-Period Fiber Grating Interrogated by Ring-Down Spectroscopy

An etched long-period grating was used as a refractive index sensor for vapours of four volatile organic compounds, i.e. m-xylene, cyclohexane, trichloroethylene and commercial gasoline. The sensitivity to the vapours was further increased by solid-phase microextraction into a coating made of polydimethylsiloxane (PDMS)/polymethyl-octylsiloxane (PMOS) co-polymer. By further amplification of the optical loss in an optical cavity made of two identical fiber-Bragg gratings and interrogation by phase-shift cavity ring-down spectroscopy we could detect and distinguish xylene (detection limit: 134ppm) from trichloroethylene (3300ppm), cyclohexane (1850ppm) and gasoline (10,500ppm).

Loss Determination in Microsphere Resonators by Phase-Shift Cavity Ring-Down Measurements

The optical loss of whispering gallery modes of resonantly excited microresonator spheres is determined by optical lifetime measurements. The phase-shift cavity ring-down technique is used to extract ring-down times and optical loss from the difference in amplitude modulation phase between the light entering the microresonator and light scattered from the microresonator. In addition, the phase lag of the light exiting the waveguide, which was used to couple light into the resonator, was measured. The intensity and phase measurements were fully described by a model that assumed interference of the cavity modes with the light propagating in the waveguide.

Ring-Down Absorption Spectroscopy for Analytical Microdevices

Ring-down absorption spectroscopy is an emerging ‘‘label-free’’ detection method for analytical microdevices, such as micrototal analysis systems (l-TAS). Developed from the related gas-phase cavity ring-down absorption spectroscopy, fiber-optic-based ring-down techniques for liquid samples offer low detection limits, high sensitivity and fast response. ª 2006 Elsevier Ltd. All rights reserved.

Fiber-Optic Ring-Down Spectroscopy Using a Tunable Picosecond Gain-Switched Diode Laser

Visible and near-infrared laser light pulses were coupled into two different types of optical fiber cavities. One cavity consisted of a short strand of fiber waveguide that contained two identical fiber Bragg gratings. Another cavity was made using a loop of optical fiber. In either cavity ∼ 40 ps laser pulses, which were generated using a custom-built gainswitched diode laser, circulated for a large number of round trips. The optical loss of either cavity was determined from the ring-down times. Cavity ring-down spectroscopy was performed on 200 pL volumes of liquid samples that were injected into the cavities using a 100 μm gap in the fiber loop. A detection limit of 20 ppm of methylene blue dye in aqueous solution, corresponding to a minimum absorptivity of εC < 6 cm−1, was realized.