Luminescence Lifetime Imaging of O2 with a Frequency-Domain-Based Camera System

We describe a method to image dissolved oxygen (O2), in 2D at high spatial (< 50-100 µm) and temporal (< 10 s) resolution. The method employs O2 sensitive luminescent sensor foils (planar optodes) in combination with a specialized camera system for imaging luminescence lifetime in the frequency-domain. Planar optodes are prepared by dissolving the O2-sensitive indicator dye in a polymer and spreading the mixture on a solid support in a defined thickness via knife coating. After evaporation of the solvent, the planar optode is placed in close contact with the sample of interest - here demonstrated with the roots of the aquatic plant Littorella uniflora. The O2 concentration-dependent change in the luminescence lifetime of the indicator dye within the planar optode is imaged via the backside of the transparent carrier foil and aquarium wall using a special camera. This camera measures the luminescence lifetime (µs) via a shift in phase angle between a modulated excitation signal and emission signal. This method is superior to luminescence intensity imaging methods, as the signal is independent of the dye concentration or intensity of the excitation source, and solely relies on the luminescence decay time, which is an intrinsically referenced parameter. Consequently, an additional reference dye or other means of referencing are not needed. We demonstrate the use of the system for macroscopic O2 imaging of plant rhizospheres, but the camera system can also easily be coupled to a microscope

Removal of Tetramethylammonium Cations from Zeolites

Zeolite α (high-silica LTA), a potential shape-selective catalyst, is synthesized in the presence of tetramethylammonium (TMA) ions. Since TMA+ ions are incapable of forming olefins at low temperature, temperatures in excess of 500ºC are required to thermally decompose them and burn off the carbonaceous deposits, frequently causing damage to the structure. In this paper, the thermal decomposition of zeolitic TMA+ ions is investigated. This work led to a less severe method for removing TMA+ ions by stepwise reaction with ammonia at low temperatures. TMA+ ions located in the supercage can easily be removed at a temperature as low as 250ºC, generating mono- and dimethylamine. Sodalite cage TMA+ ions require a temperature of not more than 400ºC to be degraded. Although this treatment raises the Si/Al ratio somewhat, damage to the structure is minimal. Since the size of the zeolitic pores defines the type of molecules capable of escaping from the zeolite cavities, decomposition of TMA+ ions in NaTMA-Y and NaTMA-high-silica sodalite have been included for comparison

An Examination of Brønsted-Acid Sites in H-[Fe]ZSM-5 for Olefin Oligomerization and Adsorption

The adsorption and reaction properties of an Al-free H-[Fe]ZSM-5 were examined and compared to an H-[Al]ZSM-5 sample with the same site density. H-[Fe]ZSM-5 was shown to have Brønsted-acid sites in a concentration equal to the framework Fe concentration. Differential heats of adsorption for ammonia and pyridine were shown to be identical to that obtained in H-[Al]ZSM-5, with differential heats of ~150 kJ/mol for ammonia and 200 kJ/mol for pyridine. For H-[Al]ZSM-5, adsorption of either propylene or 1-butene at room temperature results in rapid oligomerization. TPD-TGA measurements of the oligomers in H-[Al]ZSM-5 show evidence for hydride-transfer reactions, in addition to simple oligomer cracking. By contrast, it is necessary to heat H-[Fe]ZSM-5 to 370 K for rapid oligomerization of propylene and oligomerization of 1-butene occurs only slowly at 295 K. TPD-TGA measurements of the oligomers in H-[Fe]ZSM-5 show no evidence for hydride-transfer reactions and H-[Fe]ZSM-5 forms much less coke than H-[Al]ZSM-5 during steady-state reaction in 1-butene at 573 K. Adsorption measurements of 1-butene on D-[Fe]ZSM-5 suggest that the protonated complexes of 1-butene are formed but that these are relatively stable towards reaction, implying that the carbocation transition states are relatively unstable

Systems biology and ecology of microbial mat communities

Microbial mat communities consist of dense populations of microorganisms embedded in exopolymers and/or biomineralized solid phases, and are often found in mm-cm thick assemblages, which can be stratified due to environmental gradients such as light, oxygen or sulfide. Microbial mat communities are commonly observed under extreme environmental conditions, deriving energy primarily from light and/or reduced chemicals to drive autotrophic fixation of carbon dioxide. Microbial mat ecosystems are regarded as living analogues of primordial systems on Earth, and they often form perennial structures with conspicuous stratifications of microbial populations that can be studied in situ under stable conditions for many years. Consequently, microbial mat communities are ideal natural laboratories and represent excellent model systems for studying microbial community structure and function, microbial dynamics and interactions, and discovery of new microorganisms with novel metabolic pathways potentially useful in future industrial and/or medical applications. Due to their relative simplicity and organization, microbial mat communities are often excellent testing grounds for new technologies in microbiology including micro-sensor analysis, stable isotope methodology and modern genomics. Integrative studies of microbial mat communities that combine modern biogeochemical and molecular biological methods with traditional microbiology, macro-ecological approaches, and community network modeling will provide new and detailed insights regarding the systems biology of microbial mats and the complex interplay among individual populations and their physicochemical environment. These processes ultimately control the biogeochemical cycling of energy and/or nutrients in microbial systems. Similarities in microbial community function across different types of communities from highly disparate environments may provide a deeper basis for understanding microbial community dynamics and the ecological role of specific microbial populations. Approaches and concepts developed in highly-constrained, relatively stable natural communities may also provide insights useful for studying and understanding more complex microbial communities

A novel measuring system for oxygen microoptodes based on a phase modulation technique

New fiber optic oxygen microsensors (microoptrodes) for use in aquatic environments have recently been developed as an alternative to commonly used CLark-type oxygen microelectrodes. The microoptrodes have the advantage of no oxygen consumption and no stirring sensitivity combined with a simple manufacturing process of the sensors. To avoid problems inherent to luminescence intensity measurements like photobleaching, signal dependency on the optical properties of the surrounding medium and system drifts, a novel measuring system was developed. This system uses a phase modulation method to evaluate a signal phase shift that is caused by the oxygen dependent luminescence lifetime. The measuring system is based on simple solid state technology. High reliability and low costs of the system can therefore be combined with the ability of miniaturization and low power consumption. The system consists of three units: 1) the microoptrode with the optical setup [glass fiber coupler, optical filters, lenses, light source (light emitting diode) and light detection (photon multiplier tube)], 2) the analogue signal processing unit, including a special phase detection module, and 3) the digital signal processing unit, a personal computer or a microcontroller for control of the measuring system, display and data storage. First measurements of oxygen depth profiles in sediments and biofilms at high levels of ambient light demonstrated the advantages of phase shift based O2 measurements as compared to intensity based measurements with microoptrodes