Evolution of Granular Structure and the Enhancement of Electron Field Emission Properties of Nanocrystalline and Ultrananocrystalline Diamond Films Due to Plasma Treatment Process.

The present work reports the plasma post treatment (ppt) process that instigates the evolution of granular structure of nanocrystalline diamond (NCD), consequently conducing the enhancement of the electron field emission (EFE) properties. The NCD films contain uniform and nanosized diamond grains (∼20 nm) with negligible thickness for grain boundaries that is distinctly different from the microstructure of ultrananocrystalline (UNCD) films with uniformly sized ultrananodiamond grains (∼5 nm) having relatively thick grain boundaries (∼0.1 nm). The turn-on of the electron field emission (EFE) process occurs at ( E0)NCD = 24.1 V/µm and ( E0)UNCD = 18.6 V/µm for the pristine NCD and UNCD materials, respectively. The granular structure of the starting diamond films largely influenced the microstructure evolution behavior and EFE properties of the materials subject to plasma annealing. The CH4/(Ar-H2) ppt-process leads to formation of a hybrid granular structured diamond (HiDNCD and HiDUNCD) via isotropic conjoining of nanosized diamond grains, whereas the CH4/N2 ppt-process leads to the formation of acicular granular structured diamond films (NNCD and NUNCD) via inducing aeolotropic growth of nanodiamond grains. While both of the HiDNCD and HiDUNCD films contain hybrid granular structure, the HiDUNCD films contain a larger proportion of nanographite phase and result in improved EFE properties, viz. ( E0)HiD-UNCD = 7.7 V/µm and ( E0)HiD-NCD = 12.3 V/µm. In contrast, when the films were CH4/N2 ppt-processed, the acicular diamond grains were formed for NUNCD and NNCD films; however, carbon nanoclusters attached to the diamond grains of NNCD films and the nanographitic layers encasing diamond cores are not crystallized very well, as compared with NUNCD films. Therefore, the NNCD films exhibit slightly inferior EFE properties than the NUNCD films, viz. ( E0)N-UNCD = 5.3 V/µm and ( E0)N-NCD = 11.8 V/µm. The difference in EFE properties for ppt-processed NCD and UNCD films corresponds to the dissimilar granular structure evolution behavior in these films that is, in turn, due to the distinct different microstructure of the pristine NCD and UNCD films.

Flow-FISH analysis and isolation of clostridial strains in an anaerobic semi-solid bio-hydrogen producing system by hydrogenase gene target.

By using hydrogenase gene-targeted polymerase chain reaction (PCR) and reverse transcriptase PCR (RT-PCR), the predominant clostridial hydrogenase that may have contributed to biohydrogen production in an anaerobic semi-solid fermentation system has been monitored. The results revealed that a Clostridium pasteurianum-like hydrogenase gene sequence can be detected by both PCR and RT-PCR and suggested that the bacterial strain possessing this specific hydrogenase gene was dominant in hydrogenase activity and population. Whereas another Clostridium saccharobutylicum-like hydrogenase gene can be detected only by RT-PCR and suggest that the bacterial strain possessing this specific hydrogenase gene may be less dominant in population. In this study, hydrogenase gene-targeted fluorescence in situ hybridization (FISH) and flow cytometry analysis confirmed that only 6.6% of the total eubacterial cells in a hydrogen-producing culture were detected to express the C. saccharobutylicum-like hydrogenase, whereas the eubacteria that expressed the C. pasteurianum-like hydrogenase was 25.6%. A clostridial strain M1 possessing the identical nucleotide sequences of the C. saccharobutylicum-like hydrogenase gene was then isolated and identified as Clostridium butyricum based on 16S rRNA sequence. Comparing to the original inoculum with mixed microflora, either using C. butyricum M1 as the only inoculum or co-culturing with a Bacillus thermoamylovorans isolate will guarantee an effective and even better production of hydrogen from brewery yeast waste.

Molecular detection of the clostridia in an anaerobic biohydrogen fermentation system by hydrogenase mRNA-targeted reverse transcription-PCR.

Molecular biological approaches were developed to monitor the potential biohydrogen-producing clostridia in an anaerobic semisolid fermentation system that used brewery yeast waste as the fermentation substrate. The denaturing gradient gel electrophoresis with 16S rDNA gene-targeted polymerase chain reaction (PCR) analysis was employed to confirm the existence of clostridia in the system. Remarkably, reproducible nucleotide sequences of clostridia were obtained from different hydrogen production stages by using hydrogenase gene-targeted reverse transcription (RT)-PCR. These RNA-based information suggested that the predominant hydrogen-producing strains possess either a specific Clostridium pasteurianum-like or a specific Clostridium saccharobutylicum-like hydrogenase sequence. Comparison of the hydrogenase gene-targeted sequence profiles between PCR and RT-PCR revealed that the specific C. pasteurianum-like hydrogenase harboring bacterial strains were dominant in both mRNA and bacterial population level. On the other hand, the specific C. saccharobutylicum-like hydrogenase harboring strains expressed high level of hydrogenase mRNA but may not be dominant in population. Furthermore, quantitative real-time RT-PCR analysis showed the expression pattern of the clostridial hydrogenase mRNA and may serve as an activity index for the system.