On the Mass Fractal Character of Si-Based Structural Networks in Amorphous Polymer Derived Ceramics
The intermediate-range packing of SiNxC4−x (0 ≤ x ≤ 4) tetrahedra in polysilycarbodiimide and polysilazane-derived amorphous SiCN ceramics is investigated using 29Si spin-lattice relaxation nuclear magnetic resonance (SLR NMR) spectroscopy. The SiCN network in the polysilylcarbodiimide-derived ceramic consists predominantly of SiN4 tetrahedra that are characterized by a 3-dimensional spatial distribution signifying compact packing of such units to form amorphous Si3N4 clusters. On the other hand, the SiCN network of the polysilazane-derived ceramic is characterized by mixed bonded SiNxC4−x tetrahedra that are inefficiently packed with a mass fractal dimension of Df ~2.5 that is significantly lower than the embedding Euclidean dimension (D = 3). This result unequivocally confirms the hypothesis that the presence of dissimilar atoms, namely, 4-coordinated C and 3-coordinated N, in the nearest neighbor environment of Si along with some exclusion in connectivity between SiCxN4−x tetrahedra with widely different N:C ratios and the absence of bonding between C and N result in steric hindrance to an efficient packing of these structural units. It is noted that similar inefficiencies in packing are observed in polymer-derived amorphous SiOC ceramics as well as in proteins and binary hard sphere systems.
Spectroscopic Observation of Fractal Packing of Oxygen in Variably Modified Glassy Tetrahedral Networks.
The spatial distribution of bridging and nonbridging oxygen atoms in silicate glass networks with a wide range of connectivity is studied using (17)O nuclear magnetic resonance spin-lattice relaxation spectroscopy. The results demonstrate a mass fractal spatial distribution of both oxygen species in the network at the nanometer length scale. The fractal dimension increases with increasing relative fraction of these oxygen species and reaches a maximum value of ∼2.6. Such locally fractal character of the structural network is key to the understanding of the apparently anomalous transport, relaxation, and localization properties that are the hallmarks of the glassy state.
Effect of Aeration and Agitation Regimes on Lipase Production by Newly Isolated Rhodotorula mucilaginosa–MTCC 8737 in Stirred Tank Reactor Using Molasses as Sole Production Medium
The influence of media and process parameters (aeration and agitation) on fermentation broth rheology and biomass formation has been studied in 1.5-l stirred tank reactor for lipase production using Rhodotorula mucilaginosa MTCC 8737. Molasses, as sole production medium, is used for lipase production by varying aeration (1, 2, and 3 vvm) and agitation speeds (100, 200, and 300 rpm). Maximum lipase activity of 72 U/ml was obtained during 96 h of fermentation at 2 vvm, 200 rpm, pH 7, and 25 ± 2°C temperature. Lipase production kinetics with respect to dry cell weight of biomass showed YP/S of 25.71 U/mg, specific product formation of 10.9 U/mg DC, and YX/S 2.35 mg/mg. Maximum lipase activity (MC 2) of 56 U/ml was observed at 1% molasses, and a further increase in the molasses concentration of (%) 1.5 and 2 inhibited the product formation of lipase with 15 and 8.5 U/ml, respectively. The production kinetics of molasses media showed YP/X was 14 U/mg DC, YP/S 16 U/mg, and YX/S 1.14 mg/mg during 96 h of bioreactor operation. The kLa values for all batches (MC 1–MC 4) at 96 h of fermentation were 32, 28, 21, and 19/h, and the |oxygen transfer rate were 54.4, 56, 35.7, and 17.29 mg/l h, respectively. Increase in molasses concentration resulted in decreased lipase activity by increase in viscosity of the fermentation broth.