Dicationic Bis-Pyridinium Hydrazone-Based Amphiphiles Encompassing Fluorinated Counteranions: Synthesis, Characterization, TGA-DSC, and DFT Investigations.

Quaternization and metathesis approaches were used to successfully design and synthesize the targeted dicationic bis-dipyridinium hydrazones carrying long alkyl side chain extending from C8 to C18 as countercation, and attracted to halide (I-) or fluorinated ion (PF6-, BF4-, CF3COO-) as counteranion. Spectroscopic characterization using NMR and mass spectroscopy was used to establish the structures of the formed compounds. In addition, their thermal properties were investigated utilizing thermogravimetric analyses (TGA), and differential scanning calorimetry (DSC). The thermal study illustrated that regardless of the alkyl group length (Cn) or the attracted anions, the thermograms of the tested derivatives are composed of three stages. The mode of thermal decomposition demonstrates the important roles of both anion and alkyl chain length. Longer chain length results in greater van der Waals forces; meanwhile, with anions of low nucleophilicity, it could also decrease the intramolecular electrostatic interaction, which leads to an overall interaction decrease and lower thermal stability. The DFT theoretical calculations have been carried out to investigate the thermal stability in terms of the Tonset. The results revealed that the type of the counteranion and chain length had a substantial impact on thermal stability, which was presumably related to the degree of intermolecular interactions. However, the DFT results illustrated that there is no dominant parameter affecting the thermal stability, but rather a cumulative effect of many factors of different extents.

Impact of nanoparticles on transcriptional regulation of catabolic genes of petroleum hydrocarbon-degrading bacteria in contaminated soil microcosms.

This study was conducted to determine what effects nanoparticles (NPs) like TiO2 , ZnO, and Ag may pose on natural attenuation processes of petroleum hydrocarbons in contaminated soils. The solid NPs used were identified using x-ray diffraction technique and their average size was certified as 18.2, 16.9, and 18.3 nm for Ag-NPs, ZnO-NPs, and TiO2 -NPs, respectively. NPs in soil microcosms behave differently where it was dissolved as in case of Ag-NPs, partially dissolved as in ZnO-NPs or changed into other crystalline phase as in TiO2 -NPs. In this investigation, catabolic gene encoding catechol 2,3 dioxygenase (C23DO) was selected specifically as biomarker for monitoring hydrocarbon biodegradation potential by measuring its transcripts by RT-qPCR. TiO2 -NPs amended microcosms showed almost no change in C23DO expression profile or bacterial community which were dominated by Bacillus sp., Mycobacterium sp., Microbacterium sp., Clostridium sp., beside uncultured bacteria, including uncultured proteobacteria, Thauera sp. and Clostridia. XRD pattern suggested that TiO2 -NPs in microcosms were changed into other non-inhibitory crystalline phase, consequently, showing the maximum degradation profile for most low molecular weight oil fractions and partially for the high molecular weight ones. Increasing ZnO-NPs concentration in microcosms resulted in a reduction in the expression of C23DO with a concomitant slight deteriorative effect on bacterial populations ending up with elimination of Clostridium sp., Thauera sp., and uncultured proteobacteria. The oil-degradation efficiency was reduced compared to TiO2 -NPs amended microcosms. In microcosms, Ag-NPs were not detected in the crystalline form but were available in the ionic form that inhibited most bacterial populations and resulted in a limited degradation profile of oil, specifically the low molecular weight fractions. Ag-NPs amended microcosms showed a significant reduction (80%) in C23DO gene expression and a detrimental effect on bacterial populations including key players like Mycobacterium sp., Microbacterium sp., and Thauera sp. involved in the biodegradation of petroleum hydrocarbons.

Extending the working pH of nitrobenzene degradation using ultrasonic/heterogeneous Fenton to the alkaline range via amino acid modification.

Oxides of iron, α-Fe2O3 (I), and copper, CuO (II) prepared by usual precipitation method without surfactant were used at room temperature in the process of nitrobenzene (10mgL(-1)) degradation at different pH values with ultrasonic at 20kHz. The degradation was complete in 20 and 30min for (I) and (II), respectively in the pH range 2-7 using1.0gL(-1) of solids and 10mM of H2O2. A remarkable decrease in degradation efficiency was recorded on increasing the pH to values higher than the neutral range. This loss in efficiency was cancelled to a great extent through modifying the used oxides with amino acids. Arginine showed higher improving effect to (II) (1:1 weight ration) than glycine or glutamic acid. Modification of both oxides with increasing amounts of arginine increased the degradation efficiency of (I) in a more regular way than in case of (II). However, the extent of improvement due to amino acid modification was higher in case of (II) because of its originally low degradation efficiency in strongly alkaline media.

Ultrasonic assisted-Fenton-like degradation of nitrobenzene at neutral pH using nanosized oxides of Fe and Cu.

Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe2O3 and CuO were prepared, characterized and tested in degradation of NB (10 mg L(-1)) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H2O2 after 10 min of sonication in presence of α-Fe2O3 (1.0 g L(-1)), (k=0.58 min(-1)) and after 25 min in case of CuO (k=0.126 min(-1)). α-Fe2O3 showed also effective degradation under the conditions of 0.1 g L(-1) oxide and 5.0 mM of H2O2, even though with a lower rate constant (0.346 min(-1)). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.