Partial Density of States Ligand Field Theory (PDOS-LFT): Recovering a LFT-Like Picture and Application to Photoproperties of Ruthenium(II) Polypyridine Complexes

Gas phase density-functional theory (DFT) and time-dependent DFT (TD-DFT) calculations are reported for a data base of 98 ruthenium(II) polypyridine complexes. Comparison with X-ray crystal geometries and with experimental absorption spectra measured in solution show an excellent linear correlation with the results of the gas phase calculations. Comparing this with the usual chemical understanding based upon ligand field theory (LFT) is complicated by the large number of molecular orbitals present and especially by the heavy mixing of the antibonding metal e*$_{g}$ orbitals with ligand orbitals. Nevertheless, we show that a deeper understanding can be obtained by a partial density-of-states (PDOS) analysis which allows us to extract approximate metal t$_{2g}$ and e*$_{g}$ and ligand \pi* orbital energies in a well-defined way, thus providing a PDOS analogue of LFT (PDOS-LFT). Not only do PDOS-LFT energies generate a spectrochemical series for the ligands, but orbital energy differences provide good estimates of TD-DFT absorption energies. Encouraged by this success, we use frontier-molecular-orbital-theory-like reasoning to construct a model which allows us in most, but not all, of the cases studied to use PDOS-LFT energies to provide a semiquantitative relationship between luminescence lifetimes at room temperature and liquid nitrogen temperature

Efficacy of combination therapy using extracts of Aloe secundiflora Eng L and Callistemon citrinus William C. in Leishmania major infected BALB/c mice

Background: Leishmania major causes cutaneous leishmaniasis which leads to painful skin sores in humans. In the current study, efficacy of combination therapy of A. secundiflora and C. citrinus against L. major infected mice treated intra-peritoneally and orally was studied. Pentostam administered intra-peritoneally and phosphate buffered saline intra-peritoneally and orally were used as a controls.Objective: To determine the efficacy of combined therapy of C. citrinus and A. secundiflora extracts in Leishmania major infected BALB/c mice.Design: Experimental-Laboratory based studySetting: Kenya Medical Research Institute (Leishmania Department)Subjects: Eight weeks Male BALB/c MiceResults: The minimum inhibitory concentration (MICs) of aqueous extracts of A. secundiflora (A), and C. citrinus (B) were 2 mg/ml and 5 mg/ml respectively while the IC50 for the same extracts were 467.09μg/ml and 457.88μg/ml respectively. The combination of these extracts at ratio (1:1) supported minimal growth of L. major promastigotes and had IC50 of 58.45μg/ml as compared to MICs of 12.50μg/ml for Pentostam. The combination therapy had Infection rate (IR) of 19% and MI of 52.81% compared to Pentostam (IR=21% and MI=11.64%). The combination therapy reduced the footpad lesion size significantly (P < 0.05) just like the Pentostam control drug and no significant nitric oxide was stimulated. The oral and intra-peritoneal combination treatment reduced spleen amastigotes in mice by 73.46% and 78.12% corresponding to total LDUs of 10.87±0.64 and 8.96±0.82 respectively compared to Pentostam at 94.58% and LDU of 2.22±0.13. The difference between efficacy of Pentostam and that of combined extracts was almost significant (t= 2.653, P= 0.057).Conclusion: The combination therapy was active against L. major parasite, reduced lesion size significantly and did not prevent visceralisation but reduced spleen parasite load significantly

Impacts of savanna trees on forage quality for a large African herbivore

Recently, cover of large trees in African savannas has rapidly declined due to elephant pressure, frequent fires and charcoal production. The reduction in large trees could have consequences for large herbivores through a change in forage quality. In Tarangire National Park, in Northern Tanzania, we studied the impact of large savanna trees on forage quality for wildebeest by collecting samples of dominant grass species in open grassland and under and around large Acacia tortilis trees. Grasses growing under trees had a much higher forage quality than grasses from the open field indicated by a more favourable leaf/stem ratio and higher protein and lower fibre concentrations. Analysing the grass leaf data with a linear programming model indicated that large savanna trees could be essential for the survival of wildebeest, the dominant herbivore in Tarangire. Due to the high fibre content and low nutrient and protein concentrations of grasses from the open field, maximum fibre intake is reached before nutrient requirements are satisfied. All requirements can only be satisfied by combining forage from open grassland with either forage from under or around tree canopies. Forage quality was also higher around dead trees than in the open field. So forage quality does not reduce immediately after trees die which explains why negative effects of reduced tree numbers probably go initially unnoticed. In conclusion our results suggest that continued destruction of large trees could affect future numbers of large herbivores in African savannas and better protection of large trees is probably necessary to sustain high animal densities in these ecosystems

Comparative analysis of peripheral whole blood transcriptome from asymptomatic carriers reveals upregulation of subsets of surface proteins implicated in Plasmodium falciparum phenotypic plasticity

The molecular mechanism underlying Plasmodium falciparum's persistence in the asymptomatic phase of infection remains largely unknown. However, large-scale shifts in the parasites' gene expression during asymptomatic infections may enhance phenotypic plasticity, maximizing their fitness and leading to the persistence of the asymptomatic infections. To uncover these mechanisms, we aimed to identify parasite genetic factors implicated in asymptomatic infections through whole transcriptome analysis. We analyzed publicly available transcriptome datasets containing asymptomatic malaria (ASM), uncomplicated malaria (SM), and malaria-naïve (NSM) samples from 35 subjects for differentially expressed genes (DEGs) and long noncoding RNAs. Our analysis identified 755 and 1773 DEGs in ASM vs SM and NSM, respectively. These DEGs revealed sets of genes coding for proteins of unknown functions (PUFs) upregulated in ASM vs SM and ASM, suggesting their role in underlying fundamental molecular mechanisms during asymptomatic infections. Upregulated genes in ASM vs SM revealed a subset of 24 clonal variant genes (CVGs) involved in host-parasite and symbiotic interactions and modulation of the symbiont of host erythrocyte aggregation pathways. Moreover, we identified 237 differentially expressed noncoding RNAs in ASM vs SM, of which 11 were found to interact with CVGs, suggesting their possible role in regulating the expression of CVGs. Our results suggest that P. falciparum utilizes phenotypic plasticity as an adaptive mechanism during asymptomatic infections by upregulating clonal variant genes, with long noncoding RNAs possibly playing a crucial role in their regulation. Thus, our study provides insights into the parasites' genetic factors that confer a fitness advantage during asymptomatic infections