RESUMO
The present work describes ultrafast thermalized and hot hole transfer processes from photo-excited CdSe quantum dots (QDs) and CdSe/ZnS core-shell QDs (CSQDs) to newly synthesized thiols. Three thiols namely 2-mercapto-N-phenylacetamide (AAT), 3-mercapto-N-phenylpropanamide (APT) and 3-mercapto-N-(4-methoxyphenyl) propanamide (ADPT) were synthesized and their interaction with both CdSe QDs and CdSe/ZnS CSQDs was monitored. Steady state absorption study suggests the exciton delocalization from CdSe QDs in the presence of the thiols. However similar features were not observed in the presence of a ZnS shell over a CdSe core, instead a broadening in the excitonic peak was observed with both APT and ADPT but not with AAT. This exciton delocalization and broadening in the excitonic peak was also confirmed by ultrafast transient absorption studies. Steady state and time resolved emission studies show hole transfer from photo-excited QDs and CSQDs to the thiols. A signature of hot hole extraction was observed in transient absorption studies which was confirmed by fluorescence upconversion studies. Both hot and thermalized hole transfer rates from CdSe QDs and CdSe/ZnS CSQDs to the thiols were determined using the fluorescence up-conversion technique. Experiments with different ZnS shell thicknesses have been carried out which suggest that hole transfer is possible till 2.5 monolayer of the ZnS shell. To the best of our knowledge we are reporting for the first time the extraction of hot holes from CdSe/ZnS type I CSQDs by a molecular adsorbate.
RESUMO
Enrichment factor (EF) of elements including geo-accumulation indices for soil quality and principal component analysis (PCA) were used to identify the contributions of the origin of sources in the studied area. Results of (40)K, (137)Cs, (238)U and (232)Th including their decay series isotopes in the agricultural soil of Mansa and Bathinda districts in the state of Punjab were presented and discussed. The measured mean radioactivity concentrations for (238)U, (232)Th and (40)K in the agricultural soil of the studied area differed from nationwide average crustal abundances by 51, 17 and 43 %, respectively. The sequence of the EFs of radionuclides in soil from the greatest to the least was found to be (238)U > (40)K > (226)Ra > (137)Cs > (232)Th > (228)Ra. Even though the enrichment of naturally occurring radionuclides was found to be higher, they remained to be in I(geo) class of '0', indicating that the soil is uncontaminated with respect to these radionuclides. Among non-metals, N showed the highest EF and belonged to I(geo) class of '2', indicating that soil is moderately contaminated due to intrusion of fertiliser. The resulting data set of elemental contents in soil was also interpreted by PCA, which facilitates identification of the different groups of correlated elements. The levels of the (40)K, (238)U and (232)Th radionuclides showed a significant positive correlation with each other, suggesting a similar origin of their geochemical sources and identical behaviour during transport in the soil system.