RESUMEN
Electronic relaxation dynamics of neutral Au38(SC6H13)24 monolayer-protected clusters (MPCs), following excitation of the mixed 15 875 cm-1 charge transfer resonance, were studied using femtosecond transient absorption (fsTA) and two-dimensional electronic spectroscopy (2DES). The excited carriers relax by three different mechanisms, including an â¼100 fs HOMO-12/-13 to HOMO-4/-6 hole transfer, picosecond HOMO-4/-6 to HOMO hole transfer, and subsequent electron-hole recombination that persisted beyond the hundreds of picoseconds measurement range. The fsTA data revealed two transient bleach components at 15 820 and 15 625 cm-1, where the lower frequency component exhibited a delayed first-order buildup of 80 ± 25 fs that matched the decay of the high-energy bleach component (110 ± 45 fs). These results suggested that the excited charge carriers internally relax within the exited-state manifold in ≈100 fs. 2DES resolved multiple electronic fine-structure transient peaks that spanned excitation frequencies ranging from 15 500 to 16 100 cm-1. State-to-state dynamics were understood by the analysis of time-dependent 2DES transient signal amplitudes at numerous excitation-detection frequency combinations. An off-diagonal cross peak at 15 825-15 620 cm-1 excitation-detection signified the HOMO-12/-13 to HOMO-4/-6 hole transfer process. The lowest-frequency (15 620 cm-1) 2DES diagonal fine-structure peak exhibited instantaneous amplitude but intensified following a 75 ± 10 fs buildup when compared to diagonal peaks at higher frequencies. This observation indicated that the charge transfer resonance in Au38(SC6H13)24 MPCs is comprised of several electronic transitions of unique spectral weights, which may result from different orbital contributions associated with specific cluster domains. The use of 2DES in combination with structurally precise MPCs can provide a platform for understanding structure-dependent electronic dynamics in metal nanoclusters and technologically important metal-chalcogenide interfaces.
RESUMEN
OBJECTIVES: Despite progress in addressing health disparities among vulnerable populations, minority populations are at risk for chronic health conditions associated with multiple determinants of health, which affects their health status and access to care. We offer a potential solution, which creates an unconventional medical team between a pharmacist and a community health worker (CHW). We explore weaknesses and challenges in our medication use system in the context of adherence as a drug therapy problem, the role of culture in shaping medication use, and finally offer a unique paradigm for a collaborative interprofessional team consisting of CHWs and pharmacists. SUMMARY: Medication adherence is far from optimal, especially in minority ethnic populations. Members of an ethnic group may acquire beliefs about illness consistent with their culture's shared customs. These findings intimate that ethnocultural minority groups may have their own remedies for illness that shape their decision to use medications as prescribed. An interprofessional team in which CHWs and pharmacists collaborate offers an opportunity to improve the effectiveness of pharmacists to address adherence-related problems, especially among minority populations in which culturally determined beliefs can shape medication use decisions. This approach holds promise because CHWs are usually embedded within the community in which their patients live, having experienced the same life experiences. These shared experiences may lead CHWs to uncover medication use practices that pharmacists are not able to discover on their own because the relationship with their patients is often not authentic, which, for many minority patients, can only be established through shared experiences. CONCLUSION: This paper argues that creating teams of CHWs and pharmacists will help address challenges in achieving health equity and health disparities among vulnerable populations in the medication use system.