Enhancing Long-Range Energy Transport in Supramolecular Architectures by Tailoring Coherence Properties

Efficient long-range energy transport along supramolecular architectures of functional organic molecules is a key step in nature for converting sunlight into a useful form of energy. Understanding and manipulating these transport processes on a molecular and supramolecular scale is a long-standing goal. However, the realization of a well-defined system that allows for tuning morphology and electronic properties as well as for resolution of transport in space and time is challenging. Here we show how the excited-state energy landscape and thus the coherence characteristics of electronic excitations can be modified by the hierarchical level of H-type supramolecular architectures. We visualize, at room temperature, long-range incoherent transport of delocalized singlet excitons on pico- to nanosecond time scales in single supramolecular nanofibers and bundles of nanofibers. Increasing the degree of coherence, i.e., exciton delocalization, via supramolecular architectures enhances exciton diffusivities up to 1 order of magnitude. In particular, we find that single supramolecular nanofibers exhibit the highest diffusivities reported for H-aggregates so far

Energy transport and light propagation mechanisms in organic single crystals

Unambiguous information about spatiotemporal exciton dynamics in three-dimensional nanometer- to micrometer-sized organic structures is difficult to obtain experimentally. Exciton dynamics can be modified by annihilation processes, and different light propagation mechanisms can take place, such as active waveguiding and photon recycling. Since these various processes and mechanisms can lead to similar spectroscopic and microscopic signatures on comparable time scales, their discrimination is highly demanding. Here, we study individual organic single crystals grown from thiophene-based oligomers. We use time-resolved detection-beam scanning microscopy to excite a local singlet exciton population and monitor the subsequent broadening of the photoluminescence (PL) signal in space and on pico- to nanosecond time scales. Combined with Monte Carlo simulations, we were able to exclude photon recycling for our system, whereas leakage radiation upon active waveguiding leads to an apparent PL broadening of about 20% compared to the initial excitation profile. Exciton–exciton annihilation becomes important at high excitation fluence and apparently accelerates the exciton dynamics leading to apparently increased diffusion lengths. At low excitation fluences, the spatiotemporal PL broadening results from singlet exciton diffusion with diffusion lengths of up to 210 nm. Surprisingly, even in structurally highly ordered single crystals, the transport dynamics is subdiffusive and shows variations between different crystals, which we relate to varying degrees of static and dynamic electronic disorders

Results of a multicenter phase I/II trial of TCRαβ and CD19-depleted haploidentical hematopoietic stem cell transplantation for adult and pediatric patients

Hematopoietic stem cell transplantation (HSCT) from haploidentical donors is a viable option for patients lacking HLA-matched donors. Here we report the results of a prospective multicenter phase I/II trial of transplantation of TCRαβ and CD19-depleted peripheral blood stem cells from haploidentical family donors after a reduced-intensity conditioning with fludarabine, thiotepa, and melphalan. Thirty pediatric and 30 adult patients with acute leukemia (n = 43), myelodysplastic or myeloproliferative syndrome (n = 6), multiple myeloma (n = 1), solid tumors (n = 6), and non-malignant disorders (n = 4) were enrolled. TCR αβ/CD19-depleted grafts prepared decentrally at six manufacturing sites contained a median of 12.1 × 1