Mechanism of Ligand-Controlled Emission in Silicon Nanoparticles.

Although bulk silicon (Si) is known to be a poor emitter, Si nanoparticles (NPs) exhibit size-dependent photoluminescence in the red or near-infrared due to quantum confinement. Recently, it has been shown that surface modification of Si NPs with nitrogen-capped ligands results in bluer emission wavelengths and quantum yields of up to 90%. However, the emission mechanism operating in these surface-modified Si NPs and the factors that determine their emission maxima are still unclear. Here, the emission in these species is shown to arise from a charge-transfer state between the Si surface and the ligand. The energy of this state is linearly correlated to the calculated ground-state dipole moment of the free ligand. This trend can be used in a predictive fashion for the design and synthesis of Si NPs with a broader range of emission wavelengths.

Differential Expression of Ccn4 and Other Genes Between Metastatic and Non-metastatic EL4 Mouse Lymphoma Cells.

BACKGROUND: Previous work characterized variants of the EL4 murine lymphoma cell line. Some are non-metastatic, and others metastatic, in syngenic mice. In addition, metastatic EL4 cells were stably transfected with phospholipase D2 (PLD2), which further enhanced metastasis. MATERIALS AND METHODS: Microarray analyses of mRNA expression was performed for non-metastatic, metastatic, and PLD2-expressing metastatic EL4 cells. RESULTS: Many differences were observed between non-metastatic and metastatic cell lines. One of the most striking new findings was up-regulation of mRNA for the matricellular protein WNT1-inducible signaling pathway protein 1 (CCN4) in metastatic cells; increased protein expression was verified by immunoblotting and immunocytochemistry. Other differentially expressed genes included those for reproductive homeobox 5 (Rhox5; increased in metastatic) and cystatin 7 (Cst7; decreased in metastatic). Differences between PLD2-expressing and parental cell lines were limited but included the signaling proteins Ras guanyl releasing protein 1 (RGS18; increased with PLD2) and suppressor of cytokine signaling 2 (SOCS2; decreased with PLD2). CONCLUSION: The results provide insights into signaling pathways potentially involved in conferring metastatic ability on lymphoma cells.

Modeling Field-Induced Quenching in Poly(p-phenylene vinylene) Polymers and Oligomers.

Field-induced fluorescence quenching of poly(p-phenylene vinylene) (PPV) oligomers due to nonradiative relaxation through free electron-hole pair (FEHP) states is modeled using singles configuration interaction computations with the intermediate neglect of differential overlap Hamiltonian. The computations find FEHP states with energies that drop linearly with applied field and undergo avoided crossings with the fluorescent state. The coupling between the FEHP and fluorescent state, computed for multiple FEHP states on a variety of oligomer lengths, is found to depend primarily on the field strength required for the state to cross the fluorescent state. The rate of decay to these dark FEHP states is then calculated from Marcus theory, which is modified to take into account dielectric in addition to other bulk measurement considerations. The results predict that individual molecules go from being emissive to fully quenched over a small range of applied field strengths. Phenomenological introduction of inhomogeneous broadening for the energies of the FEHP states leads to a more gradual dependence on applied field. The fluorescence quenching mechanism considered here is found to be important for applied fields above about 1 MV cm(-1), which is similar in magnitude to those present in light-emitting diodes.