Incorporating
chiral organic molecules into organic/inorganic hybrid
2D metal-halide perovskites results in a novel family of chiral hybrid
semiconductors with unique spin-dependent properties. The embedded
chiral organic moieties induce a chiroptical response from the inorganic
metal–halide sublattice. However, the structural interplay
between the chiral organic molecules and the inorganic sublattice,
as well as their synergic effect on the resulting electronic band
structure need to be explored in a broader material scope. Here we
present three new layered tin iodide perovskites templated by chiral
(R/S-)methylbenzylammonium (R/S-MBA), i.e., (R-/S-MBA)2SnI4, and their racemic phase (rac-MBA)2SnI4. These MBA2SnI4 compounds exhibit the largest level of octahedral bond distortion
compared to any other reported layered tin iodide perovskite. The
incorporation of chiral MBA cations leads to circularly polarized
absorption from the inorganic Sn–I sublattice, displaying chiroptical
activity in the 300–500 nm wavelength range. The bandgap and
chiroptical activity are modulated by alloying Sn with Pb, in the
series of (MBA)2Pb1–x
Sn
x
I4. Finally, we show that
vertical charge transport through oriented (R-/S-MBA)2SnI4 thin films is highly spin-dependent,
arising from a chiral-induced spin selectivity (CISS) effect. We demonstrate
a spin-polarization in the current–voltage characteristics
as high as 94%. Our work shows the tremendous potential of these chiral
hybrid semiconductors for controlling both spin and charge degrees
of freedom.
Background and aimsHBV infection represents a major health problem worldwide, but the immunological mechanisms by which HBV causes chronic persistent infection remain only partly understood. Recently, cell subsets with suppressive features have been recognised among monocytes and natural killer (NK) cells. Here we examine the effects of HBV on monocytes and NK cells.MethodsMonocytes and NK cells derived from chronic HBV-infected patients and healthy controls were purified and characterised for phenotype, gene expression and cytokines secretion by flow cytometry, quantitative real-time (qRT)-PCR, ELISA and western blotting. Culture and coculture of monocytes and NK cells were used to determine NK cell activation, using intracellular cytokines staining.ResultsIn chronic HBV infection, monocytes express higher levels of PD-L1, HLA-E, interleukin (IL)-10 and TGF-β, and NK cells express higher levels of PD-1, CD94 and IL-10, compared with healthy individuals. HBV employs hepatitis B surface antigen (HBsAg) to induce suppressive monocytes with HLA-E, PD-L1, IL-10 and TGF-β expression via the MyD88/NFκB signalling pathway. HBV-treated monocytes induce NK cells to produce IL-10, via PD-L1 and HLA-E signals. Such NK cells inhibit autologous T cell activation.ConclusionsOur findings reveal an immunosuppressive cascade, in which HBV generates suppressive monocytes, which initiate regulatory NK cells differentiation resulting in T cell inhibition.
We consider the Pb-free perovskite Cs2TiBr6 and provide complementary experimental and theoretical results suggesting that Cs2TiBr6 in its pristine form might not be suitable for solar energy applications.
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