Molybdenum disulfide (MoS2) is systematically studied using Raman spectroscopy with ultraviolet and visible laser lines. It is shown that only the Raman frequencies of $ E_{2{\rm g}}^1 $ and $ A_{{\rm 1g}}^{} $ peaks vary monotonously with the layer number of ultrathin MoS2 flakes, while intensities or widths of the peaks vary arbitrarily. The coupling between electronic transitions and phonons are found to become weaker when the layer number of MoS2 decreases, attributed to the increased electronic transition energies or elongated intralayer atomic bonds in ultrathin MoS2. The asymmetric Raman peak at 454 cm−1, which has been regarded as the overtone of longitudinal optical M phonons in bulk MoS2, is actually a combinational band involving a longitudinal acoustic mode (LA(M)) and an optical mode ($ A_{{\rm 2u}}^{} $). Our findings suggest a clear evolution of the coupling between electronic transition and phonon when MoS2 is scaled down from three‐ to two‐dimensional geometry.
Checkpoint blockade enhances effector T cell function and has elicited long-term remission in a subset of patients with a broad spectrum of cancers. TIGIT is a checkpoint receptor thought to be involved in mediating T cell exhaustion in tumors; however, the relevance of TIGIT to the dysfunction of natural killer (NK) cells remains poorly understood. Here we found that TIGIT, but not the other checkpoint molecules CTLA-4 and PD-1, was associated with NK cell exhaustion in tumor-bearing mice and patients with colon cancer. Blockade of TIGIT prevented NK cell exhaustion and promoted NK cell-dependent tumor immunity in several tumor-bearing mouse models. Furthermore, blockade of TIGIT resulted in potent tumor-specific T cell immunity in an NK cell-dependent manner, enhanced therapy with antibody to the PD-1 ligand PD-L1 and sustained memory immunity in tumor re-challenge models. This work demonstrates that TIGIT constitutes a previously unappreciated checkpoint in NK cells and that targeting TIGIT alone or in combination with other checkpoint receptors is a promising anti-cancer therapeutic strategy.
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