Dynamic morphology evolution of potassium chloride (KCl) crystals was demonstrated by surface optical trapping with a focused continuous-wave near-infrared laser. Optical trapping at an air/solution interface triggered the crystallization, and then, the dynamic change in crystal morphology was observed in real time. We observed three different crystal morphologies of needle, rectangle, and cubic at the early stage of crystallization. As the laser power increases, the probability of generation of a cubic crystal increases, especially upon the irradiation with linear polarization. We also found laser polarization-dependent morphology evolution by the continuous irradiation to the generated crystals. Upon linearly polarized laser irradiation, the stepwise morphology evolves from needle to rectangle, and eventually to cubic, which is an equilibrium shape of KCl crystals. Meanwhile, circularly polarized laser irradiation only induced morphology evolution from needle to rectangle, without morphology change into cubic, because the rectangle crystal was dissolved while the crystal was rotating. It was made possible to observe such a unique morphological evolution due to the spatiotemporal controllability of our crystallization method. The dynamics and mechanism of these intriguing phenomena are discussed from the perspective of a dense cluster domain formed by optical trapping before nucleation.
Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO 3 ). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO 3 D 2 O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.
USP7, one of the most abundant ubiquitin-specific proteases (USP), plays multifaceted roles in many cellular events, including oncogenic pathways. Accumulated studies have suggested that USP7, through modulating the MDM2/MDMX-p53 pathway, is a promising target for cancer treatment; however, little is known about the function of USP7 in p53-deficient tumors. Here we report that USP7 regulates the autoregulation of SMAD3, a key regulator of transforming growth factor β (TGFβ) signaling, that represses the cell progression of p53-deficient lung cancer. CRISPR/Cas9-mediated inactivation of USP7 in p53-deficient lung cancer H1299 line resulted in advanced cell proliferation in vitro and in xenograft tumor in vivo. Genome-wide analyses (ChIP-seq and RNA-seq) of USP7 KO H1299 cells reveal a dramatic reduction of SMAD3 autoregulation, including decreased gene expression and blunted function of associated super-enhancer (SE). Furthermore, biochemical assays show that SMAD3 is conjugated by mono-ubiquitin, which negatively regulates the DNA-binding function of SMAD3, in USP7 KO cells. In addition, cell-free and cell-based analyses further demonstrate that the deubiquitinase activity of USP7 mediates the removal of mono-ubiquitin from SMAD3 and facilitates the DNA-binding of SMAD3-SMAD4 dimer at SMAD3 locus, and thus enhance the autoregulation of SMAD3. Collectively, our study identified a novel mechanism by which USP7, through catalyzing the SMAD3 de-monoubiquitination, facilitates the positive autoregulation of SMAD3, and represses the cancer progression of p53-deficient lung cancer.
We previously reported that giant crystal enantiomeric excess (CEE) can be obtained when sodium chlorate (NaClO3) chiral crystallization from a solution is induced by the excitation of localized surface plasmon resonance (LSPR) of a Au triangle trimer nanostructure by a circularly polarized laser. However, the role of the LSPR excitation in the giant CEE remains unclear. In this work, we showed, by finite-difference time-domain analysis of plasmonic near-field, that the magnitude of a chiral optical gradient force originating from the strong superchiral near-field at the Au trimer nanogap on a virtual NaClO3 chiral crystalline cluster is comparable to that of the electric-field gradient force in previous laser-trapping-induced crystallization from unsaturated solution. We revealed that the giant CEE resulted from a difference in the frequency of attachment of chiral crystalline clusters to crystal nuclei or in the local concentration due to chirally biased diffusion rather than enantioselective optical trapping.
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