Realizing Molecular Pixel System for Full-Color Fluorescence Reproduction: RGB-Emitting Molecular Mixture Free from Energy Transfer Crosstalk

A full-color molecular pixel system is realized for the first time using simple mixtures composed of RGB-emitting excited-state intramolecular proton transfer (ESIPT) dyes, each of which has delicately tailored Stokes shift and independent emission capability completely free from energy transfer crosstalk between them. It is demonstrated that the whole range of emission colors enclosed within the RGB color triangle on the CIE 1931 diagram is predictable and conveniently reproducible from the RGB molecular pixels not only in the solution but also in the polymer film. It must be noted that mixing ratios to reproduce the desired color coordinates can be precisely calculated on the basis of additive color theory according to their molecular pixel behavior

Highly Fluorescent Chameleon Nanoparticles and Polymer Films: Multicomponent Organic Systems that Combine FRET and Photochromic Switching

We describe the preparation of highly efficient stimulus-responsive fluorescence color-tuning in self-assembled supramolecular scaffold systems. The systems consisted of a photochromic compound (BP-BTE) in combination with unique luminescent organic materials (CN-MBE, TPS-CNMBE, TPA-2CNMBE) that exhibited intense fluorescence in the solid state. The emission spectrum was tuned by introducing fluorescence resonance energy transfer and photochromic switching capabilities into the system. The materials were used to successfully demonstrate novel fluorescence patterns that were responsive to multiple stimuli, displayed reversible fluorescence switching, and provided a nondestructive readout of the fluorescence signal

Self-Healing of Molecular Catalyst and Photosensitizer on Metal–Organic Framework: Robust Molecular System for Photocatalytic H₂ Evolution from Water

Inspired by self-repair mechanism of PSII in plants, we report a self-healing system which spontaneously repairs molecular catalyst and photosensitizer during photocatalytic H₂ evolution. A bipyridine-embedded UiO-type metal–organic framework (MOF), namely Pt_<i>n</i>_Ir_BUiO, which incorporated H₂-evolving catalyst and photosensitizer, was synthesized and subject to photocatalytic H₂ evolution reaction (HER). Impressively, HER with Pt_0.1_Ir_BUiO showed very stable molecular photocatalysis without significant decrease in its activity and colloidal formation for 6.5 days at least; in the homogeneous counterpart, the molecular catalyst became a colloid just after 7.5 h. It was revealed that the arrangement of diimine sites which closely and densely surrounded the H₂-evolving catalyst and photosensitizer in the MOF enabled such a highly efficient self-healing

Wholly π‑Conjugated Low-Molecular-Weight Organogelator That Displays Triple-Channel Responses to Fluoride Ions

A novel salicylidene aniline-based wholly π-conjugated molecule that could be self-assembled into an organogel was synthesized. The rigid organogel collapsed into fluid solutions with significant changes in UV–vis absorption and fluorescence colors in response to fluoride ions. It was found that the hydroxyl group in the salicylidene aniline moiety played a key role not only in the gelation but also in fluoride ion responses

Water-Soluble Fluorinated and PEGylated Cyanostilbene Derivative: An Amphiphilic Building Block Forming Self-Assembled Organic Nanorods with Enhanced Fluorescence Emission

We report synthesis and optical/structural characterization of new fluorescent rod–coil amphiphiles based on the PEGylated α-cyanostilbene skeleton (12EO-CNMBE and 12EO-CNTFMBE) and their self-assembly behaviors in water. Distinct from the common amphiphilic behavior of nonfluorinated 12EO-CNMBE forming spherical nanostructures, fluorinated 12EO-CNTFMBE has proven to be the first example of a molecular building block that can self-assemble in water into small-dimension, small-aspect-ratio organic nanorods with aggregation-induced enhanced emission (AIEE). The robust structural integrity and hydrophobic/π-conjugated nature of the fluorinated block assembly, as well as the antifouling coating by the hydrophilic PEG block, enabled stable encapsulation of a model drug (Nile Red) within the self-assembled nanorod structure and its successful delivery through membrane filters. By virtue of these advantageous attributes along with high intracellular uptake efficiency, the 12EO-CNTFMBE nanorods manifested potential as a self-signaling fluorescent nanocarrier for the intracellular delivery of hydrophobic cargos

High-Contrast On/Off Fluorescence Switching via Reversible <i>E</i>–<i>Z</i> Isomerization of Diphenylstilbene Containing the α‑Cyanostilbenic Moiety

Fluorescence switching or modulation of π-conjugated molecules is of great interest in the area of optoelectronic materials science and technology because of their promising applications. However, the “concentration fluorescence quenching” problems commonly associated with conventional π-conjugated molecules in the solid state were occasionally an obstacle to use of π-conjugated molecules in high-contrast memory storage devices. We designed and synthesized a novel class of fluorescence switching π-conjugated molecule, (<i>Z</i>)-CN-MBE, that exhibits a reversible photo/thermal <i>E/Z</i> isomerization process, accompanied by a remarkable fluorescence on/off switching in the solid state. This may provide a promising way to construct high-contrast optical binary memory storage devices. (<i>Z</i>)-CN-MBE is virtually nonfluorescent but exhibits an extraordinary <i>Z</i> to <i>E</i> isomerization upon external light/thermal stimuli even in the solid state with a concomitant drastic fluorescence enhancement owing to the unique “aggregation-induced enhanced emission” (AIEE)’ phenomenon of its trans isomer

Survival analysis in full cohort (A) and early-stage subgroup (B) of lung adenocarcinoma.

<p>Survival analysis in full cohort (A) and early-stage subgroup (B) of lung adenocarcinoma.</p

Kaplan–Meier curves depicting the prognostic impact of programmed cell death ligand-1 (PD-L1) protein expression on overall survival in early stage (I and IIA) non-small cell lung cancer subgroup.

<p>Cases with PD-L1 protein expression over 1% showing a shorter overall survival duration (<i>p</i> = 0.02).</p

Correlation between PD-L1 mRNA and protein expression.

<p>Correlation between PD-L1 mRNA and protein expression.</p

Association between PD-L1 status and clinicopathologic variables in lung adenocarcinoma.

<p>Association between PD-L1 status and clinicopathologic variables in lung adenocarcinoma.</p