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Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cages are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (|g lum|: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality.

Metal phosphorous trichalcogenides (MPX3) are novel 2D nanomaterials that have recently been exploited as efficient photothermal–chemodynamic agents for cancer therapy. As a representative MPX3, FePSe3 has the potential to be developed as magnetic resonance imaging (MRI) and photoacoustic imaging (PAI) agents due to the composition of Fe and the previously revealed PA signal. Here, a FePSe3‐based theranostic agent, FePSe3@APP@CCM, loaded with anti‐PD‐1 peptide (APP) as the inner component and CT26 cancer cell membrane (CCM) as the outer shell is reported, which acts as a multifunctional agent for MR and PA imaging and photothermal and immunotherapy against cancer. FePSe3@APP@CCM induces highly efficient tumor ablation and suppresses tumor growth by photothermal therapy under near‐infrared laser excitation, which further activates immune responses. Moreover, APP blocks the PD‐1/PD‐L1 pathway to activate cytotoxic T cells, causing strong anticancer immunity. The combined therapy significantly prolongs the lifespan of experimental mice. The multimodal imaging and synergistic therapeutic effects of PTT and its triggered immune responses and APP‐related immunotherapy are clearly demonstrated by in vitro and in vivo experiments. This work demonstrates the potential of MPX3‐based biomaterials as novel theranostic agents. [ABSTRACT FROM AUTHOR]

The acidic microenvironment of tumor tissues has been proven to be a major characteristic for differentiation from normal tissues, thereby providing a desirable target for both disease diagnosis and functional imaging. We herein introduce a way to endow gold nanoparticles with aggregation behaviour induced by pH tuning. The nanoparticle surface was modified with two thiol conjugate molecules, which could smartly stabilize it at the pH of blood and normal tissues but induce aggregation in response to the acidic extracellular pH in tumor. The surface conjugate molecule composition effect was studied systematically, and at the optimal surface conjugate molecule composition, a pH-responsive active tumor-targeting c(RGDyk)-MHDA/LSC@AuNP nanoprobe was successfully obtained and showed a significantly enhanced contrast effect for both in vitro and in vivo photoacoustic (PA) imaging. Intravenous administration of our nanoprobe to U87MG tumor-bearing nude mice showed PA imaging contrasts almost 3-fold higher than those for the blocking group. Quantitative biodistribution data revealed that 9.7 μg g -1 of nanoprobe accumulated in the U87MG tumor 4 h post-injection. These findings might provide an effective strategy for developing new classes of intelligent and biocompatible contrast agents with a high efficiency for PA imaging and PA imaging-guided cancer therapy., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We have developed energy migration upconversion (EMU) nanoparticles (UCNPs) with optimal Nd 3+ -sensitization under excitation of an 808 nm laser to avoid over-heating effects caused by a 980 nm laser while maximizing the excitation efficiency. To realize efficient 808 nm sensitization, a "Nd 3+ -Trinity system" was implemented in the energy migration upconversion (EMU) cores (NaGdF 4 :Yb,Tm@NaGdF 4 :Yb,X, X = Eu/Tb), resulting in a core-multishell structure of EMU cores (accumulation layer@activation layer)@transition layer@harvest layer@activation layer. The spatially separated dopants and optimized Yb 3+ /Nd 3+ content effectively prevented severe quenching events in the UCNPs and their Nd 3+ -sensitized EMU-based photoluminescence mechanism was studied under 808 nm excitation. These Nd 3+ -Trinity EMU system UCNPs presented enhanced upconversion luminescence and prolonged lifetime compared to the 980 nm excited UCNPs of the EMU system. It is proposed that 975 nm and 1056 nm NIR photons induced from the Nd 3+ → Yb 3+ energy transfer facilitate the Tm 3+ accumulation process due to the matched energy gaps, which contributes to the extended lifetimes. More importantly, the synthesized UCNPs had a small average size of sub-15 nm and they not only exhibited color-tunability via Eu 3+ /Tb 3+ activators, but also released a larger portion of Tm 3+ red emission at 647 nm and had better penetration ability in water under 808 nm excitation, which are favorable for bioimaging applications.

Predictable stereoselective formation of supramolecular assembly is generally believed to be an important but complicated process. Here, we show that point chirality of a ligand decisively influences its supramolecular assembly behavior. We designed three closely related chiral ligands with different point chiralities, and observe their self-assembly into europium (Eu) tetrametallic tetrahedral cages. One ligand exhibits a highly diastereoselective assembly into homochiral (either ΔΔΔΔ or ΛΛΛΛ) Eu tetrahedral cages whereas the two other ligands, with two different approaches of loosened point chirality, lead to a significant breakdown of the diastereoselectivity to generate a mixture of (ΔΔΔΔ and ΛΛΛΛ) isomers. The cages are highly emissive (luminescence quantum yields of 16(1) to 18(1)%) and exhibit impressive circularly polarized luminescence properties (|g lum |: up to 0.16). With in-depth studies, we present an example that correlates the nonlinear enhancement of the chiroptical response to the nonlinearity dependence on point chirality.