Temporal Control of Fluorescent EuW10 Aggregates for Autonomous DNA Capture and Information Encryption.

Self-assembly exploits noncovalent interaction to offer an effective method for the fabrication of materials. For Na9 [EuW10 O36 ] ⋅ 32H2 O (EuW10 ), the negative charges and abundant oxygen atoms on its surface provide a handle for static self-assembly. New properties are envisioned for EuW10 aggregates which are able to display such kinetics and time-programming characteristics, in order to satisfy more complex and intelligent application scenarios, such as DNA binding and information encryption. In this work, EuW10 coupling with stimuli-responsive dodecyl dimethylamine oxide (C12 DMAO) can generate versatile aggregates with pH-responsive properties. We demonstrated the temporal programming of the assembly and disassembly of EuW10 nanospheres using a pH clock reaction of acid/urease hydrolysis. The pH clock reaction endows EuW10 assemblies with dynamical properties, in which the charges and fluorescence changes are coded in this system. These fluorescent assemblies provide new application in time-programmed DNA capture and information encryption.

Design, synthesis and in vitro evaluation of amidoximes as histone deacetylase inhibitors for cancer therapy.

Amindoximes are geometric isomers of N-hydroxyamidines which are bioisosteres of hydroxamates. Since amindoxime group is capable of chelating transition metal ions including zinc ion, amindoximes should possess histone deacetylases (HDACs) inhibitory activity. In this work, we designed and synthesized a series of amindoximes, examined their inhibitory activities against HDACs, and investigated their cytotoxicity to human cancer cells. Preliminary results demonstrated that amindoximes possessed submicromolar HDACs inhibitory activity, with noteworthy enhancement compared with hydroxamates. Furthermore, the amindoximes arrested HCT116 and A549 cells in G2/M phase and showed good efficacy in inducing cells death. We provided a proof-of-concept that amindoximes could be used as HDACs inhibitors and hold great promise as epigenetic drugs.

Fe-CP-based Catalytic Oxidation and Dissipative Self-Assembly of a Ferrocenyl Surfactant Applied in DNA Capture and Release.

Dissipative self-assembly plays a vital role in fabricating intelligent and transient materials. The selection and design of the molecular structure is critical, and the introduction of valuable stimuli-responsive motifs into building blocks would bring about a novel perspective on the fuel driven nonequilibrium assemblies. For redox-responsive surfactants, novel methods of catalytic oxidation are very important for their activation/deactivation process through designing fuel input/energy dissipation. As an enzyme with a fast catalytic rate, Fe-based coordination polymers (Fe-CPs) are found to be highly effective oxidase-like enzymes to induce a reversible switch of a ferrocene-based surfactant over a wide range of temperatures and pH. This builds a bridge between the CPs materials and surfactants. Furthermore, glucose oxidase can also induce a switchable transition of a ferrocene-based surfactant. The GOX-catalyzed, glucose-fueled transient surfactant assemblies have been fabricated for many cycles, which has a successful application in a time-controlled and autonomous DNA capture and release process. The intelligent use of enzymes including CPs and GOX in ferrocene-based surfactants will pave the way for the oxidation of redox surfactants, which extends the application of stable or transient ferrocenyl self-assemblies.

Nanoporous PdCu alloy as an excellent electrochemical sensor for H2O2 and glucose detection.

Nanoporous (NP) PdCu alloy is easily fabricated by dealloying PdCuAl ternary alloy in dilute sulfuric acid. Selectively dissolving Al from PdCuAl alloy generates the three-dimensional uniform nanosponge architecture with narrow ligament size distribution. Benefitting from the unique nanoporous architecture and the alloying effect, the as-made NP-PdCu exhibits outstanding sensing performance towards the detection of hydrogen peroxide (H2O2) and glucose. Compared with NP-Pd and commercial Pd/C catalysts, the NP-PdCu alloy presents high sensitivity, wide linear range of 0.1-2.0mM, low detection limit of 2.1µM, and long-term stability toward H2O2 detection. In addition, the NP-PdCu can efficiently detect glucose in a wide concentration range (1-30mM) with the low detection limit of 1.9µM. Moreover, the NP-PdCu exhibits good anti-interference toward ascorbic acid, uric acid, and dopamine. Characterized by easy preparation, unique electrocatalytic activity, and high structure stability, the NP-PdCu alloy possesses great application prospect to construct platform for electrochemical sensing.

Enhancing both CT imaging and natural killer cell-mediated cancer cell killing by a GD2-targeting nanoconstruct.

Although nanomaterials have been widely investigated for drug delivery, imaging and immunotherapy, their potential roles in triggering innate cellular immune responses while simultaneously serving as imaging enhancer remain unexplored. In this work, gold nanoparticles (GNPs) conjugated to the tumor-targeting anti-GD2 antibody hu14.18K322A, namely HGNPs, were designed and synthesized to specifically enhance computerized tomography (CT) imaging contrast and to stimulate the attack of neuroblastoma and melanoma cells by natural killer (NK) cells. The HGNPs specifically targeted GD2-positive neuroblastoma (NB1691) and melanoma (M21) cells, with an enhancement of CT contrast images of the HGNP-labeled cell pellets by 5.27- and 7.66-fold, respectively, compared to images of unlabeled cell pellets. The HGNPs also triggered NK-mediated antibody-dependent cellular cytotoxicity (ADCC) in NB1691 and M21 cells with a two-fold higher efficacy compared to that elicited by hu14.18K322A alone, with no adverse effect to GD2-negative PC-3 cells. These results suggest that HGNPs are promising theranostic agents for neuroblastoma and melanoma cancers.