Magneto-electrochemical method for chiral recognition of amino acid enantiomers.

Chiral recognition of enantiomers with identical mirror-symmetric molecular structures is important for the analysis of biomolecules, and it conventionally relies on stereoselective interactions in chiral chemical environments. Here, we develop a magneto-electrochemical method for the enhanced detection of chiral amino acids (AAs), that combines the advantages of the high sensitivity of electrochemiluminescent (ECL) biosensors and chirality-induced effects under a magnetic field. The ECL difference between L- and D-enantiomers can be amplified over 35-fold under a field of 3.5 kG, and the chiral discrimination can be achieved in dilute AA solutions down to the nM level. The field-dependent ECL and chronocoulometry measurements suggest that chiral AAs can lock the spins on their radicals and thus enlarge the ECL change under applied magnetic fields (magneto-ECL, MECL), which explains the field-enhanced chiral discrimination of AA enantiomers. Finally, a detailed protocol is demonstrated for the identification of unknown AA solutions, in which the species, chirality and concentration of AAs can be determined simultaneously from the 2D plots of the ECL and MECL results. This work benefits the development of field-assisted detection methods and represents a promising and universal strategy for the comprehensive analysis of chiral biomolecules.

Optically Triggering and Monitoring Single-Cell-Level Metabolism Using Ormosil-Decorated Ultrathin Fibers.

The integration of biological components and artificial devices requires a bio-machine interface that can simultaneously trigger and monitor the activities in biosystems. Herein, we use an organically modified silicate (ormosil) composite coating containing a light-responsive nanocapsule and a fluorescent bioprobe for reactive oxygen species (ROS) to decorate ultrathin optical fibers, namely, ormosil-decorated ultrathin fibers (OD-UFs), and demonstrate that these OD-UFs can optically trigger and monitor the intracellular metabolism activities in living cells. The sizes and shapes of UF tips were finely controlled to match the dimension and mechanical properties of living cells. The increased elasticity of the ormosil coating of OD-UFs reduces possible mechanical damage during the cell membrane penetration. The light-responsive nanocapsule was physically absorbed on the surface of the ormosil coating and could release a stimulant to trigger the metabolism activities in cells upon the guided laser through OD-UFs. The fluorescent bioprobe was covalently linked with the ormosil matrix for monitoring the intracellular ROS generation, which was verified by the in vitro experiments on the microdroplets of a hydrogen peroxide solution. Finally, we found that the living cells could maintain most of their viability after being inserted with OD-UFs, and the intracellular metabolism activities were successfully triggered and monitored at the single-cell level. The OD-UF provides a new platform for the investigation of intracellular behaviors for drug stimulations and represents a new proof of concept for a bio-machine interface based on the optical and chemical activities of organic functional molecules.

Magnetically Boosted Generation of Intracellular Reactive Oxygen Species toward Magneto-Photodynamic Therapy.

The generation of reactive oxygen species (ROS) in photodynamic therapy (PDT) involves excited-state intermediates with both singlet and triplet spin configurations, which provides possibilities to modulate the ROS production in PDT under an external magnetic field. Here, we present that magnetically modulated ROS production can promote PDT efficacy and develop a magnetic-field-assisted PDT (magneto-PDT) method for effectively and selectively killing cancer cells. The photosensitization reaction between excited-state riboflavin and oxygen molecules is influenced by the applied field, and the overall magnetic field effect (MFE) shows a moderate increase at a low field (<1000 G) and then a boost up to the saturation ∼100% at a high field (>1000 G). It is found that the spin precession occurring in radical ion pairs (electron transfer from riboflavin to oxygen) facilitates the O2•- generation at the low field. In comparison, the spin splitting in an encounter complex (energy transfer from riboflavin to oxygen) benefits the production of 1O2 species at the high field. The field modulation on the two types of ROS in PDT, i.e., O2•- and 1O2, is also demonstrated in living cells. The magneto-PDT strategy shows the capability to inhibit the proliferation of cancer cells (e.g., HeLa, RBL-2H3, and MCF-7) effectively and selectively, which reveals the potential of using the MFE on chemical reactions in biological applications.

Magnetically modulated photochemical reaction pathways in anthraquinone molecules and aggregates.

The chemical reactions involving excited-state radical pairs (RPs) of parallel/anti-parallel spin configurations are sensitive to magnetic field, leading to the possibilities of magnetically controlled synthesis of chemical compounds. Here we show that the reaction of anthraquinone (AQ) in sodium dodecyl sulfate (SDS) micellar solution under UV excitation is significantly influenced by applying external field. The steady state and time-resolved spectroscopies reveal that the reaction intermediate (pairs of AQH-SDS radicals) can undergo two distinct pathways depending on whether it is spin singlet or triplet, and the field is beneficial to the conversion between spin configurations of RPs. The applied field not only affects the reaction rate constant but also changes the final products. Besides, the aggregation of AQ molecules would change the population of singlets and triplets and thus enhance magnetic field effect. This work represents a promising way of controlling chemical reaction and improving reaction selectivity via magnetic field methods.

Lanthanide MOFs for inducing molecular chirality of achiral stilbazolium with strong circularly polarized luminescence and efficient energy transfer for color tuning.

We present herein an innovative host-guest method to achieve induced molecular chirality from an achiral stilbazolium dye (DSM). The host-guest system is exquisitely designed by encapsulating the dye molecule in the molecule-sized chiral channel of homochiral lanthanide metal-organic frameworks (P-(+)/M-(-)-TbBTC), in which the P- or M-configuration of the dye is unidirectionally generated via a spatial confinement effect of the MOF and solidified by the dangling water molecules in the channel. Induced chirality of DSM is characterized by solid-state circularly polarized luminescence (CPL) and micro-area polarized emission of DSM@TbTBC, both excited with 514 nm light. A luminescence dissymmetry factor of 10-3 is obtained and the photoluminescence quantum yield (PLQY) of the encapsulated DSM in DSM@TbTBC is ∼10%, which is close to the PLQY value of DSM in dilute dichloromethane. Color-tuning from green to red is achieved, owing to efficient energy transfer (up to 56%) from Ln3+ to the dye. Therefore, this study for the first time exhibits an elegant host-guest system that shows induced strong CPL emission and enables efficient energy transfer from the host chiral Ln-MOF to the achiral guest DSM with the emission color tuned from green to red.

A defective MOF architecture threaded by interlaced carbon nanotubes for high-cycling lithium-sulfur batteries.

Metal organic frameworks (MOFs) have been deemed among the most promising sulfur hosts for lithium-sulfur (Li-S) batteries owing to their high specific surface areas, novel pore structures and open metal sites. However, their highly coordinated, electronically insulating and structurally unstable nature overshadows the merits of MOFs to a great extent. In this work, a novel UiO-66/carbon nanotube (UC) composite was initially synthesized via a facile one-pot synthesis strategy, in which abundant linker-missing defects were caused by introduced competitive coordination. Meanwhile, flexible and interlaced carbon nanotubes (CNTs) throughout mechanically stable UiO-66 nanoparticles constructed a reliable conductive network. Because of its superior structural stability, high electronic conductivity and strong polysulfide chemisorption, the UC architecture as the sulfur cathode in Li-S batteries shows stable cycling, delivering an initial capacity of 925 mA h g-1 at 0.5 A g-1 and a very low fading rate over 800 cycles of 0.071% per cycle at 1 A g-1. A strong chemical affinity between coordination defects and LiPSs was revealed by first principles calculations and apparent absorption, which indicates significant entrapment of soluble polysulfides by the UC composite, thus leading to the outstanding cycling performance of S@UC electrodes.