ABSTRACT
Real-time monitoring of biocatalytic-based processes is significantly improved and simplified when they can be visualized. Visual monitoring can be achieved by integrating a fluorescent unit with the biocatalyst. Herein, we outline the design strategies of fluorescent probes for monitoring biocatalysis: (1) probes for monitoring biocatalytic transfer: γ-glutamine is linked to the fluorophore as both a recognition group and for intramolecular charge transfer (ICT) inhibition; the probe is initially in an off state and is activated via the transfer of the γ-glutamine group and the release of the free amino group, which results in restoration of the "Donor-π-Acceptor" (D-π-A) system and fluorescence recovery. (2) Probes for monitoring biocatalytic oxidation: a propylamine is connected to the fluorophore as a recognition group, which cages the hydroxyl group, leading to the inhibition of ICT; propylamine is oxidized and subsequently ß-elimination occurs, resulting in exposure of the hydroxyl group and fluorescence recovery. (3) Probes for monitoring biocatalytic reduction: a nitro group attached to a fluorophore as a fluorescence quenching group, this is converted to an amino group by catalytic reduction, resulting in fluorescence recovery. (4) Probes for monitoring biocatalytic hydrolysis: ß-D-galactopyranoside or phosphate acts as a recognition group attached to hydroxyl groups of the fluorophore; the subsequent biocatalytic hydrolysis reaction releases the hydroxyl group resulting in fluorescence recovery. Following these 4 mechanisms, fluorophores including cyanine, coumarin, rhodamine, and Nile-red, have been used to develop systems for monitoring biocatalytic reactions. We anticipate that these strategies will result in systems able to rapidly diagnose and facilitate the treatment of serious diseases.
Subject(s)
Fluorescent Dyes , Glutamine , Biocatalysis , Rhodamines , PropylaminesABSTRACT
Sulfur functionalized biocarbons were prepared from naturally abundant lignin alkali with sodium thiocyanate as an activation agent and a sulfur source. The resultant biocarbon sorbents showed a high mercury isolation ability from aqueous solutions, where high surface area and doping of sulfur significantly aid the uptake of mercury, i.e., 0.05 g of biocarbon sorbent removed 99% of mercury from 250 mL of simulated wastewater with an initial concentration of mercury of 10 mg L-1.
ABSTRACT
Mechanical response luminescence (MRL) describes the photophysical properties triggered by mechanical stimulation. Usually, MRL can be regulated by intermolecular interactions, molecular conformation or molecular packing, to achieve the desirable optical properties. Herein, at the molecular level, this review covers the factors that influence mechanically responsive fluorescent materials, involving the single- or multifactorial modulation of aliphatic chains, donor-receptor switch, substituent adjustment, and position isomerism. According to these factors, the structure-activity strategies can be summarized as: (i) the self-recovery of optical properties, from the final to initial state, can be regulated by introducing long alkyl chains to a fluorophore. (ii) The sensitivity of MRL materials can be controlled by modifying the donor-acceptor structure via the changed ICT (intramolecular charge transfer) and intramolecular interaction. (iii) The electronic and steric effects of substituents can affect ICT and intermolecular interactions, thereby resulting in high quantum yield and high-contrast MRL materials via changing the molecular stacking of crystalline states. (iv) Intermolecular interaction is modulated by the position isomerism of the substituents, which results in switched molecular packing for the extended response toward a wide range of stimuli. It is anticipated that the molecular mechanisms of these structure-activity relationships will serve as a significant reference for developing novel, high contrast, recyclable mechanical response luminous materials.
