Bioorthogonal Ligations and Cleavages in Chemical Biology.

Bioorthogonal reactions including the bioorthogonal ligations and cleavages have become an active field of research in chemical biology, and they play important roles in chemical modification and functional regulation of biomolecules. This review summarizes the developments and applications of the representative bioorthogonal reactions including the Staudinger reactions, the metal-mediated bioorthogonal reactions, the strain-promoted cycloadditions, the inverse electron demand Diels-Alder reactions, the light-triggered bioorthogonal reactions, and the reactions of chloroquinoxalines and ortho-dithiophenols.

A bioorthogonally activatable photosensitiser for site-specific photodynamic therapy.

A boron dipyrromethene based photosensitiser substituted with a 1,2,4,5-tetrazine moiety has been prepared of which the photoactivity can be activated upon an inverse-electron-demand Diels-Alder reaction with trans-cyclooctene derivatives. By using a biotin-conjugated trans-cyclooctene to tag the biotin-receptor-positive HeLa cells, this photosensitiser exhibits site-specific activation through cycloaddition, leading to high photocytotoxicity.

Near-infrared light-responsive alginate hydrogels based on diselenide-containing cross-linkage for on demand degradation and drug release.

A biodegradable, near-infrared (NIR) - responsive hydrogel is one of the most promising strategies as a remotely triggered drug carrier. In this study, novel NIR-responsive hydrogels based on alginate structures were prepared for controllable drug release. The hydrogels were formed rapidly by reacting norbornene-functionalized alginates and tetrazine cross-linkers containing diselenide bonds via inverse electron demand Diels-Alder click chemistry. In order to manipulate their properties, we prepared hydrogels with various cross-linking densities. NIR sensitive indocyanine green (ICG) and a drug, doxorubicin (DOX) were incorporated in the hydrogel matrix during gelation. The hydrogels showed a suppressed release profile under physiological conditions, while NIR light triggered a rapid release of DOX. Under NIR-light irradiation, ICG generated reactive oxygen species which could decompose diselenide bonds in the hydrogel matrix, inducing the gel-sol transition and release of entrapped DOX. The degradation of hydrogels could be also controlled by the ratio of the precursors.

Equilibrium versus Nonequilibrium Peptide Dynamics: Insights into Transient 2D IR Spectroscopy.

Over the past two decades, two-dimensional infrared (2D IR) spectroscopy has evolved from the theoretical underpinnings of nonlinear spectroscopy as a means of investigating detailed molecular structure on an ultrafast time scale. The combined time and spectral resolution over which spectra can be collected on complex molecular systems has led to the precise structural resolution of dynamic species that have previously been impossible to directly observe through traditional methods. The adoption of 2D IR spectroscopy for the study of protein folding and peptide interactions has provided key details of how small changes in conformations can exert major influences on the activities of these complex molecular systems. Traditional 2D IR experiments are limited to molecules under equilibrium conditions, where small motions and fluctuations of these larger molecules often still lead to functionality. Utilizing techniques that allow the rapid initiation of chemical or structural changes in conjunction with 2D IR spectroscopy, i.e., transient 2D IR, a vast dynamic range becomes available to the spectroscopist uncovering structural content far from equilibrium. Furthermore, this allows the observation of reaction pathways of these macromolecules under quasi- and nonequilibrium conditions.

Explosives: fate, dynamics, and ecological impact in terrestrial and marine environments.

An explosive or energetic compound is a chemical material that, under the influence of thermal or chemical shock, decomposes rapidly with the evolution of large amounts of heat and gas. Numerous compounds and compositions may be classified as energetic compounds; however, secondary explosives, such as TNT, RDX, and HMX pose the largest potential concern to the environment because they are produced and used in defense in the greatest quantities. The environmental fate and potential hazard of energetic compounds in the environment is affected by a number of physical, chemical, and biological processes. Energetic compounds may undergo transformation through biotic or abiotic degradation. Numerous organisms have been isolated with the ability to degrade/transform energetic compounds as a sole carbon source, sole nitrogen source, or through cometabolic processes under aerobic or anaerobic conditions. Abiotic processes that lead to the transformation of energetic compounds include photolysis, hydrolysis, and reduction. The products of these reactions may be further transformed by microorganisms or may bind to soil/sediment surfaces through covalent binding or polymerization and oligomerization reactions. Although considerable research has been performed on the fate and dynamics of energetic compounds in the environment, data are still gathering on the impact of TNT, RDX, and HMX on ecological receptors. There is an urgent need to address this issue and to direct future research on expanding our knowledge on the ecological impact of energetic transformation products. In addition, it is important that energetic research considers the concept of bioavailability, including factors influencing soil/sediment aging, desorption of energetic compounds from varying soil and sediment types, methods for modeling/predicting energetic bioavailability, development of biomarkers of energetic exposure or effect, and the impact of bioavailability on ecological risk assessment.

Degradation kinetics and mechanism of RDX and HMX in TiO2 photocatalysis.

This study was undertaken to examine the photocatalytic degradation of explosives hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) with a circular photocatalytic reactor, using a UV lamp as a light source and TiO2 as a photocatalyst. The effects of various parameters, such as the RDX or HMX concentration, the amount of TiO, and the initial pH, on the photocatalytic degradation rates of explosives were examined. In the presence of both UV light and TiO2 RDX and HMX were more effectively degraded than with either UV or TiO2 alone. The degradation rates were found to obey pseudo-first-order kinetics represented by the Langmuir-Hinshelwood model. Increases in the RDX and HMX degradation rates were obtained with decreasing initial concentrations of the explosives. The RDX and HMX degradation rates were higher at pH 7 than at either pH 3 or pH 11. A dose of approximately 0.7 g l(-1) of TiO2 degraded HMX more rapidly than did higher or lower TiO2 doses. RDX (20 mg l(-1)) photocatalysis resulted in an approximately 20% decrease in TOC, and HMX (5 mg l(-1)) photocatalysis resulted in a 60%, decrease in TOC within 150 minutes. A trace amount of formate was produced as an intermediate that was further mineralized by RDX or HMX photocatalysis. The nitrogen byproducts from the photocatalysis of RDX and HMX were mainly NO3- with NO2-, and NH4+. The total nitrogen recovery was about 60% from RDX (20 mg l(-1)), and 70% from HMX (5 mg l(-1)), respectively. Finally, a mechanism for RDX/HMX photocatalysis was proposed, along with supporting qualitative and quantitative evidence.

Optical switching in chiropticenes.

Chiropticenes are a novel class of predesigned chiral molecular switches that are triggered and controlled by a combination of both light and electric field. Chiropticenes contain an optically active (chiral) center and, as a consequence, provide two accessible equal energy bistable states resembling the molecular elements of binary logic. Structural engineering of the basic switch design is investigated to modulate the thermal and optical switching behavior of the resulting compounds. A simple screening methodology is presented to detect switching behavior in the solid state employing standard NMR and FT-IR spectroscopy. Validation of this method is demonstrated by the switching properties of newly synthesized anthraquinone dye based Chiropticenes. Functioning as a chiroptical dipole switch, Chiropticenes promise broad applications in emerging optoelectronic and molecular electronic technologies.