RESUMO
We investigated the feasibility of creating cyclic azobenzene/azobenzene-based photo-switchable drugs that can fine-tune antibacterial activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) with light dependence. Furthermore, a "light-controlled drug combination" of these obtained drugs could be reversibly controlled to efficiently improve the antibiotic effect so as to reduce the minimum inhibitory concentrations (MICs) with different wavelength light illumination. Importantly, their antimicrobial activity could be easily manipulated by using light in bacterial patterning studies with high spatiotemporal precision, which might allow for localized activation of drugs and provide an alternative solution for practical clinical application in photopharmacology.
Assuntos
Escherichia coli , Staphylococcus aureus , Antibacterianos/farmacologia , Testes de Sensibilidade Microbiana , Combinação de MedicamentosRESUMO
Tetra-ortho-substituted, heteroaryl and cyclic azobenzenes have emerged as three key strategies on morphology design of photoswitch to diversify controllability. Cyclic azobenzene is of particular utilization in photo-energy conversion due to rigid and ring-strain structure. Despite the well-recognized diazocine, the photo-switching properties of seven-membered cyclic azobenzenes (diazepines) have yet been exploited. Herein, we report a family of dibenzo[b,f][1,4,5]chalcogenadiazepines (DBChDs) and their T-type photo-switching nature with tunable relaxation rate. Based on experiments together with DFT calculations, we found that an unsymmetric 2-bithiophenyl-dibenzo[b,f][1,4,5]thiadiazepine exhibited an efficient response to 445â nm laser stimulation (quantum efficiency, ΦZâE =0.71) with millisecond relaxation half-life (t1/2 =40â ms). Photo-energy transduction efficiency was also exceptionally high with 29.1 % converted into ring-strain energy mainly loaded on azo π-bond.
Assuntos
Compostos Azo , Luz , Compostos Azo/químicaRESUMO
Cyclic azodicarbonyl derivatives, particularly 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), commonly serve as arenophile, dienophile, enophile and electrophile. Perplexed by its instability in aqueous environment, there are few studies focused on the transient intermediate produced by hydrolysis of PTAD to achieve synthetic significance. Herein, we describe a "photo-click" method that involves nitrile imine (NI) from diarylsydnone to capture the diazenecarbonyl-phenyl-carbamic acid (DACPA) generated by water-promoted ring-opening of PTAD. DFT calculation reveal that H-bonding interactions between PTAD and water are vital to form DACPA which exhibited an umpolung effect during ligation by nature bond orbit (NBO) analysis. The ultra-fast ligation resulted in carbamoyl formazans, as a unique ZâE photo-switchable linker on target molecules, including peptide and drugs, with excellent anti-fatigue performance. This strategy is showcased to construct highly functionalized carbamoyl formazans inâ situ for photo-pharmacology and material studies, which also expands the chemistry of PTAD in aqueous media.
Assuntos
Triazóis , Água , Formazans , NitrilasRESUMO
We report a visible-light induced photo-click and release platform between monoarylsydnone (MASyd) and phenoxylfumarates. The pyrazoline produced by the cycloaddition undergoes a photo-aromatization to form a fluorescent pyrazole. Meanwhile, the photo-aromatization also serves as the driving force to release fluorophores that are quenched in the form of phenoxylfumarates.
RESUMO
A set of photo-switchable monopeptides derived from cis-ß-dibenzodiazocine-l-alanine (cis-DBDAA) have been designed and synthesized, which are capable of photo-click reacting with diaryltetrazoles or diarylsydnones in a hydrophobic phospholipid bilayer environment. The DBDAA monopeptides include both a hydrophobic tail on C-terminal, providing high affinity toward lipid membrane, and a modularized functional moiety on N-terminal, enabling rapid optimization of the self-assembly strength to form multifunctional supramolecules. With the cis-DBDAA monopeptides photo-switched into trans-configuration, we were able to disrupt the supramolecular assembly through an efficient photo-click reaction across the lipid bilayer of liposomes. We reveal that the performance of the photo-click reactions between the monopeptides and photo-generated nitrile imine intermediates is significantly enhanced by enrichment of both reactants in the hydrophobic membrane lamel of liposomes. Enrichment of the DBDAA monopeptide in lipid phase serves as a convenient method to introduce bioorthogonal chemical handles on live cell membranes, which enables fluorescence labelling of single cell's membrane with high spatiotemporal resolution to facilitate the studies on cell membrane dynamics.
Assuntos
Iminas , Lipossomos , Membrana Celular , Química Click , Bicamadas Lipídicas , NitrilasRESUMO
In response to an increasing demand for understanding electrochemical processes on the nanometer scale, it now becomes possible to monitor electron transfer reactions at the single-nanoparticle level, namely particle collision electrochemistry. This technique has great potential in the development of research tools towards single-particle electrocatalysis and selective and multiplexed particle sizing. However, one existing problem that may discourage these applications is the relatively weak colloidal stability of nanoparticles in an electrolytic solution. Here we report on a facile but efficient way to achieve a good stability of gold nanoparticles in an acidic media so that 'zero-aggregation' collisions can be achieved at a carbon ultramicroelectrode. This allows us to obtain anodic dissolution currents from individual nanoparticles in a 'one particle at a time' manner, based on which accurate particle sizing with a resolution of 1-2 nm can be achieved. Our work strongly suggests that to maintain a well dispersed nanoparticle solution during a particle impact electrochemical experiment is critically important for accurate particle sizing, as well as other applications that require information to be extracted from individual nanoparticles (not their aggregates).
RESUMO
Silver nanoparticles (AgNPs), which are stable in strongly ionic solutions and appear as a single sharp band during gel electrophoresis, are synthesized by a facile one-pot process, allowing for the first time realization of AgNP-DNA bio-nano-conjugates bearing a discrete number of DNA ligands.
Assuntos
DNA/química , Nanopartículas Metálicas/química , Nanoconjugados/química , Prata/química , Espermatozoides/química , Animais , Peixes , Masculino , Tamanho da PartículaRESUMO
Discrete DNA decorations of Pt nanoparticles (PtNPs) are realized for the first time, which provide a valence control over the quasi-molecular self-assembly of Au-Pt bimetallic heteronanostructures with DNA as the guide.
Assuntos
DNA/química , Ouro/química , Nanopartículas Metálicas/química , Platina/química , Nanopartículas Metálicas/ultraestrutura , Microscopia Eletrônica de Transmissão , Fosfinas/química , Compostos de Sulfidrila/químicaRESUMO
Surface-initiated DNA polymerization has been employed in this work as an appealing signal amplification strategy for electrochemical DNA sensors. This strategy is especially superior in that enzymes, colloidal particles and other bulky structures are not involved in order to achieve amplified signals, and thus is highly promising in circumventing problems due to uncontrolled nucleation, adsorption, aggregation or disassembly of nanoparticles, liposomes and proteins, as well as enzyme deactivations. Our preliminary results have shown that a decrease (as compared to an amplification-free system) in detection limit by a factor greater than 300 can be easily achieved by cyclic voltammetry under still not optimized conditions, with an ability of differentiating a single base mutation.