The spatiotemporal stimulation of liposome-liposome or liposome-membrane fusion processes attracts growing interest as a means to mimic cell-cell interactions in nature and for using these processes for biomedical applications. We report the use of o-nitrobenzyl phosphate functionalized-cholesterol tethered nucleic acid-modified liposomes as functional photoresponsive units for inducing, by NIR-irradiation, spatiotemporal liposome-liposome or liposome-membrane fusion processes. Pyrvinium The liposomes are loaded with upconversion nanoparticles (UCNPs) and their NIR irradiation (λ = 980 nm) yields luminescence at λ = 365 nm, providing a localized light-source to deprotect the o-nitrobenzyl phosphate groups and resulting in the fragmentation of the nucleic acid structures. In one system, the NIR-triggered fusion of two liposomes, L1 and L2, is exemplified. Liposome L1 is loaded with UCNPs and Tb3+ ions, and the liposome boundary is functionalized with a cholesterol-tethered, o-nitrobenzyl phosphate caged hairpin nucleic unit is exemplified. The effect of DOX-loaded L1/HeLa cell fusion on the cytotoxicity towards HeLa cells is addressed. The NIR UCNP-stimulated cleavage of the o-nitrobenzyl phosphate caged hairpin units associated with L1 leads to the fragmentation of the hairpin units and the resulting nucleic acid tethers hybridize with the nucleic acid-modified HeLa cells, resulting in the liposome-HeLa cell fusion and the release of DOX into the HeLa cells. Selective spatiotemporal cytotoxicity towards HeLa cells is demonstrated (ca. 40% cell killing within two days). The study presents a comprehensive stepwise set of experiments directed towards the development of NIR-driven liposome-liposome or liposome-membrane fusion processes.Peptide-based molecules hold great potential as targeted inhibitors of intracellular protein-protein interactions (PPIs). Indeed, the vast diversity of chemical space conferred through their primary, secondary and tertiary structures allows these molecules to be applied to targets that are typically deemed intractable via small molecules. However, the development of peptide therapeutics has been hindered by their limited conformational stability, proteolytic sensitivity and cell permeability. Several contemporary peptide design strategies are aimed at addressing these issues. Strategic macrocyclization through optimally placed chemical braces such as olefinic hydrocarbon crosslinks, commonly referred to as staples, may improve peptide properties by (i) restricting conformational freedom to improve target affinities, (ii) improving proteolytic resistance, and (iii) enhancing cell permeability. As a second strategy, molecules constructed entirely from d-amino acids are hyper-resistant to proteolytic cleavage, but generally lack conformational stability and membrane permeability. Since neither approach is a complete solution, we have combined these strategies to identify the first examples of all-d α-helical stapled and stitched peptides. As a template, we used a recently reported all d-linear peptide that is a potent inhibitor of the p53-Mdm2 interaction, but is devoid of cellular activity. To design both stapled and stitched all-d-peptide analogues, we used computational modelling to predict optimal staple placement. The resultant novel macrocyclic all d-peptide was determined to exhibit increased α-helicity, improved target binding, complete proteolytic stability and, most notably, cellular activity.An asymmetric thia-Michael addition of arylthiols to α,β-unsaturated carboxylic acids using a thiourea catalyst that bears arylboronic acid and tertiary amine moieties is reported. Both enantiomers of the Michael adducts can be obtained in high enantioselectivity and good yield merely by changing the solvent. The origin of the chirality switch in the products was examined in each solvent via spectroscopic analyses.By integrating azulene with a quinoid moiety, a novel non-alternant polycyclic aromatic hydrocarbon molecule BCHF1 exhibiting manifold zwitterionic, quinoidal and diradical behaviors is designed and synthesized. Its zwitterionic feature is evidenced by the changes shown by the 1H-NMR and absorption spectra when the molecule undergoes reversible protonation and deprotonation reactions at varied pH. The diradical facet, manifesting a small singlet-triplet energy gap (ΔES-T), is characterized with a paramagnetic resonance signal detected by the EPR spectroscopy at room temperature. As the diradical properties are not observed in the protonated form, BCHF1+H+ , a pH-controlled reversible magnetic switching behavior is illustrated by monitoring the on and off cycles of EPR signals upon successively adding bases and acids to a solution or exposing a thin film of BCHF1+H+ to base vapor followed by acid vapor.Aside from simple Lewis acid-base chemistry, the reaction chemistry of aluminacyclopentadienes, which are commonly referred to as aluminoles or simply alumoles, remains relatively underdeveloped. To date, few attempts to extend their inherent insertion and cycloaddition reactivity to the construction of stable aluminum-containing heterocycles have been reported. Herein, we demonstrate the selective ring expansion of a cyclopentadienyl-substituted alumole with a series of organic azides to form unsaturated six-membered AlN heterocycles. Depending on the substituent on the azide, the reaction proceeds either with or without loss of dinitrogen, leading to incorporation of only the "NR" unit of the azide or the entire azo substituent into the periphery of the heterocycle. A deeper understanding of these ring expansion reactions is reached through computational studies, illustrating deviations in the mechanism as a function of the organic azide employed.In this article, we report continuous sorting of two microplastics in a trifurcated microfluidic channel using a new method called serial faradaic ion concentration polarization (fICP). fICP is an electrochemical method for forming ion depletion zones and their corresponding locally elevated electric fields in microchannels. By tuning the interplay between the forces of electromigration and convection during a fICP experiment, it is possible to control the flow of charged objects in microfluidic channels. The key findings of this report are threefold. First, fICP at two bipolar electrodes, configured in series and operated with a single power supply, yields two electric field gradients within a single microfluidic channel (i.e., serial fICP). Second, complex flow variations that adversely impact separations during fICP can be mitigated by minimizing convection by electroosmotic flow in favor of pressure-driven flow. Finally, serial fICP within a trifurcated microchannel is able to continuously and quantitatively focus, sort, and separate microplastics.