Covalent Organic Network Membranes with Tunable Nanoarchitectonics from Macrocycle Building Blocks for Graded Molecular Sieving.

Traditional piperazine-based polyamide membranes usually suffer from the intrinsic trade-off relationship between selectivity and permeance. The development of macrocycle membranes with customized nanoscale pores is expected to address this challenge. Herein, we introduce 1,4-diazacyclohexane (2N), 1,4,7-triazacyclononane (3N), and 1,4,8,11-tetraazacyclotetradecane (4N) as molecular building blocks to construct the nanoarchitectonics of polyamide membranes prepared from interfacial polymerization (IP). The permeance of covalent organic network membranes follows the trend of 4N-TMC > 3N-TMC > 2N-TMC, while the molecular weight cutoff (MWCO) also follows the same trend of 4N-TMC > 3N-TMC > 2N-TMC, according to their nanopore size of the membranes. The microporosity, orientation, and surface chemistry of covalent organic network membranes can be rationally designed by macrocycle building units. The ordered nanoarchitectonics allows the membranes to attain an excellent performance in graded molecular sieving. Importantly, the novel covalent organic network membranes with tunable nanoarchitectonics prepared from macrocycle building units exhibited high water permeance (32.5 LMH/bar) and retained long-term stability after 100 h of test and bovine serum albumin fouling. These results reveal the enormous potential of 3N-TMC and 4N-TMC membranes in saline textile wastewater treatments and precise molecular sieving.

Inhibitory Effect of Azamacrocyclic Ligands on Polyphenol Oxidase in Model and Food Systems.

Enzymatic browning is one of the main problems faced by the food industry due to the enzyme polyphenol oxidase (PPO) provoking an undesirable color change in the presence of oxygen. Here, we report the evaluation of 10 different azamacrocyclic compounds with diverse morphologies as potential inhibitors against the activity of PPO, both in model and real systems. An initial screening of 10 ligands shows that all azamacrocyclic compounds inhibit to some extent the enzymatic browning, but the molecular structure plays a crucial role on the power of inhibition. Kinetic studies of the most active ligand (L2) reveal a S-parabolic I-parabolic noncompetitive inhibition mechanism and a remarkable inhibition at micromolar concentration (IC50 = 10 µM). Furthermore, L2 action has been proven on apple juice to significantly reduce the enzymatic browning.

Macrocyclic polyamine-functionalized silica as a solid-phase extraction material coupled with ionic liquid dispersive liquid-liquid extraction for the enrichment of polycyclic aromatic hydrocarbons.

In this study, silica modified with a 30-membered macrocyclic polyamine was synthesized and first used as an adsorbent material in SPE. The SPE was further combined with ionic liquid (IL) dispersive liquid-liquid microextraction (DLLME). Five polycyclic aromatic hydrocarbons were employed as model analytes to evaluate the extraction procedure and were determined by HPLC combined with UV/Vis detection. Acetone was used as the elution solvent in SPE as well as the dispersive solvent in DLLME. The enrichment of analytes was achieved using the 1,3-dibutylimidazolium bis[(trifluoromethyl)sulfonyl]imide IL/acetone/water system. Experimental conditions for the overall macrocycle-SPE-IL-DLLME method, such as the amount of adsorbent, sample solution volume, sample solution pH, type of elution solvent as well as addition of salt, were studied and optimized. The developed method could be successfully applied to the analysis of four real water samples. The macrocyclic polyamine offered higher extraction efficiency for analytes compared with commercially available C18 cartridge, and the developed method provided higher enrichment factors (2768-5409) for model analytes compared with the single DLLME. Good linearity with the correlation coefficients ranging from 0.9983 to 0.9999 and LODs as low as 0.002 µg/L were obtained in the proposed method.

Synthetic polyamines: new compounds specific to actin dynamics for mammalian cell and fission yeast.

Actin is a major actor in the determination of cell shape. On the one hand, site-directed assembly/disassembly cycles of actin filaments drive protrusive force leading to lamellipodia and filopodia dynamics. Force produced by actin similarly contributes in membrane scission in endocytosis or Golgi remodeling. On the other hand, cellular processes like adhesion, immune synapse, cortex dynamics or cytokinesis are achieved by combining acto-myosin contractility and actin assembly in a complex and not fully understood manner. New chemical compounds are therefore needed to disentangle acto-myosin and actin dynamics. We have found that synthetic, cell permeant, short polyamines are promising new actin regulators in this context. They generate growth and stabilization of lamellipodia within minutes by slowing down the actin assembly/disassembly cycle and facilitating nucleation. We now report that these polyamines also slow down cytokinetic ring closure in fission yeast. This shows that these synthetic compounds are active also in yeasts, and these experiments specifically highlight that actin depolymerization is involved in the ring closure. Thus, synthetic polyamines appear to be potentially powerful agents in a quantitative approach to the role of actin in complex processes in cell biology, developmental biology and potentially cancer research.