A novel in situ strategy for the preparation of a β‐cyclodextrin/polydopamine‐coated capillary column for capillary electrochromatography enantioseparations

Inspired by the chiral recognition ability of β‐cyclodextrin and the natural adhesive properties of polydopamine under alkaline conditions, in this study, a rapid and in situ modification strategy was developed to fabricate β‐cyclodextrin/polydopamine composite material coated‐capillary columns for open tubular capillary electrochromatography. The results of scanning electron microscopy, FTIR spectroscopy, streaming potential, and electro‐osmotic flow studies indicated that β‐cyclodextrin/polydopamine was successfully fixed on the inner wall of the capillary column. This coating can be achieved within 1 h affording a greatly reduced capillary preparation time. The performance of the β‐cyclodextrin/polydopamine‐coated capillary was validated by the analysis of seven pairs of chiral analytes, namely epinephrine, norepinephrine, isoprenaline, terbutaline, verapamil, tryptophane, carvedilol. Good enantioseparation efficiencies were achieved for all. For three consecutive runs, the relative standard deviations for the migration times of the analytes for intraday, interday, and column‐to‐column repeatability were in the range of 0.41–1.74, 1.03–4.18, and 1.66–8.24%, respectively. Moreover, the separation efficiency of the β‐cyclodextrin/polydopamine‐coated capillary column did not decrease obviously over 90 runs. The strategy should also be feasible to introduce and immobilize other chiral selectors on the inner walls surface of capillary columns.     

Facile preparation of a polydopamine‐based monolith for multiple monolithic fiber solid‐phase microextraction of triazine herbicides in environmental water samples

A new multiple monolithic fiber solid‐phase microextraction using a polydopamine‐based monolith as the extraction medium is proposed. The monolith was synthesized by facile in situ copolymerization of N‐methacryldopamine and dual cross‐linkers (divinylbenzene/ethylenedimethacrylate) in the presence of N ,N‐dimethylformamide. The effect of the contents of N‐methacryldopamine and porogen in the polymerization mixture on the extraction performance was investigated thoroughly. A series of characterization studies was performed to validate the structure and properties of the monolith. The prepared multiple monolithic fibers were used for the extraction of triazine herbicides in environmental water samples. After the optimization of the extraction parameters, a convenient, sensitive, cost‐effective, and environmentally friendly method for the determination of trace triazine herbicides in water samples was developed by coupling multiple monolithic fibers solid‐phase microextraction with high‐performance liquid chromatography and diode array detection. The results indicated that the limits of detection and quantification for the target compounds were 0.031–0.14 and 0.10–0.45 μg/L, respectively. Good precision and reproducibility were obtained with the relative standard deviations below 10%. The developed method was applied to the analysis of the triazine herbicides in different water samples (lake, river, and farmland waters). The recoveries of the method were in the range between 79.6 and 117%.     

Polydopamine‐assisted immobilization of zeolitic imidazolate framework‐8 for open‐tubular capillary electrochromatography

In this work, we developed a capillary column modified with zeolitic imidazolate framework‐8 as a novel stationary phase for open‐tubular capillary electrochromatography. To immobilize zeolitic imidazolate framework‐8 onto the inner surface of silica capillary, a bio‐inspired polydopamine functionalization was used to functionalize the capillary surface with polydopamine. First, a polydopamine layer was assembled inside the capillary. Second, due to noncovalent adsorption and covalent reaction ability, polydopamine could attract and anchor zeolitic imidazolate framework‐8 onto the inner surface of capillary. It has been demonstrated that zeolitic imidazolate framework‐8 was successfully grafted on the inner wall of the capillary by scanning electron microscopy, and Fourier transform infrared spectroscopy. The electro‐osmotic flow characteristics of capillaries were also investigated by varying the pH value and acetonitrile content of mobile phase. The zeolitic imidazolate framework‐8 coating not only increased the phase ratio of open‐tubular column, but also improved the interactions between tested analytes and the stationary phase. Three groups of isomers including acidic, basic, and neutral compounds were well separated on the zeolitic imidazolate framework‐8 bonded column, with theoretic plate numbers up to 1.9 × 10⁵ N for catechol. The repeatability of the prepared columns was also studied, and the relative standard deviations for intra‐ and interday runs were less than 5%.     

Facile Synthesis of Free‐Standing Polymer Brush Films Based on a Colorless Polydopamine Thin Layer

A free‐standing polymer brush film with tailored thicknesses based on a colorless polydopamine (PDA) thin layer is prepared and characterized. The surface‐initiated atom transfer radical polymerization (ATRP) of 2‐hydroxyethyl methacrylate (HEMA) is performed on a PDA layer with thickness of ca. 6 nm, which generated an optically transparent and colorless free‐standing PHEMA brush film (1.5 cm × 1.5 cm). Because the cross‐linked PDA layer is used as the base for the polymer brushes, the reported method does not require cross‐linking the polymer brushes. The free‐standing film thicknesses of ≈16–75 nm are controlled by simply changing the ATRP reaction time. The results show that the free‐standing PHEMA brush film transferred onto a plate exhibits a relatively smooth surface and is stable in any solvent.

     

Multifaceted Influences of Melanin‐Like Particles on Amyloid‐beta Aggregation

The properties of eumelanin‐like particles (EMPs) and pheomelanin‐like particles (PMPs) in regulating the process of amyloid formation of amyloid‐beta 42 (Aβ42) were examined. EMPs and PMPs are effective both in interfering with amyloid aggregation of Aβ42 and in remodeling matured Αβ42 fibers. The results suggest that some (but not all) molecular species consisting of melanin‐like particles (MPs) are responsible for their inhibiting property toward amyloid formation, and the influence is likely manifested by long‐range interactions. Incubating preformed Aβ42 fibers with catechols or MPs leads to the formation of mesh‐like, interconnected Aβ42 fibers encapsulated with melanin‐like material. MPs are kinetically more effective than catechol monomers in this process, and a detailed investigation reveals that 4,5‐dihydroxyindole, a major intermediate in the formation of melanin‐like species, and its derivatives are mainly responsible for remodeling amyloid fibers.     

Sulfonated poly(ether ether ketone) composite membranes based on amino-modified halloysite nanotubes that effectively immobilize phosphotungstic acid

In this work, we prepared amino-modified halloysite nanotubes (PEI-DHNTs) via the co-deposition of self-polymerized dopamine and polyethylenimine (PEI) on the surface of nanotubes, which was confirmed by X-ray photoelectron spectroscopy (XPS) and Thermogravimetric analysis (TGA). A series of composite proton exchange membranes (PEMs) were prepared by incorporating PEI-DHNTs and phosphotungstic acid (HPW) into sulfonated poly(ether ether ketone) (SPEEK). It was found that both PEI-DHNTs and HPW were well dispersed in the polymer matrix, exhibiting excellent filler-matrix compatibility. The composite membranes demonstrated enhanced proton conductivity, reaching as high as 0.078 S cm⁻¹ with 33.3 wt.% HPW loading, which was ~90% higher than that of SPEEK control membrane. Such improvement was mainly attributed to the strong acid–base pairs formed by PEI-DHNT with both SPEEK and HPW, which shortened proton hopping distance and created more continuous proton conduction pathways. Furthermore, the membrane conductivity remained almost constant after 1 year's immersion in liquid water, indicating the successful immobilization of HPW in the composite membranes.     

Surface functionalizing effect of fillers on the tribological properties of MWCNT reinforcement HSGFs/phenolic laminate composites under water lubrication

Multi‐wall carbon nanotubes (MWCNTs) and high strength glass fabrics (HSGFs) were modified by polydopamine and polyethyleneimine, respectively. The aim is to improve the friction and wear performance of the synthesized laminate composites in water environment. In this work, polydopamine was used to improve the dispersibility of MWCNTs in phenolic resin matrix, and polyethyleneimine was utilized to enhance the wettability and reactivity of HSGFs. The modified results showed that the dispersibility of MWCNTs treated by polydopamine in water had a distinct improvement in comparison with that of the pristine MWCNTs. Furthermore, it can be clearly observed that good dispersibility can improve the friction and wear performance of the laminate composites. After functionalizing HSGFs by polyethyleneimine, the laminate composites exhibited excellent interfacial bonding, also greatly enhancing the friction and wear properties of the composites.     

Fabrication of Defined Polydopamine Nanostructures by DNA Origami‐Templated Polymerization

A versatile, bottom‐up approach allows the controlled fabrication of polydopamine (PD) nanostructures on DNA origami. PD is a biosynthetic polymer that has been investigated as an adhesive and promising surface coating material. However, the control of dopamine polymerization is challenged by the multistage‐mediated reaction mechanism and diverse chemical structures in PD. DNA origami decorated with multiple horseradish peroxidase‐mimicking DNAzyme motifs was used to control the shape and size of PD formation with nanometer resolution. These fabricated PD nanostructures can serve as “supramolecular glue” for controlling DNA origami conformations. Facile liberation of the PD nanostructures from the DNA origami templates has been achieved in acidic medium. This presented DNA origami‐controlled polymerization of a highly crosslinked polymer provides a unique access towards anisotropic PD architectures with distinct shapes that were retained even in the absence of the DNA origami template.     

A Biodegradable Polydopamine‐Derived Electrode Material for High‐Capacity and Long‐Life Lithium‐Ion and Sodium‐Ion Batteries

Polydopamine (PDA), which is biodegradable and is derived from naturally occurring products, can be employed as an electrode material, wherein controllable partial oxidization plays a key role in balancing the proportion of redox‐active carbonyl groups and the structural stability and conductivity. Unexpectedly, the optimized PDA derivative endows lithium‐ion batteries (LIBs) or sodium‐ion batteries (SIBs) with superior electrochemical performances, including high capacities (1818 mAh g^?1 for LIBs and 500 mAh g^?1 for SIBs) and good stable cyclabilities (93 % capacity retention after 580 cycles for LIBs; 100 % capacity retention after 1024 cycles for SIBs), which are much better than those of their counterparts with conventional binders.     

Cytocompatible Polymer Grafting from Individual Living Cells by Atom‐Transfer Radical Polymerization

A cytocompatible method of surface‐initiated, activator regenerated by electron transfer, atom transfer radical polymerization (SI‐ARGET ATRP) is developed for engineering cell surfaces with synthetic polymers. Dopamine‐based ATRP initiators are used for both introducing the ATRP initiator onto chemically complex cell surfaces uniformly (by the material‐independent coating property of polydopamine) and protecting the cells from radical attack during polymerization (by the radical‐scavenging property of polydopamine). Synthetic polymers are grafted onto the surface of individual yeast cells without significant loss of cell viability, and the uniform and dense grafting is confirmed by various characterization methods including agglutination assay and cell‐division studies. This work will provide a strategic approach to the generation of living cell–polymer hybrid structures and open the door to their application in multitude of areas, such as sensor technology, catalysis, theranostics, and cell therapy.