Metal-Organic Frameworks-Based Immobilized Enzyme Microreactors Integrated with Capillary Electrochromatography for High-Efficiency Enzyme Assay.

Enzyme assays are important for studying enzyme-mediated biochemical reactions and for clinical diagnosis and drug development. The technique of an immobilized enzyme microreactor (IMER) integrated with capillary electrophoresis (CE) has been frequently utilized in online enzyme assays. However, the traditional approaches for IMER-CE enzyme analysis have some defects such as low loading capacity and poor stability. Herein, metal-organic frameworks (MOFs), which have enormous potential in the fields of enzyme immobilization and capillary electrochromatographic (CEC) separation, were first explored as novel support materials with good enzyme immobilization performance and stationary phases with excellent separation abilities to construct an integrated MOFs-IMER-CEC microanalysis system for a high-efficiency online enzyme assay. As a proof-of-concept demonstration, acetylcholinesterase (AChE) was immobilized on a densely packed UiO-66-NH2 nanocrystal coating on a capillary inner surface with abundant intercrystalline mesoporosity and was employed as a highly effective and robust IMER for CEC-integrated online enzyme analysis. The excellent separation performance of the UiO-66-NH2-modified capillary was verified by high-efficiency separation of three types of neutral, acidic, and basic compounds. The Michaelis-Menten constant and enzyme inhibition kinetics of UiO-66-NH2-IMER were systematically assessed, exhibiting distinct advantages such as remarkably increased enzyme loadability, superior affinity for substrates, and greatly improved stability and repeatability compared to CE-integrated IMERs prepared by the traditional covalent bonding method. Furthermore, the developed method was successfully utilized for detecting organophosphorus pesticides in leguminous vegetable samples, demonstrating its strong practicality. The study not only proposed a novel support material and construction strategy for a high-performance microchannel-based IMER but also can be widely used in bioanalysis and biosensing research.

High-Efficiency and Versatile Approach To Fabricate Diverse Metal-Organic Framework Coatings on a Support Surface as Stationary Phases for Electrochromatographic Separation.

A large number of metal-organic frameworks (MOFs) have exhibited increasingly wide utilization in the field of chromatographic separation owing to their intrinsic fascinating properties. However, the previous studies on supported MOF coating-based chromatographic separation focused only on the synthesis and chromatographic performance of a certain kind of supported MOF coatings as stationary phases using the multiple-step, complicated, and time-consuming modification methods, which severely impeded the widespread application of MOFs in separation science. Herein, a high-efficiency and versatile methodology toward diverse supported MOF coating-based stationary phases to achieve high-efficiency chromatographic separation was first reported based on the immobilized cysteine (Cys)-triggered in situ growth (ICISG) strategy. As a proof-of-concept demonstration, four types of MOF crystals consisting of different ligands and metal ions (Zn2+, Cu2+, Fe3+, and Zr4+) were conveniently and firmly grown on a Cys-modified capillary using the ICISG strategy and employed as the functional stationary phase for electrochromatographic separation. A broad variety of neutral, acidic, and basic compounds were all separated in a highly efficient manner on the developed four MOF-coated columns. The maximum theoretical plate number for Cys-MIL-100(Fe)@capillary was close to 1.0 × 105 plates/m, and the intraday, interday, and column-to-column repeatabilities of retention times for the four MOF-modified columns were all less than 5.25%. More interestingly, the diversified separation performance of the developed MOF-coated columns indicated that the preparation strategy and the skeletal structure of the MOF coating-based stationary phases have a significant influence on the electrochromatographic separation performance and column capacity. Benefiting from the strong universality and high applicability of the developed ICISG strategy, the present study provides an effective route to facilitate the design and fabrication of novel functional MOF-based chromatographic stationary phases.

Polydopamine-Assisted Rapid One-Step Immobilization of L-Arginine in Capillary as Immobilized Chiral Ligands for Enantioseparation of Dansyl Amino Acids by Chiral Ligand Exchange Capillary Electrochromatography.

Herein, a novel L-arginine (L-Arg)-modified polydopamine (PDA)-coated capillary (PDA/L-Arg@capillary) was firstly fabricated via the basic amino-acid-induced PDA co-deposition strategy and employed to constitute a new chiral ligand exchange capillary electrochromatography (CLE-CEC) method for the high-performance enantioseparation of D,L-amino acids (D,L-AAs) with L-Arg as the immobilized chiral ligand coordinating with the central metal ion Zn(II) as running buffer. Assisted by hydrothermal treatment, the robust immobilization of L-Arg on the capillary inner wall could be facilely achieved within 1 h, prominently improving the synthesis efficiency and simplifying the preparation procedure. The successful preparation of PDA/L-Arg coatings in the capillary was systematically characterized and confirmed using several methods. In comparison with bare and PDA-functionalized capillaries, the enantioseparation capability of the presented CLE-CEC system was significantly enhanced. Eight D,L-AAs were completely separated and three pairs were partially separated under the optimal conditions. The prepared PDA/L-Arg@capillary showed good repeatability and stability. The potential mechanism of the greatly enhanced enantioseparation performance obtained by PDA/L-Arg@capillary was also explored. Moreover, the proposed method was further utilized for studying the enzyme kinetics of L-glutamic dehydrogenase, exhibiting its promising prospects in enzyme assays and other related applications.

Nanoscale Hierarchically Micro- and Mesoporous Metal-Organic Frameworks for High-Resolution and High-Efficiency Capillary Electrochromatographic Separation.

Metal-organic frameworks (MOFs) have been widely applied in a variety of fields. However, most of the developed MOFs are micrometer scale in crystal size and contain only micropores, which will limit the mass transport and diffusion of various analytes into their internal interaction sites, severely restricting the potential of MOFs in separation science. Herein, nanoscale hierarchically porous MOFs (NHP-MOFs) were first explored as a novel MOF-based stationary phase with excellent mass transfer performance and abundant accessible interaction sites for high-performance chromatographic separation. As a proof-of-concept demonstration, the nanoscale hierarchically micro- and mesoporous UiO-66 (NHP-UiO-66) was firmly immobilized on the capillary inner surface and utilized as the porous stationary phase for high-resolution and high-efficiency electrochromatographic separation. A wide range of low-, medium-, and high-molecular-weight analytes, including substituted benzenes, chlorobenzenes, polycyclic aromatic hydrocarbons, nucleosides, polypeptides, and proteins were all separated well on a NHP-UiO-66-coated column with excellent resolution and repeatability, exhibiting significantly improved column efficiency and separation ability compared to those of a microporous UiO-66-modified column. The maximum column efficiencies for all the six kinds of analytes reached up to 1.2 × 105 plates/m, and the relative standard deviations of the migration times of substituted benzenes for intraday, interday, and column-to-column were all lower than 5.8%. These results reveal that NHP-MOFs can effectively combine the advantages of the high specific surface area of microporous MOFs and the excellent mass transfer performance and abundant accessible interaction sites of NHP materials, possessing great prospect for high-performance chromatographic separation.

Solvothermal-assisted in situ rapid growth of octadecylamine functionalized polydopamine-based permanent coating as stationary phase for open-tubular capillary electrochromatography.

In recent years, mussel-inspired polydopamine (PDA) based materials have been widely used as stationary phases for open-tubular capillary electrochromatography (OT-CEC) because of their various excellent properties. Nevertheless, the traditional synthesis routes of functionalized PDA-based capillary columns usually are time-consuming and limited in aqueous solutions. Herein, we report a facile and rapid route to prepare octadecylamine (ODA) functionalized PDA coated OT-CEC columns in organic solvents via a novel one-step in situ solvothermal-assisted coating strategy. Through this developed solvothermal-assisted approach, the growth rate of ODA/PDA coating was significantly speeded up and their hybrid coating process on the capillary inner surface could be rapidly completed in 60 min. The successful preparation of the solvothermal-assisted ODA/PDA hybrid coating were systematically characterized and confirmed by several methods. The influence of the preparation parameters on the formation of hybrid coating and the separation ability of the ODA/PDA modified columns were systematically explored. Consequently, the high-efficiency baseline separation of four kinds of neutral, acidic and basic analytes were achieved based on the ODA/PDA modified columns. The repeatability of the solvothermal-assisted ODA/PDA coated column was also studied, and the relative standard deviations for intra-day, inter-day and column-to-column were all less than 5%. Additionally, the solvothermal-assisted ODA/PDA modified column exhibited good stability and long lifetime.

In situ one-pot synthesis of polydopamine/octadecylamine co-deposited coating in capillary for open-tubular capillary electrochromatography.

Mussel-inspired polydopamine (PDA) based materials are attractive as stationary phase for open-tubular capillary electrochromatography (OT-CEC) due to their many fascinating properties. However, all of the existing strategies for fabricating PDA based OT-CEC columns are limited in aqueous solutions. Consequently, it is a challenge work to directly immobilize the hydrophobic functional materials onto the inner wall of PDA modified capillary. Herein, by using the organic amine-inducing co-deposition strategy, a novel preparative method was developed for in situ one-pot synthesis of PDA/octadecylamine (ODA) co-deposited coating inside capillary as OT-CEC stationary phase. The formation and morphology of the PDA/ODA co-deposited coating were characterized by field emission scanning electron microscopy, atomic force microscope, attenuated total reflectance Fourier transform infrared spectroscopy and contact angle measurements. The separation performance of the fabricated PDA/ODA modified columns was validated by the separation of alkylbenzenes and steroids, which could achieve baseline separation with high separation efficiency. Their separation was found to follow the reversed phase chromatographic retention mechanism. The co-deposited column showed good stability and long lifetime. The repeatability of the PDA/ODA co-deposited column was also evaluated, with the relative standard deviations for intra-day and inter-day runs less than 5% and column-to-column runs less than 6%.

Carbon source self-heating: ultrafast, energy-efficient and room temperature synthesis of highly fluorescent N, S-codoped carbon dots for quantitative detection of Fe(iii) ions in biological samples.

In recent years, photoluminescent (PL) carbon dots (CDs) have attracted enormous attention because of their many fascinating properties. However, the traditional synthesis routes of PL CDs usually suffer from relatively low quantum yields (QYs) and require complicated operation processes as well as lots of externally supplied energy. Herein, we report a room temperature, green, ultrafast and energy-efficient route for large scale synthesis of highly PL N, S-codoped CDs without any external energy supply. The N, S-codoped CDs are prepared through a novel carbon source self-heating strategy, using the sole precursor tetraethylenepentamine (TEPA) simultaneously as the carbon, nitrogen and heat source, triggered by the heat initiator sodium persulfate (Na2S2O8). The large amount of heat released from Na2S2O8-triggered oxidation of TEPA could effectively promote the spontaneous polymerization and carbonization of TEPA precursors themselves as well as the in situ co-doping of sulfur, which had marked synergistic effects on the fluorescence enhancement of CDs, eventually leading to the high-yield (58.0%) preparation of highly fluorescent N, S-codoped CDs (QY 26.4%) at room temperature within 2 min. Moreover, the fluorescence of N, S-codoped CDs could be selectively quenched by Fe3+ ions in the presence of EDTA, in an ultra-wide range of 0.2-600 µM, with a detection limit of 0.10 µM. Ultimately, the fluorescent nanoprobe was successfully used for the quantitative detection of Fe3+ in human serum samples, indicating its great potential for sensing and biomedical applications.

[Advances in polydopamine surface modification for capillary electrochromatography].

Capillary electrophoresis (CE) has a wide range of applications in analytical fields due to its advantages of low sample consumption, short separation time, and high separation efficiency. The cathodic electroosmotic flow (EOF) and single electrophoretic separation mechanism are not optimal for many CE applications. Hence, the use of an unmodified fused-silica capillary leads to insufficient separation performance that cannot meet the requirements for various complex sample systems, especially neutral and chiral compounds. Therefore, it is necessary to introduce various capillary modification strategies in CE so that its potential for practical application can be expanded. Mussel-inspired polydopamine (PDA) and PDA-derived coating materials have fascinating advantages such as simple surface coating procedures, strong surface adhesiveness, good chemical stability, latent reactivity with many functionalized molecules, and good biocompatibility. Thus, they have been widely utilized in different research fields, including catalysis, sensing, water treatment, sample pretreatment, biomedicine, chromatographic separation, and CE. The preparation of PDA coatings is simple as it involves physical adsorption, and the obtained surface adhesive coatings possess good stability similar to covalently bonded coatings. Therefore, PDA and PDA-derived coatings are well suited for the modification of fused-silica capillaries. More importantly, the PDA coating can be utilized as an intermediate reaction platform for diverse subsequent surface modification because of its strong surface adhesive property and strong latent reactivity with many functionalized molecules (such as polymers, proteins, and nanomaterials). Consequently, various chromatographic retention mechanisms can be introduced on the inner wall of the capillary, thereby contributing to the fabrication of multi-functional PDA-based stationary phases for CEC. Owing to these outstanding advantages, researchers are paying increasing attention to the great application potential of PDA and PDA-derived coatings in CEC. In this paper, recent advances in the methods for preparing PDA coatings, especially the recently developed fabrication strategies and various applications of PDA-modified silica capillary in open tubular-capillary electrochromatography (OT-CEC) and capillary electrochromatography monolithic columns, are summarized and discussed. Furthermore, the application prospects of PDA-based coating materials in CEC are prospected in this review. Although PDA and PDA-derived coating materials are seeing widespread utilization in field of CEC, researchers have still not reached a definite conclusion regarding the PDA formation and coating mechanisms, and further investigation is needed in this direction. The PDA coatings formed using existing methods are generally thin. In the early stage, many studies adopted the strategy of repeated coating to improve the coating effect of PDA in capillaries, but this method was found to be time-consuming and less efficient. In order to improve the preparation efficiency of PDA-modified CEC columns, many researchers have focused on fast deposition induced by a strong oxidant to obtain PDA-coated columns. However, the controllability of the PDA coating obtained by this method is poor. Thus, it is necessary to further explore new preparation strategies for PDA-coated CEC capillaries with better reproducibility and stronger operability. On the other hand, although a strategy for directly synthesizing functional PDA-coated CEC columns in the organic phase has been proposed, its application potential in CEC remains to be further explored. In addition, the PDA coating itself has poor porosity and a small specific surface area, which may be significantly improved by modifying the coating on the porous monolithic column surface. However, there has been limited research on the use of PDA coatings in monolithic columns, and their application potential remains to be expanded. With in-depth research into the formation mechanism and preparation methodologies of PDA coatings, PDA, which is a highly malleable biomimetic material, will play a more important role in advances in the fields of CE and CEC.

Melanin-mimetic multicolor and low-toxicity hair dye.

Most commercial permanent hair dyeing technologies are based on the oxidative process of p-phenylenediamine and its derivative materials. However, concerns about their toxicological issues have been raised throughout the years. Herein, we report an innovative surface coloration strategy for fabricating melanin-mimetic multicolor and low-toxicity hair dyes through sodium periodate-induced rapid deposition of eumelanin-like polydopamine (PDA) and pheomelanin-like PDA/cysteine co-deposited coatings on the hair surface. The color and morphology of the resulting hair were characterized in detail by several spectroscopy methods and the possible mechanism for the multi-coloring effects and structural differences of the melanin-mimetic coating was proposed. Our strategy eliminates the use of toxic dye precursors or organic solvents, and the favorable safety of the PDA-based formulations is demonstrated. The fabricated dyes can be applied to hair simply by combing, resulting in uniform multi-coloring effects within a short time. Furthermore, the melanin-mimetic hair dyes have excellent durability and ultraviolet protection performance. This work provides a facile and versatile methodology to develop the next generation of safe, sustainable and multicolor hair dyes and pave new avenues for advancing the field of surface coloration, nanoreactors, nanogenerators, energy storage materials and biomimetic sensing devices.