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Although Silicon monoxide (SiO) is regarded as the most promising next-generation anode material, the large volume expansion, poor conductivity, and low initial Coulombic efficiency (ICE) severely hamper its commercialization application. Designing a multilayer conductive skeleton combined with advanced prelithiation technology is considered an effective approach to address these problems. Herein, a reliable strategy is proposed that utilizes MXene and carbon nanotube (CNT) as dual-conductive skeletons to encapsulate SiO through simple electrostatic interaction for high-performance anodes in LIBs, while also performing chemical prelithiation. Various characterizations and electrochemical measurements indicate that both MXene and CNT, as conductive networks and buffer interfaces, synergistically enhance the electron transport and lithium storage properties of the electrode. Moreover, the chemical prelithiation process effectively improves the ICE and cycling stability. Consequently, the prepared SiO@MXene@CNT anode delivers a high capacity of 1032 mAh g -1 after 200 cycles at 200 mA g -1 and an ultrahigh capacity retention rate of 89.5% beyond 1000 cycles at 1000 mA g -1 . More importantly, the ICE of the SiO@MXene@CNT anode increases from 65.1% to 92.3% after chemical prelithiation. The work opens a new avenue for significantly improving the lithium storage performance of SiO-based anodes and is expected to promote their commercialization progress., (© 2025 Wiley‐VCH GmbH.)

Achieving long-wavelength infrared (LWIR) cameras with high sensitivity and shorter exposure times faces challenges due to series reflections from high-refractive index lenses within compact optical systems. However, designing effective antireflective coatings to maximize light throughput in these systems is complicated by the limited range of transparent materials available for the LWIR. This scarcity narrows the degrees of freedom in design, complicating the optimization process for a system that aims to minimize the number of physical layers and address the inherent large refractive mismatch from high-index lenses. In this study, we use discrete-to-continuous optimization to design a subwavelength-thick antireflective multilayer coating on high-refractive index Si substrate for LWIR cameras, where the coating consists of few (e.g., five) alternating stacks of high- and low-refractive-index thin films (e.g., Ge-YF 3 , Ge-ZnS, or ZnS-YF 3 ). Discrete optimization efficiently reveals the configuration of physical layers through binary optimization supported by a machine learning model. Continuous optimization identifies the optimal thickness of each coating layer using the conventional gradient method. As a result, considering the responsivity of a LWIR camera, the discrete-to-continuous strategy finds the optimal design of a 2.3-μm-thick antireflective coating on Si substrate consisting of five physical layers based on the Ge-YF 3 high-low index pair, showing an average reflectance of 0.54 % within the wavelength range of 8-13 μm. Moreover, conventional thin-film deposition (e.g., electron-beam evaporator) techniques successfully realize the designed structure, and Fourier-transform infrared spectroscopy (FTIR) and thermography confirm the high performance of the antireflective function., Competing Interests: Conflict of interest: Authors state no conflicts of interest., (© 2024 the author(s), published by De Gruyter, Berlin/Boston.)

Local recurrence after surgical and therapeutic treatment remains a significant clinical problem in oncology. Recurrence may be due to imperfections in existing therapies, particularly chemotherapy. To improve antitumor activity and prevent local cancer recurrence while keeping toxicity at acceptable levels, we have developed and demonstrated a biodegradable local chemotherapy platform that provides controlled and prolonged drug release. The platform consists of a polycaprolactone (PCL) substrate, which provides the structural integrity of the platform and the predominant unidirectional drug release, and a thin multilayer coating (∼200 nm) containing doxorubicin (DOX). The coating is an electrostatic complex obtained by the layer-by-layer (LbL) assembly and consists of natural polyelectrolytes [poly-γ-glutamic acid (γ-PGA) and chitosan (CS) or poly-l-lysine (PLL)]. To improve the release stability, an ionic conjugate of DOX and γ-PGA was prepared and incorporated into the multilayer coating. By varying the structure of the coating by adding empty (without DOX) bilayers, we were able to control the kinetics of drug release. The resulting platforms contained equal numbers of empty bilayers and DOX-loaded bilayers (15 + 15 or 30 + 30 bilayers) with a maximum loading of 566 ng/cm 2 . The platforms demonstrated prolonged and fairly uniform drug release for more than 5 months while retaining antitumor activity in vitro on ovarian cancer cells (SKOV-3). The empty platforms (without DOX) showed good cytocompatibility and no cytotoxicity to human fibroblasts and SKOV-3 cells. This study presents the development of a local chemotherapy platform consisting of a PCL-based substrate which provides structural stability and a biodegradable polyelectrolyte layered coating which combines layers containing a polyanion ionic complex with DOX with empty bilayers to ensure prolonged and controlled drug release. Our results may provide a basis for improving the efficacy of chemotherapy using drug delivery systems.

Multilayer coatings offer significant advantages in protecting materials' surfaces by shielding the underlying materials hierarchically from damage and wear. The layering morphology and structure of multilayer coatings directly affect their wear resistance capacity. Using a systematic set of experiments and molecular dynamics (MD) simulations, we studied the effect of layering thickness on the macroscale wear response of DLC/WC multinanolayer coatings. Our study revealed the existence of a critical bilayer thickness where maximum scratch hardness and wear resistance can be achieved. Our large-scale MD simulations showed that reducing the WC layer thickness to a certain limit increases the scratch hardness due to the confinement of dislocation motion. However, when the thickness of the WC layers falls below 2 nm, the deformation mechanism transitions from the interface-induced dislocation confinement to the interface-mediated amorphization of WC layers, reducing the scratch hardness of the coating. This finding offers a procedure for optimizing the macroscale wear performance of multinanolayer coatings.

To exert their beneficial effects, it is essential for the commensal bacteria of probiotic supplements to be sufficiently protected as they pass through the low pH environment of the stomach, and effectively colonize the intestinal epithelium downstream. Here, we investigated the effect of a multilayer coating containing red ginseng dietary fiber, on the acid tolerance, and the adhesion and proliferation capacities of three Lactobacillus strains ( Limosilactobacillus reuteri KGC1901, Lacticaseibacillus casei KGC1201, Limosilactobacillus fermentum KGC1601) isolated from Panax ginseng , using HT-29 cells, mucin-coated plates, and human pluripotent stem cell-derived intestinal epithelial cells as in vitro models of human gut physiology. We observed that the multilayer-coated strains displayed improved survival rates after passage through gastric juice, as well as high adhesion and proliferation capacities within the various gut epithelial systems tested, compared to their uncoated counterparts. Our findings demonstrated that the multilayer coat effectively protected commensal microbiota and led to improved adhesion and colonization of intestinal epithelial cells, and consequently to higher probiotic efficacy.

The versatility of sol-gel systems makes them ideal for functional coatings in industry. However, existing coatings are either too thin or take too long to cure. To address these issues, this paper proposes using an atmospheric pressure plasma source to fully cure and functionalize thicker sol-gel coatings in a single step. The study explores coating various substrates with sol-gel layers to make them scratch-resistant, antibacterial, and antiadhesive. Microparticles like copper, zinc, or copper flakes are added to achieve antibacterial effects. The sol-gel system can be sprayed on and quickly functionalized on the substrate. The study focuses on introducing and anchoring particles in the sol-gel layer to achieve an excellent antibacterial effect by changing the penetration depth. Overall, this method offers a more efficient and effective approach to sol-gel coatings for industrial applications. In order to achieve a layer thickness of more than 100 µm, the second part of the study proposes a multilayer system comprising 15 to 30 µm thick monolayers that can be modified by introducing fillers (such as TiO 2 ) or scratch-resistant chemicals like titanium isopropoxide. This system also allows for individual plasma functionalization of each sol-gel layer. For instance, the top layer can be introduced with antibacterial particles, while another layer can be enhanced with fillers to increase wear resistance. The study reveals the varying antibacterial effects of spherical particles versus flat flakes and the different scratch hardnesses induced by changes in pH, number of layers, and particle introduction.

In last few decades, multilayer coatings have achieved enormous attention owing to their unique ability to tune thickness, topography, and chemical composition for developing various functional materials. Such multilayer coatings were mostly and conventionally derived by following a simple layer-by-layer (LbL) deposition process through the strategic use of electrostatic interactions, hydrogen bonding, host-guest interactions, covalent bonding, etc. In the conventional design of multilayer coatings, the chemical composition and morphology of coatings are modulated during the process of multilayer constructions. In such an approach, the postmodulations of the porous multilayers with different and desired chemistries are challenging to achieve due to the lack of availability of readily and selectively reactive moieties. Recently, the design of readily and selectively reactive multilayer coatings (RMLCs) provided a facile basis for postmodulating the prepared coating with various desired chemistries. In fact, by taking advantage of the inherent ability of co-optimizing the topography and various chemistries in porous RMLCs, different durable bioinspired liquid wettabilities (i.e., superhydrophobicity, underwater superoleophobicity, underwater superoleophilicity, slippery property, etc.) were successfully derived. Such interfaces have enormous potential in various prospective applications. In this review, we intend to give an overview of the evolution of LbL multilayer coatings and their synthetic strategies and discuss the key advantages of porous RMLCs in terms of achieving and controlling wettability properties. Recent attempts toward various applications of such multilayer coatings that are strategically embedded with different desired liquid wettabilities will be emphasized.

TiC-Ti 3 SiC 2 gradient hybrid interphase on the surface of SiC fibers was successfully obtained through the molten salt method. The electromagnetic parameters of the prepared samples can be accurately controlled by adjusting the reaction temperature. A significant bimodal effect is observed in electromagnetic parameters patterns, corresponding to the double interface layer. TiC-Ti 3 SiC 2 gradient hybrid interphase plays a dominant role in impedance matching, as well as in the attenuation layer through multi-interfacial polarization and conduction loss. Through the co-evaluation of the suppression of specular reflection and non-specular scattering properties of the samples, the SiC fiber with the TiC-Ti 3 SiC 2 gradient hybrid interphase is expected to be a high temperature resistant radar absorbing material for future stealth aircraft.

A comprehensive experimental investigation of the wear behaviour of coated spur polymer gears made of POM is performed in this study. Three different thicknesses of aluminium (Al) coatings were investigated and deposited by the Physical Vapour Deposition (PVD) process. The Al coating was deposited in three steps: By plasma activation, metallisation of the aluminium by the magnetron sputtering process, and plasma polymerisation. The wear of the gears was tested on an in-house developed testing rig for different torques (16, 20, and 24 Nm) and a rotational speed of 1000 rpm. The duration of the experiments was set to 13 h, when the tooth thickness and, consequently, the wear of the tooth flank were recorded. The experimental results showed that the influence of metallisation with aluminium surface coatings on the wear behaviour of the analysed polymer gear is not significantly important. The results also showed that the gears with a thicker aluminium coating showed greater wear than gears with a thinner coating or even without a coating. This is probably due to the fact that the aluminium particles that started to deviate during gear operation represented the abrasive material, which led to the faster wear of the contacting surfaces of the meshing gear flanks.

This work is devoted to the study of the formation of nanostructured multilayer coatings (TiZr/Nb)N on the surface of an AISI 321 steel substrate depending on the deposition parameters of the Arc-PVD method. The results of the X-ray diffraction analysis showed the formation of solid solution (TiNb)N and ZrN in the multilayer coatings with an FCC structure, ε-NbN with a hexagonal structure, as well as with a small volume fraction of the ε-Ti 2 N and β-Nb 2 N phase. On the basis of phase composition data, it is possible to assume that an increase in the number of bilayers leads to a decrease in the nitrogen concentration in the bilayers and, consequently, to a decrease in the volume fraction of ε-NbN and β-Nb 2 N nitrides. In all investigated systems obtained at -100 V and -200 V bias potentials, ε-NbN is the main phase. The study of the element distribution over the thickness of the (TiZr/Nb)N coating confirms the results of the X-ray diffraction analysis. The use of the structure model in the form of alternating layers allows for significantly improving the adhesion characteristics of the protective coating, as well as ensuring their high hardness. Based on the experimental results, it is possible to analyze changes in the mechanical and tribological properties of multilayer coatings depending on the number of applied bilayers. The results of the study of the elastic modulus and hardness of multilayer coatings (TiZrNb)N with different numbers of bilayers showed that a large number of bilayers (small thickness of each individual layer) shows the lowest value of hardness. It is assumed that as the bilayer thickness decreases, the coating characteristics are closer to the monolayer alloy than to the multilayer structure.

A TiN/TiNC/Al 2 O 3 multilayer coating was deposited on an Inconel 625 alloy by the chemical vapor deposition method as a protective barrier to improve the corrosion resistance in supercritical water. The corrosion characteristics were evaluated in a reactor at 500 °C and 25 MPa for 72 h. The surface morphology of the coated samples was relatively dense with no obvious cracks or pores observed. The XRD analysis revealed that the coatings were composed of TiN, TiNC and α-Al 2 O 3 phases. After exposure to supercritical water, the surface morphology of the coatings was still dense and kept integrity. The phase composition of the coatings was also not changed, with no obvious corrosion scales detected. This result demonstrates the effectiveness of TiN/TiNC/Al 2 O 3 coatings as a protective coating under harsh supercritical water environments.

Minimizing friction and wear is one of the continuing challenges in many mechanical industries. Recent research efforts have been focused on accelerating the antifriction and antiwear properties of hard coatings through the incorporation of self-lubricant materials or the development of new architectures. In this present study, carbon-rich MoC, MoCN, and multilayer MoC/MoCN coatings were deposited using reactive magnetron sputtering. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy were used to evaluate their properties, which revealed the presence of ceramic cubic crystallites, covalent bonds between primary elements, and an excess of amorphous carbon (a-C) in all of the coatings. The multilayer architecture and possible segregation of a-C around the ceramic crystallites resulted in improved mechanical properties for all coatings, with MoC/MoCN coatings having a maximum hardness of 21 GPa and elastic modulus of 236 GPa. Friction and wear behavior are initially determined by the structural-composition-property relationships of the respective coatings; later, the tribological characteristics are altered depending on the nature of tribolayer on both mating surfaces at the contact interface. The highest wear resistance of multilayer MoC/MoCN coating (8.7 × 10 -8 mm 3 /N m) and MoC coating (3.9 × 10 -7 mm 3 /N m) was due to the dissipation of contact stress by the tribofilm consisting of carbon tribo products like graphitic sp 2 carbon, diamond-like sp 3 carbon, and pyrrolic-N. On the other hand, MoCN coating depicted a lower wear resistance due to the frequent termination of C-H bonds by N, which restricts the strong formation of tribofilms as well as poor mechanical properties.

Friction and wear usually lead to huge energy loss and failure of machine pairs, which usually causes great economic losses. Researchers have made great efforts to reduce energy dissipation and enhance durability through advanced lubrication technologies. Single-layer coatings have been applied in many sectors of engineering, but the performance of single-layer coatings still has many limitations. One solution to overcome these limitations is to use a multilayer coating that combines different components with varied physical and chemical properties. In addition, multilayer coating with alternating layers only containing two components can lead to improved performance compared to a coating with only two different layers. This paper systematically reviews the design concept and properties of different types of multilayer coatings, including transition-metal nitride coatings, diamond-like carbon-based coatings, and other multilayer coatings. The inherent functional mechanisms of the multilayer structures are also detailed and discussed.

Cobalt-cemented carbide micro-end mills were coated with diamond grown by chemical vapor deposition (CVD), with the purpose of micro-machining cemented carbides. The diamond coatings were designed with a multilayer architecture, alternating between sub-microcrystalline and nanocrystalline diamond layers. The structure of the coatings was studied by transmission electron microscopy. High adhesion to the chemically pre-treated WC-7Co tool substrates was observed by Rockwell C indentation, with the diamond coatings withstanding a critical load of 1250 N. The coated tools were tested for micro-end-milling of WC-15Co under air-cooling conditions, being able to cut more than 6500 m over a period of 120 min, after which a flank wear of 47.8 μm was attained. The machining performance and wear behavior of the micro-cutters was studied by scanning electron microscopy and energy-dispersive X-ray spectroscopy. Crystallographic analysis through cross-sectional selected area electron diffraction patterns, along with characterization in dark-field and HRTEM modes, provided a possible correlation between interfacial stress relaxation and wear properties of the coatings. Overall, this work demonstrates that high adhesion of diamond coatings can be achieved by proper combination of chemical attack and coating architecture. By preventing catastrophic delamination, multilayer CVD diamond coatings are central towards the enhancement of the wear properties and mechanical robustness of carbide tools used for micro-machining of ultra-hard materials.

Refractory materials hold great promise to develop functional multilayer coating for extreme environments and temperature applications but require high temperature and complex synthesis to overcome their strong atomic bonding and form a multilayer structure. Here, a spontaneous reaction producing sophisticated multilayer refractory carbide coatings on carbon fiber (CF) is reported. This approach utilizes a relatively low-temperature (950 °C) molten-salt process for forming refractory carbides. The reaction of titanium (Ti), chromium (Cr), and CF yields a complex, high-quality multilayer carbide coating composed of 1) Cr carbide (Cr 3 C 2 ), 2) Ti carbide, and 3) Cr 3 C 2 layers. The layered sequence arises from a difference in metal dissolutions, reactions, and diffusion rates in the salt media. The multilayer-coated CFs act as a permeable oxidation barrier with no crystalline degradation of the CFs after extreme temperature (1,200 °C) and environment (oxyacetylene flame) exposure. The synthesis of high-quality multilayer refractory coating in a fast, efficient, easy, and clean manner may answer the need for industrial applications that develop cheap and reliable extreme environment protection barriers., Competing Interests: The authors declare no competing interest.

One of the most critical issues encountered by polymeric membranes for the gas separation process is the trade-off effect between gas permeability and selectivity. The aim of this work is to develop a simple yet effective coating technique to modify the surface properties of commonly used polysulfone (PSF) hollow fiber membranes to address the trade-off effect for CO 2 /CH 4 and O 2 /N 2 separation. In this study, multilayer coated PSF hollow fibers were fabricated by incorporating a graphene oxide (GO) nanosheet into the selective coating layer made of polyether block amide (Pebax). In order to prevent the penetration of Pebax coating solution into the membrane substrate, a gutter layer of polydimethylsiloxane (PDMS) was formed between the substrate and Pebax layer. The impacts of GO loadings (0.0-1.0 wt%) on the Pebax layer properties and the membrane performances were then investigated. XPS data clearly showed the existence of GO in the membrane selective layer, and the higher the amount of GO incorporated the greater the sp2 hybridization state of carbon detected. In terms of coating layer morphology, increasing the GO amount only affected the membrane surface roughness without altering the entire coating layer thickness. Our findings indicated that the addition of 0.8 wt% GO into the Pebax coating layer could produce the best performing multilayer coated membrane, showing 56.1% and 20.9% enhancements in the CO 2 /CH 4 and O 2 /N 2 gas pair selectivities, respectively, in comparison to the membrane without GO incorporation. The improvement is due to the increased tortuous path in the selective layer, which created a higher resistance to the larger gas molecules (CH 4 and N 2 ) compared to the smaller gas molecules (CO 2 and O 2 ). The best performing membrane also demonstrated a lower degree of plasticization and a very stable performance over the entire 50-h operation, recording CO 2 /CH 4 and O 2 /N 2 gas pair selectivities of 52.57 (CO 2 permeance: 28.08 GPU) and 8.05 (O 2 permeance: 5.32 GPU), respectively.

Artificial superhydrophobic coatings with mechanical stability, chemical stability, and strong adhesion have been achieved separately. However, a simultaneous demonstration of these features along with stability to high-temperature exposure is challenging. Herein, inspired by the micro/nanoscale hierarchical superhydrophobic surfaces of solid cactus plants, we propose a novel plasma-enhanced high temperature liquid-phase-assisted oxidation and crosslinking (PHLOC) in-situ co-growth strategy to design superhydrophobic nanocomposite coatings on metals based on organic-inorganic multilayer structures in which PTFE nanoparticles cross-linked to form a compact top layer with hierarchical surface textures on a ceramic skeleton with a papilla array, integrating multiple robust wettability characteristics with mechanochemical strength to isolate the underlying materials from the external environment. Remarkably, the superhydrophobic coating exhibits strong mechanical robustness undergoing the 120th linear abrasion or 40th rotary abrasion cycle and can be applied on large area and arbitrary shapes of metal substrates. Moreover, the samples sustain exposure to highly corrosive media, namely, aqua regia, sodium hydroxide solutions, and simulated seawater solution, to reflect long-term chemical robustness. More importantly, the multilayer coating demonstrates excellent high-temperature endurance, thermal cycling stability of 500 °C, and thermal repairability of superhydrophobicity. With multifaceted robustness and scalability, the superhydrophobic multilayer coating should find potential usage in the field of high-tech equipment with severe alternating or impact loads, high-temperature service, and chemical corrosion.

The multilayer antimony-doped tin dioxide coating was obtained by cathodic deposition of multilayer metal-hydroxide coating with near 100-nm thickness layers on the alloy underlayer accompanied by the anodic oxidation of this coating. The potential regions of deposition of tin, antimony, tin-antimony alloy, and mixture of this metals and their hydroxides in the pyrophosphate-tartrate electrolyte were revealed by the cyclic voltammetric method. The possibility of oxidation of cathodic deposit consisting of tin and Sn(II) hydroxide compounds to the hydrated tin dioxide in the same electrolyte was demonstrated.The operations of alloy underlayer deposition and oxidation of multilayer metal-hydroxide coating were proposed to carry out in the diluted pyrophosphate-tartrate electrolyte, similar to the main electrolyte.The accelerated tests showed higher service life of the titanium electrode with multilayer antimony-doped tin dioxide coating compared to both electrode with single-layer electrodeposited coating and the electrode with the coating obtained using prolonged heat treatment step.

A novel functional multilayer coating with periodically stacked nanolayers of amorphous carbon (a:C)/tungsten carbide (WC) and an adhesion layer of chromium (Cr) was deposited on 304 stainless steel using a dual magnetron sputtering technique. Through process optimization, highly densified coatings with high elasticity and shear modulus, excellent wear resistance, and minimal susceptibility to corrosive and caustic media could be acquired. The structural and mechanical properties of the optimized coatings were studied in detail using a variety of analytical techniques. Furthermore, finite element method simulations indicated that the stress generated due to contact against a steel ball was distributed well within the coating, which allowed the stresses to be lower than the yield threshold of the coating. Thus, an ultralow wear rate of ∼10 -12 mm 3 /N mm could be achieved in dry sliding conditions under relatively high Hertzian contact pressures of ∼0.4-0.9 GPa. The amorphous and pinhole-free structure of the individual layers, sufficient number of pairs, and the relatively dense stacked layers resulted in significant polarization resistance (Z″ = 5.5 × 10 6 Ω cm 2 ) and increased the corrosion resistance of the coating by 10-fold compared to that of recently reported corrosion-resistant coatings.

Wear is an important phenomenon that affects the efficiency and life of all moving machines. In this regard, extensive efforts have been devoted to achieve the lowest possible wear in sliding systems. With the advent of novel materials in recent years, technology is moving toward realization of zero wear. Here, we report on the development of new functional coatings comprising periodically stacked nanolayers of amorphous carbon and cobalt that are extremely wear resistant at the micro and macro scale. Because of their unique structure, these coatings simultaneously provide high elasticity and ultrahigh shear strength. As a result, almost zero wear was observed even after one million sliding cycles without any lubrication. The wear rate was reduced by 8-10-fold compared with the best previously reported data on extremely low wear materials.

We describe the design, fabrication, and characterization of mechanically stable, reproducible, and highly reflecting distributed Bragg reflectors (DBR) composed of thermally evaporated thin films of calcium fluoride (CaF2) and zinc sulfide (ZnS). CaF2 and ZnS were chosen as the low and high refractive index components of the multilayer DBR structures, with n = 1.43 and n = 2.38 respectively, because neither material requires substrate heating during the deposition process in order to produce optical quality thin films. DBRs consisting of seven pairs of CaF2 and ZnS layers, were fabricated with thicknesses of 96 and 58 nm, respectively, as characterized by high-resolution scanning electron microscopy (HR-SEM), and exhibited a center wavelength of λc = 550 nm and peak reflectance exceeding 99%. The layers showed good adhesion to each other and to the glass substrate, resulting in mechanically stable DBR coatings. Complete optical microcavities consisting of two such DBR coatings and a CaF2 spacer layer between them could be fabricated in a single deposition run. Optically, these structures exhibited a resonator quality factor of Q > 160. When a CaF2/ZnS DBR was grown, without heating the substrate during deposition, on top of a thin film containing the fluorescent dye Rhodamine 6G, the fluorescence intensity showed no degradation compared to an uncoated film, in contrast to a MgF2/ZnS DBR coating grown with substrate heating which showed a 92% reduction in signal. The ability to fabricate optical quality CaF2/ZnS DBRs without substrate heating, as introduced here, can therefore enable formation of low-loss high-reflectivity coatings on top of more delicate heat-sensitive materials such as organics and other nanostructured emitters, and hence facilitate the development of nanoemitter-based microcavity device applications.

A CE method using dual cationic and neutral cyclodextrins (CD) was optimized for the enantiomeric separation of a compound presenting a diaryl sulfonamide group. Preliminary studies were made to select the optimal CDs and pH of the BGE. Two CDs (amino-β-CD and β-CD) were selected to separate the enantiomers in a 67 mM phosphate buffer at pH 7.4. However, the repeatability of the analyses obtained on bare-fused silica capillary was not acceptable owing to the adsorption of the amino-β-CD to the capillary. To prevent this, a dynamic coating of the capillary was used employing five layers of ionic-polymer (poly(diallyldimethylammonium) chloride (PDADMAC) and poly(sodium 4-styrenesulfonate). The efficiency of the coating was assessed by measuring the EOF stability. Repeatability of the injections was obtained when intermediate coating with PDADMAC was performed between each run. Secondly, this enantioseparation method was optimized using a central composite circumscribed design including three factors: amino-β-CD and β-CD concentrations and the percentage of methanol. Under the optimal conditions (i.e. 16.6 mM of amino-β-CD, 2.6 mM of β-CD, 0% MeOH in 67 mM phosphate buffer (pH 7.4) as BGE, cathodic injection 0.5 psi, 5 s, separation voltage 15 kV and a temperature of 15°C), complete enantioresolution of the analyte was obtained. It is worth mentioning that the design of experiments (DOE) protocol employed showed a significant interaction between CDs, highlighting the utility of DOE in method development. Finally, small variations in the ionic-polymer concentrations did not significantly influence the EOF, confirming the robustness of the coating method., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The aim of this study was to develop a new multilayer coating with crosslinked quaternary ammonium chitosan (hydroxypropyltrimethyl ammonium chloride chitosan; HACC) and κ-carrageenan for use in capillary electrophoresis. A new semi-permanent multilayer coating was formed using the procedure developed and the method does not require the presence of polymers in the background electrolyte (BGE). The new capillary multilayer coating showed a cathodic electroosmotic flow (EOF) of around 30×10(-9) m(2) V(-1) s(-1) which is pH-independent in the range of pH 2 to 10. The enhanced EOF at low pH obtained contributed significantly to the development of a fast method of separation. The multilayer coating was then applied in the development of a fast separation method to determine betaine and methionine in pharmaceutical formulations by capillary zone electrophoresis (CZE). The BGE used to determine the betaine and methionine concentrations was composed of 10 mmol L(-1) tris(hydroxymethyl) aminomethane, 40 mmol L(-1) phosphoric acid and 10% (v/v) ethanol, at pH 2.1. A fused-silica capillary of 32 cm (50 µm ID×375 µm OD) was used in the experiments and samples and standards were analyzed employing the short-end injection procedure (8.5 cm effective length). The instrumental analysis time of the optimized method was 1.53 min (approx. 39 runs per hour). The validation of the proposed method for the determination of betaine and methionine showed good linearity (R(2)>0.999), adequate limit of detection (LOD <8 mg L(-1)) for the concentration in the samples and inter-day precision values lower than 3.5% (peak area and time migration). The results for the quantification of the amino acids in the samples determined by the CZE-UV method developed were statistically equal to those obtained with the comparative LC-MS/MS method according to the paired t-test with a confidence level of 95%., (Copyright © 2014 Elsevier B.V. All rights reserved.)