Search Results (100)

This study introduces a novel approach for analyzing theoretical Raman spectra, designed to facilitate spectral interpretation, particularly for complex systems such as functional mesoporous silica-based thin films. The proposed methodology relies on spectral decomposition supported by theoretical calculations, representing a step toward the development of autonomous research laboratories. The method assigns vibrational shifts to individual atoms within a molecular model and uses this information to generate partial spectra corresponding to specific atomic groupings. Unlike separate calculations for isolated components, this approach preserves the mutual interactions within the entire molecular structure, providing a more accurate representation of the vibrational environment. Decomposing the theoretical spectrum into contributions from atomic groups significantly simplifies the assignment of Raman bands to specific structural units, thereby enhancing the interpretative power of theoretical spectra and their correlation with experimental data. The method was demonstrated using real Raman spectroscopic data obtained from mesoporous SBA-15 silica thin films containing copper phosphonate groups. This work also highlights the critical role of molecular modeling and DFT calculations in Raman spectral analysis and outlines future perspectives for the use of artificial intelligence to automate and optimize the spectral interpretation process. Full article

The recent COVID-19 pandemic has made the public aware of the importance of combating pathogenic microorganisms before they enter the human body. This growing threat from microorganisms prompted us to conduct research into a new type of coating that would be an alternative to the continuous disinfection of touch surfaces. Our goal was to design, synthesise and thoroughly characterise such a coating. In this work, we present a nanocomposite material composed of a thin-layer mesoporous SBA-15 silica matrix containing copper phosphonate groups, which act as catalytic centres responsible for the generation of reactive oxygen species (ROS). In order to verify the structure of the material, including its molecular structure, microscopic observations and Raman spectroscopy were performed. The generation of ROS was confirmed by fluorescence microscopy analysis using a fluorogenic probe. The antimicrobial activity was tested against a wide spectrum of Gram-positive and Gram-negative bacteria, while cytotoxicity was tested on BALB/c3T3 mouse fibroblast cells and HeLa cells. The studies fully confirmed the expected structure of the obtained material, its antimicrobial activity, and the absence of cytotoxicity towards fibroblast cells. The results obtained confirmed the high application potential of the tested nanocomposite coating. Full article

Mesoporous silicon dioxide films have been shown to be well suited as adhesion-promoting interlayers for generating high-strength polymer–metal interfaces. These films can be fabricated via microwave plasma-enhanced chemical vapor deposition using the precursor hexamethyldisiloxane and oxygen as working gas. The resulting mesoporous structures enable polymer infiltration during overmolding, which leads to a nanoscale form-locking mechanism after solidification. This mechanism allows for efficient stress transfer across the interface and makes the resulting adhesion highly dependent on the morphology of the deposited film. To gain a deeper understanding of the underlying deposition mechanisms and improve process stability, this work investigates the growth behavior of mesoporous silica films using a multiple regression analysis approach. The seven process parameters coating time, distance, chamber pressure, substrate temperature, flow rate, plasma pulse duration, and pause-to-pulse ratio were systematically varied within a Design of Experiments framework. The resulting films were characterized by their free surface area, mean agglomerate diameter, and film thickness using digital image analysis, white light interferometry, and atomic force microscopy. The deposited films exhibit a wide range of morphological appearances, ranging from quasi-dense to dust-like structures. As part of this research, the free surface area varied from 15 to 55 percent, the mean agglomerate diameter from 17 to 126 nm, and the film thickness from 35 to 1600 nm. The derived growth model describes the deposition process with high statistical accuracy. Furthermore, all coatings were overmolded via injection molding and subjected to mechanical testing, allowing a direct correlation between film morphology and their performance as adhesion-promoting interlayers. Full article

Development of sensitive and convenient alkaline phosphatase (ALP) detection methods is of great significance for food analysis, biomedical applications, and clinical tests. In this work, a sensitive detection method for ALP was established based on nanochannel-modified electrodes, where the electrochemical luminescence (ECL) signal was quenched by the enzymatic reaction product. Vertically ordered mesoporous silica film (VMSF) was rapidly grown on low-cost ITO via the electrochemically assisted self-assembly (EASA) method. The resulting modified electrode (VMSF/ITO) exhibited a uniform and ordered nanochannel structure with nanochannel diameter of 2–3 nm and charge-selective permeability, enabling the enrichment of cationic ECL emitter tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺). Compared to the ITO electrode, VMSF/ITO increased the ECL signal by 60 times. In the presence of ALP, it catalyzes the hydrolysis of its substrate, disodium phenyl phosphate hydrate (DPP), generating phenol (Phe), which quenched the ECL signal of Ru(bpy)₃²⁺ and the co-reactant N,N-Dipropyl-1-propanamine (TPA). Based on this principle, ECL detection of ALP can be achieved. The linear detection range for ALP was 0.01 U/L to 30 U/L, with a limit of detection (LOD) of 0.008 U/L. The sensor exhibited high selectivity. Combined with the anti-contamination and anti-interference capabilities of VMSF, the constructed sensor enabled the detection of ALP levels in milk samples. Full article

Smart packaging not only has a preservation effect on food, but can also monitor the change of food quality in real time to ensure food safety. In this study, hollow mesoporous silica loaded with cinnamaldehyde was used as the antimicrobial agent, anthocyanin as the color developer, and nanocellulose as the film matrix, to obtain smart packaging with excellent antimicrobial activity and pH-responsive color development (CBF). Modified silica has a good regulatory characteristic on the release of cinnamaldehyde, and the cumulative release rate of cinnamaldehyde in the NH₂-HMSN@CA preservative reaches 72% after 7 days. Additionally, the film has good antibacterial properties, with inhibition rates of 82% and 92% against E. coli and S. aureus, respectively. In addition, the film has good mechanical properties and water vapor permeability. In terms of pH response, the film shows excellent color rendering and good stability. Therefore, the CBF films can be applied to preservation and real-time monitoring of fruits and vegetables, meat, and other food products, which has great potential for intelligent food packaging. Full article

Homogeneous aptasensors that eliminate the need for probe labeling or immobilization hold significant potential for the rapid detection of tumor biomarkers. Herein, a homogeneous aptasensor with electrochemical (EC) and electrochemiluminescence (ECL) dual detection channels was developed by integrating nanochannel-based probe enrichment and DNase I cleavage for selective detection of the tumor biomarker, carbohydrate antigen 125 (CA125). A two-dimensional (2D) composite probe was prepared by assembling the CA125-specific aptamer and the cationic probe tris(2,2′-bipyridyl)Ru(II) (Ru(bpy)₃²⁺), which exhibited both EC and ECL properties, onto graphene oxide (GO) nanosheets (Ru(bpy)₃²⁺/Apt@GO). A vertically ordered mesoporous silica film (VMSF) with ultrasmall, uniform, and vertically aligned nanochannel arrays was rapidly grown on the inexpensive and disposable indium tin oxide (ITO) electrode, forming the detection interface. Due to the size exclusion effect of the ultrasmall nanochannels in VMSF, the Ru(bpy)₃²⁺/Apt@GO probe was unable to penetrate the nanochannels, resulting in no detectable Ru(bpy)₃²⁺ signal on the electrode. Upon specific recognition of CA125 by the aptamer, an aptamer-CA125 complex was formed and subsequently detached from GO. DNase I then cleaved the aptamer-CA125 complex, releasing CA125 and allowing Ru(bpy)₃²⁺ to dissociate into the solution. This enzymatic cleavage enabled CA125 to re-enter the binding cycle, amplifying the release of Ru(bpy)₃²⁺ into the solution. The electrostatic adsorption of the cationic Ru(bpy)₃²⁺ by VMSF significantly enhanced both the EC and ECL signals. The constructed aptasensor exhibited a linear EC detection range for CA125 from 0.1 U/mL to 100 ng/mL, with a limit of detection (LOD) of 91 mU/mL. For ECL detection, CA125 was detected over a range from 0.001 to 100 U/mL, with a LOD as low as 0.4 mU/mL. The developed aptasensor demonstrated excellent selectivity and was successfully applied to the dual-mode EC/ECL detection of CA125 in fetal bovine serum samples. Full article

The sensitive detection of inflammatory biomarkers in gingival crevicular fluid (GCF) is highly desirable for the evaluation of periodontal disease. Luminol-based electrochemiluminescence (ECL) immunosensors offer a promising approach for the fast and convenient detection of biomarkers. However, luminol’s low ECL efficiency under neutral conditions remains a challenge. This study developed an immunosensor by engineering an immunorecognition interface on the outer surface of mesoporous silica nanochannel film (SNF) and confining a Co₃O₄ nanocatalyst within the SNF nanochannels to improve the luminol ECL efficiency. The SNF was grown on an indium tin oxide (ITO) electrode using the simple Stöber solution growth method. A Co₃O₄ nanocatalyst was successfully confined within the SNF nanochannels through in situ electrodeposition, confirmed by X-ray photoelectron spectroscopy (XPS) and electrochemical measurements. The confined Co₃O₄ demonstrated excellent electrocatalytic activity, effectively enhancing luminol and H₂O₂ oxidation and boosting the ECL signal under neutral conditions. Using interleukin-6 (IL-6) as a proof-of-concept demonstration, the epoxy functionalization of the SNF outer surface enabled the covalent immobilization of capture antibodies, forming a specific immunorecognition interface. IL-6 binding induced immunocomplex formation, which reduced the ECL signal and allowed for quantitative detection. The immunosensor showed a linear detection range for IL-6 from 1 fg mL⁻¹ to 10 ng mL⁻¹, with a limit of detection (LOD) of 0.64 fg mL⁻¹. It also demonstrated good selectivity and anti-interference capabilities, enabling the successful detection of IL-6 in artificial GCF samples. Full article

The resistivity of the silica SBA-15 type can be significantly improved by forming a thin layer of carbon on the pore surface. This is possible through the carbonization reaction of a surfactant used as a structure-directing agent in the synthesis of mesostructured silica materials. The synthesis of this type of silica-carbon composite (SBA-C) is based on the use of sulfuric acid to create a carbon layer from surfactant molecules encapsulated in silica mesopores. The action of sulfuric acid takes place through dehydration and sulfonation reactions, which promote the formation of aromatic structures and favor crosslinking processes. The same procedure was applied to prepare MTF-C composites based on mesostructured thin films (MTFs). Compared to pure silica materials, these silica-carbon composites exhibit reduced pore diameter and volume while maintaining morphology and structure. The pore structure characteristics were obtained by scanning and transmission electron microscopy, X-ray energy dispersive spectroscopy, Raman spectroscopy, X-ray diffraction, thermogravimetry, and isothermal sorption analysis. The composite obtained after carbon layer formation exhibited enhanced conductivity in comparison to pure silica SBA-15. The resistivity of SBA-C composite material after annealing at 800 °C under a nitrogen atmosphere decreased to 1980 $\Omega$cm in comparison with pure SBA-15. Full article

The textural properties of synthetic and natural clays in the sodium form and exchanged with tetramethylammonium cations (TMA⁺) were characterized using N₂ and Ar physisorption isotherms at cryogenic temperatures. Specific surface areas and micro/mesoporous volumes were determined using the BET and the t-plot models. The t-plot analysis requires the use of reference isotherms measured at the same temperature on the surface of non-porous materials with an identical chemical composition. In order to better assess the effects of chemical heterogeneities in the clay particles, reference isotherms representative of silica surfaces were taken into account in the analysis of the t-curve and corrected to account for variations in curvature at the interface of the film adsorbed in the micropores. In addition, high-resolution Ar adsorption isotherms at 87 K were analyzed using the Derivative Isotherm Summation (DIS) method to quantify the energy contributions of adsorption sites and determine the fractions of basal and lateral surfaces of clay particles. The high-energy adsorption sites, identified in the low-pressure range, were attributed to intra-particle microporosity due to stacking defects and/or open inter-layer spaces. These sites were differentiated from those on the lateral and basal surfaces of the particles. A modification of the DIS method was proposed to measure these contributions and improve the fit with the experimental data. The results show that TMA⁺ cation exchange significantly increases the microporosity of clays compared to their sodic form, which can be attributed to the increased contribution of intra-particle adsorption sites due to interlayer expansion. Full article

Simple development of an electrochemiluminescence (ECL) immunosensor for convenient detection of tumor biomarker is of great significance for early cancer diagnosis, treatment evaluation, and improving patient survival rates and quality of life. In this work, an immunosensor is demonstrated based on an enhanced ECL signal boosted by nanochannel-confined Au nanomaterial, which enables sensitive detection of the tumor biomarker—carcinoembryonic antigen (CEA). Vertically-ordered mesoporous silica film (VMSF) with a nanochannel array and amine groups was rapidly grown on a simple and low-cost indium tin oxide (ITO) electrode using the electrochemically assisted self-assembly (EASA) method. Au nanomaterials were confined in situ on the VMSF through electrodeposition, which catalyzed both the conversion of dissolved oxygen (O₂) to reactive oxygen species (ROS) and the oxidation of a luminol emitter and improved the electrode active surface. The ECL signal was enhanced fivefold after Au nanomaterial deposition. The recognitive interface was fabricated by covalent immobilization of the CEA antibody on the outer surface of the VMSF, followed with the blocking of non-specific binding sites. In the presence of CEA, the formed immunocomplex reduced the diffusion of the luminol emitter, resulting in the reduction of the ECL signal. Based on this mechanism, the constructed immunosensor was able to provide sensitive detection of CEA ranging from 1 pg·mL⁻¹ to 100 ng·mL⁻¹ with a low limit of detection (LOD, 0.37 pg·mL⁻¹, S/N = 3). The developed immunosensor exhibited high selectivity and good stability. ECL determination of CEA in fetal bovine serum was achieved. Full article

Background: Cellulose derivatives are gaining much attention in medical research due to their excellent properties such as biocompatibility, hydrophilicity, non-toxicity, sustainability, and low cost. Unfortunately, cellulose does not exhibit antimicrobial activity. However, derivatives like hydroxyethyl cellulose represent a proper matrix to incorporate antimicrobial agents with beneficial therapeutic effects. Methods: Combining more antimicrobial agents into a single composite material can induce stronger antibacterial activity by synergism. Results: Therefore, we have obtained a hydroxyethyl-cellulose-based material loaded with zinc oxide nanoparticles and cinnamon essential oil as the antimicrobial agents. The cinnamon essential oil was loaded in mesoporous silica particles to control its release. Conclusions: The composite films demonstrated high antibacterial activity against Staphylococcus aureus and Escherichia coli strains, impairing the bacterial cells’ viability and biofilm development. Such antimicrobial films can be used in various biomedical applications such as topical dressings or as packaging for the food industry. Full article

Vertically ordered mesoporous silica films (VMSF) are a class of porous materials composed of ultrasmall pores and ultrathin perpendicular nanochannels, which are attractive in the areas of electroanalytical sensors and molecular separation. However, VMSF easily falls off from the carbonaceous electrodes and thereby impacts their broad applications. Herein, carbon nitride nanosheets (CNNS) were served as an adhesive layer for stable growth of VMSF on the glassy carbon electrode (GCE). CNNS bearing plentiful oxygen-containing groups can covalently bind with silanol groups of VMSF, effectively promoting the stability of VMSF on the GCE surface. Benefiting from numerous open nanopores of VMSF, modification of VMSF’s external surface with carbohydrate antigen 15-3 (CA15-3)-specific antibody allows the target-controlled transport of electrochemical probes through the internal silica nanochannels, yielding sensitive quantitative detection of CA15-3 with a broad detection range of 1 mU/mL to 1000 U/mL and a low limit of detection of 0.47 mU/mL. Furthermore, the proposed VMSF/CNNS/GCE immunosensor is capable of highly selective and accurate determination of CA15-3 in spiked serum samples, which offers a simple and effective electrochemical strategy for detection of various practical biomarkers in complicated biological specimens. Full article

The convenient and sensitive detection of metabolites is of great significance for understanding human health status and drug development. Solid-phase electrochemiluminescence (ECL) enzyme electrodes show great potential in metabolite detection based on the enzyme-catalyzed reaction product hydrogen peroxide (H₂O₂). Herein, a solid-phase ECL enzyme sensor was fabricated based on a confined emitter and an immobilized enzyme using electrostatic nanocage array, constructing a platform for the sensitive detection of cholesterol. The electrostatic cage nanochannel consists of a bipolar and bilayer vertically aligned mesoporous silica film (bp-VMSF). The upper layer of bp-VMSF is an amino-modified, positively charged VMSF (p-VMSF), and the lower layer is a negatively charged VMSF (n-VMSF). The most commonly used ECL probe tris(bipyridine)ruthenium(II) (Ru(bpy)₃²⁺) is fixed in n-VMSF by electrostatic adsorption from n-VMSF and electrostatic repulsion from the upper p-VMSF, generating significantly enhanced and stable ECL signals. The successful preparation of the electrostatic cage was characterized by scanning electron microscopy (SEM) and electrochemical methods. After amino groups on the outer surface of bp-VMSF were derivatized with aldehyde, cholesterol oxidase (ChOx) molecules were covalently immobilized. The successful construction of the enzyme electrode was characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). When the corresponding enzyme substrate, cholesterol, was present in the solution, the ECL signal of Ru(bpy)₃²⁺ was quenched by the enzyme-catalyzed reaction product H₂O₂, enabling the high-sensitivity detection of cholesterol. The linear range for detecting cholesterol was from 0.05 mM to 5.0 mM, with a limit of detection (LOD) of 1.5 μM. Full article

Polymers with a low dielectric constant (D_k) are promising materials for high-speed communication networks, which demand exceptional thermal stability, ultralow D_k and dissipation factor, and minimum moisture absorption. In this paper, we prepared a series of novel low-D_k polyimide films containing an MCM-41-type amino-functionalized mesoporous silica (AMS) via in situ polymerization and subsequent thermal imidization and investigated their morphologies, thermal properties, frequency-dependent dielectric behaviors, and water permeabilities. Incorporating 6 wt.% AMS reduced the D_k at 1 MHz from 2.91 of the pristine fluorinated polyimide (FPI) to 2.67 of the AMS-grafted FPI (FPI-g-AMS), attributed to the free volume and low polarizability of fluorine moieties in the backbone and the incorporation of air voids within the mesoporous AMS particles. The FPI-g-AMS films presented a stable dissipation factor across a wide frequency range. Introducing a silane coupling agent increased the hydrophobicity of AMS surfaces, which inhibited the approaching of the water molecules, avoiding the hydrolysis of Si–O–Si bonds of the AMS pore walls. The increased tortuosity caused by the AMS particles also reduced water permeability. All the FPI-g-AMS films displayed excellent thermooxidative/thermomechanical stability, including a high 5% weight loss temperature (>531 °C), char residue at 800 °C (>51%), and glass transition temperature (>300 °C). Full article

In this study, a series of amine-modified mesoporous silica (AMS)-based epoxy composites with superhydrophobic biomimetic structure surface of Xanthosoma sagittifolium leaves (XSLs) were prepared and applied as anti-corrosion and anti-biofilm coatings. Initially, the AMS was synthesized by the base-catalyzed sol–gel reaction of tetraethoxysilane (TEOS) and triethoxysilane (APTES) through a non-surfactant templating route. Subsequently, a series of AMS-based epoxy composites were prepared by performing the ring-opening polymerization of DGEBA with T-403 in the presence of AMS spheres, followed by characterization through FTIR, TEM, and CA. Furthermore, a nano-casting technique with polydimethylsiloxane (PDMS) as the soft template was utilized to transfer the surface pattern of natural XSLs to AMS-based epoxy composites, leading to the formation of AMS-based epoxy composites with biomimetic structure. From a hydrophilic CA of 69°, the surface of non-biomimetic epoxy significantly increased to 152° upon introducing XSL surface structure to the AMS-based epoxy composites. Based on the standard electrochemical anti-corrosion and anti-biofilm measurements, the superhydrophobic BEAMS3 composite was found to exhibit a remarkable anti-corrosion efficiency of ~99% and antimicrobial efficacy of 82% as compared to that of hydrophilic epoxy coatings. Full article