Effect of water glass treatment for zirconia and silane coupling on bond strength of resin cement.

OBJECTIVE: To evaluate the ability of the water glass treatment to penetrate zirconia and improve the bond strength of resin cement. MATERIAL AND METHODS: Water glass was applied to zirconia specimens, which were then sintered. The specimens were divided into water-glass-treated and untreated zirconia (control) groups. The surface properties of the water-glass-treated specimens were evaluated using surface roughness and electron probe micro-analyser (EPMA) analysis. A resin cement was used to evaluate the tensile bond strength, with2 and without a silane-containing primer. After 24 h in water storage at 37 °C and thermal cycling, the bond strengths were statistically evaluated with t-test, and the fracture surfaces were observed using SEM. RESULTS: The water glass treatment slightly increased the surface roughness of the zirconia specimens, and the EPMA analysis detected the water glass penetration to be 50 µm below the zirconia surface. The application of primer improved the tensile bond strength in all groups. After 24 h, the water-glass-treated zirconia exhibited a tensile strength of 24.8 ± 5.5 MPa, which was significantly higher than that of the control zirconia (17.6 ± 3.5 MPa) (p < 0.05). After thermal cycling, the water-glass-treated zirconia showed significantly higher tensile strength than the control zirconia. The fracture surface morphology was mainly an adhesive pattern, whereas resin cement residue was occasionally detected on the water-glass-treated zirconia surfaces. CONCLUSION: The water glass treatment resulted in the formation of a stable silica phase on the zirconia surface. This process enabled silane coupling to the zirconia and improved the adhesion of the resin cement.

Generalized Multifunctional Coating Strategies Based on Polyphenol-Amine-Inspired Chemistry and Layer-by-Layer Deposition for Blood Contact Catheters.

Blood-contacting catheters play a pivotal role in contemporary medical treatments, particularly in the management of cardiovascular diseases. However, these catheters exhibit inappropriate wettability and lack antimicrobial characteristics, which often lead to catheter-related infections and thrombosis. Therefore, there is an urgent need for blood contact catheters with antimicrobial and anticoagulant properties. In this study, we employed tannic acid (TA) and 3-aminopropyltriethoxysilane (APTES) to create a stable hydrophilic coating under mild conditions. Heparin (Hep) and poly(lysine) (PL) were then modified on the TA-APTES coating surface using the layer-by-layer (LBL) technique to create a superhydrophilic TA/APTES/(LBL)4 coating on silicone rubber (SR) catheters. Leveraging the superhydrophilic nature of this coating, it can be effectively applied to blood-contacting catheters to impart antibacterial, antiprotein adsorption, and anticoagulant properties. Due to Hep's anticoagulant attributes, the activated partial thromboplastin time and thrombin time tests conducted on SR/TA-APTES/(LBL)4 catheters revealed remarkable extensions of 276 and 103%, respectively, when compared to uncoated commercial SR catheters. Furthermore, the synergistic interaction between PL and TA serves to enhance the resistance of SR/TA-APTES/(LBL)4 catheters against bacterial adherence, reducing it by up to 99.9% compared to uncoated commercial SR catheters. Remarkably, the SR/TA-APTES/(LBL)4 catheter exhibits good biocompatibility with human umbilical vein endothelial cells in culture, positioning it as a promising solution to address the current challenges associated with blood-contact catheters.

Regulating molecular brush structure on cotton textiles for efficient antibacterial properties.

The molecular brush structures have been developed on cotton textiles for long-term and efficient broad-spectrum antimicrobial performances through the cooperation of alkyl-chain and quaternary ammonium sites. Results show that efficient antibacterial performances can be achieved by the regulation of the alkyl chain length and quaternary ammonium sites. The antibacterial efficiency of the optimized molecular brush structure of [3-(N,N-Dimethylamino)propyl]trimethoxysilane with cetyl modification on cotton textiles (CT-DM-16) can reach more than 99 % against both E. coli and S. aureus. Alkyl-chain grafting displayed significantly improvement in the antibacterial activity against S. aureus with (N,N-Diethyl-3-aminopropyl)trimethoxysilane modification on cotton textiles (CT-DE) based materials. The positive N sites and alkyl chains played important roles in the antibacterial process. Proteomic analysis reveals that the contributions of cytoskeleton and membrane-enclosed lumen in differentially expressed proteins have been increased for the S. aureus antibacterial process, confirming the promoted puncture capacity with alkyl-chain grafting. Theoretical calculations indicate that the positive charge of N sites can be enhanced through alkyl-chain grafting, and the possible distortion of the brush structure in application can further increase the positive charge of N sites. Uncovering the regulation mechanism is considered to be important guidance to develop novel and practical antibacterial materials.

A mixed-mode reversed-phase/strong-anion-exchange stationary phase: Analyte-retention stability and application in the analysis of nonsteroidal anti-inflammatory drugs.

Mixed-mode reversed-phase/anion-exchange chromatography (RP/AEX) is an effective method for the chromatographic analysis of acidic drugs because it combines reversed-phase chromatography (RP) with anion-exchange chromatography (AEX). However, the result repeatability for the RP/AEX analysis of acidic drugs is frequently compromised by the detrimental effects of residual silanol groups in an RP/AEX stationary phase on peak separation and analyte retention. In this study, an RP/weak-AEX stationary phase with amino anion-exchange groups, Sil-AA, was prepared. Subsequently, an RP/strong-AEX stationary phase, Sil-PBQA, was prepared by replacing the amino groups in Sil-AA with a benzene ring and a benzyl-containing quaternary ammonium salt. The chromatographic behaviors of Sil-PBQA and Sil-AA were compared, and the effect of residual silanol groups on the chromatographic behavior of an RP/AEX stationary phase was evaluated. Residual silanol groups not only caused additional electrostatic interactions for acidic analytes, but also competed with the analytes for the anion-exchange sites in an RP/AEX stationary phase. The effects of different salt-containing mobile-phase systems on the analyte-retention behavior of Sil-PBQA were investigated to develop a method that enhanced the repeatability of the RP/AEX acidic-analyte-analysis results obtained using Sil-PBQA and facilitated the separation of nonsteroidal anti-inflammatory drugs on Sil-PBQA. The ideas presented in this paper can improve the separation of peaks and repeatability of results in the RP/AEX analysis of acidic drugs.

Adjustable chromatographic performance of silica-based mixed-mode stationary phase through the control of co-grafting amounts of imidazole and C18 chain.

In this paper, three imidazole- and C18- bifunctional silica stationary phases (Sil-Im-C18) were prepared by adjusting introduction interval of octadecyltrichlorosilane (ODS) and 3-imidazol-1-ylpropyl(trimethoxy)silane (TMPImS), which can be used for reversed-phase liquid chromatography (RPLC) and ion exchange chromatography (IEC) with adjustable performance. The successful preparation of Sil-Im-C18 were confirmed by the characterizations of elemental analysis, infrared spectroscopy (FTIR) and contact angle (CA). Chromatographic performance of Sil-Im-C18 were evaluated by the separation of Tanaka test mixture, alkylbenzenes, linear PAHs and a set of analytes with different properties (uracil, phenol, 1,2-dinitrobenzene and naphthalene), and compared with commonly used C18 column. It was found that the chromatographic performance of Sil-Im-C18 changed significantly with the difference in bonding amount of imidazole and C18. Sil-Im-C18 demonstrated the excellent separation performance towards polycyclic aromatic hydrocarbons (PAHs), phenylesters, phenylamines, phenols and inorganic anions, and notably, nucleobases and nucleosides can be separated using pure water as mobile phases. The van Deemter plot showed that the column efficiency of Sil-Im-C18-3 was 64,933 plate·m-1 for naphthalene, indicated that Sil-Im-C18 was reasonably chromatographic columns. The RSD values of retention time were 0.22 %-0.61 % for 10 needles alkylbenzenes injected continuously at 50 °C to investigate thermal stability and repeatability, all the fluctuations of k of naphthalene were less than 2.3 % for Sil-Im-C18-1 during flushing 24 h with the mobile phase at different pH values (pH = 3 and 8), the retention time of alkylbenzenes were almost same for Sil-Im-C18-1 at different time, the RSD values of retention time of alkylbenzenes were 0.45 %-2.28 % for two batches Sil-Im-C18-1, revealing the excellent repeatability, thermal stability, durability and reproducibility of Sil-Im-C18, and implying a commercial prospect.

Development of Improved Spectrophotometric Assays for Biocatalytic Silyl Ether Hydrolysis.

Reported herein is the development of assays for the spectrophotometric quantification of biocatalytic silicon-oxygen bond hydrolysis. Central to these assays are a series of chromogenic substrates that release highly absorbing phenoxy anions upon cleavage of the sessile bond. These substrates were tested with silicatein, an enzyme from a marine sponge that is known to catalyse the hydrolysis and condensation of silyl ethers. It was found that, of the substrates tested, tert-butyldimethyl(2-methyl-4-nitrophenoxy)silane provided the best assay performance, as evidenced by the highest ratio of enzyme catalysed reaction rate compared with the background (uncatalysed) reaction. These substrates were also found to be suitable for detailed enzyme kinetics measurements, as demonstrated by their use to determine the Michaelis-Menten kinetic parameters for silicatein.

Promising Anticancer Prodrugs Based on Pt(IV) Complexes with Bis-organosilane Ligands in Axial Positions.

We report two novel prodrug Pt(IV) complexes with bis-organosilane ligands in axial positions: cis-dichloro(diamine)-trans-[3-(triethoxysilyl)propylcarbamate]platinum(IV) (Pt(IV)-biSi-1) and cis-dichloro(diisopropylamine)-trans-[3-(triethoxysilyl) propyl carbamate]platinum(IV) (Pt(IV)-biSi-2). Pt(IV)-biSi-2 demonstrated enhanced in vitro cytotoxicity against colon cancer cells (HCT 116 and HT-29) compared with cisplatin and Pt(IV)-biSi-1. Notably, Pt(IV)-biSi-2 exhibited higher cytotoxicity toward cancer cells and lower toxicity on nontumorigenic intestinal cells (HIEC6). In preclinical mouse models of colorectal cancer, Pt(IV)-biSi-2 outperformed cisplatin in reducing tumor growth at lower concentrations, with reduced side effects. Mechanistically, Pt(IV)-biSi-2 induced permanent DNA damage independent of p53 levels. DNA damage such as double-strand breaks marked by histone gH2Ax was permanent after treatment with Pt(IV)-biSi-2, in contrast to cisplatin's transient effects. Pt(IV)-biSi-2's faster reduction to Pt(II) species upon exposure to biological reductants supports its superior biological response. These findings unveil a novel strategy for designing Pt(IV) anticancer prodrugs with enhanced activity and specificity, offering therapeutic opportunities beyond conventional Pt drugs.

Surface treatments of the zirconia-reinforced lithium disilicate ceramic in the adhesion to the resin cement.

This study verified the effect of surface treatments of the zirconia-reinforced lithium disilicate ceramic bonded to resin cement. Ceramic blocks were divided according to treatments (n=10): FA+SRX (Fluoric acid + silane RX), FA+MDP (Fluoric acid + MDP), FA+SCF+MDP (Fluoric acid + silane CF + MDP), FA+MEP (Fluoric acid + MEP), and MEP (Self-etch primer). Resin cement cylinders were made in the ceramic blocks, photoactivated with 1,200 mW/cm² for 40s, stored in water at 37°C for 24h, and evaluated by the microshear strength test, optical failure descriptive analysis (%), surface characterization (SEM) and contact angle (Goniometer). Other samples were submitted to 10,000 thermocycles between 5°C and 55°C. Bond strength data were submitted to two-way ANOVA and Tukey's test. Contact angle to one-way ANOVA and Games-Howell's test (5%). At 24h, MEP showed higher bond strength, and FA+SRX the lower. FA+MDP and FA+SCF+MDP showed similar values and FA+MEP was intermediate. After thermocycling, FA+SCF+MDP, FA+MEP, and MEP showed higher values, and FA+SRX the lower while FA+MDP was intermediate. When the periods were compared, FA+MDP, FA+SCF+MDP, FA+MEP, and MEP showed higher values for 24h while FA+SRX was similar. SEM showed retentive surface and crystal exposure when treated with FA+SCF+MDP. The less retentive surface was obtained with MEP, and the other treatments promoted intermediate irregularities. In conclusion, surface treatment and thermocycling promoted different values of adhesive strength and contact angle in a zirconia-reinforced lithium silicate ceramic. Failures were predominantly adhesive, and the ceramic surface was characterized by different levels of roughness and selective exposure of crystals.

Preheated acid associated with silane and electric current in the adhesion of the resin cement to ceramic.

This study verified the effect of the combination of preheated hydrofluoric acid/silane/electric current in the adhesion of the resin cement to ceramic. IPS E.max Press ceramic discs embedded in PVC rigid tubes were divided into four groups associating preheated hydrofluoric acid and silane applied with electrical current (n=10): Ha+S (Heated acid + silane); Ha+S+Ec (Heated acid + silane + electrical current); A+S (Acid + silane) and A+S+Ec (Acid + silano + electrical current). Resin cement/ceramic samples were stored in water at 37°C for 24h. After storage, they were submitted to the microshear test, fracture analysis, and contact angle at 24h or after thermocycling (10,000 cycles/5-55ºC). Bond strength data were evaluated by two-way ANOVA. For comparison between evaluation times (24h or thermocycling) was applied unpaired t-test. A significance post-hoc test of p=0.05 was assumed for analyses and graphs (GraphPad Prism 9.0 software). At 24h, the microshear strength showed similar values between Ha+S, Ha+S+Ec, and A+S+Ec groups, while A+S showed the lowest value with a statistical difference. After thermocycling, Ha+S and Ha+S+Ec were similar, as well as A+S and A+S+Ec. There was a significant difference in all groups comparing 24h (highest value) with after thermocycling (lowest value). Adhesive fracture was predominant in all groups and evaluation times. Ha+S and A+S groups showed higher contact angle values compared to the Ha+S+Ec and A+S+Ec with lower values. In conclusion, the association of preheated hydrofluoric acid/silane applied or not with electric current promoted different microshear strength values, fracture types, and contact angles in the resin cement/ceramic bond.

Enhanced BSA Detection Precision: Leveraging High-Performance Dual-Gate Ion-Sensitive Field-Effect-Transistor Scheme and Surface-Treated Sensing Membranes.

Bovine serum albumin (BSA) is commonly incorporated in vaccines to improve stability. However, owing to potential allergic reactions in humans, the World Health Organization (WHO) mandates strict adherence to a BSA limit (≤50 ng/vaccine). BSA detection with conventional techniques is time-consuming and requires specialized equipment. Efficient alternatives such as the ion-sensitive field-effect transistor (ISFET), despite rapid detection, affordability, and portability, do not detect BSA at low concentrations because of inherent sensitivity limitations. This study proposes a silicon-on-insulator (SOI) substrate-based dual-gate (DG) ISFET platform to overcome these limitations. The capacitive coupling DG structure significantly enhances sensitivity without requiring external circuits, owing to its inherent amplification effect. The extended-gate (EG) structure separates the transducer unit for electrical signal processing from the sensing unit for biological detection, preventing chemical damage to the transducer, accommodating a variety of biological analytes, and affording easy replaceability. Vapor-phase surface treatment with (3-Aminopropyl) triethoxysilane (APTES) and the incorporation of a SnO2 sensing membrane ensure high BSA detection efficiency and sensitivity (144.19 mV/log [BSA]). This DG-FET-based biosensor possesses a simple structure and detects BSA at low concentrations rapidly. Envisioned as an effective on-site diagnostic tool for various analytes including BSA, this platform addresses prior limitations in biosensing and shows promise for practical applications.

Towards high performance wood composites through interface customization with cellulose-based adhesive.

How to efficiently produce high performance plywood is of particular interest, while its sensitivity to moisture is overcome. This paper presents a simple and scalable strategy for the preparation of high-performance plywood based on the chemical bonding theory; a wood interfacial functionalized platform (WIFP) based on (3-aminopropyl) triethoxysilane (APTES) was established. Interestingly, the APTES-enhanced dialdehyde cellulose-based adhesive (DAC-APTES) was able to effectively establish chemically active adhesive interfaces; the dry/wet shear strength of WIFP/DAC-APTES adhesive was 3.15/1.31 MPa, which was much higher than 0.7 MPa (GB/T 9846-2015). The prepared plywood showed excellent wood-polymer interface adhesion, which exceeded the force that the wood itself could withstand. In addition, the DAC-APTES adhesive exhibits moisture evaporation-induced curing behavior at room temperature and can easily support the weight of an adult weighing 65.7 Kg. This research provides a novel approach for functionalized interface design of wood products, an effective means to prepare high-performance plywood.

Iridium(III) complexes decorated with silicane-modified rhodamine: near-infrared light-initiated photosensitizers for efficient deep-tissue penetration photodynamic therapy.

Meeting the demand for efficient photosensitizers in photodynamic therapy (PDT), a series of iridium(III) complexes decorated with silicane-modified rhodamine (Si-rhodamine) was meticulously designed and synthesized. These complexes demonstrate exceptional PDT potential owing to their strong absorption in the near-infrared (NIR) spectrum, particularly responsive to 808 nm laser stimulation. This feature is pivotal, enabling deep-penetration laser excitation and overcoming depth-related challenges in clinical PDT applications. The molecular structures of these complexes allow for reliable tuning of singlet oxygen generation with NIR excitation, through modification of the cyclometalating ligand. Notably, one of the complexes (4) exhibits a remarkable ROS quantum yield of 0.69. In vivo results underscore the efficacy of 4, showcasing significant tumor regression at depths of up to 8.4 mm. This study introduces a promising paradigm for designing photosensitizers capable of harnessing NIR light effectively for deep PDT applications.

Molecular mechanism of action of imidazolium carbosilane dendrimers on the outer bacterial membrane - From membrane damage to permeability to antimicrobial endolysin.

The outer bacterial membrane of drug-resistant bacteria is a significant barrier to many antimicrobials. Therefore, the development of new antibacterials primarily focuses on damaging the outer bacterial membrane of Gram-negative bacteria. Among many membrane-disrupting substances, the most promising are cationic dendritic systems. However, the mode of action may vary among different strains due to variations in the lipid compositions of the membrane. Here, we investigated the interaction of two types of cationic imidazolium carbosilane dendrimers: one with a single cationic group (methyl imidazolium) and the other with the same cationic group but attached to a functional group (a pendant pyridyl moiety), capable of establishing interactions with membranes through H-bonding or ion-dipole electrostatic interactions. We used different models of the outer membrane of Gram-negative bacteria - Escherichia coli, Pseudomonas aeruginosa, and Acinetobacter baumannii. Additionally, we assessed the combined effect of the dendrimers and the antibacterial endolysin on P. aeruginosa. Our results show that the mechanism of action depends on the type of dendrimer and the lipid composition of the membrane. We also demonstrate that the alteration of membrane fluidity and permeability to endolysin by the methyl imidazolium and pyridyl imidazolium dendrimers may play a more significant role in antimicrobial activity compared to membrane damage caused by positively charged dendrimers.

How the repair bonding strength of hybrid ceramic CAD/CAM blocks is influenced by the use of surface treatments and universal adhesives.

We examined how different methods of surface treatment and different universal adhesives with or without extra silane affected the repair bonding strength of hybrid ceramic CAD/CAM restorations. Cerasmart specimens (n=320) were subjected to thermocycling and assigned to the following surface pretreatment protocols: control, diamond bur (DB), hydrofluoric acid (HF), and tribochemical silica coating (TSC). Half the specimens received a coating of silane, followed by application of the universal adhesives Futurabond M+ (FMU), Tokuyama Universal Bond (TUB), Single Bond Universal (SBU), or Clearfil Universal Bond Quick (CUQ) (n=10). A hybrid composite resin was used to simulate repair; then the specimens underwent further thermocycling. Shear bond strength (SBS) was determined and modes of failure were examined. The TSC-CUQ silane (-) group showed the highest SBS values. The best repairs were obtained when the surface was treated with TSC, with the exception of the DB-TUB silane (-) group. TUB increased SBS more than the other adhesives. Additional silane decreased SBS in the HF-TUB and TSC-CUQ groups, while increasing it in the TSC-TUB and DB-FMU groups (p<0.05).

A new class of polyphenolic carbosilane dendrimers binds human serum albumin in a structure-dependent fashion.

The use of dendrimers as drug and nucleic acid delivery systems requires knowledge of their interactions with objects on their way to the target. In the present work, we investigated the interaction of a new class of carbosilane dendrimers functionalized with polyphenolic and caffeic acid residues with human serum albumin, which is the most abundant blood protein. The addition of dendrimers to albumin solution decreased the zeta potential of albumin/dendrimer complexes as compared to free albumin, increased density of the fibrillary form of albumin, shifted fluorescence spectrum towards longer wavelengths, induced quenching of tryptophan fluorescence, and decreased ellipticity of circular dichroism resulting from a reduction in the albumin α-helix for random coil structural form. Isothermal titration calorimetry showed that, on average, one molecule of albumin was bound by 6-10 molecules of dendrimers. The zeta size confirmed the binding of the dendrimers to albumin. The interaction of dendrimers and albumin depended on the number of caffeic acid residues and polyethylene glycol modifications in the dendrimer structure. In conclusion, carbosilane polyphenolic dendrimers interact with human albumin changing its structure and electrical properties. However, the consequences of such interaction for the efficacy and side effects of these dendrimers as drug/nucleic acid delivery system requires further research.

Modified mesoporous silica derived from bamboo leaf using cetyltrimethylammonium bromide and 3-aminopropyl triethoxysilane as CO2 adsorbent in biogas purification.

The calorific value of post-fermentation biogas is a way down below standard and quite low due to the presence of high amount level of carbon dioxide (CO2) biogas mixture. Therefore, it raises the need to process the biogas, separating it from CO2 in order to obtain high-purity biogas as well as to maximize its calorific value. One widely available material that can be used as a sustainable carbon capture adsorbent is silica extracted from bamboo leaves. However, so that silica can act as CO2 adsorber, it is necessary to modify the surface of silica with CTAB and APTES (3-aminopropyl triethoxysilane). In this study, 2-stage method was carried out, namely preparation of mesoporous silica and surface modification using APTES on the mesoporous silica. Experiments in synthesizing APTES-modified silica were obtained by varying its composition: CTAB (1.5-5%w), (HCl 1.5-5 N), and APTES (10-30%). A central composite design (CCD) was employed in exploring the interaction between all variables and also performed for the optimization. Through analysis of variance, it shows that optimum CO2 adsorption capacity reaches 47.02 mg g-1, by applying 4.98% of CTAB, 4.28 N of HCl and 10.08% of APTES. Pseudo-second-order kinetic and Redlich-Peterson isotherm models are more representative to show the adsorption behavior of CO2 into the modified silica. The results show that the modified silica with APTES shows a prospective application of silica for CO2 removal from biogas.

A non-residue surface modification strategy for active-targeting fluorescent silica nanoparticles to cellular organelles.

Silica nanoparticles (SiNPs) with a chemically modified surface typically have a complicated chemical composition, which can significantly differ from their intended design. In this study, we systematically studied the effects of two surface modification methods on active-targeting of intracellular organelles of SiNPs: (1) the widely used step-by-step approach, which involves modifying SiNPs in two steps, i.e., the outer surface of SiNPs was firstly modified with amino groups and then these amino groups were linked with targeting groups, and (2) a newly developed one-step approach in which the ligand-silane complex is initially synthesized, followed by chemically immobilizing the complex on the surface of SiNPs. In the one-step approach, the molar ratio of reactants was precisely tuned so that there are no reactive groups left on the outer surface of SiNPs. Two essential organelles, mitochondria and the nucleus, were selected to compare the targeting performances of SiNPs synthesized via these two approaches. By characterizing physicochemical properties, including structural properties, the number of amino groups, surface charge, polydispersity, and cell colocalization, we demonstrated that SiNPs synthesized via the one-step approach with no residual linkage groups on their surface showed significantly improved mitochondria- and nucleus-targeting performances. This precise control of surface properties allows for optimized biological behavior and active-targeting efficiency of SiNPs. We anticipate that such simple and efficient synthetic strategies will enable the synthesis of effective SiNPs for active-targeting organelles in various biological applications.

Effects of combined modification of sulfonation, oxygen plasma and silane on the bond strength of PEEK to resin.

OBJECTIVE: This study aimed to evaluate the combined effects of sulfonation, non-thermal oxygen plasma and silane on the shear bond strength (SBS) of PEEK to resin materials. MATERIALS AND METHODS: Two hundred and eighty specimens were randomly divided into four groups: (A) untreated; (B) sulfonation for 60 s; (C) oxygen plasma for 20 min; (D) sulfonation for 60 s and oxygen plasma for 20 min. According to the instructions, 120 samples (N = 30) were coated with silane, adhesive, and resin composites. Each group of bonding specimens was divided into two subgroups (n = 15) to measure immediate and post-aging SBS. The surface morphology and the interface between the samples and adhesive were analyzed through SEM. Physicochemical characteristics of the surface and mechanical properties were determined through XPS, FTIR, light interferometry, contact angle measurement, and three-point bending tests. RESULTS: Sulfonation produced a porous layer of approximately 20 µm thickness on the surface, and the oxygen plasma increased the O/C ratio and oxygen-containing groups of the sample surface. After coating with silane, the SBS values of sulfonated PEEK and plasma-treated PEEK increased (9.96 and 10.72 MPa, respectively), and dual-modified PEEK exhibited the highest SBS value (20.99 MPa), which was significantly higher than that of blank group (p > 0.01). After 10,000 thermal cycles, the dual-modified PEEK still displayed a favorable SBS (18.68 MPa). SIGNIFICANCE: Sulfonation strengthened the mechanical interlocking between PEEK and the resin while oxygen plasma established a chemical bonding between silane and PEEK. This dual modification of the surface microstructure and chemical state synergistically improved the bond strength of PEEK to resin and resulted in considerable long-term effects.

Assessment of flusilazole residues on apples: Detection, quantification and health risk implications.

Apple, a major fruit of temperate Himalayas, is sprayed with chemical pesticides around 12 times during the cropping season. Various systemic and contact fungicides are applied for the management of major diseases. In order to manage disease, flusilazole 40 EC is frequently used. However, excessive chemical application has been found to be detrimental for consumer safety. Keeping in view consumer safety, risk assessment, the half-life and waiting period for flusilazole 40 EC were evaluated on the Red Velox variety of apple. The QuEChERS (quick, easy, cheap, effective, rugged and safe) method and high-performance liquid chromatography were adapted for sample processing and analysis, respectively. The recovery percentages of flusilazole at three fortification levels (0.04, 0.09 and 0.50 mg kg-1) were 98.85, 99.83 and 98.98%, respectively. Flusilazole at the recommended dose (80 g a.i. ha-1) left an initial deposit of 0.733 mg kg-1, which dissipated by 93.45% in 60 days and was non-detectable beyond this period. Meanwhile flusilazole at double the recommended dose (160 g a.i. ha-1) left an initial deposit of 0.913 mg kg-1, which dissipated by 93.43% in 70 days and was non-detectable beyond this period. Based on the maximum residue limit of 0.3 mg kg-1 as prescribed by the Codex Alimentarius Commission, a waiting period of 28.74 and 46.03 days was recorded for single and double doses, respectively. Moreover, in order to assess the consumer risk, theoretical maximum residue contributions (TMRCs) were derived using flusilazole residues (average and maximum) recorded at various time intervals and compared with the maximum permissible intake, which was found to be 0.42 mg per person per day. Based on the average per capita daily consumption of 6.76 g apple in India, the TMRC values were computed. Although the values of TMRC decreased below maximum permissible intake at the first day after application, indicating minimal consumer health risks, fruits sprayed with a double dose of flusilazole carried the risk even up to the tenth day after flusilazole application. The results of the present study will be valuable for safe and timely use of flusilazole on apple.