Search Results (256)

Lipopolysaccharides (LPSs) are key components of the bacterial outer envelope, determining its structural integrity, barrier properties, and interactions with the surrounding environment. This review analyzes the relationship between the molecular architecture of LPSs and their physicochemical properties. Particular attention is being paid to the organization of LPS-containing supramolecular assemblies, including bacterial outer membranes, bilayers, micelles, and LPS brushes. The review further focuses on theoretical frameworks employed to describe LPS layers and discusses the physical meaning of the parameters involved in these models. The simulations involve a wide range of approaches starting from all-atom molecular treatment and up to polymer and colloidal approaches. When considering these models, we focus on the relationships between parameters that are addressed at each level of modeling. It is shown that biological functions such as membrane stability and bacterial adhesion are largely governed by the molecular organization of LPS. This structure–property relationship provides a basis for predicting the performance of anti-adhesive biomaterials, antimicrobial strategies, and bactericidal agents. Full article

The shear behavior of basalt fiber-reinforced polymer (BFRP) bars is crucial for their applications in geotechnical reinforcement and composite structures. In this study, double-side direct shear tests were conducted to investigate the progressive failure mechanism of BFRP bars. The results reveal a three-stage process: initial matrix-dominated vertical shear, followed by fiber-bridging dominated oblique tension-shear, and finally formation of a “brush-like” fracture surface with significant residual strength. The average peak shear strength of the ten specimens was 204.04 MPa with a coefficient of variation of 7.25%, while the initial shear modulus averaged 3.37 GPa with a coefficient of variation of 11.82%. Based on statistical damage theory, a shear constitutive model incorporating fiber bridging and residual strength is established. Parameter analysis indicates that the shape parameter m governs the post-peak softening rate, while the residual strength τ_res essentially determines the height of the residual plateau. The model achieves a goodness-of-fit (R²) exceeding 0.98 for most specimens, accurately describing the mechanical behavior from linear elasticity, damage-induced hardening, peak softening, to the residual stage. This study provides theoretical and experimental support for the engineering application of BFRP bars under complex stress states. Full article

The interface between synthetic materials and biological systems is a critical determinant of performance in medical devices and biosensors. This review examines the evolution of biointerface science through the lens of self-assembled monolayers (SAMs) of thiols on gold, a model system that offers atomic-level control over surface chemistry. We trace the field from the foundational structural characterization to the establishment of empirical design rules for bio-inertness. While early theoretical models attributed protein resistance to steric repulsion forces in polymer brushes, contemporary understanding has shifted toward the “water barrier” hypothesis, which posits that tightly bound interfacial water prevents direct biomolecular contact. We highlight recent studies that extend these concepts into “realistic” crowded biological environments. Their work reveals that fouling surfaces in crowded media generate a “viscous interphase layer” (VIL) that extends tens of nanometers into solution, whereas zwitterionic surfaces maintain a robust hydration shell that prevents this accumulation. Furthermore, this hydration barrier is shown to fundamentally alter bacterial mechanics, forcing microorganisms into a reversible, tethered “hovering” state at a significant biological interaction distance (>100 nm) from the surface, effectively precluding biofilm nucleation. These insights underscore that the future of antifouling material design lies in the precise engineering of interfacial hydration structures. Full article

Ultra-soft injectable hydrogels are paramount in biomedical applications such as tissue fillers, drug depots, and tissue regeneration scaffolds. Synthetic approaches relying on linear polymers are confronted by the necessity for significant dilution of polymer solutions to reduce chain entanglements. Bottlebrush polymers offer an alternative approach due to suppressed chain overlap and entanglements, which facilitates lower solution viscosities and increased gel softness. Leveraging the bottlebrush architecture in linear-bottlebrush-linear (LBL) block copolymer systems, where L is a thermosensitive linear poly(N-isopropylacrylamide) block, and B is a hydrophilic polyethylene glycol brush block, injectable hydrogels were designed to mimic tissues as soft as the extracellular matrix at high polymer concentrations. Compared to an analogous system with shorter brush side chains, increasing the side chain length enables a decrease in modulus by up to two orders of magnitude within 1–100 Pa at 20 wt% polymer concentrations, near to the physiological water content of ~70%. This system further exhibits thermal hysteresis, enabling stability with inherent body temperature fluctuations. The observed features are ascribed to kinetically hindered network formation by bulky macromolecules. Full article

Bottle-brush polymers with aggrecan-like side chains represent a class of biomimetic macromolecules that replicate key structural and functional features of natural complexes of aggrecans with hyaluronic acid (HA) which are the major components of articular cartilage. In this study, we employ numerical self-consistent field (SCF) modeling combined with analytical theory to investigate the conformational properties of cylindrical molecular bottle-brushes composed of aggrecan-like double-comb side chains tethered to the main chain (the backbone of the bottle-brush). We demonstrate that the architecture of the brush-forming double-comb chains and, in particular, the distribution of polymer mass between the root and peripheral domains significantly influences the spatial distribution of primary side chain ends, leading to formation of a “dead” zone near the backbone of the bottle-brush and non-uniform density profiles. The axial stretching force imposed by grafted double-combs in the main chain, as well as normal force acting at the junction point between the bottle-brush backbone and the double-comb side chain are shown to depend strongly on the side-chain architecture. Furthermore, we analyze the induced bending rigidity and persistence length of the bottle-brush, revealing that while the overall scaling behavior follows established power laws, the internal structure can be finely tuned without altering the backbone stiffness. These theoretical findings provide valuable insights into relations between architecture and properties of bottle-brush-like supra-biomolecular structures, such as aggrecan-hyaluronan complexes. Full article

Newly developed hygrosensitive poly(vinyl alcohol) derivatives comprising grafted poly(N,N-dimethylacrylamide) chains of varied length and graft density are presented. The optical, sensing, and hydration properties of these copolymer thin films prepared by spin-coating were systematically studied. Refractive indices (n), absorption coefficients (k), and thicknesses (d) were calculated via curve fitting of the reflection spectra. Reflectance measurements across a relative humidity range of 5% to 95% were used to evaluate the humidity sensing behavior. Coating swelling exceeding 100% was observed. Hydration levels under high humidity conditions were studied using a quartz crystal microbalance method. This revealed approximately 24% water content in the polymer with the higher grafting density and shorter PDMA chains compared to around 31% in the copolymer with longer PDMA brushes that were loosely grafted The potential application of these copolymers as responsive materials for advanced humidity sensing is discussed. A combined optical and gravimetric approach for characterizing the humidity sensing properties of thin nanosized coatings is demonstrated, providing opportunities for advanced characterization of new functional materials, thus broadly contributing to the state of the art of sensor technologies. Full article

Background: The aesthetic performance of single-shade polymer-based restorative materials (SPRs) can be compromised by extrinsic stains. Understanding the effects of novel whitening interventions on SPRs is crucial. Objective: This in vitro study aimed to evaluate the effects of different whitening interventions, including a novel purple tooth serum and charcoal-based whitening toothpaste with and without in-office bleaching, on the color of a new coffee-stained SPR. Materials and Methods: Seventy disc-shaped SPR specimens were prepared, stained, and then divided into seven groups (n = 10). Three groups were subjected directly to 2500 cycles of brushing simulation with regular toothpaste (control), charcoal toothpaste, or purple tooth serum. The rest were divided into bleaching groups, and the four groups underwent a simulation of bleaching and then brushing with the three products. The color parameters were recorded at the stained baseline, after brushing, after bleaching, and after post-bleaching brushing. The color change (ΔE00) was calculated, and the data were analyzed statistically using the Kruskal–Wallis test and Dunn–Bonferroni pairwise comparisons (p < 0.05). Results: In-office bleaching without brushing had a statistically significantly higher ΔE00 value than all other groups (p < 0.001). Post hoc tests indicated that the ΔE00 values of the brushed specimens were not significantly different from each other when assessed with and without bleaching (p > 0.05). When using the charcoal toothpaste, the post-bleaching brushed specimens had a noticeable color change above the PT. Conclusions: Bleaching improved the stained SPR color initially, but other treatments may offer longer-lasting aesthetics. The charcoal toothpaste showed promising results when combined with bleaching. The purple serum showed limited effectiveness. Full article

The present work analyzes the combined viscoelectric and steric effects on electroosmotic flow in a soft channel with polyelectrolyte coating. The structured channel surface, which controls the electric potential, creates two different flow regions: the electrolyte flow within the permeable polyelectrolyte layer (PEL) and the bulk electrolyte. Thus, this study discusses the interaction of various electrostatic effects to predict the electroosmotic flow field. The nonlinear governing equations describing the fluid flow are the modified Poisson–Boltzmann equation for the electric potential distribution, the mass conservation equation, and the modified Navier–Stokes equations for the flow field, which are solved numerically using a one-dimensional (1D) scheme. The results indicate that the flow enhances when increasing the electric potential magnitude across the channel cross-section via the rise in different dimensionless parameters, such as the PEL thickness, the steric factor, and the ratio of the electrokinetic parameter of the PEL to that of the electrolyte layer. This research demonstrates that the PEL significantly enhances control over electroosmotic flow. However, it is crucial to consider that viscoelectric effects at high electric fields and the friction generated by the grafted polymer brushes of the PEL can reduce these benefits. Full article

Molecular-mimetic nanocolloids (MMNCs) are promising for advanced materials, yet self-assembly fabrication faces challenges in purity and programmability. We report a total synthesis strategy for surfactant-mimetic nanocolloids (SMNCs), an amphiphilic MMNC subclass. SMNCs consist of a ~5 nm silica nanoparticle head and a bottlebrush polymer tail. Regioselective silica deposition on linear-block-brush polymers via the modified sol–gel method enables precise control. This strategy is versatile and can be adapted to synthesize other MMNCs with different components. It offers a more controlled alternative to self-assembly methods, advancing MMNC synthesis and enabling their broader use in emerging technologies. Full article

Titanium is widely recognized as an interesting material for electrodes due to its excellent corrosion resistance, mechanical strength, and biocompatibility. However, further functionalization is often necessary to impart advanced interfacial properties, such as selective ion transport or stimuli responsiveness. In this context, the integration of smart polymers, such as poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)—noted for its dual pH- and thermo-responsive behavior—has emerged as a promising approach to tailor surface properties for next-generation devices. This work compares two covalent immobilization strategies for PDMAEMA on titanium: the “graft-to” method, involving the attachment of pre-synthesized polymer chains, and the “graft-from” method, based on surface-initiated polymerization. The resulting materials were characterized with size exclusion chromatography (SEC) for molecular weight, Fourier-transform infrared spectroscopy (FTIR) for chemical structure, scanning electron microscopy (SEM) for surface morphology, and contact angle measurements for wettability. Electrochemical impedance spectroscopy and polarization studies were used to assess electrochemical performance. Both strategies yielded uniform and stable coatings, with the mode of grafting influencing both surface morphology and functional stability. These findings provide valuable insights into the development of adaptive, stimuli-responsive titanium-based interfaces in advanced electrochemical systems. Full article

The development of sustainable and functional nanocomposites has attracted considerable attention in recent years due to their broad spectrum of potential applications, including wood preservation. Also, a global goal is to reuse the large volumes of waste for environmental issues. In this context, the aim of the study was to obtain soda lignin particles, to graft ZnO nanoparticles onto their surface and to apply these hybrids, embedded into a biodegradable polymer matrix, as protection/preservation coating for oak wood. The organic–inorganic hybrids were characterized in terms of compositional, structural, thermal, and morphological properties that confirm the efficacy of soda lignin extraction and ZnO grafting by physical adsorption onto the decorating support and by weak interactions and coordination bonding between the components. The developed solution based on poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and lignin-ZnO was applied to oak wood specimens by brushing, and the improvement in hydrophobicity (evaluated by water absorption that decreased by 48.8% more than wood, humidity tests where the treated sample had a humidity of 4.734% in comparison with 34.911% for control, and contact angle of 97.8° vs. 80.5° for untreated wood) and UV and fungal attack protection, while maintaining the color and aspect of specimens, was sustained. L.ZnO are well dispersed into the polymer matrix, ensuring a smooth and less porous wood surface. According to the results, the obtained wood coating using both a biodegradable polymeric matrix and a waste-based preservative can be applied for protection against weathering degradation factors, with limited water uptake and swelling of the wood, UV shielding, reduced wood discoloration and photo-degradation, effective protection against fungi, and esthetic quality. Full article

Polysodiumoxy(methyl)siloxane is a highly functional polymer matrix that can be used for the preparation of both functional and non-functional polymers, including molecular brushes. To determine the molecular weight parameters of the matrix, as well as its chemical structure, it is necessary to develop an effective method of blocking functional (in our case, sodiumoxy) groups due to their high reactivity. At the same time, the blocking product should represent a complete non-functionalized replica of polysodiumoxy(methyl)siloxane. Since the obtained polysodiumoxy(methyl)siloxane can contain both sodium- and hydroxy groups in its composition, the presence of both types of functional groups should be considered in the blocking process. In this work, we investigated the blocking process of polysodiumoxy(methyl)siloxane and the influence of blocking conditions on the blocked product. We carried out several variants of blocking, which differed in the order and method of introduction of reagents, as well as in the temperature regime. The chemical structure and molecular weight characteristics of the obtained polymers were analyzed by ¹H NMR spectroscopy and gel permeation chromatography (GPC), respectively. According to the blocking results, only in one case, complete non-functionalized replicas of polysodiumoxy(methyl)siloxane were obtained, which allows this technique to be used as a tool for the analysis of complex, highly functionalized organosilicon systems. Full article

Polymer brushes (PBs) are transformative surface-modifying nanostructures, yet their synthesis via controlled methods like copper-mediated surface-initiated atom-transfer radical polymerization (Cu⁰-SI-ATRP) faces reproducibility challenges due to a lack of understanding of parameter interdependencies. This study systematically evaluates the Cu⁰-SI-ATRP process for polyacrylamide brushes (PAM-PBs), aiming to clarify key parameters that influence the synthesis process. This evaluation followed a step-by-step characterization that tracked molecular changes through infrared spectroscopy (IR) and surface development by contact angle (CA) through two different mixing methods: ultrasonic mixing and process simplification (Method A) and following literature-based parameters (Method B). Both methods, consisting of surface activation, 3-aminopropyltriethoxysilane (APTES) deposition, bromoisobutyryl bromide (BiBB) anchoring, and polymerization, were analyzed by varying parameters like concentration, temperature, and time. Results showed ultrasonication during surface activation enhanced siloxane (1139→1115 cm⁻¹) and amine (1531 cm⁻¹) group availability while reducing APTES concentration to 1 Vol% without drying sufficed for BiBB anchoring. BiBB exhibited insensitivity to concentration but benefited from premixing, evidenced by sharp C–Br (~1170 cm⁻¹) and methyl (3000–2800 cm⁻¹) bands. Additionally, it was observed that PAM-PBs improved with Method A, which had reduced variance in polymer fingerprint regions compared to Method B. Adding to the above, CA measurements gave complementary step-by-step information along the modifications of the surface, revealing distinct wettability behaviors between bulk PAM and synthesized PAM-PBs (from 51° to 37°). As such, this work identifies key parameter influence (e.g., mixing, BiBB concentration), simplifies steps (drying omission, lower APTES concentration), and demonstrates a step-by-step, systematic parameter decoupling that reduces variability. In essence, this detailed parameter analysis addresses the PAM-PBs synthesis process with better reproducibility than the previously reported synthesis method and achieves the identification of characteristic behaviors across the step-by-step process without the imperative need for higher-cost characterizations. Full article

Protein phosphorylation is one of the most common and important post-translational modifications (PTMs) and is highly involved in various biological processes. Ideal adsorbents with high sensitivity and specificity toward phosphopeptides with large coverage are therefore essential for enrichment and mass spectroscopy-based phosphoproteomics analysis. In this study, a newly designed IMAC adsorbent composite was constructed on the graphene matrix coated with mesoporous silica. The outer functional 3D-network layer was prepared by free radical polymerization of the phosphonate-functionalized vinyl imidazolium salt monomer and subsequent metal immobilization. Due to its unique structural feature and high content of Ti⁴⁺ ions, the resulting phosphonate-immobilized adsorbent composite G@mSiO₂@PPFIL-Ti⁴⁺ exhibits excellent performance in phosphopeptide enrichment with a low detection limit (0.1 fmol, tryptic β-casein digest) and superior selectivity (molar ratio of 1:15,000, digest mixture of β-casein and bovine serum albumin). G@mSiO₂@PPFIL-Ti⁴⁺ displays high tolerance to loading and elution conditions and thus can be reused without a marked decrease in enrichment efficacy. The captured phosphopeptides can be released globally, and mono-/multi-phosphopeptides can be isolated stepwise by gradient elution. When applying this material to enrich phosphopeptides from human lung cell lysates, a total of 3268 unique phosphopeptides were identified, corresponding to 1293 phosphoproteins. Furthermore, 2698 phosphorylated peptides were found to be differentially expressed (p < 0.05) between human lung adenocarcinoma cells (SPC-A1) and human normal epithelial cells (Beas-2B), of which 1592 were upregulated and 1106 were downregulated in the cancer group. These results demonstrate the material’s superior enrichment efficiency in complex biological samples. Full article

With the rapid advancement of electronic devices toward higher frequencies, faster speeds, increased integration, and miniaturization, the resulting elevated operating temperatures pose significant challenges to the performance and longevity of electronic components. These developments have intensified the demand for high-performance thermal interface materials (TIMs). Conventional silicone rubber-based TIMs often suffer from silicone oil-bleeding and the volatilization of low-molecular-weight siloxanes under elevated temperatures and mechanical stress. The release of these volatile organic compounds can lead to their deposition on circuit boards and electronic components, causing signal interference or distortion in optical and electronic systems, ultimately compromising device functionality. Additionally, the intrinsic thermal conductivity of traditional TIMs is insufficient to meet the escalating demands for efficient heat dissipation. To overcome these limitations, this study introduces a novel, non-silicone TIM based on a calcium ion-crosslinked sodium alginate matrix, prepared via ion-exchange curing. This bio-derived polymer matrix serves as an environmentally benign alternative to silicone rubber. Furthermore, a brush-coating technique is employed to induce the oriented alignment of boron nitride (BN) fillers within the alginate matrix. Experimental characterization reveals that this aligned microstructure markedly enhances the thermal conductivity of the composite, achieving a value of 7.87 W·m⁻¹·K⁻¹. The resulting material also exhibits outstanding thermal and mechanical stability, with no observable leakage or condensate formation under high-temperature and high-pressure conditions. This work offers a new design paradigm for environmentally friendly, high-performance TIMs with considerable potential for advanced electronic and optoelectronic applications. Full article