Nanotribological Investigation of Polymer Brushes with Lithographically Defined and Systematically Varying Grafting Densities.

Following controlled photodeprotection of a 2-nitrophenylpropyloxycarbonyl-protected (aminopropyl)triethoxysilane (NPPOC-APTES) film and subsequent derivatization with a bromoester-based initiator, poly(2-(methacryloyloxy)ethylphosphorylcholine) (PMPC) brushes with various grafting densities were grown from planar silicon substrates using atom transfer radical polymerization (ATRP). The grafting density correlated closely with the extent of deprotection of the NPPOC-APTES. The coefficient of friction for such PMPC brushes was measured by friction force microscopy in water and found to be inversely proportional to the grafting density due to the osmotic pressure that resists deformation. Deprotection of NPPOC-APTES via near-field photolithography using a range of writing rates enabled the fabrication of neighboring nanoscopic polymeric structures with dimensions ranging from 100 to 1000 nm. Slow writing rates enable complete deprotection to occur; hence, polymer brushes are formed with comparable thicknesses to macroscopic brushes grown under the same conditions. However, the extent of deprotection is reduced at higher writing rates, resulting in the concomitant reduction of the brush thickness. The coefficient of friction for such polymer brushes varied smoothly with brush height, with lower coefficients being obtained at slower writing rate (increasing initiator density) because the solvated brush layer confers greater lubricity. However, when ultrasharp probes were used for nanotribological measurements, the coefficient of friction increased with brush thickness. Under such conditions, the radius of curvature of the tip is comparable to the mean spacing between brush chains, allowing the probe to penetrate the brush layer leading to a relatively large contact area

Nanotribological properties of nanostructured poly(cysteine methacrylate) brushes

The nanomechanical properties of zwitterionic poly(cysteine methacrylate) (PCysMA) brushes grown from planar surfaces by atom transfer radical polymerisation have been characterised by friction force microscopy (FFM). FFM provides quantitative insights into polymer structure–property relationships and in particular illuminates the dependence of brush swelling on chain packing in nanostructured materials. In ethanol, which is a poor solvent for PCysMA, a linear friction–load relationship is observed, indicating that energy dissipation occurs primarily through ploughing. In contrast, in a good solvent for PCysMA such as water, a non-linear friction–load relationship is observed that can be fitted by Derjaguin–Muller–Toporov (DMT) mechanics, suggesting that the relatively small modulus of the swollen polymer leads to a large contact area and consequently a significant shear contribution to energy dissipation. The brush grafting density was varied by using UV photolysis of C–Br bonds at 244 nm to dehalogenate the surface in a controlled fashion. The surface shear strength increases initially as the brush grafting density is reduced, but then decreases for UV doses greater than 0.5 J cm−2, reaching a limiting value when the brush thickness is ca. 50% that of a brush monolayer. Below this critical grafting density, a collapsed brush layer is obtained. For nm-scale gradient brush structures formed via interferometric lithography, the mean width increases as the period is increased, and the lateral mobility of brushes in these regions is reduced, leading to an increase in brush height as the grafted chains become progressively more extended. For a width of 260 nm, the mean brush height in water and ethanol is close to the thickness of a dense unpatterned brush monolayer synthesised under identical conditions. Both the surface shear stress measured for PCysMA brushes under water and the coefficient of friction measured in ethanol are closely correlated to the feature height, and hence to the chain conformation

Effect of Salt on Phosphorylcholine-based Zwitterionic Polymer Brushes.

A quantitative investigation of the responses of surface-grown biocompatible brushes of poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) to different types of salt has been carried out using ellipsometry, quartz crystal microbalance (QCM) measurements, and friction force microscopy. Both cations and anions of varying valency over a wide range of concentrations were examined. Ellipsometry shows that the height of the brushes is largely independent of the ionic strength, confirming that the degree of swelling of the polymer is independent of the ionic character of the medium. In contrast, QCM measurements reveal significant changes in mass and dissipation to the PMPC brush layer, suggesting that ions bind to phosphorylcholine (PC) groups in PMPC molecules, which results in changes in the stiffness of the brush layer, and the binding affinity varies with salt type. Nanotribological measurements made using friction force microscopy show that the coefficient of friction decreases with increasing ionic strength for a variety of salts, supporting the conclusion drawn from QCM measurements. It is proposed that the binding of ions to the PMPC molecules does not change their hydration state, and hence the height of the surface-grown polymeric brushes. However, the balance of the intra- and intermolecular interactions is strongly dependent upon the ionic character of the medium between the hydrated chains, modulating the interactions between the zwitterionic PC pendant groups and, consequently, the stiffness of the PMPC molecules in the brush layer

Facile formation of highly mobile supported lipid bilayers on surface-quaternized pH-responsive polymer brushes

Poly(2-dimethylamino)ethyl methacrylate) (PDMA) brushes are grown from planar substrates via surface atom transfer radical polymerization (ATRP). Quaternization of these brushes is conducted using 1-iodooctadecane in n-hexane, which is a non-solvent for PDMA. Ellipsometry, AFM, and water contact angle measurements show that surface-confined quaternization occurs under these conditions, producing pH-responsive brushes that have a hydrophobic upper surface. Systematic variation of the 1-iodooctadecane concentration and reaction time enables the mean degree of surface quaternization to be optimized. Relatively low degrees of surface quaternization (ca. 10 mol % as judged by XPS) produce brushes that enable the formation of supported lipid bilayers, with the hydrophobic pendent octadecyl groups promoting in situ rupture of lipid vesicles. Control experiments confirm that quaternized PDMA brushes prepared in a good brush solvent (THF) produce non-pH-responsive brushes, presumably because the pendent octadecyl groups form micelle-like physical cross-links throughout the brush layer. Supported lipid bilayers (SLBs) can also be formed on the non-quaternized PDMA precursor brushes, but such structures proved to be unstable to small changes in pH. Thus, surface quaternization of PDMA brushes using 1-iodooctadecane in n-hexane provides the best protocol for the formation of robust SLBs. Fluorescence recovery after photobleaching (FRAP) studies of such SLBs indicate diffusion coefficients (2.8 ± 0.3 μm s–1) and mobile fractions (98 ± 2%) that are comparable to the literature data reported for SLBs prepared directly on planar glass substrates

Highly Efficient and Rapid Removal of Methylene Blue from Aqueous Solution Using Folic Acid-Conjugated Dendritic Mesoporous Silica Nanoparticles

Dendritic Mesoporous Silica Nanoparticles (DMSNs) are considered superior in the adsorption of unfavorable chemical compounds and biological pollutants. Herein, we have synthesized folic acid-terminated dendritic mesoporous silica nanoparticles (FA-DMSN) for the removal of cationic dyes, methylene blue (MB), from aqueous solutions. The structural, morphological, functional, specific surface area, pore size distribution, and thermal properties of the synthesized DMSNs were identified using a scanning electron microscope (SEM), a transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), Brunauer−Emmett−Teller (BET), and Thermogravimetric Analyzer (TGA). The synthesized DMSNs exhibited a high surface area (521 m2 −1) and pore volume (1.2 cm3 g−1). In addition, it features both wide pore size and narrow distributions, which strongly affect the adsorption performance in terms of the equilibrium uptake time. Moreover, the impact of pH, contacting time, and dye’s initial concentration on the removal efficiency of MB was studied. The extraction efficiency of FA-DMSN was found to be three times more effective than the bare DMSN materials. Langmuir isotherm fitted the experimental data very well with a correlation coefficient value of 0.99. According to the Langmuir model, the maximum adsorption capacity was 90.7 mg/g. Furthermore, the intra−particle diffusion model revealed a significantly fast intra-particle diffusion which can be attributed to the presence of the large pore’s channels. Finally, the fast adsorption of MB molecules, reaching their equilibrium capacity within tens of seconds, as well as the low cost and ease of FA-DMSN fabrication, makes the developed material an effective adsorbent for water remediations

Fabrication of Polysulfone-Surface Functionalized Mesoporous Silica Nanocomposite Membranes for Removal of Heavy Metal Ions from Wastewater

Membranes are an efficient way to treat emulsified heavy metal-based wastewater, but they generally come with a trade-off between permeability and selectivity. In this research, the amine and sulphonic groups on the inner and outer surface of mesoporous silica nanoparticles (MSNs) were first modified by a chemical approach. Then, MSNs with amine and sulphonic groups were utilized as new inorganic nanofiller to fabricate mixed matrix polysulfone (PSU) nanocomposite membranes using the classical phase inversion approach. The resultant nanoparticles and membranes were characterized by their physico-chemical characteristics as well as determination of pure water permeability along with cadmium and zinc ion removal. Embedding nanoparticles resulted in a significant rise in the water permeability as a result of changes in the surface properties and porosity of the membrane. Furthermore, the efficiency of developed membranes to remove cadmium and zinc was significantly improved by more than 90% due to the presence of functional groups on nanoparticles. The functionalized-MSNs/PSU nanocomposite membrane has the potential to be an effective industrial effluent removal membrane

Quaternization of Poly(2-diethyl aminoethyl methacrylate) Brush-Grafted Magnetic Mesoporous Nanoparticles Using 2-Iodoethanol for Removing Anionic Dyes

Magnetic mesoporous silica nanoparticles (Fe3O4-MSNs) were successfully synthesized with a relatively high surface area of 568 m2g−1. Fe3O4-MSNs were then modified with poly(2-diethyl aminoethyl methacrylate) (PDEAEMA) brushes using surface-initiated ARGET atom transfer radical polymerization (ATRP) (Fe3O4@MSN-PDMAEMA). Since the charge of PDEAEMA is externally regulated by solution pH, tertiary amines in the polymer chains were quaternized using 2-iodoethanol to obtain cationic polymer chains with a permanent positive charge (Fe3O4@MSN-QPDMAEMA). The intensity of the C−O peak in the C1s X-ray photoelectron spectrum increased after reaction with 2-iodoethanol, suggesting that the quaternization process was successful. The applicability of the synthesized materials on the removal of methyl orange (MO), and sunset yellow (E110) dyes from an aqueous solution was examined. The effects of pH, contact time, and initial dyes concentrations on the removal performance were investigated by batch experiments. The results showed that the Fe3O4@MSN-PDMAEMA sample exhibited a weak adsorption performance toward both MO and E110, compared with Fe3O4@MSN-QPDMAEMA at a pH level above 5. The maximum adsorption capacities of MO and E110 using Fe3O4@MSN-QPDMAEMA were 294 mg g−1 and 194.8 mg g−1, respectively

Stabilization of Tetrachloride with Mn (II) and Co (II)Complexes and 4-Tert-Butylpyridinium Organic Cation: Elaboration of the Structure and Hirshfeld Surface, Optical, Spectroscopic and Thermal Analyses

[C9H14N]2[MnCl4] (I) and [C9H14N]2[CoCl4] (II) are isostructural compounds produced via gradual evaporation at room temperature. Both compounds consolidate in the tetragonal space group I4¯2d (No. 122), as shown by single-crystal X-ray diffraction observations. A slightly deformed tetrahedral geometry is formed by four chloride atoms around each cation MII (M = Mn or Co). The [C9H14N]+ groups and the isolated [MCl4]2− units are connected via C–H…Cl and N–H…Cl H-bonds to form sheets parallel to the (101¯), (011), (01¯1) and (101) planes. The morphology and the chemical composition of compounds (I) and (II)were determined here using SEM and EDX. The functional groups contained in both compounds were determined using FT-IR spectroscopy. The study of the optical characteristics showed that the two compounds exhibited semiconductor behavior. The thermal analysis (TGA-DTA) was used to determine their thermal stability