Aleeza Farrukh

Design of polymer-brush-grafted magnetic nanoparticles for highly efficient water remediation.

Highly efficient removal of mercury(II) ions (Hg(II)) from water has been reported by employing polymer-brush-functionalized magnetic nanoparticles (MNPs). Surface-initiated conventional radical polymerization (SI-cRP) was used to grow poly(2-aminoethyl methacrylate hydrochloride) (poly-AEMA·HCl) polymer chains on magnetite nanoparticles (Fe3O4), followed by the transformation of pendant amino groups into dithiocarbamate (DTC) groups, which showed high chelating affinity toward Hg(II) ions. This polymer-brush-based DTC-functionalized MNP (MNPs-polyAEMA·DTC) platform showed the complete removal of Hg(II) from aqueous solutions. The Hg(II) ion removal capacity and efficiency of MNPs-polyAEMA·DTC were compared with its monolayer analogue, which was derived from the direct transformation of amino groups of (3-aminopropyl) triethoxysilane (APTES)-functionalized MNPs (MNPs-APTES) to DTC functional groups (MNPs-DTC). The surface chemical modifications and higher chelating functional group density, in the case of MNPs-polyAEMA·DTC, were ascertained by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), physical property measurement system (PPMS), attenuated total reflectance infrared (ATR-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The Hg(II) ion removal capacity and efficiency of monolayer and polymer-brush-based DTC-functionalized MNPs (MNPs-DTC and MNPs-polyAEMA·DTC, respectively) were evaluated and compared by studying the effect of various factors on the percentage removal of Hg(II) such as adsorbent amount, temperature, and contact time. Furthermore, the adsorption behavior of MNPs-DTC and MNPs-polyAEMA·DTC was analyzed by applying Langmuir and Freundlich adsorption isotherm models. In addition, the adsorption thermodynamics, as well as the adsorption kinetics, were also evaluated in detail. The higher surface functional group density of MNPs-polyAEMA·DTC led to superior remediation characteristics toward Hg(II) ions than its monolayer analogue.

Polymer brush functionalized SiO2 nanoparticle based Nafion nanocomposites: a novel avenue to low-humidity proton conducting membranes

Polyelectrolyte membranes showing proton conductivity at moderate levels of relative humidity and temperatures are essential for the development of polyelectrolyte membrane fuel cells (PEMFCs). Herein, monomethoxy oligoethylene glycol methacrylate derived polymer brush functionalized silica nanoparticles (SiO2 NPs) are presented as humidifying-nanoadditives for the fabrication of Nafion nanocomposite membranes, exhibiting improved proton conductivities at moderate levels of relative humidity and temperatures. Polymer brush functionalized SiO2 NPs (SiO2-polymer-brush), fabricated via surface initiated atom transfer radical polymerization (SI-ATRP), are dispersed in the Nafion resin solution, and nanocomposite membranes (Nafion/SiO2-polymer-brush) are fabricated via solution casting. For comparison, composite membranes of Nafion are also prepared with bare SiO2 NPs. Spectroscopic measurements confirm the presence of polymer brushes in the final membranes and demonstrate increased water uptake in membranes with polymer brush-functionalized nanocomposite membranes. Electrochemical impedance analyses reveal that 1 wt% of functionalized SiO2 NPs is sufficient to achieve Nafion nanocomposite membranes with superior proton conductivities at ambient and moderately high temperatures over the entire range of relative humidity (RH). This study presents a facile avenue to membranes with superior proton conductivities under moderate levels of RH and temperature, and provides important insights into the scope of nanocomposite PEMs for fuel cell applications.

Bifunctional Poly(acrylamide) Hydrogels through Orthogonal Coupling Chemistries

Biomaterials for cell culture allowing simple and quantitative presentation of instructive cues enable rationalization of the interplay between cells and their surrounding microenvironment. Poly(acrylamide) (PAAm) hydrogels are popular 2D-model substrates for this purpose. However, quantitative and reproducible biofunctionalization of PAAm hydrogels with multiple ligands in a trustable, controlled, and independent fashion is not trivial. Here, we describe a method for bifunctional modification of PAAm hydrogels with thiol- and amine- containing biomolecules with controlled densities in an independent, orthogonal manner. We developed copolymer networks of AAm with 9% acrylic acid and 2% N-(4-(5-(methylsulfonyl)-1,3,4-oxadiazol-2-yl)phenyl)acrylamide. The covalent binding of thiol- and amine-containing chromophores at tunable concentrations was demonstrated and quantified by UV spectroscopy. The morphology, mechanical properties, and homogeneity of the copolymerized hydrogels were characterized by scanning electron microscopy, dynamic mechanical analysis, and confocal microscopy studies. Our copolymer hydrogels were bifunctionalized with polylysine and a laminin-mimetic peptide using the specific chemistries. We analyzed the effect of binding protocol of the two components in the maturation of cultured postmitotic cortical neurons. Our substrates supported neuronal attachment, proliferation, and neuronal differentiation. We found that neurons cultured on our hydrogels bifunctionalized with ligand-specific chemistries in a sequential fashion exhibited higher maturation at comparable culture times than using a simultaneous bifunctionalization strategy, displaying a higher number of neurites, branches, and dendritic filopodia. These results demonstrate the relevance of quantitative and optimized coupling chemistries for the performance of simple biomaterials and with sensitive cell types.

Bioconjugating Thiols to Poly(acrylamide) Gels for Cell Culture Using Methylsulfonyl Co‐monomers

Poly(acrylamide) P(AAm) gels have become relevant model substrates to study cell response to the mechanical and biochemical properties of the cellular microenvironment. However, current bioconjugation strategies to functionalize P(AAm) gels, mainly using photoinduced arylazide coupling, show poor specificity and hinder conclusive studies of material properties and cellular responses. We describe methylsulfonyl-containing P(AAm) hydrogels for cell culture. These gels allow easy, specific and functional covalent coupling of thiol containing bioligands in tunable concentrations under physiological conditions, while retaining the same swelling, porosity, cytocompatibility, and low protein adsorption of P(AAm) gels. These materials allow quantitative and standardized studies of cell-materials interactions with P(AAm) gels.

Surface-functionalized silica gel adsorbents for efficient remediation of cationic dyes

Abstract The toxic and non-biodegradable nature of organic dyes necessitates the design and synthesis of novel adsorbents for their effective removal from the environment. This study reports an effective remediation behavior of surface-functionalized silica gel against water-soluble cationic dyes (up to 98 % removal). Thiol groups were functionalized at the surface of silica gel (SiO2–SH). The surface-tethered –SH groups were further oxidized to sulfonic acid groups to generate the negatively charged moieties at the surface of silica gel (SiO2–SO3 H). The morphology of the developed adsorbents and the surface modifications were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). Uptake study of three cationic dyes, namely, rhodamine B (Rh B), rhodamine 6G (Rh 6G), and crystal violet (CV) with SiO2–SH and SiO2–SO3 H adsorbents was performed by varying the adsorbent amount, contact time, pH of solution, and temperature. The presence of negatively charged species at the surface of SiO2–SO3 H results in an increased electrostatic interaction with the cationic dyes, which leads to better remediation characteristics for SiO2–SO3 H as compared to SiO2–SH. The reusability of the developed adsorbents was also assessed by investigating adsorption/desorption of dyes. The simple fabrication process provides a facile avenue to the adsorbents with efficient remediation towards cationic dyes.

Microenvironments designed to support growth and function of neuronal cells

Strategies for neural tissue repair heavily depend on our ability to temporally reconstruct the natural cellular microenvironment of neural cells. Biomaterials play a fundamental role in this context, as they provide the mechanical support for cells to attach and migrate to the injury site, as well as fundamental signals for differentiation. This review describes how different cellular processes (attachment, proliferation, and (directional) migration and differentiation) have been supported by different material parameters, in vitro and in vivo. Although incipient guidelines for biomaterial design become visible, literature in the field remains rather phenomenological. As in other fields of tissue regeneration, progress will depend on more systematic studies on cell-materials response, better understanding on how cells behave and understand signals in their natural milieu from neurobiology studies, and the translation of this knowledge into engineered microenvironments for clinical use.

Photoactivatable Adhesive Ligands for Light-Guided Neuronal Growth

Neuro‐regeneration after trauma requires growth and reconnection of neurons to reestablish information flow in particular directions across the damaged tissue. To support this process, biomaterials for nerve tissue regeneration need to provide spatial information to adhesion receptors on the cell membrane and to provide directionality to growing neurites. Here, photoactivatable adhesive peptides based on the CASIKVAVSADR laminin peptidomimetic are presented and applied to spatiotemporal control of neuronal growth to biomaterials in vitro. The introduction of a photoremovable group [6‐nitroveratryl (NVOC), 3‐(4,5‐dimethoxy‐2‐nitrophenyl)butan‐2‐yl (DMNPB), or 2,2′‐((3′‐(1‐hydroxypropan‐2‐yl)‐4′‐nitro‐[1,1′‐biphenyl]‐4‐yl)azanediyl)bis(ethan‐1‐ol) (HANBP)] at the amino terminal group of the K residue temporally inhibited the activity of the peptide. The bioactivity was regained through controlled light exposure. When used in neuronal culture substrates, the peptides allowed light‐based control of the attachment and differentiation of neuronal cells. Site‐selective irradiation activated adhesion and differentiation cues and guided seeded neurons to grow in predefined patterns. This is the first demonstration of ligand‐based light‐controlled interaction between neuronal cells and biomaterials.