Polyethylene Glycol Precursors Research Articles

Reversible Hydrogels with Switchable Diffusive Permeability

AbstractHydrogels are polymer networks swollen in water that are characterized by soft mechanics and high permeability. This makes them good candidates for separation and membrane technologies. The diffusion is controlled by the mesh size of the network, and this can be made tunable through the introduction of thermoresponsive polymers. However, this is still a developing field. To contribute to this development, a dual dynamic network is formed composed of four‐arm polyethylene glycol precursors in which each arm is functionalized with both a terpyridine moiety capable of forming reversible metal–ligand complexes along with branches of poly(N‐isopropylacrylamide) (pNIPAAm), which can be switched between expanded and collapsed states and therewith offers a path for switching the microscopic gel‐network mesh size, along with the macroscopic gel elasticity. The dually sensitive hydrogel has the capability of doubling its elastic modulus when going above the lower critical solution temperature (LCST) of pNIPAAm. In addition, the diffusive permeability of the hydrogel is switched upon change of temperature, whereby diffusants are trapped above the LCST of pNIPAAm. Moreover, it is possible to disassemble and reform the gel upon change of pH. With that, the hydrogel has potential application as a switchable and reversible membrane.

Hybrid Organosilica Coatings for Solid Phase Microextraction: Highly Efficient Adsorbents for Determination of Trace Parabens

New hybrid organosilica coatings with different amount of alkyl functional groups on a quartz fiber for solid phase microextraction (SPME) have been obtained by the of sol–gel synthesis in the presence of polyethylene glycol (PEG). The structural-sorption properties of the synthesized silica coatings of various compositions have been studied. According to the thermogravimetric analysis, the main thermolysis of the adsorption coatings’ organic layer was observed at temperatures higher than 350°C. The effect of synthesis conditions on the thermal stability of the obtained PEG-based organosilica coating has been studied. It has been established that the textural characteristics of the produced coatings for SPME and their adsorption properties can be controlled using different PEG and silica precursors and the equivalence ratio in the reaction mixture. Good prospects of application of the fabricated coatings for SPME have been demonstrated in paraben extraction and concentration in aqueous solutions at 24°C and pH 3.0–5.5 with their subsequent gas chromatography determination. The suggested technique was characterized by good accuracy and reproducibility (RSD ≤ 2.3%). Comparative studies of the obtained hybrid organosilica coatings for SPME with a commercially available fiber with a bipolar polymer coating—divinylbenzene/carboxen/polydimethylsiloxane—have been conducted.

Shape-Preserved Transformation of Biological Cells into Synthetic Hydrogel Microparticles.

The synthesis of materials that can mimic the mechanical, and ultimately functional, properties of biological cells can broadly impact the development of biomimetic materials, as well as engineered tissues and therapeutics. Yet, it is challenging to synthesize, for example, microparticles that share both the anisotropic shapes and the elastic properties of living cells. Here, a cell-directed route to replicate cellular structures into synthetic hydrogels such as polyethylene glycol (PEG) is described. First, the internal and external surfaces of chemically fixed cells are replicated in a conformal layer of silica using a sol-gel process. The template is subsequently removed to render shape-preserved, mesoporous silica replicas. Infiltration and cross-linking of PEG precursors and dissolution of the silica result in a soft hydrogel replica of the cellular template as demonstrated using erythrocytes, HeLa, and neuronal cultured cells. The elastic modulus can be tuned over an order of magnitude (≈10-100 kPa) though with a high degree of variability. Furthermore, synthesis without removing the biotemplate results in stimuli-responsive particles that swell/deswell in response to environmental cues. Overall, this work provides a foundation to develop soft particles with nearly limitless architectural complexity derived from dynamic biological templates.

Plasma-polymerized antifouling biochips for label-free measurement of protease activity in cell culture media

We report polyethylene glycol (PEG)-grafting antifouling surfaces using a plasma copolymerized (PcP) technique to monitor protease activity in complex media. By varying the mixing ratio of the PEG and ethylenediamine (EDA) precursors, the PcP-PEG-EDA (PcP-PE) film was able to easily control surface amine density with good preservation of the internal PEG structure. We found that nonspecific protein adsorption was dramatically reduced in serum-containing media on the PcP-PE films, as opposed to that on plasma polymerized-EDA (PP-E) films without PEG. When SPR sensor chips coated with PcP-PE film were employed to detect protease activity, biotinylated luciferase probes (luciferase-peptide-biotin) on streptavidin-conjugated SPR chips enabled real-time and label-free measurement of matrix metalloproteinase activity in cell culture media. Owing to its excellent antifouling ability, this newly developed method boasts minimal nonspecific binding and can serve as a biochip platform to promote a wide range of applications in the biological field.

Towards a sulfur clean fuel: Deep extraction of thiophene and dibenzothiophene using polyethylene glycol-based deep eutectic solvents

In this work, extractive desulfurization of model fuel containing dibenzothiophene (DBT) and thiophene (Th) as sulfur compounds was carried out using 16 different Deep Eutectic Solvents (DES) based on polyethylene glycol (PEG) and its precursors. The aim of this study is the reduction of the sulfur content of fuels below the environmental regulation (10 ppm), using PEG-based DES as low-cost extraction media under mild conditions and to compare their extractive performance with that of PEG alone, which by itself is a green solvent. For that purpose, 7 different quaternary ammonium and phosphonium salts were combined with four different molecular weight grades of PEG and PEG precursors such as ethylene glycol and triethylene glycol. The best results were obtained for the DES composed of tetrabutylammonium chloride (TBAC) and PEG400, which showed that it is possible to achieve, in single extraction step, 85% and 68% of extraction efficiency, and deep desulfurization in 2 and 3 cycles, for DBT and Th, respectively. In addition, this DES is not soluble in the model fuel and its extraction capacity is independent on the starting sulfur concentration. Finally, after being reused six times, TBAC:PEG400 DES still maintained 53% and 17% of its capacity, for DBT and Th removal, respectively, and after a regeneration step the performance of the DES was fully recovered.

Proteolytically stabilizing fibronectin without compromising cell and gelatin binding activity

Excessive proteolytic degradation of fibronectin (FN) has been implicated in impaired tissue repair in chronic wounds. We previously reported two strategies for stabilizing FN against proteolytic degradation; the first conjugated polyethylene glycol (PEG) through cysteine residues and the second conjugated PEG chains of varying molecular weight on lysine residues. PEGylation of FN via lysine residues resulted in increased resistance to proteolysis with increasing PEG size, but an overall decrease in biological activity, as characterized by cell and gelatin binding. Our latest method to stabilize FN against proteolysis masks functional regions in the protein during lysine PEGylation. FN is PEGylated while it is bound to gelatin Sepharose beads with 2, 5, and 10 kDa PEG precursors. This results in partially PEGylated FN that is more stable than native FN and whose proteolytic stability increases with PEG molecular weight. Unlike completely PEGylated FN, partially PEGylated FN has cell adhesion, gelatin binding, and matrix assembly responses that are comparable to native FN. This is new evidence of how PEGylation variables can be used to stabilize FN while retaining its activity. The conjugates developed herein can be used to dissect molecular mechanisms mediated by FN stability and functionality, and address the problem of FN degradation in chronic wounds.

Thermoresponsive hydrogels from BSA esterified with low molecular weight PEG

ABSTRACTBovine serum albumin (BSA) and low molecular weight polyethylene glycol (PEG) were reacted in a single‐step reaction to synthesize translucent hydrogels with a sol–gel transition at temperatures between 37 and 40°C. Gelation occurred by aggregation of smaller assemblies of BSA–PEG precursors within minutes. The sol–gel transition concentration depended on the molecular weight of PEG only at temperatures below 35°C; above 45°C phase separation occurred and a precipitate formed. Microscopic examination showed the porous structure of the gels. At a fairly low grafting ratio, BSA preserved its native secondary and tertiary structure and maintained its capability for binding and enclosing small molecules. Drug delivery was assessed by a discontinuous method in vitro using 5‐fluorouracil. Degradation tests with trypsin confirmed that the hydrogels were biodegradable. This novel material holds promise for biomedical applications as potentially injectable drug delivery vehicle. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40946.

Facile synthesis of an organic–inorganic nanocomposite, PEG–silica, by sol–gel method; its characterization and application as an efficient catalyst in regioselective nucleophilic ring opening of epoxides: Preparation of β-azido alcohols and β-cyanohydrins

Abstract The sol–gel method was used for the synthesis of a PEG–silica hybrid. In order to introduce PEG into the cavities of silica gel, first, the bis(3-trimethoxysilylpropyl)-polyethylene glycol precursor was synthesized by the reaction of 3-chloropropyltrimethoxysilane with alkoxides formed on the PEG terminals. The organic–inorganic hybrid silica was then synthesized by hydrolysis and polycondensation of the precursor under mild acidic conditions. The characteristics results of FT–IR, XRD and TGA confirmed the coexistence of silica and PEG networks. The catalytic ability of this heterogeneous catalyst to the regioselective ring opening of epoxides by azide and cyanide anions in H 2 O was also investigated.

Supramolecular Hydrogel Capsules Based on PEG: A Step Toward Degradable Biomaterials with Rational Design

Supramolecular microgel capsules based on polyethylene glycol (PEG) are a promising class of soft particulate scaffolds with tailored properties. An approach to fabricate such particles with exquisite control by droplet-based microfluidics is presented. Linear PEG precursor polymers that carry bipyridine moieties on both chain termini are gelled by complexation to iron(II) ions. To investigate the biocompatibility of the microgels, living mammalian cells are encapsulated within them. The microgel elasticity is controlled by using PEG precursors of different molecular weights at different concentrations and the influence of these parameters on the cell viabilities, which can be optimized to exceed 90% is studied. Reversion of the supramolecular polymer cross-linking allows the microcapsules to be degraded at mild conditions with no effect on the viability of the encapsulated and released cells.

Synthesis and Characterization of ZnO-SiO<sub>2</sub>/Epoxy Nanocomposite Coating by Sol-Gel Process

In this paper, we report preparation of hydrophilic hybrid nanocomposite coatings on glass substrates using Zinc acetate solutions based on 3-glycidoxypropyltrimethoxysilane (GPTMS), epoxy resin, aromatic amine (HY850), polyethylene glycol (PEG) and surfactant (polyoxyethylene(4)laurylether) by the sol-gel process. Furthermore, the effects of PEG addition to the precursor solutions on the hydrophilic property and microstructure of the resultant coating film were studied. The hydrophilic behavior study of the synthesized hybrid was performed by adding different amounts of polyethylene glycol precursor to the hybrid solution. Experimental results show that, among different amounts of PEGs, the best results are obtained by addition of PEGs (400) to the hybrid solution which can decrease the water contact angles down to 16 and using surfactant down to 0, and increase the free surface energy. Coated glass exhibits a higher strength than uncoated glass. Attenuated total reflectance infrared spectroscopic (ATR-IR) technique was used to characterize the structure of the hybrid films. The chemical structure of obtained network affects morphology of the coating. The morphology of the hybrid coatings was examined by transmission electron microscopy (TEM). The hybrid systems have a unit form structure and the inorganic phases were in the nanosize scale,

Improved radiolabeling of PEGylated protein: PEGylated annexin V for noninvasive imaging of tumor apoptosis.

We have developed a one-step procedure to introduce both polyethylene glycol (PEG) and the metal chelator diethylenetriaminepentaacetic acid (DTPA) to proteins through a heterofunctional PEG precursor. The PEG precursor contains DTPA at one end and an amine-reactive isothiocyanate (SCN-) functional group at the other end. It was obtained as lyophilized powder and could be stored at 4 degrees C for several months. Protein conjugation was achieved by simply mixing the proteins and the PEG precursor SCN-PEG-DTPA in an aqueous solution. As exemplified by the PEGylation and radiolabeling of annexin V, the resulting conjugate 111In-DTPA-PEG-annexin V showed selective binding to apoptotic cells in vitro and increased blood half-life in vivo. The PEGylated, radiolabeled annexin V may be useful in the noninvasive imaging of apoptosis.

Influence of PEG additive and precursor concentration on the preparation of LaCoO 3 film with perovskite structure

LaCoO 3 thin films with perovskite structure were prepared on Si(111) substrate successfully by using an amorphous heteronuclear complex, LaCo(DTPA)·6H 2O (DTPA, diethylenetriaminepentaacetic acid), as a precursor. X-Ray diffraction (XRD) results indicated that the crystalline sizes of LaCoO 3 films grew from 17.8 to 34.3 nm with the calcination temperature increasing from 550 to 800°C for 1 h and the crystalline sizes of LaCoO 3 films grew from 22.3 to 25.3 nm with the calcination time increasing from 1 to 6 h at 650°C. Auger electron spectroscopy (AES) depth profile analysis indicated that the composition of the thin film was homogenous with depth, the interface diffusion took place between LaCoO 3 layer and Si substrate. The thickness of LaCoO 3 thin film depended on the concentration of the precursor solution and could be described approximately by the following equation: d=0.580 c+0.285 c 2. Scanning electron microscopy (SEM) indicated that the texture of the film was governed by the concentration of precursor solution. When the concentration of precursor solution was lower than 15%, a smooth film without microcrack was obtained. The texture of the film could be modified significantly by adding polyethylene glycol (PEG). But the thickness of the film was hardly influenced by the addition of PEG.