Novel biobased photo-crosslinked polymer networks prepared from vegetable oil and 2,5-furan diacrylate

USDA-ARS?s Scientific Manuscript database

Novel biobased crosslinked polymer networks were prepared from vegetable oil with 2,5-furan diacrylate as a difunctional stiffener through UV photopolymerization, and the mechanical properties of the resulting films were evaluated. The vegetable oil raw materials used were acrylated epoxidized soybe...

Large Area Projection Microstereolithography: Characterization and Optimization of 3D Printing Parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ng, Melissa R.; Moran, Bryan; Bekker, Logan

2016-08-12

Large Area Projection Microstereolithography (LAPμSL) is a new technology that allows the additive manufacture of parts that have feature sizes spanning from centimeters to tens of microns. Knowing the accuracy of builds from a system like this is a crucial step in development. This project explored the capabilities of the second and newest LAPμSL system that was built by comparing the features of actual builds to the desired structures. The system was then characterized in order to achieve the best results. The photo polymeric resins that were used were Autodesk PR48 and HDDA. Build parameters for Autodesk PR48 were foundmore » that allowed the prints to progress while using the full capacity of the system to print quality parts in a relatively short amount of time. One of the larger prints in particular had a print time that was nearly eighteen times faster than it would have been had printed in the first LAPμSL system. The characterization of HDDA resin helped the understanding that the flux of the light projected into the resin also affected the quality of the builds, rather than just the dose of light given. Future work for this project includes exploring the use of other resins in the LAPμSL systems, exploring the use of Raman Spectroscopy to analyze builds, and completing the characterization of the LAPμSL system.« less

Temperature dependences of characteristics of 2,5-hexanediol and 1,2,6-hexanetriol cluster structures according to dielectric radiospectroscopy

NASA Astrophysics Data System (ADS)

Usacheva, T. M.; Zhuravlev, V. I.

2013-03-01

Dielectric radiospectra (DRS) of 2,5-hexanediol and 1,2,6-hexanetriol at frequencies of 1 MHz, 9.375, 36.885, and 74.569 GHz in a temperature range of 303-423 K (above the glass transition temperatures) are studied. Experimental DRS are analyzed using the Dissado-Hill (DH) cluster model. The dependence of the equilibrium and relaxation characteristics of DRS on the number of OH groups is studied. The dipole moments of the clusters are calculated. The change in the orientation of the dipole moments of the molecules in the cluster during the rearranging of its structure is characterized through the unit vector of the longitudinal component of dipole moment M e of the cluster. The relation between a change in the Onsager-Kirkwood-Fröhlich correlation factor and the behavior of M e is shown.

Preparation and characterization of photocured poly (ε-caprolactone) diacrylate/poly (ethylene glycol) diacrylate/chitosan for photopolymerization-type 3D printing tissue engineering scaffold application.

PubMed

Cheng, Yih-Lin; Chen, Freeman

2017-12-01

Because of its biocompatible, biodegradable and antimicrobial properties, chitosan is an attractive biomaterial for use in tissue engineering scaffolds. This work builds on previous research by incorporating 95% DD chitosan into a visible-light curable resin which is compatible with a digital light processing (DLP™) projection additive manufacturing (3D printing) system. Different concentrations of chitosan were added to a poly (ε-caprolactone)-diacrylate/poly (ethylene glycol)-diacrylate baseline resin and the samples were extensively characterized. Thermal and mechanical analysis conformed to established scaffold requirements. L929 cells were cultured on the photo-crosslinked films and MTT assays were performed at 1, 3, and 5days to assess cytocompatibility of the resins. Data and SEM images verified a correlation between the concentration of chitosan in the photocurable resin and the adhesion, proliferation, and viability of cell cultures. Finally, the processability of the resins with the dynamic masking DLP system was demonstrated by constructing multi-layer scaffolds with actual measurements that were consistent with the CAD models. These findings encourage the use of chitosan as an additive in visible-light curable resins to improve desired properties in tissue engineering scaffolds. Copyright © 2017 Elsevier B.V. All rights reserved.

Long-chain 3-hydroxy fatty acids accumulating in long-chain 3-hydroxyacyl-CoA dehydrogenase and mitochondrial trifunctional protein deficiencies uncouple oxidative phosphorylation in heart mitochondria.

PubMed

Tonin, Anelise M; Amaral, Alexandre U; Busanello, Estela N B; Grings, Mateus; Castilho, Roger F; Wajner, Moacir

2013-02-01

Cardiomyopathy is a common clinical feature of some inherited disorders of mitochondrial fatty acid β-oxidation including mitochondrial trifunctional protein (MTP) and isolated long-chain 3-hydroxyacyl-CoA dehydrogenase (LCHAD) deficiencies. Since individuals affected by these disorders present tissue accumulation of various fatty acids, including long-chain 3-hydroxy fatty acids, in the present study we investigated the effect of 3-hydroxydecanoic (3 HDCA), 3-hydroxydodecanoic (3 HDDA), 3-hydroxytetradecanoic (3 HTA) and 3-hydroxypalmitic (3 HPA) acids on mitochondrial oxidative metabolism, estimated by oximetry, NAD(P)H content, hydrogen peroxide production, membrane potential (ΔΨ) and swelling in rat heart mitochondrial preparations. We observed that 3 HTA and 3 HPA increased resting respiration and diminished the respiratory control and ADP/O ratios using glutamate/malate or succinate as substrates. Furthermore, 3 HDDA, 3 HTA and 3 HPA decreased ΔΨ, the matrix NAD(P)H pool and hydrogen peroxide production. These data indicate that these fatty acids behave as uncouplers of oxidative phosphorylation. We also verified that 3 HTA-induced uncoupling-effect was not mediated by the adenine nucleotide translocator and that this fatty acid induced the mitochondrial permeability transition pore opening in calcium-loaded organelles since cyclosporin A prevented the reduction of mitochondrial ΔΨ and swelling provoked by 3 HTA. The present data indicate that major 3-hydroxylated fatty acids accumulating in MTP and LCHAD deficiencies behave as strong uncouplers of oxidative phosphorylation potentially impairing heart energy homeostasis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saunders, C.B.; Carmichael, A.A.; Kremers, W.

The mechanical and physical properties of electron-beam (EB) curable carbon-fiber-reinforced composites were investigated, using a resin matrix made from a mixture of 50 percent of an epoxy diacrylate oligomer, 30 percent of a polybutadiene diacrylate oligomer, and 20 percent of dipentaerythritol monohydroxypentaacrylate monomer, and applying varying EB doses for curing the mixture. It was found that the gel content in the cured prepreg polymer depended upon the total EB dose below 50 kGy, the dose rate, and, at a low dose of 16 kGy/hr, on the atmosphere and pressure during irradiation. 14 refs.

77 FR 24705 - Certain New Chemicals; Receipt and Status Information

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-25

..., Corporation. adhesive used polymer with 1,6- for panel hexanediol, [alpha]- lamination and hydro-[omega... used benzenedicarboylic for panel acid, polymer with lamination and 1,4- other assemblies...- isocyanatobenzene]. P-12-0273......... 03/28/2012 06/25/2012 CBI (S) Industrial (S) Coconut oil, coating. polymer...

Attraction of Mosquitoes to Diethyl Methylbenzamide and Ethyl Hexanediol

DTIC Science & Technology

1990-09-01

tant to the biting midges Culicoides pulicaris that 8% ethyl acetate was attractant to the Linn. and Culicoides puncticoUis Becker (Cera- vinegar fly...Drosoph- finding by mosquitoes (Diptera: Culcidae): a review. ila melanogaster Meigen to the products of ferment - Bull. Entomol. Res. 70:525-532. ing banana

Influence of polymerization conditions on the refractive index of poly(ethylene glycol) diacrylate (PEGDA) hydrogels

NASA Astrophysics Data System (ADS)

Zhang, Zhi Feng; Ma, Xinxian; Wang, Haibin; Ye, Fei

2018-04-01

This paper studies the influences of fabrication parameters on the optical properties of poly(ethylene glycol) diacrylate(PEGDA) hydrogels during polymerization, including the irradiation intensity, irradiation time, photoinitiator concentration, and water content. The refractive index of PEGDA hydrogels polymerized under various conditions is measured, with the results shown to be valuable for future research applying PEGDA hydrogels as optical materials. In addition, it is found that the photoinitiator concentration used can be as low as 1.0 wt%, which is severalfold lower than that previously reported, making PEGDA hydrogels more desirable for bioapplications.

Polar stationary phases based on poly(oligo ethylene glycol)diacrylates for capillary gas chromatography

NASA Astrophysics Data System (ADS)

Shiryaeva, V. E.; Popova, T. P.; Korolev, A. A.; Kanat'eva, A. Yu.; Kurganov, A. A.

2017-08-01

New stationary phases for capillary columns in GC are synthesized and studied. The phases are prepared by depositing oligo(ethylene glycol)diacrylates on the column walls and subsequent polymerization (crosslinking) in the presence of peroxide initiators. It is shown that stationary phases based on monomers with molecular weights of 10 kDa or higher exhibit separation properties similar to those of conventional stationary phases based on polyethylene glycol (PEG); however, their thermal stability is higher because they have a higher degree of crosslinking and a more ordered structure of the crosslinked polymers than the respective parameters of phases based on native PEG.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saunders, C.B.; Dickson, L.W.; Singh, A.

A radiation-curable prepreg designed to meet the specifications set by a major aircraft company is described. The resin, consisting of a mixture of an epoxy diacrylate, polybutadiene diacrylate, and a multifunctional monomer, was used to impregnate a plain weave carbon fabric by a solvent process. The cured polymer, produced by irradiation in air to a dose of 40 kGy, is amorphous, with a gel fraction of 85 percent. The linear thermal expansion coefficient of the polymer was found to be 0.00017 m/m deg C from 25 to 150 C; it was not affected by varying the applied irradiation dose frommore » 30 to 50 kGy. 14 references.« less

40 CFR 721.10594 - Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, hydrazine, 3-hydroxy...

Code of Federal Regulations, 2013 CFR

2013-07-01

... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10594...) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...-173; CAS No. 1138156-39-4) is subject to reporting under this section for the significant new uses...

40 CFR 721.10594 - Hexanedioic acid, polymer with 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, hydrazine, 3-hydroxy...

Code of Federal Regulations, 2014 CFR

2014-07-01

... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10594...) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as...-173; CAS No. 1138156-39-4) is subject to reporting under this section for the significant new uses...

Laboratory evolution of Pyrococcus furiosus alcohol dehydrogenase to improve the production of (2S,5S)-hexanediol at moderate temperatures

PubMed Central

Leferink, Nicole G. H.; Hendriks, Annemarie; Brouns, Stan J. J.; Hennemann, Hans-Georg; Dauβmann, Thomas; van der Oost, John

2008-01-01

There is considerable interest in the use of enantioselective alcohol dehydrogenases for the production of enantio- and diastereomerically pure diols, which are important building blocks for pharmaceuticals, agrochemicals and fine chemicals. Due to the need for a stable alcohol dehydrogenase with activity at low-temperature process conditions (30°C) for the production of (2S,5S)-hexanediol, we have improved an alcohol dehydrogenase from the hyperthermophilic archaeon Pyrococcus furiosus (AdhA). A stable S-selective alcohol dehydrogenase with increased activity at 30°C on the substrate 2,5-hexanedione was generated by laboratory evolution on the thermostable alcohol dehydrogenase AdhA. One round of error-prone PCR and screening of ∼1,500 mutants was performed. The maximum specific activity of the best performing mutant with 2,5-hexanedione at 30°C was tenfold higher compared to the activity of the wild-type enzyme. A 3D-model of AdhA revealed that this mutant has one mutation in the well-conserved NADP(H)-binding site (R11L), and a second mutation (A180V) near the catalytic and highly conserved threonine at position 183. PMID:18452026

Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers.

PubMed

Dubois, F; Derouiche, Y; Leblond, J M; Maschke, U; Douali, R

2015-09-01

The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009)10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

Compensated Arrhenius formalism applied to a conductivity study in poly(propylene glycol) diacrylate monomers

NASA Astrophysics Data System (ADS)

Dubois, F.; Derouiche, Y.; Leblond, J. M.; Maschke, U.; Douali, R.

2015-09-01

The temperature dependence of the ionic conductivity is studied in a series of poly(propylene glycol) diacrylate monomers. The experimental data are analyzed by means of the approach recently proposed by Petrowsky et al. [J. Phys. Chem. B. 113, 5996 (2009), 10.1021/jp810095g]. This so-called compensated Arrhenius formalism (CAF) approach takes into account the influence of the dielectric permittivity on the exponential prefactor in the classical Arrhenius equation. The experimental data presented in this paper show a good agreement with the CAF; this means that the exponential prefactor is principally dielectric permittivity dependent. The compensated data revealed two conduction processes with different activation energies; they correspond to low and high temperature ranges, respectively.

Soft Polymers for Building up Small and Smallest Blood Supplying Systems by Stereolithography

PubMed Central

Meyer, Wolfdietrich; Engelhardt, Sascha; Novosel, Esther; Elling, Burkhard; Wegener, Michael; Krüger, Hartmut

2012-01-01

Synthesis of a homologous series of photo-polymerizable α,ω-polytetrahydrofuranether-diacrylate (PTHF-DA) resins is described with characterization by NMR, GPC, DSC, soaking and rheometrical measurements. The curing speeds of the resins are determined under UV light exposure. Young’s modulus and tensile strength of fully cured resins show flexible to soft material attributes dependent on the molar mass of the used linear PTHF-diacrylates. Structuring the materials by stereo lithography (SL) and multiphoton polymerization (MPP) leads to tubes and bifurcated tube systems with a diameter smaller than 2 mm aimed at small to smallest supplying systems with capillary dimensions. WST-1 biocompatibility tests ofm polymer extracts show nontoxic characteristics of the adapted polymers after a washing process. Some polymers show shape memory effect (SME). PMID:24955530

Optical, structural and nonlinear optical properties of laser ablation synthesized Ag nanoparticles and photopolymer nanocomposites based on them

NASA Astrophysics Data System (ADS)

Zulina, Natalia A.; Pavlovetc, Ilia M.; Baranov, Mikhail A.; Denisyuk, Igor Yu.

2017-03-01

In this work Ag nanoparticles (NPs) stable colloid solution were prepared by laser ablation of chemically pure silver rod in liquid monomer isodecyl acrylate (IDA). Sizes of obtained nanoparticles were determined by scanning electron microscope and vary from 27 to 120 nm. Nanocomposites films were prepared from obtained stable colloid solution of AgNPs by photocuring. For aliphatic polymer IDA long molecules cross-linking Diurethane dimethacrylate, 1,6-Hexandiol diacrylate and Tetra (ethylene glycol) diacrylate were used. Prepared nanomaterials exhibit strong third-order nonlinear optical responses, which was estimated by using z-scan technique. The third-order nonlinear optical coefficients of the studied nanocomposites were found to be up to Reχ(3)=1.31×10-5 (esu) and Imχ(3)=7.64×10-5 (esu).

Development of ketoconazole nanovesicular system using 1,2-hexanediol and 1,4-cyclohexanediol for dermal targeting delivery: physicochemical characterization and in vitro/in vivo evaluation

NASA Astrophysics Data System (ADS)

Wang, Jinping; Guo, Fang; Ma, Man; Li, Nan; Tan, Fengping

2014-07-01

The present study was aimed at the encapsulation of ketoconazole (KCZ) in the novel modified nanovesicles for dermal targeting delivery. To this purpose, innovative modified vesicles were prepared with soy phospholipid and aqueous solutions containing different concentrations of two targeting modifiers, 1,2-hexanediol and 1,4-cyclohexanediol. Conventional liposomes, with soy phospholipid and cholesterol, were used as control. The prepared formulations were characterized in terms of entrapment efficiency, size distribution, morphology, and stability. Dermal KCZ targeting delivery from modified vesicles was investigated in vitro and in vivo through newborn pig and rat skin, respectively. All vesicles showed a mean size ranging from 58 to 147 nm with fairly narrow size distribution and drug entrapment efficiency between 20 and 75 %. Results of in vitro and in vivo studies indicated that modified vesicles provided an improved KCZ targeting delivery into skin layers. Images of the confocal laser scanning microscopy analyses supported the conclusion that modified vesicles could enhance the drug deposition into the skin strata and reduce the drug permeation into the blood, due to a synergic effect of phospholipid and modifiers. Finally, histological evaluation showed that KCZ-loaded modified vesicles caused no irritation to the skin. The results obtained encouraged the use of the KCZ-loaded modified vesicles as the formulation for the potential topical treatment of fungal infections.

Detection of disseminated peritoneal tumors by fluorescein diacrylate in mice

NASA Astrophysics Data System (ADS)

Harada, Yoshinori; Furuta, Hirokazu; Murayama, Yasutoshi; Dai, Ping; Fujikawa, Yuta; Urano, Yasuteru; Nagano, Tetsuo; Morishita, Koki; Hasegawa, Akira; Takamatsu, Tetsuro

2009-02-01

Tumor invasion to the peritoneum is a poor prognostic factor in cancer patients. Accurate diagnosis of disseminated peritoneal tumors is essential to accurate cancer staging. To date, peritoneal washing cytology during laparotomy has been used for diagnosis of peritoneal dissemination of gastrointestinal cancer, but its sensitivity has not been satisfactory. Thus, a more direct approach is indispensable to detect peritoneal dissemination in vivo. Fluorescein diacrylate (FDAcr) is an esterase-sensitive fluorescent probe derived from fluorescein. In cancer cells, fluorescent fluorescein generated by exogenous application of FDAcr selectively deposits owing to its stronger hydrolytic enzyme activity and its lower leakage rate. We examined whether FDAcr can specifically detect disseminated peritoneal tumors in athymic nude mouse models. Intraperitoneally administered FDAcr revealed disseminated peritoneal microscopic tumors not readily recognized on white-light imaging. These results suggest that FDAcr is a useful probe for detecting disseminated peritoneal tumors.

Effect of silane coupling agents on the chemical and physical properties of photocrosslinked poly(dimethylsiloxane) dimethacrylate/poly(ethylene glycol) diacrylate hydrogel

NASA Astrophysics Data System (ADS)

Lim, K. W.; Hamid, Z. A. A.

2017-07-01

Inorganic-organic hydrogels based on dimethacrylated polydimethylsiloxane (PDMSMA) and diacrylated poly(ethylene glycol) (PEGDA) macromers were prepared via photocrosslinking method. Silane coupling agent was incorporated into the hydrogel formulations to overcome the phase incompatibility. Pure PEGDA (0:100) hydrogels showed the highest value of ESR %, while pure PDMSMA (100:0) hydrogels showed no swelling as we expected. Inclusion of more hydrophobic domains resulted in a lower value of ESR %, i.e. in 75:25 hybrid hydrogels. Beside, we had noticed 50:50 and 75:25 hybrid hydrogels disintegrate during swelling period. However, their integrity was improved and sustained after the coupling agent was added. Similarly, the value of E* for the hybrid hydrogels showed an increment after the coupling agent was incorporated, and this is in a good agreement with the SEM micrograph which display an improved interfacial adhesion.

Click chemistry modification of natural keratin fibers for sustained shrink-resist performance.

PubMed

Yu, Dan; Cai, Jackie Y; Church, Jeffrey S; Wang, Lijing

2015-01-01

This paper introduces a novel chemical treatment for achieving sustained shrink-resist performance on natural keratin fibers. The new treatment involves the controlled reduction of keratin in the cuticle region of the fiber, and the application of a water soluble diacrylate, namely glycerol 1,3-diglycerolate diacrylate (GDA), on the reduced keratin substrate. The acrylate groups of the GDA react with cysteine residues in the reduced keratin through thiol-ene click reactions at room temperature, leading to GDA grafting and the formation of GDA crosslinks in the keratin structure. The modified substrates were characterized by infrared spectroscopy and scanning electron microscopy, and assessed for its shrink-resistance and wet burst strength. This chemical modification has shown to alter the fiber surface morphology and hydrophilicity, resulting in substantially improved shrink-resistance with good fiber strength retention. Possible shrink-resistance mechanisms were also discussed. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Controlled drug delivery through a novel PEG hydrogel encapsulated silica aerogel system.

PubMed

Giray, Seda; Bal, Tuğba; Kartal, Ayse M; Kızılel, Seda; Erkey, Can

2012-05-01

A novel composite material consisting of a silica aerogel core coated by a poly(ethylene) glycol (PEG) hydrogel was developed. The potential of this novel composite as a drug delivery system was tested with ketoprofen as a model drug due to its solubility in supercritical carbon dioxide. The results indicated that both drug loading capacity and drug release profiles could be tuned by changing hydrophobicity of aerogels, and that drug loading capacity increased with decreased hydrophobicity, while slower release rates were achieved with increased hydrophobicity. Furthermore, higher concentration of PEG diacrylate in the prepolymer solution of the hydrogel coating delayed the release of the drug which can be attributed to the lower permeability at higher PEG diacrylate concentrations. The novel composite developed in this study can be easily implemented to achieve the controlled delivery of various drugs and/or proteins for specific applications. Copyright © 2012 Wiley Periodicals, Inc.

Collaborative study of the determination of boric acid in caviar by emission spectroscopy.

PubMed

Franco, V; Holak, W

1975-03-01

Caviar samples were spiked at the 0.1 and 0.2% levels and digested with nitric acid in a closed Teflon-lined digestion vessel to prevent volatility losses. The boron was complexed with 2-ethyl-1,3-hexanediol and extracted into methylisobulty ketone. The emission of the boron oxide band was measured in a nitrous oxidehydrogen flame. The mean recoveries at the 0.1 and 0.2% levels for 6 collaborators were 95.7 and 97.1%, respectively.

(2E,6Z,9Z)-2,6,9-Pentadecatrienal as a Male-Produced Aggregation-Sex Pheromone of the Cerambycid Beetle Elaphidion mucronatum.

PubMed

Millar, Jocelyn G; Mitchell, Robert F; Meier, Linnea R; Johnson, Todd D; Mongold-Diers, Judith A; Hanks, Lawrence M

2017-12-01

An increasing body of evidence suggests that the volatile pheromones of cerambycid beetles are much more diverse in structure than previously hypothesized. Here, we describe the identification, synthesis, and field testing of (2E,6Z,9Z)-2,6,9-pentadecatrienal as a male-produced aggregation-sex pheromone of the cerambycid Elaphidion mucronatum (Say) (subfamily Cerambycinae, tribe Elaphidiini). This novel structure is unlike any previously described cerambycid pheromone, and in field bioassays attracted only this species. Males produced about 9 μg of pheromone per 24 h period, and, in field trials, lures loaded with 10, 25, and 100 mg of synthetic pheromone attracted beetles of both sexes, whereas lures loaded with 1 mg of pheromone or less were not significantly attractive. Other typical cerambycine pheromones such as 3-hydroxy-2-hexanone, syn-2,3-hexanediol, and anti-2,3-hexanediol were not attractive to E. mucronatum, and when combined with (2E,6Z,9Z)-2,6,9-pentadecatrienal, the former two compounds appeared to inhibit attraction. Unexpectedly, adults of the cerambycine Xylotrechus colonus (F.) were attracted in significant numbers to a blend of 3-hydroxyhexan-2-one and (2E,6Z,9Z)-2,6,9-pentadecatrienal, even though there is no evidence that this species produces the latter compound. From timed pheromone trap catches, adults of E. mucronatum were determined to be active from dusk until shortly after midnight.

Stereoselective oxidation of aliphatic diols and reduction of hydroxy-ketones with galactitol dehydrogenase from Rhodobacter sphaeroides D.

PubMed

Kohring, G W; Wiehr, P; Jeworski, M; Giffhorn, F

2003-01-01

From the Rhodobacter sphaeroides mutant D a galactitol dehydrogenase (GDH) was isolated and characterized in an earlier investigation (1). The enzyme expressed activity with a wide spread substrate spectrum, like sugars, sugar alcohols, secondary alcohols or the corresponding ketones and it can be used for the production of the rare sugar L-tagatose by regioselective oxidation of galactitol (2). This study focuses on the preparation of optically pure aliphatic diols by oxidation of one enantiomer or stereospecific reduction of keto-alcohols and diketones. The oxidation of 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol and 1,2-hexanediol occurred highly specific with the S-enantiomer leaving the R-enantiomer of the diols in the reaction vessel. Also (S)-1,2,6-hexanetriol was oxidized by GDH to 1,6-dihydroxy-2-hexanone. The Km values of these reactions decreased with increasing length of the carbon chain. Reduction of hydroxyacetone or 1-hydroxy-2-butanone resulted in an excess of 93% (S)-1,2-propanediol and more than 98% of (S)-1,2-butanediol, respectively. The diketone 2,3-hexanedione was only reduced to (2R,3S)-2,3-hexanediol, one of the possible four configurations. The wide substrate spectrum on one hand and the selectivity in the reaction on the other hand make GDH a very interesting enzyme for the production of optically pure building blocks in the chemical synthesis of bioactive compounds.

Strain rate dependent hyperelastic stress-stretch behavior of a silica nanoparticle reinforced poly (ethylene glycol) diacrylate nanocomposite hydrogel.

PubMed

Zhan, Yuexing; Pan, Yihui; Chen, Bing; Lu, Jian; Zhong, Zheng; Niu, Xinrui

2017-11-01

Poly (ethylene glycol) diacrylate (PEGDA) derivatives are important biomedical materials. PEGDA based hydrogels have emerged as one of the popular regenerative orthopedic materials. This work aims to study the mechanical behavior of a PEGDA based silica nanoparticle (NP) reinforced nanocomposite (NC) hydrogel at physiological strain rates. The work combines materials fabrication, mechanical experiments, mathematical modeling and structural analysis. The strain rate dependent stress-stretch behaviors were observed, analyzed and quantified. Visco-hyperelasticity was identified as the deformation mechanism of the nano-silica/PEGDA NC hydrogel. NPs showed significant effect on both initial shear modulus and viscoelastic materials properties. A structure-based quasi-linear viscoelastic (QLV) model was constructed and capable to describe the visco-hyperelastic stress-stretch behavior of the NC hydrogel. A group of unified material parameters was extracted by the model from the stress-stretch curves obtained at different strain rates. Visco-hyperelastic behavior of NP/polymer interphase was not only identified but also quantified. The work could provide guidance to the structural design of next-generation NC hydrogel. Copyright © 2017. Published by Elsevier Ltd.

Soft and flexible poly(ethylene glycol) nanotubes for local drug delivery.

PubMed

Newland, B; Taplan, C; Pette, D; Friedrichs, J; Steinhart, M; Wang, W; Voit, B; Seib, F P; Werner, C

2018-05-10

Nanotubes are emerging as promising materials for healthcare applications but the selection of clinically relevant starting materials for their synthesis remains largely unexplored. Here we present, for the first time, the synthesis of poly(ethylene glycol) (PEG) based nanotubes via the photopolymerization of poly(ethylene glycol) diacrylate and other diacrylate derivatives within the pores of anodized aluminum oxide templates. Template-assisted synthesis allowed the manufacture of a diverse set of polymeric nanotubes with tunable physical characteristics including diameter (∼200-400 nm) and stiffness (405-902 kPa). PEG nanotubes were subjected to cytotoxicty assessment in cell lines and primary stem cells and showed excellent cytocompatability (IC50 > 120 μg ml-1). Nanotubes were readily drug loaded but released the majority of the drug over 5 days. Direct administration of drug loaded nanotubes to human orthotopic breast tumors substantially reduced tumor growth and metastasis and outperformed i.v. administration at the equivalent dose. Overall, this nanotube templating platform is emerging as a facile route for the manufacture of poly(ethylene glycol) nanotubes.

Microfluidic Valves Made From Polymerized Polyethylene Glycol Diacrylate

PubMed Central

Rogers, Chad I.; Oxborrow, Joseph B.; Anderson, Ryan R.; Tsai, Long-Fang; Nordin, Gregory P.; Woolley, Adam T.

2013-01-01

Pneumatically actuated, non-elastomeric membrane valves fabricated from polymerized polyethylene glycol diacrylate (poly-PEGDA) have been characterized for temporal response, valve closure, and long-term durability. A ~100 ms valve opening time and a ~20 ms closure time offer valve operation as fast as 8 Hz with potential for further improvement. Comparison of circular and rectangular valve geometries indicates that the surface area for membrane interaction in the valve region is important for valve performance. After initial fabrication, the fluid pressure required to open a closed circular valve is ~50 kPa higher than the control pressure holding the valve closed. However, after ~1000 actuations to reconfigure polymer chains and increase elasticity in the membrane, the fluid pressure required to open a valve becomes the same as the control pressure holding the valve closed. After these initial conditioning actuations, poly-PEGDA valves show considerable robustness with no change in effective operation after 115,000 actuations. Such valves constructed from non-adsorptive poly-PEGDA could also find use as pumps, for application in small volume assays interfaced with biosensors or impedance detection, for example. PMID:24357897

Direct laser writing of synthetic poly(amino acid) hydrogels and poly(ethylene glycol) diacrylates by two-photon polymerization.

PubMed

Käpylä, Elli; Sedlačík, Tomáš; Aydogan, Dogu Baran; Viitanen, Jouko; Rypáček, František; Kellomäki, Minna

2014-10-01

The additive manufacturing technique of direct laser writing by two-photon polymerization (2PP-DLW) enables the fabrication of three-dimensional microstructures with superior accuracy and flexibility. When combined with biomimetic hydrogel materials, 2PP-DLW can be used to recreate the microarchitectures of the extracellular matrix. However, there are currently only a limited number of hydrogels applicable for 2PP-DLW. In order to widen the selection of synthetic biodegradable hydrogels, in this work we studied the 2PP-DLW of methacryloylated and acryloylated poly(α-amino acid)s (poly(AA)s). The performance of these materials was compared to widely used poly(ethylene glycol) diacrylates (PEGdas) in terms of polymerization and damage thresholds, voxel size, line width, post-polymerization swelling and deformation. We found that both methacryloylated and acryloylated poly(AA) hydrogels are suitable to 2PP-DLW with a wider processing window than PEGdas. The poly(AA) with the highest degree of acryloylation showed the greatest potential for 3D microfabrication. Copyright © 2014 Elsevier B.V. All rights reserved.

Monodisperse Polyethylene Glycol Diacrylate Hydrogel Microsphere Formation by Oxygen-Controlled Photopolymerization in a Microfluidic Device

PubMed Central

Krutkramelis, K.; Xia, B.; Oakey, J.

2016-01-01

PEG-based hydrogels have become widely used as drug delivery and tissue scaffolding materials. Common among PEG hydrogel-forming polymers are photopolymerizable acrylates such as polyethylene glycol diacrylate (PEGDA). Microfluidics and microfabrication technologies have recently enabled the miniaturization of PEGDA structures, thus enabling many possible applications for nano- and micro- structured hydrogels. The presence of oxygen, however, dramatically inhibits the photopolymerization of PEGDA, which in turn frustrates hydrogel formation in environments of persistently high oxygen concentration. Using PEGDA that has been emulsified in fluorocarbon oil via microfluidic flow focusing within polydimethylsiloxane (PDMS) devices, we show that polymerization is completely inhibited below critical droplet diameters. By developing an integrated model incorporating reaction kinetics and oxygen diffusion, we demonstrate that the critical droplet diameter is largely determined by the oxygen transport rate, which is dictated by the oxygen saturation concentration of the continuous oil phase. To overcome this fundamental limitation, we present a nitrogen micro-jacketed microfluidic device to reduce oxygen within the droplet, enabling the continuous on-chip photopolymerization of microscale PEGDA particles. PMID:26987384

Microbial-based synthesis of highly elastomeric biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate) thermoplastic.

PubMed

Huong, Kai-Hee; Teh, Chin-Hoe; Amirul, A A

2017-08-01

This study reports the production of P(3HB-co-4HB) [Poly(3-hydroxybutyrate-co-4-hydroxybutyrate)] in possession of high molecular weight and elastomeric properties by Cupriavidus sp. USMAA1020 in single-stage mixed-substrate cultivation system. 1,4-butanediol and 1,6-hexanediol are found to be efficient substrate mixture that has resulted in high copolymer yield, occupying a maximum of 70wt% of the total biomass and producing higher 4HB monomer composition ranging from 31mol% to 41mol%. In substrate mixtures involving 1,6-hexanediol, cleavage of the 6-hydroxyhexanoyl-CoA produces Acetyl-CoA and 4-hydroxybutyryl-CoA. Acetyl-CoA is instrumental in initiating the cell growth in the single-stage fermentation system, preventing 4-hydroxybutyryl-CoA from being utilized via β-oxidation and retained the 4HB monomer at higher ratios. Macroscopic kinetic models of the bioprocesses have revealed that the P(3HB-co-4HB) formation appears to be in the nature of mixed-growth associated with higher formation rate during exponential growth phase; evidenced by higher growth associated constants, α, from 0.0690g/g to 0.4615g/g compared to non-growth associated constants, β, from 0.0092g/g/h to 0.0459g/g/h. The P(3HB-co-31mol% 4HB) produced from the substrate mixture exhibited high weight-average molecular weight, M w of 927kDa approaching a million Dalton, and possessed elongation at break of 1637% upon cultivation at 0.56wt% C. This is the first report on such properties for the P(3HB-co-4HB) copolymer. The copolymer is highly resistant to polymer deformation after being stretched. Copyright © 2017 Elsevier B.V. All rights reserved.

Reactions of hexadehydro-Diels-Alder benzynes with structurally complex multifunctional natural products

NASA Astrophysics Data System (ADS)

Ross, Sean P.; Hoye, Thomas R.

2017-06-01

An important question in organic chemistry concerns the extent to which benzynes—one of the classical reactive intermediates in organic chemistry—can react in discriminating fashion with trapping reagents. In particular, whether these species can react selectively with substrates containing multiple functional groups and possible sites of reactivity has remained unanswered. Natural products comprise a palette of multifunctional compounds with which to address this question. Here, we show that benzynes produced by the hexadehydro-Diels-Alder (HDDA) reaction react with many secondary metabolites with a preference for one among several pathways. Examples demonstrating such selectivity include reactions with: phenolics, through dearomatizing ortho-substitution; alkaloids, through Hofmann-type elimination; tropolone and furan, through cycloaddition; and alkaloids, through three-component fragmentation-coupling reactions. We also demonstrate that the cinchona alkaloids quinidine and quinine give rise to products (some in as few as three steps) that enable subsequent and rapid access to structurally diverse polyheterocyclic compounds. The results show that benzynes are quite discriminating in their reactivity—a trait perhaps not broadly enough appreciated.

Dermal oncogenicity bioassays of monofunctional and multifunctional acrylates and acrylate-based oligomers.

PubMed

DePass, L R; Maronpot, R R; Weil, C S

1985-01-01

Several important components of photocurable coatings were studied for dermal tumorigenic activity by repeated application to the skin of mice. The substances tested were 2-ethylhexyl acrylate (EHA) and methylcarbamoyloxyethyl acrylate (MCEA) (monomers); neopentyl glycol diacrylate (NPGDA), esterdiol-204-diacrylate (EDDA), and pentaerythritol tri(tetra)acrylate (PETA) (cross-linkers); and three acrylated urethane oligomers. For each bioassay, 40 C3H/HeJ male mice were dosed 3 times weekly on the dorsal skin for their lifetime with the highest dose of the test agent that caused no local irritation or reduction in body weight gain. Two negative control groups received acetone (diluent) only. A positive control group received 0.2% methylcholanthrene (MC). NPGDA and EHA had significant tumorigenic activity with tumor yields of eight and six tumor-bearing mice (three and two malignancies), respectively. The MC group had 34 mice with carcinomas and 1 additional mouse with a papilloma. MCEA had no dermal tumorigenic activity but resulted in early mortality. No skin tumors in the treatment area were observed in the other groups. Additional studies will be necessary to elucidate possible relationships between structure and tumorigenic activity for the acrylates.

Polyethyleneglycol diacrylate hydrogels with plasmonic gold nanospheres incorporated via functional group optimization

NASA Astrophysics Data System (ADS)

Ponnuvelu, Dinesh Veeran; Kim, Seokbeom; Lee, Jungchul

2017-12-01

We present a facile method for the preparation of polyethyleneglycol diacrylate (PEG-DA) hydrogels with plasmonic gold (Au) nanospheres incorporated for various biological and chemical sensing applications. Plasmonic Au nanospheres were prepared ex situ using the standard citrate reduction method with an average diameter of 3.5 nm and a standard deviation of 0.5 nm, and evaluated for their surface functionalization process intended for uniform dispersion in polymer matrices. UV-Visible spectroscopy reveals the existence of plasmonic properties for pristine Au nanospheres, functionalized Au nanospheres, and PEG-DA with uniformly dispersed functionalized Au nanospheres (hybrid Au/PEG-DA hydrogels). Hybrid Au/PEG-DA hydrogels examined by using Fourier transform infra-red spectroscopy (FT-IR) exhibit the characteristic bands at 1635, 1732 and 2882 cm-1 corresponding to reaction products of OH- originating from oxidized product of citrate, -C=O stretching from ester bond, and C-H stretching of PEG-DA, respectively. Thermal studies of hybrid Au/PEG-DA hydrogels show three-stage decomposition with their stabilities up to 500 °C. Optical properties and thermal stabilities associated with the uniform dispersion of Au nanospheres within hydrogels reported herein will facilitate various biological and chemical sensing applications.

Evaluation of the laboratory mouse model for screening topical mosquito repellents.

PubMed

Rutledge, L C; Gupta, R K; Wirtz, R A; Buescher, M D

1994-12-01

Eight commercial repellents were tested against Aedes aegypti 0 and 4 h after application in serial dilution to volunteers and laboratory mice. Results were analyzed by multiple regression of percentage of biting (probit scale) on dose (logarithmic scale) and time. Empirical correction terms for conversion of values obtained in tests on mice to values expected in tests on human volunteers were calculated from data obtained on 4 repellents and evaluated with data obtained on 4 others. Corrected values from tests on mice did not differ significantly from values obtained in tests on volunteers. Test materials used in the study were dimethyl phthalate, butopyronoxyl, butoxy polypropylene glycol, MGK Repellent 11, deet, ethyl hexanediol, Citronyl, and dibutyl phthalate.

Demodex folliculitis presenting as periocular vesiculopustular rash.

PubMed

Yun, Samuel H; Levin, Flora; Servat, Javier

2013-12-01

To report an unusual case of Demodex folliculitis presenting as periocular vesiculopustular rash. Case report. A 68 year-old woman presented with a unilateral periocular rash that was initially treated by her primary ophthalmologist with topical steroids and antivirals. Slit-lamp examination revealed severe bilateral blepharitis, right greater than left, with waxy sleeves around the eyelashes. The diagnosis of Demodex infestation was considered. Treatment with daily lid scrub with polyhexamethylene biguanide (PHMB), 1,2-hexanediol and 1,2-octanediol (OCuSOFT PLUS) and erythromycin ointment twice a day resulted in complete resolution of the symptoms after 4 weeks. Ophthalmologists should be aware of Demodex and consider it in the differential diagnosis of periocular skin lesions.

Digital One-Disc-One-Compound Method for High-Throughput Discovery of Prostate Cancer - Targeting Ligands

DTIC Science & Technology

2015-10-01

shown in Fig. 1a, the prepolymer mixture was sandwiched between photo mask and glass slide. Microdiscs were fabricated on the glass substrate through...polymerization of the prepolymer mixture and the acrylated silane under UV exposure. To achieve the more stable microdiscs for peptide synthesis, the...composition of prepolymer mixture was changed to PEG (Polyethylene Glycol)-diacrylate, crosslinker, photo initiator, 2-aminoethylmethacrylate, water

Interactions between Ethanol, syn-2,3-Hexanediol, 3-Hydroxyhexan-2-one, and 3-Hydroxyoctan-2-one Lures on Trap Catches of Hardwood Longhorn Beetles in Southeastern United States.

PubMed

Miller, D R; Crowe, C M; Mayo, P D; Reid, L S; Silk, P J; Sweeney, J D

2017-10-01

The effectiveness of a four-component "super lure" consisting of ethanol (E) and the cerambycid pheromones syn-2,3-hexanediol (D6), racemic 3-hydroxyhexan-2-one (K6), and racemic 3-hydroxyoctan-2-one (K8) on trap catches of Cerambycidae (Coleoptera) was determined in southeast United States with seven trapping experiments in 2011-2013. We captured 74 species of longhorn beetles in our three-year study. Ethanol significantly increased the mean catches of seven species and increased the number of cerambycid species detected. Traps with the "super lure" were effective for 8 of 13 species of Cerambycidae previously shown to be attracted to binary combinations of ethanol plus one of the three pheromones. However, the "super lure" was less effective for the remaining five species with catch reductions of 40-90% compared with combinations of ethanol and one or two of the pheromones. For example, K6 + K8 lures reduced catches of Anelaphus villosus (F.) in traps with E + D6 by 90%. Similarly, catches of Anelaphus pumilus (Newman) in traps with E + K6 + D6 were reduced by 50% with the addition of K8. Catches of Knulliana cincta (Drury) in traps with K6 + K8 lures were interrupted by D6, an effect negated by the addition of ethanol. Given the interruptive effects on trap catches of some species when lures are combined in a single trap, developing optimal lure blends to maximize detection efficacy will be a challenge for managers of detection programs for non-native invasive species of longhorn beetles. Published by Oxford University Press on behalf of Entomological Society of America 2017. This work is written by (a) US Government employee(s) and is in the public domain in the US.

Optical-strain characteristics of anisotropic polymer films fabricated from a liquid crystal diacrylate

NASA Astrophysics Data System (ADS)

Escuti, Michael J.; Cairns, Darran R.; Crawford, Gregory P.

2004-03-01

The optomechanical characteristics of oriented polymer films made from a photopolymerizable liquid crystal diacrylate (BASF LC242) were examined, with general implications for oriented films of similar materials being used and considered for display-component applications. The birefringence of these uniaxial films before and after polymerization was determined by measuring the retardation between crossed polarizers, (resulting in Δn=0.142±0.002 at 633 nm for the cured polymer films). Optical-strain characteristics were also determined by measuring the transmittance of the films between crossed polarizers at two wavelengths (612 and 633 nm) during the application of a monotonically increasing tensile strain. Under the conservative assumption that Poisson's ratio is constant for the relatively small strains in our experiment, we develop a strained-waveplate model to detect changes in birefringence directly from the modulation in transmittance with increasing strain. We show that strain applied along the axis of the polymer chains did not substantially affect the birefringence, and strain applied perpendicularly caused only a slight decrease (˜1% decrease for 10% strain). These results highlight the robustness of fully polymerized reactive mesogen optical films to withstand the moderate strains anticipated during manufacturing processes and in-service deformation caused by bending or impact.

Durability to oxygen reactive ion etching enhanced by addition of synthesized bis(trimethylsilyl)phenyl-containing (meth)acrylates in ultraviolet nanoimprint lithography

NASA Astrophysics Data System (ADS)

Ito, Shunya; Sato, Hiroki; Tasaki, Yuhei; Watanuki, Kimihito; Nemoto, Nobukatsu; Nakagawa, Masaru

2016-06-01

We investigated the selection of bis(trimethylsilyl)phenyl-containing (meth)acrylates as additives to improve the durability to oxygen reactive ion etching (O2 RIE) of sub-50 nm imprint resist patterns suitable for bubble-defect-free UV nanoimprinting with a readily condensable gas. 2,5-Bis(2-acryloyloxyethoxy)-1,4-bis(trimethylsilyl)benzene, which has a diacrylate chemical structure similar to that of glycerol 1,3-diglycerolate diacrylate used as a base monomer, and 3-(2-methacryloyloxyethoxy)-1-(hydroxylethoxy)-2-propoxy-3,5-bis(trimethylsilyl)benzene, which has a hydroxy group similar to the base monomer, were synthesized taking into consideration the Ohnishi and ring parameters, and the oxidization of the trimethylsilyl moiety to inorganic species during O2 RIE. The addition of the latter liquid additive to the base monomer decreased etching rate owing to the good miscibility of the additive in the base monomer, while the addition of the former crystalline additive caused phase separation after UV nanoimprinting. The latter additive worked as a compatibilizer to the former additive, which is preferred for etching durability improvement. The coexistence of the additives enabled the fabrication of a 45 nm line-and-space resist pattern by UV nanoimprinting, and its residual layer could be removed by O2 RIE.

Separation of alpha-, beta-, gamma-, delta-tocopherols and alpha-tocopherol acetate on a pentaerythritol diacrylate monostearate-ethylene dimethacrylate monolith by capillary electrochromatography.

PubMed

Chaisuwan, Patcharin; Nacapricha, Duangjai; Wilairat, Prapin; Jiang, Zhengjin; Smith, Norman W

2008-06-01

This work reports the first use of a monolith with method development for the separation of tocopherol (TOH) compounds by CEC with UV detection. A pentaerythritol diacrylate monostearate-ethylene dimethacrylate (PEDAS-EDMA) monolithic column has been investigated for an optimised condition to separate alpha-, beta-, gamma- and delta-TOHs, and alpha-tocopherol acetate (TAc). The PEDAS-EDMA monolith showed a remarkably good selectivity for separation of the TOH isomers including the beta- and gamma-isomers which are not easily separated by standard C8 or C18 particle-packed columns. Retention studies indicated that an RP mechanism was involved in the separation on the PEDAS-EDMA column, but polar interactions with the underlying ester and hydroxyl groups enhanced the separation of the problematic beta- and gamma-isomers. Separation of all the compounds was achieved within 25 min using 3:10:87 v/v/v 100 mM Tris buffer (pH 9.3)/methanol/ACN as the mobile phase. The method was successfully applied to a pharmaceutical sample with recoveries from 93 to 99%. Intraday and interday precisions (%RSD) for peak area and retention time were less than 2.3. LODs for all four TOHs and TAc were below 1 ppm.

Occupational methacrylate and acrylate allergy--cross-reactions and possible screening allergens.

PubMed

Aalto-Korte, Kristiina; Henriks-Eckerman, Maj-Len; Kuuliala, Outi; Jolanki, Riitta

2010-12-01

Acrylic resin monomers, especially acrylates and methacrylates, are important occupational allergens. To analyse patterns of concomitant patch test reactions to acrylic monomers in relation to exposure, and to suggest possible screening allergens. We reviewed the patch test files for the years 1994-2009 at the Finnish Institute of Occupational Health for allergic reactions to acrylic monomers, and analysed the clinical records of sensitized patients. In a group of 66 patients allergic to an acrylic monomer, the most commonly positive allergens were three methacrylates, namely ethyleneglycol dimethacrylate (EGDMA), 2-hydroxyethyl methacrylate (2-HEMA) and 2-hydroxypropyl methacrylate (2-HPMA), and an acrylate, namely diethyleneglycol diacrylate (DEGDA). The patterns of concomitant reactions imply that exposure to methacrylates may induce cross-reactivity to acrylates, whereas exposure to acrylates usually does not lead to cross-allergy to methacrylates. Screening for triethyleneglycol diacrylate (TREGDA) in the baseline series was found to be useful, as 3 of 8 patients with diagnosed occupational acrylate allergy might have been missed without the screening. A short screening series of four allergens, EGDMA, DEGDA, 2-HPMA and pentaerythritol triacrylate (PETA), would have screened 93% of our 66 patients; each of the remaining 5 patients reacted to different acrylic monomer(s). © 2010 John Wiley & Sons A/S.

3D cell entrapment in crosslinked thiolated gelatin-poly(ethylene glycol) diacrylate hydrogels

PubMed Central

Fu, Yao; Xu, Kedi; Zheng, Xiaoxiang; Giacomin, A. Jeffrey; Mix, Adam W.; Kao, Weiyuan John

2012-01-01

The combined use of natural ECM components and synthetic materials offers an attractive alternative to fabricate hydrogel-based tissue engineering scaffolds to study cell-matrix interactions in three-dimensions (3D). A facile method was developed to modify gelatin with cysteine via a bifunctional PEG linker, thus introducing free thiol groups to gelatin chains. A covalently crosslinked gelatin hydrogel was fabricated using thiolated gelatin and poly(ethylene glycol) diacrylate (PEGdA) via thiol-ene reaction. Unmodified gelatin was physically incorporated in a PEGdA-only matrix for comparison. We sought to understand the effect of crosslinking modality on hydrogel physicochemical properties and the impact on 3D cell entrapment. Compared to physically incorporated gelatin hydrogels, covalently crosslinked gelatin hydrogels displayed higher maximum weight swelling ratio (Qmax), higher water content, significantly lower cumulative gelatin dissolution up to 7 days, and lower gel stiffness. Furthermore, fibroblasts encapsulated within covalently crosslinked gelatin hydrogels showed extensive cytoplasmic spreading and the formation of cellular networks over 28 days. In contrast, fibroblasts encapsulated in the physically incorporated gelatin hydrogels remained spheroidal. Hence, crosslinking ECM protein with synthetic matrix creates a stable scaffold with tunable mechanical properties and with long-term cell anchorage points, thus supporting cell attachment and growth in the 3D environment. PMID:21955690

Surface forces between hydrophilic silica surfaces in a moisture-sensitive oleophilic diacrylate monomer liquid

NASA Astrophysics Data System (ADS)

Ito, Shunya; Kasuya, Motohiro; Kurihara, Kazue; Nakagawa, Masaru

2018-02-01

We measured the surface forces generated between fused silica surfaces in a low-viscosity oleophilic diacrylate monomer for reliably repeated ultraviolet (UV) nanoimprinting, and studied the influence of water in monomer liquids on the forces. Fused silica surfaces, with a static contact angle of 52.6 ± 1.7° for water, owing to the low degree of hydroxylation, hardly showed reproducible surface forces with repeated scan cycles, comprising approach and separation, even in an identical liquid monomer medium with both of low and high water content. The monomer liquid with a high water content of approximately 420 ppm showed a greater tendency to increase the surface forces at longer surface-surface distances compared with the monomer liquid with a low water content of approximately 60 ppm. On the other hand, silica surfaces with a water contact angle of < 5° after exposure to vacuum UV (VUV) light under a reduced air pressure showed reproducible profiles of surfaces forces using the monomer with a low water concentration of approximately 60 ppm for repeated surface forces scan cycles even in separately prepared silica surfaces, whilst they showed less reproducible profiles in the liquids with high water content of 430 ppm. These results suggested that water possibly adsorbed on the hydrophilic and hydrophobic silica surfaces in the monomer liquid of the high water concentration influenced the repeatability of the surface forces profiles.

Triple-Shape Memory Polymers Based on Self-Complementary Hydrogen Bonding

PubMed Central

Ware, Taylor; Hearon, Keith; Lonnecker, Alexander; Wooley, Karen L.; Maitland, Duncan J.; Voit, Walter

2012-01-01

Triple shape memory polymers (TSMPs) are a growing subset of a class of smart materials known as shape memory polymers, which are capable of changing shape and stiffness in response to a stimulus. A TSMP can change shapes twice and can fix two metastable shapes in addition to its permanent shape. In this work, a novel TSMP system comprised of both permanent covalent cross-links and supramolecular hydrogen bonding cross-links has been synthesized via a one-pot method. Triple shape properties arise from the combination of the glass transition of (meth)acrylate copolymers and the dissociation of self-complementary hydrogen bonding moieties, enabling broad and independent control of both glass transition temperature (Tg) and cross-link density. Specifically, ureidopyrimidone methacrylate and a novel monomer, ureidopyrimidone acrylate, were copolymerized with various alkyl acrylates and bisphenol A ethoxylate diacrylate. Control of Tg from 0 to 60 °C is demonstrated: concentration of hydrogen bonding moieties is varied from 0 to 40 wt %; concentration of the diacrylate is varied from 0 to 30 wt %. Toughness ranges from 0.06 to 0.14 MPa and is found to peak near 20 wt % of the supramolecular cross-linker. A widely tunable class of amorphous triple-shape memory polymers has been developed and characterized through dynamic and quasi-static thermomechanical testing to gain insights into the dynamics of supramolecular networks. PMID:22287811

Single-Monomer Formulation of Polymerized Polyethylene Glycol Diacrylate as a Nonadsorptive Material for Microfluidics

PubMed Central

Rogers, Chad I.; Pagaduan, Jayson V.; Nordin, Gregory P.; Woolley, Adam T.

2011-01-01

Nonspecific adsorption in microfluidic systems can deplete target molecules in solution and prevent analytes, especially those at low concentrations, from reaching the detector. Polydimethylsiloxane (PDMS) is a widely used material for microfluidics, but is prone to nonspecific adsorption, necessitating complex chemical modification processes to address this issue. An alternative material to PDMS that does not require subsequent chemical modification is presented here. Poly(ethylene glycol) diacrylate (PEGDA) mixed with photoinitiator forms on exposure to UV radiation a polymer with inherent resistance to nonspecific adsorption. Optimization of the polymerized PEGDA (poly-PEGDA) formula imbues this material with some of the same properties, including optical clarity, water stability, and low background fluorescence, that make PDMS so popular. Poly-PEGDA demonstrates less nonspecific adsorption than PDMS over a range of concentrations of flowing fluorescently tagged bovine serum albumin solutions, and poly-PEGDA has greater resistance to permeation by small hydrophobic molecules than PDMS. Poly-PEGDA also exhibits long-term (hour scale) resistance to nonspecific adsorption compared to PDMS when exposed to a low (1 µg/mL) concentration of a model adsorptive protein. Electrophoretic separations of amino acids and proteins resulted in symmetrical peaks and theoretical plate counts as high as 4 × 105/m. Poly-PEGDA, which displays resistance to nonspecific adsorption, could have broad use in small volume analysis and biomedical research. PMID:21728310

Adenosine triphosphate diffusion through poly(ethylene glycol) diacrylate hydrogels can be tuned by cross-link density as measured by PFG-NMR

NASA Astrophysics Data System (ADS)

Majer, Günter; Southan, Alexander

2017-06-01

The diffusion of small molecules through hydrogels is of great importance for many applications. Especially in biological contexts, the diffusion of nutrients through hydrogel networks defines whether cells can survive inside the hydrogel or not. In this contribution, hydrogels based on poly(ethylene glycol) diacrylate with mesh sizes ranging from ξ = 1.1 to 12.9 nm are prepared using polymers with number-average molecular weights between Mn = 700 and 8000 g/mol. Precise measurements of diffusion coefficients D of adenosine triphosphate (ATP), an important energy carrier in biological systems, in these hydrogels are performed by pulsed field gradient nuclear magnetic resonance. Depending on the mesh size, ξ, and on the polymer volume fraction of the hydrogel after swelling, ϕ, it is possible to tune the relative ATP diffusion coefficient D/D0 in the hydrogels to values between 0.14 and 0.77 compared to the ATP diffusion coefficient D0 in water. The diffusion coefficients of ATP in these hydrogels are compared with predictions of various mathematical expressions developed under different model assumptions. The experimental data are found to be in good agreement with the predictions of a modified obstruction model or the free volume theory in combination with the sieving behavior of the polymer chains. No reasonable agreement was found with the pure hydrodynamic model.

Glucose-Sensitive Hydrogel Optical Fibers Functionalized with Phenylboronic Acid.

PubMed

Yetisen, Ali K; Jiang, Nan; Fallahi, Afsoon; Montelongo, Yunuen; Ruiz-Esparza, Guillermo U; Tamayol, Ali; Zhang, Yu Shrike; Mahmood, Iram; Yang, Su-A; Kim, Ki Su; Butt, Haider; Khademhosseini, Ali; Yun, Seok-Hyun

2017-04-01

Hydrogel optical fibers are utilized for continuous glucose sensing in real time. The hydrogel fibers consist of poly(acrylamide-co-poly(ethylene glycol) diacrylate) cores functionalized with phenylboronic acid. The complexation of the phenylboronic acid and cis-diol groups of glucose enables reversible changes of the hydrogel fiber diameter. The analyses of light propagation loss allow for quantitative glucose measurements within the physiological range. © 2017 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and Characterisation of Photocrosslinked poly(ethylene glycol) diacrylate Implants for Sustained Ocular Drug Delivery.

PubMed

McAvoy, Kathryn; Jones, David; Thakur, Raghu Raj Singh

2018-01-16

To investigate the sustained ocular delivery of small and large drug molecules from photocrosslinked poly(ethylene glycol) diacrylate (PEGDA) implants with varying pore forming agents. Triamcinolone acetonide and ovalbumin loaded photocrosslinked PEGDA implants, with or without pore-forming agents, were fabricated and characterised for chemical, mechanical, swelling, network parameters, as well as drug release and biocompatibility. HPLC-based analytical methods were employed for analysis of two molecules; ELISA was used to demonstrate bioactivity of ovalbumin. Regardless of PEGDA molecular weight or pore former composition all implants loaded with triamcinolone acetonide released significantly faster than those loaded with ovalbumin. Higher molecular weight PEGDA systems (700 Da) resulted in faster drug release of triamcinolone acetonide than their 250 Da counterpart. All ovalbumin released over the 56-day time period was found to be bioactive. Increasing PEGDA molecular weight resulted in increased system swelling, decreased crosslink density (Ve), increased polymer-water interaction parameter (χ), increased average molecular weight between crosslinks (Mc) and increased mesh size (ε). SEM studies showed the porosity of implants increased with increasing PEGDA molecular weight. Biocompatibility showed both PEGDA molecular weight implants were non-toxic when exposed to retinal epithelial cells over a 7-day period. Photocrosslinked PEGDA implant based systems are capable of controlled drug release of both small and large drug molecules through adaptations in the polymer system network. We are currently continuing evaluation of these systems as potential sustained drug delivery devices.

Imaging dynamic and selective low-complexity domain interactions that control gene transcription.

PubMed

Chong, Shasha; Dugast-Darzacq, Claire; Liu, Zhe; Dong, Peng; Dailey, Gina M; Cattoglio, Claudia; Heckert, Alec; Banala, Sambashiva; Lavis, Luke; Darzacq, Xavier; Tjian, Robert

2018-06-21

Many eukaryotic transcription factors (TFs) contain intrinsically disordered low-complexity domains (LCDs), but how they drive transactivation remains unclear. Here, live-cell single-molecule imaging reveals that TF-LCDs form local high-concentration interaction hubs at synthetic and endogenous genomic loci. TF-LCD hubs stabilize DNA binding, recruit RNA polymerase II (Pol II), and activate transcription. LCD-LCD interactions within hubs are highly dynamic, display selectivity with binding partners, and are differentially sensitive to disruption by hexanediols. Under physiological conditions, rapid and reversible LCD-LCD interactions occur between TFs and the Pol II machinery without detectable phase separation. Our findings reveal fundamental mechanisms underpinning transcriptional control and suggest a framework for developing single-molecule imaging screens for novel drugs targeting gene regulatory interactions implicated in disease. Copyright © 2018, American Association for the Advancement of Science.

Selection of UV Resins for Nanostructured Molds for Thermal-NIL.

PubMed

Jia, Zheng; Choi, Junseo; Park, Sunggook

2018-06-18

Nanoimprint molds made of soft polymeric materials have advantages of low demolding force and low fabrication cost over Si or metal-based hard molds. However, such advantages are often sacrificed by their reduced replication fidelity associated with the low mechanical strength. In this paper, we studied replication fidelity of different UV-resin molds copied from a Si master mold via UV nanoimprint lithography (NIL) and their thermal imprinting performance into a thermoplastic polymer. Four different UV resins were studied: two were high surface energy UV resins based on tripropyleneglycol diacrylate (TPGDA resin) and polypropyleneglycol diacrylate (PPGDA resin), and the other two were commercially available, low surface energy poly-urethane acrylate (PUA resin) and fluorine-containing (MD 700) UV resins. The replication fidelity among the four UV-resins during UV nanoimprint lithograph from a Si master with sharp nanostructures was in the increasing order of (poorest) PUA resin < MD 700 < PPGDA resin < TPGDA resin (best). The results show that the high surface energy and small monomer size are keys to achieving good UV resin filling into sharp nanostructures over the viscosity of the resin solution. When the four UV-resin molds were used for thermal-NIL into a thermoplastic polymer, the replication fidelity was in the increasing order of (poorest) MD 700 < TPGDA resin < PUA resin (best), which follows the same order of their Young's moduli. Our results indicate that the selection of an appropriate UV resin for NIL molds requires consideration of the replication fidelities in the mold fabrication and the subsequent thermal-NIL into thermoplastic polymers. © 2018 IOP Publishing Ltd.

Photoinitiated polymerization of PEG-diacrylate with lithium phenyl-2,4,6-trimethylbenzoylphosphinate: polymerization rate and cytocompatibility

PubMed Central

Fairbanks, Benjamin D.; Schwartz, Michael P.; Bowman, Christopher N.; Anseth, Kristi S.

2009-01-01

Due to mild reaction conditions and temporal and spatial control over material formation, photopolymerization has become a valuable technique for the encapsulation of living cells in three dimensional, hydrated, biomimetic materials. For such applications,2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) is the most commonly used photoinitiator (by virtue of its moderate water solubility), yet this initiator has an absorption spectrum that is poorly matched with wavelengths of light generally regarded as benign to living cells, limiting the rate at which it may initiate polymerization in their presence. In contrast, acylphosphine oxide photoinitiators, generally exhibit absorption spectra at wavelengths suitable for cell encapsulation, yet commercially available initiators of this class have low water solubility. Here, a water soluble lithium acylphosphinate salt is evaluated for its ability to polymerize diacrylated poly(ethylene glycol) (PEGDA) monomers rapidly into hydrogels, while maintaining high viability during direct encapsulation of cells. Through rheometric measurements, the time to reach gelation of a PEGDA solution with the phosphinate initiator is one tenth the time for that using I2959 at similar concentrations, when exposed to 365 nm light. Further, polymerization with the phosphinate initiator at 405 nm visible light exposure is achieved with low initiator concentrations and light intensities, precluded in polymerizations initiated with I2959 by its absorbance profile. When examined 24 hours after encapsulation, survival rates of human neonatal fibroblasts encapsulated in hydrogels polymerized with the phosphinate initiator exceed 95%, demonstrating the cytocompatibility of this initiating system. PMID:19783300

Quasi-solid polymer electrolytes using photo-cross-linked polymers. Lithium and divalent cation conductors and their applications

NASA Astrophysics Data System (ADS)

Ikeda, Shoichiro; Mori, Yoichi; Furuhashi, Yuri; Masuda, Hideki; Yamamoto, Osamu

In this report, we will present the results on the photo-cross-linked poly-(ethylene glycol) diacrylate (PEGDA) based quasi-solid, i.e. gel, polymer electrolyte systems with lithium, magnesium and zinc trifluoromethanesulfonates [triflate; M n(CF 3SO 3) n] and their preliminary applications to primary cells. The Celgard® membrane-impregnated electrolytes were prepared in the same manner as Abraham et al. [K.M. Abraham, M. Alamgir, D.K. Hoffman, J. Electrochem. Soc. 142 (1995) 683]. The precursor solutions were composed of metal triflates, ethylene carbonate, propylene carbonate, and tetraethylene glycol diacrylate. The Celgard® #3401 membrane was soaked overnight in the precursor solution, then clamped between two Pyrex glass plates and irradiated with UV light to form a gel electrolyte. The maxima of the conductivity obtained were 4.5×10 -4 S cm -1 at 12 mol% for LiCF 3SO 3, 1.7×10 -4 S cm -1 at 1 mol% for Mg(CF 3SO 3) 2, and 2.1×10 -4 S cm -1 at 4 mol% for Zn(CF 3SO 3) 2 system, respectively. The Arrhenius plots of the conductivities are almost linear between 268 and 338 K with 15-25 kJ/mol of activation energy for conduction. The cell, Li|LiCF 3SO 3-SPE+Celgard® #3401|(CH 3) 4NI 5+acetylene black, showed 2.86 V of OCV and could discharge up to 25% with respect to the cathode active material at a discharging current of 0.075 mA/cm 2.

Metal-Organic Framework Photosensitized TiO2 Co-catalyst: A Facile Strategy to Achieve a High Efficiency Photocatalytic System.

PubMed

Xie, Ming-Hua; Shao, Rong; Xi, Xin-Guo; Hou, Gui-Hua; Guan, Rong-Feng; Dong, Peng-Yu; Zhang, Qin-Fang; Yang, Xiu-Li

2017-03-17

A 3D metal-organic framework (ADA-Cd=[Cd 2 L 2 (DMF) 2 ]⋅3 H 2 O where H 2 L is (2E,2'E)-3,3'-(anthracene-9,10-diyl)diacrylic acid) constructed from diacrylate substituted anthracene, sharing structural characteristics with some frequently employed anthraquinone-type dye sensitizers, was introduced as an effective sensitizer for anatase TiO 2 to achieve enhanced visible light photocatalytic performance. A facile mechanical mixing procedure was adopted to prepare the co-catalyst denoted as ADA-Cd/TiO 2 , which showed enhanced photodegradation ability, as well as sustainability, towards several dyes under visible light irradiation. Mechanistic studies revealed that ADA-Cd acted as the antenna to harvest visible light energy, generating excited electrons, which were injected to the conduction band (CB) of TiO 2 , facilitating the separation efficiency of charge carriers. As suggested by the results of control experiments, combined with the corresponding redox potential of possible oxidative species, . O 2 - , generated from the oxygen of ambient air at the CB of TiO 2 was believed to play a dominant role over . OH and h + . UV/Vis and photoluminescence technologies were adopted to monitor the generation of . O 2 - and . OH, respectively. This work presents a facile strategy to achieve a visible light photocatalyst with enhanced catalytic activity and sustainability; the simplicity, efficiency, and stability of this strategy may provide a promising way to achieve environmental remediation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sequencing and characterizing odorant receptors of the cerambycid beetle Megacyllene caryae

PubMed Central

Mitchell, Robert F.; Hughes, David T.; Luetje, Charles W.; Millar, Jocelyn G.; Soriano-Agatón, Flor; Hanks, Lawrence M.; Robertson, Hugh M.

2012-01-01

Odorant receptors (Ors) are a unique family of ligand-gated ion channels and the primary mechanism by which insects detect volatile chemicals. Here, we describe 57 putative Ors sequenced from an antennal transcriptome of the cerambycid beetle Megacyllene caryae (Gahan). The male beetles produce a pheromone blend of nine components, and we functionally characterized Ors tuned to three of these chemicals: receptor McOr3 is sensitive to (S)-2-methyl-1-butanol; McOr20 is sensitive to (2S,3R)-2,3-hexanediol; and McOr5 is sensitive to 2-phenylethanol. McOr3 and McOr20 are also sensitive to structurally-related chemicals that are pheromones of other cerambycid beetles, suggesting that orthologous receptors may be present across many cerambycid species. These Ors are the first to be functionally characterized from any species of beetle and lay the groundwork for understanding the evolution of pheromones within the Cerambycidae. PMID:22504490

Novel Approaches to Immobilized Heteropoly Acid Systems for High Temperature, Low Relative Humidity Polymer-Type Membranes - Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herring, Andrew M; Horan, James L; Aieta, Niccolo V

2012-05-20

Original research was carried out at the CSM and the 3M Company from March 2007 through September 2011. The research was aimed at developing new to the world proton electrolyte materials for use in hydrogen fuel cells, in particular with high proton conductivity under hot and dry conditions (>100mS/cm at 120°C and 50%RH). Broadly stated, the research at 3M and between 3M and CSM that led to new materials took place in two phases: In the first phase, hydrocarbon membranes that could be formed by photopolymerization of monomer mixtures were developed for the purpose of determining the technical feasibility ofmore » achieving the program's Go/No-Go decision conductivity target of >100mS/cm at 120°C and 50%RH. In the second phase, attempts were made to extend the achieved conductivity level to fluorinated material systems with the expectation that durability and stability would be improved (over the hydrocarbon material). Highlights included: Multiple lots of an HPA-immobilized photocurable terpolymer derived from di-vinyl-silicotungstic acid (85%), n-butyl acrylate, and hexanediol diacrylate were prepared at 3M and characterized at 3M to exhibit an initial conductivity of 107mS/cm at 120°C and 47%RH (PolyPOM85v) using a Bekktech LLC sample fixture and TestEquity oven. Later independent testing by Bekktech LLC, using a different preheating protocol, on the same material, yielded a conductivity value of approximately 20mS/cm at 120°C and 50%RH. The difference in measured values is likely to have been the result of an instability of properties for the material or a difference in the measurement method. A dispersed catalyst fuel cell was fabricated and tested using a 150¼m thick HPA-based photocurable membrane (above, PolyPOM75v), exhibiting a current density of greater than 300mA/cm2 at 0.5V (H2/Air 800/1800sccm 70°C/75%RH ambient outlet pressure). Multiple lots of a co-polymer based on poly-trifluorovinylether (TFVE) derived HPA were synthesized and fabricated into films, Generation II films. These materials showed proton conductivities as high as 1 S/cm under high RH conditions. However, the materials suffered from compromised properties due to impure monomers and low molecular weights. Multiple lots of an HPA-immobilized fluoropolymer derived from preformed PVDF-HFP (Generation III films) were synthesized and formed into membranes at 3M and characterized at 3M to exhibit conductivity reaching approximately 75mS/cm at 120°C/40%RH using a Bekktech sample fixture and TestEquity oven (optimized membrane, at close of program). Initial fuel cell fabrication and testing for this new class of membrane yielded negative results (no measureable proton conductivity); however, the specific early membrane that was used for the two 5cm2 MEAs was later determined to have <1 mS/cm at 80°C/80%RH using the Bekktech fixture, vs. ca. 200 mS/cm at 80°C/80%RH for samples of the later-optimized type described above. Future work in this area (beyond the presently reported contract) should include additional attempts to fabricate and test fuel cells based on the later-optimized Generation II and III polymer. A manufacturing study was performed which predicted no difficulties in any future scale up of the materials.« less

Solid electrolytes

DOEpatents

Abraham, Kuzhikalail M.; Alamgir, Mohamed

1993-06-15

This invention pertains to Li ion (Li.sup.+) conductive solid polymer electrolytes composed of solvates of Li salts immobilized (encapsulated) in a solid organic polymer matrix. In particular, this invention relates to solid polymer electrolytes derived by immobilizing complexes (solvates) formed between a Li salt such as LiAsF.sub.6, LiCF.sub.3 SO.sub.3 or LiClO.sub.4 and a mixture of aprotic organic solvents having high dielectric constants such as ethylene carbonate (EC) (dielectric constant=89.6) and propylene carbonate (PC) (dielectric constant=64.4) in a polymer matrix such as polyacrylonitrile, poly(tetraethylene glycol diacrylate), or poly(vinyl pyrrolidinone).

Poly(ethylene glycol) analogs grafted with low molecular weight poly(ethylene imine) as non-viral gene vectors.

PubMed

Zhang, Zhenfang; Yang, Cuihong; Duan, Yajun; Wang, Yanming; Liu, Jianfeng; Wang, Lianyong; Kong, Deling

2010-07-01

A novel class of non-viral gene vectors consisting of low molecular weight poly(ethylene imine) (PEI) (molecular weight 800 Da) grafted onto degradable linear poly(ethylene glycol) (PEG) analogs was synthesized. First, a Michael addition reaction between poly(ethylene glycol) diacrylates (PEGDA) (molecular weight 258 Da) and d,l-dithiothreitol (DTT) was carried out to generate a linear polymer (PEG-DTT) having a terminal thiol, methacrylate and pendant hydroxyl functional groups. Five PEG-DTT analogs were synthesized by varying the molar ratio of diacrylates to thiols from 1.2:1 to 1:1.2. Then PEI (800 Da) was grafted onto the main chain of the PEG-DTTs using 1,1'-carbonyldiimidazole as the linker. The above reaction gave rise to a new class of non-viral gene vectors, (PEG-DTT)-g-PEI copolymers, which can effectively complex DNA to form nanoparticles. The molecular weights and structures of the copolymers were characterized by gel permeation chromatography, (1)H nuclear magnetic resonance and Fourier transform infrared spectroscopy. The size of the nanoparticles was<200 nm and the surface charge of the nanoparticles, expressed as the zeta potential, was between+20 and+40 mV. Cytotoxicity assays showed that the copolymers exhibited much lower cytotoxicities than high molecular weight PEI (25 kDa). Transfection was performed in cultured HeLa, HepG2, MCF-7 and COS-7 cells. The copolymers showed higher transfection efficiencies than PEI (25 kDa) tested in four cell lines. The presence of serum (up to 30%) had no inhibitory effect on the transfection efficiency. These results indicate that this new class of non-viral gene vectors may be a promising gene carrier that is worth further investigation. Copyright 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Facile modulation of cell adhesion to a poly(ethylene glycol) diacrylate film with incorporation of polystyrene nano-spheres.

PubMed

Yang, Wenguang; Yu, Haibo; Li, Gongxin; Wang, Yuechao; Liu, Lianqing

2016-12-01

Poly(ethylene glycol) diacrylate (PEGDA) is a common hydrogel that has been actively investigated for various tissue engineering applications owing to its biocompatibility and excellent mechanical properties. However, the native PEGDA films are known for their bio-inertness which can hinder cell adhesion, thereby limiting their applications in tissue engineering and biomedicine. Recently, nano composite technology has become a particularly hot topic, and has led to the development of new methods for delivering desired properties to nanomaterials. In this study, we added polystyrene nano-spheres (PS) into a PEGDA solution to synthesize a nano-composite film and evaluated its characteristics. The experimental results showed that addition of the nanospheres to the PEGDA film not only resulted in modification of the mechanical properties and surface morphology but further improved the adhesion of cells on the film. The tensile modulus showed clear dependence on the addition of PS, which enhanced the mechanical properties of the PEGDA-PS film. We attribute the high stiffness of the hybrid hydrogel to the formation of additional cross-links between polymeric chains and the nano-sphere surface in the network. The effect of PS on cell adhesion and proliferation was evaluated in L929 mouse fibroblast cells that were seeded on the surface of various PEGDA-PS films. Cells density increased with a larger PS concentration, and the cells displayed a spreading morphology on the hybrid films, which promoted cell proliferation. Impressively, cellular stiffness could also be modulated simply by tuning the concentration of nano-spheres. Our results indicate that the addition of PS can effectively tailor the physical and biological properties of PEGDA as well as the mechanical properties of cells, with benefits for biomedical and biotechnological applications.

Engineering the bone-ligament interface using polyethylene glycol diacrylate incorporated with hydroxyapatite.

PubMed

Paxton, Jennifer Z; Donnelly, Kenneth; Keatch, Robert P; Baar, Keith

2009-06-01

Ligaments and tendons have previously been tissue engineered. However, without the bone attachment, implantation of a tissue-engineered ligament would require it to be sutured to the remnant of the injured native tissue. Due to slow repair and remodeling, this would result in a chronically weak tissue that may never return to preinjury function. In contrast, orthopaedic autograft reconstruction of the ligament often uses a bone-to-bone technique for optimal repair. Since bone-to-bone repairs heal better than other methods, implantation of an artificial ligament should also occur from bone-to-bone. The aim of this study was to investigate the use of a poly(ethylene glycol) diacrylate (PEGDA) hydrogel incorporated with hydroxyapatite (HA) and the cell-adhesion peptide RGD (Arg-Gly-Asp) as a material for creating an in vitro tissue interface to engineer intact ligaments (i.e., bone-ligament-bone). Incorporation of HA into PEG hydrogels reduced the swelling ratio but increased mechanical strength and stiffness of the hydrogels. Further, HA addition increased the capacity for cell growth and interface formation. RGD incorporation increased the swelling ratio but decreased mechanical strength and stiffness of the material. Optimum levels of cell attachment were met using a combination of both HA and RGD, but this material had no better mechanical properties than PEG alone. Although adherence of the hydrogels containing HA was achieved, failure occurs at about 4 days with 5% HA. Increasing the proportion of HA improved interface formation; however, with high levels of HA, the PEG HA composite became brittle. This data suggests that HA, by itself or with other materials, might be well suited for engineering the ligament-bone interface.

Photocurable poly(ethylene glycol) as a bioink for the inkjet 3D pharming of hydrophobic drugs.

PubMed

Acosta-Vélez, Giovanny F; Zhu, Timothy Z; Linsley, Chase S; Wu, Benjamin M

2018-04-26

Binder jetting and material extrusion are the two most common additive manufacturing techniques used to create pharmaceutical tablets. However, their versatility is limited since the powder component is present throughout the dosage forms fabricated by binder jet 3D printing and material extrusion 3D printing requires high operating temperatures. Conversely, material jetting allows for compositional control at a voxel level and can dispense material at room temperature. Unfortunately, there are a limited number of materials that are both printable and biocompatible. Therefore, the aim of this study was to engineer photocurable bioinks that are suitable for hydrophobic active pharmaceutical ingredients and have rapid gelation times upon visible light exposure. The resulting bioinks were comprised of poly(ethylene glycol) diacrylate (250 Da) as the crosslinkable monomer, Eosin Y as the photoinitiator, and methoxide-poly(ethylene glycol)-amine as the coinitiator. Additionally, poly(ethylene glycol) (200 Da) was added as a plasticizer to modulate the drug release profiles, and Naproxen was used as the model drug due to its high hydrophobicity. Various bioink formulations were dispensed into the bottom half of blank preform tablets - made via direct compression - using a piezoelectric nozzle, photopolymerized, and capped with the top half of the preform tablet to complete the pharmaceutical dosage form. Results from the release studies showed that drug release can be modulated by both the percent of poly(ethylene glycol) diacrylate in the formulation and the light exposure time used to cure the bioinks. These bioinks have the potential to expand the library of materials available for creating pharmaceutical tablets via inkjet printing with personalized drug dosages. Copyright © 2018 Elsevier B.V. All rights reserved.

Photo-Curing: UV Radiation curing of polymers

NASA Technical Reports Server (NTRS)

Inman, Christina A.

2004-01-01

The Polymers Branch of the Materials Division is dedicated to the development of high-performance for a variety of applications. Areas of significant interest include high- temperature polymers, low density, and high strength insulating materials, conductive polymers, and high density polymer electrolytes. This summer our group is working diligently on a photo-curing project. There is interest in the medical community feel the need for a new and improved balloon that will be used for angioplasty (a form of heart surgery). This product should maintain flexibility but add many other properties. Like possibly further processability and resistance to infection. Our group intends on coming up with this product by using photo-enolization (or simply, photo-curing) by Diels-Alder trapping. The main objective was to synthesize a series of new polymers by Diels-Alder cycloaddition of photoenols with more elastomeric properties. Our group was responsible for performing the proper photo-curing techniques of the polymers with diacrylates and bismaleimides, synthesizing novel monomers, and evaluating experimental results. We attempted to use a diacrylate to synthesize the polymer because of previous research done within the Polymers Branch here at NASA. Most acrylates are commercially available, have more elastometric properties than a typical rigid aromatic structure has and they contain ethylene oxides in the middle of their structure that create extensive flexibility. The problem we encountered with the acrylates is that they photo chemically and thermally self polymerize and create diradicals at low temperatures; these constraints caused a lot of unnecessary side reactions. We want to promote solely, diketone polymerization because this type of polymerization has the ability to cause very elastic polymers. We chose to direct our attention towards the usage of maleimides because they are known for eliminating these unnecessary side reactions.

An Intriguing Method for Fabricating Arbitrarily Shaped “Matreshka” Hydrogels Using a Self-Healing Template

PubMed Central

Sato, Takeshi; Uto, Koichiro; Aoyagi, Takao; Ebara, Mitsuhiro

2016-01-01

This work describes an intriguing strategy for the creation of arbitrarily shaped hydrogels utilizing a self-healing template (SHT). A SHT was loaded with a photo-crosslinkable monomer, PEG diacrylate (PEGDA), and then ultraviolet light (UV) crosslinked after first shaping. The SHT template was removed by simple washing with water, leaving behind the hydrogel in the desired physical shape. A hierarchical 3D structure such as “Matreshka” boxes were successfully prepared by simply repeating the “self-healing” and “photo-irradiation” processes. We have also explored the potential of the SHT system for the manipulation of cells. PMID:28773983

Deep eutectic solvent-based valorization of spent coffee grounds.

PubMed

Yoo, Da Eun; Jeong, Kyung Min; Han, Se Young; Kim, Eun Mi; Jin, Yan; Lee, Jeongmi

2018-07-30

Spent coffee grounds (SCGs) are viewed as a valuable resource for useful bioactive compounds, such as chlorogenic acids and flavonoids, and we suggest an eco-friendly and efficient valorization method. A series of choline chloride-based deep eutectic solvents (DESs) were tested as green extraction solvents for use with ultrasound-assisted extraction. Extraction efficiency was evaluated based on total phenolic content (TPC), total flavonoid content, total chlorogenic acids, and/or anti-oxidant activity. A binary DES named HC-6, which was composed of 1,6-hexanediol:choline chloride (molar ratio 7:1) was designed to produce the highest efficiency. Experimental conditions were screened and optimized for maximized efficiency using a two-level fractional factorial design and a central composite design, respectively. As a result, the proposed method presented significantly enhanced TPC and anti-oxidant activity. In addition, phenolic compounds could be easily recovered from extracts at high recovery yields (>90%) by adsorption chromatography. Copyright © 2018 Elsevier Ltd. All rights reserved.

Evaluation of PEMFC System Contaminants on the Performance of Pt Catalyst via Cyclic Voltammetry: Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, H.; Macomber, C.; Dinh, H. N.

2012-07-01

Using electrochemical cyclic voltammetry as a quick ex-situ screening tool, the impact of the extracted solution and the individual leachable constituents from prospective BOP component materials on the performance and recoverability of the platinum catalyst were evaluated. Taking an extract from Zytel{trademark} HTN51G35HSLR (PPA) as an example, the major leachable organic components are caprolactam and 1,6 hexanediol. While these organic compounds by themselves do poison the Pt catalyst to some extent, such influence is mostly recoverable by means of potential holding and potential cycling. The extracted solution, however, shows a more drastic poisoning effect and it was not recoverable. Thereforemore » the non-recoverable poisoning effect observed for the extracted solution is not from the two organic species studied. This demonstrates the complexity of such a contaminant study. Inorganic compounds that are known poisons like sulfur even in very low concentrations, may have a more dominant effect on the Pt catalyst and the recoverability.« less

Self-supporting hydrogel stamps for the microcontact printing of proteins.

PubMed

Coq, Naïs; van Bommel, Ties; Hikmet, Rifat A; Stapert, Hendrik R; Dittmer, Wendy U

2007-04-24

In this work we explore a new hydrogel stamp material obtained from polymerizing 2-hydroxyethyl acrylate and poly(ethylene glycol) diacrylate in the presence of water for the microcontact printing of proteins directly on gold substrates and by covalent coupling to self-assembled monolayers of alkanethiols. At high cross-link density, the hydrogel is rigid, hydrophilic, and with a high buffer holding capacity to enable the unsupported printing of protein patterns homogeneously and reproducibly, with micrometer-range precision. The stamps were used to print antibodies to human parathyroid hormone, which were shown using immunoassay tests to retain their biological function with binding capacities comparable to those of solution-adsorbed antibodies.

Transparent organic/inorganic hybrid sol-gel materials based on perfluorinated polymers and silica

NASA Astrophysics Data System (ADS)

Wojcik, Anna B.; Klein, Lisa C.

1996-01-01

Two types of hybrid gels based on silica and perfluorinated polymers have been prepared. The first type involves a perfluorinated polymer containing acrylate groups. Perfluoropolyether diol diacrylate (PFDA) was functionalized by reacting it with (3-mercapto-propyl) trimethoxysilane by a Michael addition. The resulting silyl derivative (PFDAS) was able to copolymerize with a silica precursor, tetraethylorthosilicate (TEOS), resulting in perfluorinated polymer/silica hybrid gels. For the second type, perfluoroalkylsilane (FAS), vinyltriethoxysilane (VTES), and TEOS were polymerized in one step. In both cases, the gels were transparent, crack-free and water repellent. Since the inorganic and organic components are covalently bonded to each other, these materials can be classified as organic/inorganic copolymers.

Minocycline enhances the mesenchymal stromal/stem cell pro-healing phenotype in triple antimicrobial-loaded hydrogels.

PubMed

Guerra, Alberto Daniel; Rose, Warren E; Hematti, Peiman; Kao, W John

2017-03-15

Mesenchymal stromal/stem cells (MSCs) have demonstrated pro-healing properties including an anti-inflammatory cytokine profile and the promotion of angiogenesis via expression of growth factors in pre-clinical models. MSCs encapsulated in poly(ethylene glycol) diacrylate (PEGdA) and thiolated gelatin poly(ethylene glycol) (Gel-PEG-Cys) crosslinked hydrogels have led to controlled cellular presentation at wound sites with favorable wound healing outcomes. However, the therapeutic potential of MSC-loaded hydrogels may be limited by non-specific protein adsorption on the delivery matrix that could facilitate the initial adhesion of microorganisms and subsequent virulent biofilm formation. Antimicrobials loaded concurrently in the hydrogels with MSCs could reduce microbial bioburden and promote healing, but the antimicrobial effect on the MSC wound healing capacity and the antibacterial efficacy of the hydrogels is unknown. We demonstrate that minocycline specifically induces a favorable change in MSC migration capacity, proliferation, gene expression, extracellular matrix (ECM) attachment, and adhesion molecule and growth factor release with subsequent increased angiogenesis. We then demonstrate that hydrogels loaded with MSCs, minocycline, vancomycin, and linezolid can significantly decrease bacterial bioburden. Our study suggests that minocycline can serve as a dual mechanism for the regenerative capacity of MSCs and the reduction of bioburden in triple antimicrobial-loaded hydrogels. Wound healing is a complex biological process that can be hindered by bacterial infection, excessive inflammation, and inadequate microvasculature. In this study, we develop a new formulation of poly(ethylene glycol) diacrylate and thiolated gelatin poly(ethylene glycol) crosslinked hydrogels loaded with minocycline, vancomycin, linezolid, and mesenchymal stromal/stem cells that induces a favorable wound healing phenotype in mesenchymal stromal/stem cells and prevents bacterial bioburden on the hydrogel. This combinatorial approach to biomaterial development has the potential to impact wound healing for contaminated full thickness cutaneous wounds. Copyright © 2017. Published by Elsevier Ltd.

Gradient polymer network liquid crystal with a large refractive index change.

PubMed

Ren, Hongwen; Xu, Su; Wu, Shin-Tson

2012-11-19

A simple approach for preparing gradient polymer network liquid crystal (PNLC) with a large refractive index change is demonstrated. To control the effective refractive index at a given cell position, we applied a voltage to a homogeneous cell containing LC/diacrylate monomer mixture to generate the desired tilt angle and then stabilize the LC orientation with UV-induced polymer network. By varying the applied voltage along with the cells' movement, a PNLC with a gradient refractive index distribution is obtained. In comparison with conventional approaches using patterned photomask or electrode, our method offers following advantages: large refractive index change, freedom to design specific index profile, and large panel capability. Potential applications include tunable-focus lenses, prism gratings, phase modulators, and other adaptive photonic devices.

The effect of electron beam irradiation on the mechanical properties of pineapple leaf fibre (PALF) reinforced high impact polystyrene (HIPS) composites

NASA Astrophysics Data System (ADS)

Siregar, J. P.; Sapuan, S. M.; Rahman, M. Z. A.; Zaman, H. M. D. K.

2010-05-01

The effects of electron beam irradiation on the mechanical properties of pineapple leaf fibre reinforced high impact polystyrene (HIPS) composites were studied. Two types of crosslinking agent that has been used in this study were trimethylolpropane triacrylate (TMPTA) and tripropylene gylcol diacrylate (TPGDA). A 50 wt.% of PALF was blended with HIPS and crosslinking agent using Brabender melt mixer at 165 °C. The composites were then irradiated using a 3 MeV electron beam accelerator with dosage of 0-100 kGy. The tensile strength, tensile modulus, flexural strength, flexural modulus, notched and unnotched impat and hardness of composites were measured and the effects of crosslinking agent were also compared.

Functional Domains of NEAT1 Architectural lncRNA Induce Paraspeckle Assembly through Phase Separation.

PubMed

Yamazaki, Tomohiro; Souquere, Sylvie; Chujo, Takeshi; Kobelke, Simon; Chong, Yee Seng; Fox, Archa H; Bond, Charles S; Nakagawa, Shinichi; Pierron, Gerard; Hirose, Tetsuro

2018-06-21

A class of long noncoding RNAs (lncRNAs) has architectural functions in nuclear body construction; however, specific RNA domains dictating their architectural functions remain uninvestigated. Here, we identified the domains of the architectural NEAT1 lncRNA that construct paraspeckles. Systematic deletion of NEAT1 portions using CRISPR/Cas9 in haploid cells revealed modular domains of NEAT1 important for RNA stability, isoform switching, and paraspeckle assembly. The middle domain, containing functionally redundant subdomains, was responsible for paraspeckle assembly. Artificial tethering of the NONO protein to a NEAT1_2 mutant lacking the functional subdomains rescued paraspeckle assembly, and this required the NOPS dimerization domain of NONO. Paraspeckles exhibit phase-separated properties including susceptibility to 1,6-hexanediol treatment. RNA fragments of the NEAT1_2 subdomains preferentially bound NONO/SFPQ, leading to phase-separated aggregates in vitro. Thus, we demonstrate that the enrichment of NONO dimers on the redundant NEAT1_2 subdomains initiates construction of phase-separated paraspeckles, providing mechanistic insights into lncRNA-based nuclear body formation. Copyright © 2018 Elsevier Inc. All rights reserved.

Switchable focus using a polymeric lenticular microlens array and a polarization rotator.

PubMed

Ren, Hongwen; Xu, Su; Liu, Yifan; Wu, Shin-Tson

2013-04-08

We demonstrate a flat polymeric lenticular microlens array using a mixture of rod-like diacrylate monomer and positive dielectric anisotropy nematic liquid crystal (LC). To create gradient refractive index profile in one microlens, we generate fringing fields from a planar top electrode and two striped bottom electrodes. After UV stabilization, the film is optically anisotropic and can stand alone. We then laminate this film on a 90° twisted-nematic LC cell, which works as a dynamic polarization rotator. The static polymeric lenticular lens exhibits focusing effect only to the extraordinary ray, but no optical effect to the ordinary ray. Such an integrated lens system offers several advantages, such as low voltage, fast response time, and temperature insensitivity, and can be used for switchable 2D/3D displays.

Michael Addition Polymerization of Trifunctional Amine and Acrylic Monomer: A Versatile Platform for Development of Biomaterials.

PubMed

Cheng, Weiren; Wu, Decheng; Liu, Ye

2016-10-10

Michael addition polymerizations of amines and acrylic monomers are versatile approaches to biomaterials for various applications. A combinatorial library of poly(β-amino ester)s and diverse poly(amido amine)s from diamines and diacrylates or bis(acrylamide)s have been reported, respectively. Furthermore, novel linear and hyperbranched polymers from Michael addition polymerizations of trifunctional amines and acrylic monomers significantly enrich this category of biomaterials. In this Review, we focus on the biomaterials from Michael addition polymerizations of trifunctional amines and acrylic monomers. First we discuss how the polymerization mechanisms, which are determined by the reactivity sequence of the three types of amines of trifunctional amines, i.e., secondary (2°) amines (original), primary (1°) amines, and 2° amines (formed), are affected by the chemistry of monomers, reaction temperature, and solvent. Then we update how to design and synthesize linear and hyperbranched polymers based on the understanding of polymerization mechanisms. Linear polymers containing 2° amines in the backbones can be obtained from polymerizations of diacrylates or bis(acrylamide)s with equimolar trifunctional amine, and several approaches, e.g., 2A 2 +BB'B″, A 3 +2BB'B', A 2 +BB'B″, to hyperbranched polymers are developed. Further through molecular design of monomers, conjugation of functional species to 2° amines in the backbones of linear polymers and the abundant terminal groups of hyperbranched polymers, the amphiphilicity of polymers can be adjusted, and additional stimuli, e.g., thermal, redox, reactive oxidation species (ROS), and light, responses can be integrated with the intrinsic pH response. Finally we discuss the applications of the polymers for gene/drug delivery and bioimaging through exploring their self-assemblies in various motifs, e.g., micelles, polyplexes particles/nanorings and hydrogels. Redox-responsive hyperbranched polymers can display 300 times higher in vitro gene transfection efficiency and provide a higher in vivo siRNA efficacy than PEI. Also redox-responsive micelle carriers can improve the efficacy of anticancer drug and the bioimaging contrast. Further molecular design and optimization of this category of polymers together with in vivo studies should provide safe and efficient biomaterials for clinical applications.

(R)-3-hydroxyhexan-2-one is a major pheromone component of Anelaphus inflaticollis (Coleoptera: Cerambycidae).

PubMed

Ray, A M; Swift, I P; Moreira, J A; Millar, J G; Hanks, L M

2009-10-01

We report the identification and field bioassays of a major component of the male-produced aggregation pheromone of Anelaphus inflaticollis Chemsak, an uncommon desert cerambycine beetle. Male A. inflaticollis produced a sex-specific blend of components that included (R)-3-hydroxyhexan-2-one, (S)-2-hydroxyhexan-3-one, 2,3-hexanedione, and (2R,3R)- and (2R,3S)-2,3-hexanediols. Field trials with baited bucket traps determined that the reconstructed synthetic pheromone blend and (R)-3-hydroxyhexan-2-one alone attracted adult A. inflaticollis of both sexes, with significantly more beetles being attracted to the blend. We conclude that (R)-3-hydroxyhexan-2-one is a major pheromone component of A. inflaticollis, and our results suggest that one or more of the minor components may further increase attraction of conspecifics. Scanning electron microscopy showed that male A. inflaticollis have pores on the prothorax that are consistent in structure with sex-specific pheromone gland pores in related species. Males also displayed stereotyped calling behavior similar to that observed in other cerambycine species. This study represents the first report of volatile pheromones for a cerambycine species in the tribe Elaphidiini.

Photo-crosslinked PDMSstar-PEG Hydrogels: Synthesis, Characterization, and Potential Application for Tissue Engineering Scaffolds

PubMed Central

Hou, Yaping; Schoener, Cody A.; Regan, Katherine R.; Munoz-Pinto, Dany; Hahn, Mariah S.; Grunlan, Melissa A.

2010-01-01

Inorganic-organic hydrogels with tunable chemical and physical properties were prepared from methacrylated star polydimethylsiloxane (PDMSstar-MA) and diacrylated poly(ethylene glycol) (PEG-DA) for use as tissue engineering scaffolds. Eighteen compositionally unique hydrogels were prepared by photo-crosslinking varying weight ratios of PEG-DA and PDMSstar-MA of different molecular weights (Mn): PEG-DA (Mn = 3.4k and 6k g/mol) and PDMSstar-MA (Mn = 1.8k, 5k and 7k g/mol). Introduction of PDMSstar-MA caused formation of discrete PDMS-enriched microparticles dispersed within the PEG matrix. The swelling ratio, mechanical properties in tension and compression, non-specific protein adhesion, controlled introduction of bioactivity and cytotoxicity of hydrogels were studied. This library of inorganic-organic hydrogels with tunable properties provides a useful platform to study the effect of scaffold properties on cell behavior. PMID:20146518

Highly conductive solid polymer electrolyte membranes based on polyethylene glycol-bis-carbamate dimethacrylate networks

NASA Astrophysics Data System (ADS)

Fu, Guopeng; Dempsey, Janel; Izaki, Kosuke; Adachi, Kaoru; Tsukahara, Yasuhisa; Kyu, Thein

2017-08-01

In an effort to fabricate highly conductive, stable solid-state polymer electrolyte membranes (PEM), polyethylene glycol bis-carbamate (PEGBC) was synthesized via condensation reaction between polyethylene glycol diamine and ethylene carbonate. Subsequently, dimethacrylate groups were chemically attached to both ends of PEGBC to afford polyethylene glycol-bis-carbamate dimethacrylate (PEGBCDMA) precursor having crosslinking capability. The melt-mixed ternary mixtures consisting of PEGBCDMA, succinonitrile plasticizer, and lithium trifluorosulphonyl imide salt were completely miscible in a wide compositional range. Upon photo-crosslinking, the neat PEGBCDMA network was completely amorphous exhibiting higher tensile strength, modulus, and extensibility relative to polyethylene glycol diacrylate (PEGDA) counterpart. Likewise, the succinonitrile-plasticized PEM network containing PEGBCDMA remained completely amorphous and transparent upon photo-crosslinking, showing superionic conductivity, improved thermal stability, and superior tensile properties with improved capacity retention during charge/discharge cycling as compared to the PEGDA-based PEM.

Photoinitiator-free 3D scaffolds fabricated by excimer laser photocuring.

PubMed

Farkas, Balázs; Dante, Silvia; Brandi, Fernando

2017-01-20

Photoinitiator-free fabrication of poly(ethylene glycol) diacrylate (PEGDA) scaffolds is achieved using a novel three-dimensional (3D) printing method called mask projected excimer laser stereolithography (MPExSL). The spatial resolution of photoinitiator-free curing is suitable for 3D layer-by-layer fabrication with a single layer thickness well controllable at tens to hundreds of microns using 248 nm wavelength for the irradiation. The photoinitiator-free scaffolds are superior compared to their counterparts fabricated by using photoinitiator molecules, showing a higher level of biocompatibility. A release of toxic chemicals from the photoinitiator containing scaffolds is proven by cell proliferation tests. In contrast, no toxic release is found from the photoinitiator-free scaffolds, resulting in the very same level of cell proliferation as the control sample. The demonstration of photoinitiator-free PEGDA scaffolds enables the fabrication of 3D scaffolds with the highest level of biocompatibility for both in vitro and in vivo applications.

Flow-induced fiber deformation in a confined microchannel: in situ mechanical testing of gels

NASA Astrophysics Data System (ADS)

Duprat, Camille; Berthet, Helene; Wexler, Jason; Du Roure, Olivia; Lindner, Anke

2014-11-01

Photopolymerized hydrogels are a functional template for micro-particle fabrication, microflowsensors and microbiology experiments. The control and knowledge of their mechanical properties are paramount to many applications. We have designed a novel robust method to determine these properties. We measure the deformation of a gel beam of precisely controlled shape, under a controlled flow forcing, which provides a direct measurement of the Young's modulus of the gel upon its fabrication. We then use this method to determine the mechanical properties of the commonly used poly(ethylene glycol) diacrylate (PEGDA) under various experimental conditions. The mechanical properties of the gel can be highly tuned, yielding two orders of magnitude in the Young's modulus. We provide a simple control parameter, the UV exposure time, to have a great control over the network properties, and rationalize these observations by studying the kinetics of the polymerization reaction.

Superelastic and pH-Responsive Degradable Dendrimer Cryogels Prepared by Cryo-aza-Michael Addition Reaction.

PubMed

Wang, Juan; Yang, Hu

2018-05-08

Dendrimers exhibit super atomistic features by virtue of their well-defined discrete quantized nanoscale structures. Here, we show that hyperbranched amine-terminated polyamidoamine (PAMAM) dendrimer G4.0 reacts with linear polyethylene glycol (PEG) diacrylate (575 g/mol) via the aza-Michael addition reaction at a subzero temperature (-20 °C), namely cryo-aza-Michael addition, to form a macroporous superelastic network, i.e., dendrimer cryogel. Dendrimer cryogels exhibit biologically relevant Young's modulus, high compression elasticity and super resilience at ambient temperature. Furthermore, the dendrimer cryogels exhibit excellent rebound performance and do not show significant stress relaxation under cyclic deformation over a wide temperature range (-80 to 100 °C). The obtained dendrimer cryogels are stable at acidic pH but degrade quickly at physiological pH through self-triggered degradation. Taken together, dendrimer cryogels represent a new class of scaffolds with properties suitable for biomedical applications.

Photocurable surgical tissue adhesive glues composed of photoreactive gelatin and poly(ethylene glycol) diacrylate.

PubMed

Nakayama, Y; Matsuda, T

1999-01-01

This article presents a novel photochemically driven surgical tissue adhesive technology using photoreactive gelatins and a water-soluble difunctional macromer (poly(ethylene glycol) diacrylate: PEGDA).The gelatins were partially derivatized with photoreactive groups, such as ultraviolet light (UV)-reactive benzophenone and visible light-reactive xanthene dye (e.g., fluorescein sodium salt, eosin Y, and rose bengal). A series of the prepared photocurable tissue adhesive glues, consisting of the photoreactive gelatin, PEGDA, and a saline solution with or without ascorbic acid as a reducing agent, were viscous solutions under warming, and their effectiveness was evaluated as hemostasis- and anastomosis-aid in cardiovascular surgery. Regardless of the type of photoreactive groups, the irradiation of the photocurable tissue adhesive glues by UV or visible light within 1 min produced water-swollen gels, which had a high adhesive strength to wet collagen film. These were due to the synergistic action of photoreactive group-initiated photo-cross-linking and photograft polymerization. An increase in the irradiation time resulted in increased gel yield and reduced water swellability. A decrease in the molecular weight of PEGDA and an increase in concentration of both gelatin and PEGDA resulted in reduced water swellability and increased tensile and burst strengths of the resultant gels. In rats whose livers were injured with a trephine in laparotomy, the bleeding spots were coated with the photocurable adhesive glue and irradiated through an optical fiber. The coated solution was immediately converted to a swollen gel. The gel was tightly adhered to the liver tissue presumably by interpenetration, and concomitantly hemostasis was completed. The anastomosis treatment with the photocurable glue in the canine abdominal or thoracic aortas incised with a knife resulted in little bleeding under pulsatile flow after declamping. Histological examination showed that the glues photocured on rat liver surfaces were gradually degraded with time in vivo with infiltration of inflammatory cells and connective tissues without necrotic sign in surrounding tissue. In addition, in the laparoscopic surgery, percutaneous delivery of the glue and its in situ photogelation on rat liver surfaces were demonstrated using a specially designed fiberscope. These results indicate that the photocurable glues developed here may serve as a biodegradable tissue adhesive glue usable in cardiovascular surgery and endoscopic surgery. Copyright 1999 John Wiley & Sons, Inc.

Induction and differentiation of human induced pluripotent stem cells into functional cardiomyocytes on a compartmented monolayer of gelatin nanofibers

NASA Astrophysics Data System (ADS)

Tang, Yadong; Liu, Li; Li, Junjun; Yu, Leqian; Wang, Li; Shi, Jian; Chen, Yong

2016-07-01

Extensive efforts have been devoted to develop new substrates for culture and differentiation of human induced pluripotent stem cells (hiPSCs) toward cardiac cell-based assays. A more exciting prospect is the construction of cardiac tissue for robust drug screening and cardiac tissue repairing. Here, we developed a patch method by electrospinning and crosslinking of monolayer gelatin nanofibers on a honeycomb frame made of poly(ethylene glycol) diacrylate (PEGDA). The monolayer of the nanofibrous structure can support cells with minimal exogenous contact and a maximal efficiency of cell-medium exchange whereas a single hiPSC colony can be uniformly formed in each of the honeycomb compartments. By modulating the treatment time of the ROCK inhibitor Y-27632, the shape of the hiPSC colony could be controlled from a flat layer to a hemisphere. Afterwards, the induction and differentiation of hiPSCs were achieved on the same patch, leading to a uniform cardiac layer with homogeneous contraction. This cardiac layer could then be used for extracellular recording with a commercial multi-electrode array, showing representative field potential waveforms of matured cardiac tissues with appropriate drug responses.Extensive efforts have been devoted to develop new substrates for culture and differentiation of human induced pluripotent stem cells (hiPSCs) toward cardiac cell-based assays. A more exciting prospect is the construction of cardiac tissue for robust drug screening and cardiac tissue repairing. Here, we developed a patch method by electrospinning and crosslinking of monolayer gelatin nanofibers on a honeycomb frame made of poly(ethylene glycol) diacrylate (PEGDA). The monolayer of the nanofibrous structure can support cells with minimal exogenous contact and a maximal efficiency of cell-medium exchange whereas a single hiPSC colony can be uniformly formed in each of the honeycomb compartments. By modulating the treatment time of the ROCK inhibitor Y-27632, the shape of the hiPSC colony could be controlled from a flat layer to a hemisphere. Afterwards, the induction and differentiation of hiPSCs were achieved on the same patch, leading to a uniform cardiac layer with homogeneous contraction. This cardiac layer could then be used for extracellular recording with a commercial multi-electrode array, showing representative field potential waveforms of matured cardiac tissues with appropriate drug responses. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr04545f

Transdermal thiol-acrylate polyethylene glycol hydrogel synthesis using near infrared light

NASA Astrophysics Data System (ADS)

Chung, Solchan; Lee, Hwangjae; Kim, Hyung-Seok; Kim, Min-Gon; Lee, Luke P.; Lee, Jae Young

2016-07-01

Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation via a mixed-mode reaction with a small increase in temperature (~5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications.Light-induced polymerization has been widely applied for hydrogel synthesis, which conventionally involves the use of ultraviolet or visible light to activate a photoinitiator for polymerization. However, with these light sources, transdermal gelation is not efficient and feasible due to their substantial interactions with biological systems, and thus a high power is required. In this study, we used biocompatible and tissue-penetrating near infrared (NIR) light to remotely trigger a thiol-acrylate reaction for efficient in vivo gelation with good controllability. Our gelation system includes gold nanorods as a photothermal agent, a thermal initiator, diacrylate polyethylene glycol (PEG), and thiolated PEG. Irradiation with a low-power NIR laser (0.3 W cm-2) could induce gelation via a mixed-mode reaction with a small increase in temperature (~5 °C) under the optimized conditions. We also achieved successful transdermal gelation via the NIR-assisted photothermal thiol-acryl reactions. This new type of NIR-assisted thiol-acrylate polymerization provides new opportunities for in situ hydrogel formation for injectable hydrogels and delivery of drugs/cells for various biomedical applications. Electronic supplementary information (ESI) available: FE-SEM image of thiol-acrylate hydrogels; UV/Vis spectra of Ellman's assay; the temperature increase during transdermal photothermal hydrogelation. See DOI: 10.1039/c6nr01956k

Sensitization to reactive diluents and hardeners in epoxy resin systems. IVDK data 2002-2011. Part II: concomitant reactions.

PubMed

Geier, Johannes; Lessmann, Holger; Hillen, Uwe; Skudlik, Christoph; Jappe, Uta

2016-02-01

Beside the basic resins, reactive diluents and hardeners are important sensitizers in epoxy resin systems (ERSs). Because of chemical similarities, immunological cross-reactivity may occur. To analyse concomitant reactivity among reactive diluents and hardeners in the patients concerned, as one integral part of a research project on the sensitizing capacity of ERSs (FP-0324). A retrospective analysis of data from the Information Network of Departments of Dermatology (IVDK), 2002-2011, was performed. There was close concomitant reactivity to 1,6-hexanediol diglycidyl ether and 1,4-butanediol diglycidyl ether (1,4-BDDGE), and to phenyl glycidyl ether (PGE) and cresyl glycidyl ether (CGE), whereas reactions to p-tert-butylphenyl glycidyl ether occurred more independently from those to PGE and CGE. Concomitant reactions to butyl glycidyl ether and 1,4-BDDGE may point to a common allergenic compound derived from the metabolism of 1,4-BDDGE. Among the structurally more diverse group of hardeners, there was no evidence of immunological cross-reactions. More detailed knowledge of cross-reactivity among ERS components facilitates the interpretation of patch test results and will allow safer ERSs to be composed in the future. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Characterization of polyesters by matrix-assisted laser desorption/ionization and Fourier transform mass spectrometry.

PubMed

Mize, Todd H; Simonsick, William J; Amster, I Jonathan

2003-01-01

Two homopolyesters, poly(neopentyl glycol-alt-isophthalic acid) and poly(hexanediol-alt-azelaic acid), and two copolyesters, poly(dipropoxylated bisphenol-A-alt-(isophthalic acid-co-adipic acid)) and poly(neopentyl glycol-alt-(adipic acid-co-isophthalic acid)) were analyzed by internal source matrix assisted laser desorption/ionization Fourier transform mass spectrometry (MALDI-FTMS). The high resolution and high mass accuracy provided by FTMS greatly facilitate the characterization of the polyester and copolyester samples. Isobaric resolution allows the ion abundances of overlapping isotopic envelopes to be assessed. Repeat units were confirmed and end functionality assigned. Single shot mass spectra of the entire polymeric distribution demonstrate that the dynamic range of this internal MALDI source instrument and the analyzer cell exceeds performance of those previously reported for higher field instruments. Corrections of space charge mass shift effects are demonstrated for the analytes using an external calibrant and (subsequent to confirmation of structure) via internal calibration which removes ambiguity due to space charge differences in calibrant and analyte spectra. Capillary gel permeation chromatography was used to prepare low polydispersity samples from a high polydispersity polyester, improving the measurement of molecular weight distribution two-fold while retaining the benefits of high resolution mass spectrometry for elucidation of oligomer identity.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles.

PubMed

Vatansever, Fatma; Hamblin, Michael R

2017-02-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly( n -hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was "seeded" with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n -hexyl isocyanate monomer insertion, to "build up" the surface-grown polymer layers from the "bottom-up". A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses.

Surface-Initiated Polymerization with Poly(n-hexylisocyanate) to Covalently Functionalize Silica Nanoparticles

PubMed Central

Vatansever, Fatma; Hamblin, Michael R.

2017-01-01

New methods are needed for covalent functionalization of nanoparticles-surface with organic polymer coronas to generate polymeric nanocomposite in a controlled manner. Here we report the use of a surface-initiated polymerization approach, mediated by titanium (IV) catalysis, to grow poly(n-hexylisocyanate) chains from silica surface. Two pathways were used to generate the interfacing in these nano-hybrids. In the first one, the nanoparticles was “seeded” with SiCl4, followed by reaction with 1,6-hexanediol to form hydroxyl groups attached directly to the surface via O-Si-O bonding. In the second pathway, the nanoparticles were initially exposed to a 9:1 mixture of trimethyl silyl chloride and chlorodimethyl octenyl silane which was then followed by hydroboration of the double bonds, to afford hydroxyl groups with a spatially controlled density and surface-attachment via O-Si-C bonding. These functionalized surfaces were then activated with the titanium tetrachloride catalyst. In our approach, thus surface tethered catalyst provided the sites for n-hexyl isocyanate monomer insertion, to “build up” the surface-grown polymer layers from the “bottom-up”. A final end-capping, to seal off the chain ends, was done via acetyl chloride. Compounds were characterized by FT-IR, 1H-NMR, GC-MS, GPC, and thermogravimetric analyses. PMID:28989336

Engineering Cofactor Preference of Ketone Reducing Biocatalysts: A Mutagenesis Study on a γ-Diketone Reductase from the Yeast Saccharomyces cerevisiae Serving as an Example

PubMed Central

Katzberg, Michael; Skorupa-Parachin, Nàdia; Gorwa-Grauslund, Marie-Françoise; Bertau, Martin

2010-01-01

The synthesis of pharmaceuticals and catalysts more and more relies on enantiopure chiral building blocks. These can be produced in an environmentally benign and efficient way via bioreduction of prochiral ketones catalyzed by dehydrogenases. A productive source of these biocatalysts is the yeast Saccharomyces cerevisiae, whose genome also encodes a reductase catalyzing the sequential reduction of the γ-diketone 2,5-hexanedione furnishing the diol (2S,5S)-hexanediol and the γ-hydroxyketone (5S)-hydroxy-2-hexanone in high enantio- as well as diastereoselectivity (ee and de >99.5%). This enzyme prefers NADPH as the hydrogen donating cofactor. As NADH is more stable and cheaper than NADPH it would be more effective if NADH could be used in cell-free bioreduction systems. To achieve this, the cofactor binding site of the dehydrogenase was altered by site-directed mutagenesis. The results show that the rational approach based on a homology model of the enzyme allowed us to generate a mutant enzyme having a relaxed cofactor preference and thus is able to use both NADPH and NADH. Results obtained from other mutants are discussed and point towards the limits of rationally designed mutants. PMID:20480039

Effect of carbon supports on RhRe bifunctional catalysts for selective hydrogenolysis of tetrahydropyran-2-methanol

DOE PAGES

Karanjkar, Pranav U.; Burt, Samuel P.; Chen, Xiaoli; ...

2016-09-12

Tetrahydropyran-2-methanol undergoes selective C–O–C hydrogenolysis to produce 1,6-hexanediol using a bifunctional RhRe (reducible metal with an oxophilic promoter) catalyst supported on Vulcan XC-72 carbon (VXC) with >90% selectivity. This RhRe/VXC catalyst is stable over 40 h of reaction in a continuous flow fixed bed reactor. The hydrogenolysis activity of RhRe/VXC is two orders-of-magnitude higher than that of RhRe supported on Norit Darco 12X40 activated carbon (NDC). STEM–EDS analysis reveals that, compared to the RhRe/VXC catalyst, the Re and Rh component metals are segregated on the surface of the low activity RhRe/NDC catalyst, suggesting that Rh and Re in close proximitymore » (“bimetallic” particles) are required for an active hydrogenolysis catalyst. Differences in metal distribution on the carbon surfaces are, in turn, linked to the properties of the carbons: NDC has both a higher surface area and surface oxygen content. Thus, the low areal density of Rh and Re precursors on the high area NDC and/or interactions of the precursors with its O functional groups may interfere with the formation of the bimetallic species required for an active catalyst.« less

Toxic PRn poly-dipeptides encoded by the C9orf72 repeat expansion block nuclear import and export.

PubMed

Shi, Kevin Y; Mori, Eiichiro; Nizami, Zehra F; Lin, Yi; Kato, Masato; Xiang, Siheng; Wu, Leeju C; Ding, Ming; Yu, Yonghao; Gall, Joseph G; McKnight, Steven L

2017-02-14

The toxic proline:arginine (PR n ) poly-dipeptide encoded by the (GGGGCC) n repeat expansion in the C9orf72 form of heritable amyotrophic lateral sclerosis (ALS) binds to the central channel of the nuclear pore and inhibits the movement of macromolecules into and out of the nucleus. The PR n poly-dipeptide binds to polymeric forms of the phenylalanine:glycine (FG) repeat domain, which is shared by several proteins of the nuclear pore complex, including those in the central channel. A method of chemical footprinting was used to characterize labile, cross-β polymers formed from the FG domain of the Nup54 protein. Mutations within the footprinted region of Nup54 polymers blocked both polymerization and binding by the PR n poly-dipeptide. The aliphatic alcohol 1,6-hexanediol melted FG domain polymers in vitro and reversed PR n -mediated enhancement of the nuclear pore permeability barrier. These data suggest that toxicity of the PR n poly-dipeptide results in part from its ability to lock the FG repeats of nuclear pore proteins in the polymerized state. Our study offers a mechanistic interpretation of PR n poly-dipeptide toxicity in the context of a prominent form of ALS.

Effects of high salt stress on secondary metabolite production in the marine-derived fungus Spicaria elegans.

PubMed

Wang, Yi; Lu, Zhenyu; Sun, Kunlai; Zhu, Weiming

2011-01-01

To obtain structurally novel and bioactive natural compounds from marine-derived microorganisms, the effect of high salt stress on secondary metabolite production in the marine-derived fungal strain, Spicaria elegans KLA-03, was investigated. The organism, which was isolated from marine sediment, produced different secondary metabolites when cultured in 3% and 10% saline conditions. Four characteristic metabolites, only produced in the 10% salinity culture, were isolated, and their structures were identified as (2E,2'Z)-3,3'-(6,6'-dihydroxybiphenyl-3,3'-diyl)diacrylic acid (1), aspulvinone E (2), aspochalasin E (3) and trichodermamide B (6), according to their 1D and 2D NMR spectra. Compound 1 is a new compound. High salt stress may therefore be a promising means to induce the production of new and chlorinated compounds in halotolerant fungi. Compound 1 showed moderate antibacterial activity against Pseudomonas aeruginosa and Escherichia coli with minimum inhibitory concentration (MIC) values of 0.038 and 0.767 mM, respectively.

Functionalized poly(ethylene glycol) diacrylate microgels by microfluidics: In situ peptide encapsulation for in serum selective protein detection.

PubMed

Celetti, Giorgia; Natale, Concetta Di; Causa, Filippo; Battista, Edmondo; Netti, Paolo A

2016-09-01

Polymeric microparticles represent a robustly platform for the detection of clinically relevant analytes in biological samples; they can be functionalized encapsulating a multiple types of biologics entities, enhancing their applications as a new class of colloid materials. Microfluidic offers a versatile platform for the synthesis of monodisperse and engineered microparticles. In this work, we report microfluidic synthesis of novel polymeric microparticles endowed with specific peptide due to its superior specificity for target binding in complex media. A peptide sequence was efficiently encapsulated into the polymeric network and protein binding occurred with high affinity (KD 0.1-0.4μM). Fluidic dynamics simulation was performed to optimize the production conditions for monodisperse and stable functionalized microgels. The results demonstrate the easy and fast realization, in a single step, of functionalized monodisperse microgels using droplet-microfluidic technique, and how the inclusion of the peptide within polymeric network improve both the affinity and the specificity of protein capture. Copyright © 2016 Elsevier B.V. All rights reserved.

A new photocrosslinkable polycaprolactone-based ink for three-dimensional inkjet printing.

PubMed

He, Yinfeng; Tuck, Christopher J; Prina, Elisabetta; Kilsby, Sam; Christie, Steven D R; Edmondson, Stephen; Hague, Richard J M; Rose, Felicity R A J; Wildman, Ricky D

2017-08-01

A new type of photocrosslinkable polycaprolactone (PCL) based ink that is suitable for three-dimensional (3D) inkjet printing has been developed. Photocrosslinkable Polycaprolactone dimethylacrylate (PCLDMA) was synthesized and mixed with poly(ethylene glycol) diacrylate (PEGDA) to prepare an ink with a suitable viscosity for inkjet printing. The ink performance under different printing environments, initiator concentrations, and post processes was studied. This showed that a nitrogen atmosphere during printing was beneficial for curing and material property optimization, as well as improving the quality of structures produced. A simple structure, built in the z-direction, demonstrated the potential for this material for the production of 3D printed objects. Cell tests were carried out to investigate the biocompatibility of the developed ink. © 2016 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1645-1657, 2017. © 2016 The Authors Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc.

Toroidal-spiral particles for codelivery of anti-VEGFR-2 antibody and irinotecan: a potential implant to hinder recurrence of glioblastoma multiforme.

PubMed

Sharma, Vishal; Köllmer, Melanie; Szymusiak, Magdalena; Nitsche, Ludwig C; Gemeinhart, Richard A; Liu, Ying

2014-03-10

Heterogeneous toroidal-spiral particles (TSPs) were generated by polymer droplet sedimentation, interaction, and cross-linking. TSPs provide a platform for encapsulation and release of multiple compounds of different sizes and physicochemical properties. As a model system, we demonstrate the encapsulation and independently controlled release of an anti-VEGFR-2 antibody and irinotecan for the treatment of glioblastoma multiforme. The anti-VEGFR-2 antibody was released from the TS channels and its binding to HUVECs was confirmed by confocal microscopy and flow cytometry, suggesting active antibody encapsulation and release. Irinotecan, a small molecule drug, was released from the dense polymer matrix of poly(ethylene glycol) diacrylate (MW ~ 700 g/mol; PEGDA 700). Released irinotecan inhibited the proliferation of U251 malignant glioma cells. Since the therapeutic compounds are released through different pathways, specifically diffusion through the polymer matrix versus TS channels, the release rate can be controlled independently through the design of the structure and material of particle components.

Fabrication of a Porous Fiber Cladding Material Using Microsphere Templating for Improved Response Time with Fiber Optic Sensor Arrays

PubMed Central

Henning, Paul E.; Rigo, M. Veronica; Geissinger, Peter

2012-01-01

A highly porous optical-fiber cladding was developed for evanescent-wave fiber sensors, which contains sensor molecules, maintains guiding conditions in the optical fiber, and is suitable for sensing in aqueous environments. To make the cladding material (a poly(ethylene) glycol diacrylate (PEGDA) polymer) highly porous, a microsphere templating strategy was employed. The resulting pore network increases transport of the target analyte to the sensor molecules located in the cladding, which improves the sensor response time. This was demonstrated using fluorescein-based pH sensor molecules, which were covalently attached to the cladding material. Scanning electron microscopy was used to examine the structure of the templated polymer and the large network of interconnected pores. Fluorescence measurements showed a tenfold improvement in the response time for the templated polymer and a reliable pH response over a pH range of five to nine with an estimated accuracy of 0.08 pH units. PMID:22654644

Water-Hydrogel Binding Affinity Modulates Freeze-Drying-Induced Micropore Architecture and Skeletal Myotube Formation.

PubMed

Rich, Max H; Lee, Min Kyung; Marshall, Nicholas; Clay, Nicholas; Chen, Jinrong; Mahmassani, Ziad; Boppart, Marni; Kong, Hyunjoon

2015-08-10

Freeze-dried hydrogels are increasingly used to create 3D interconnected micropores that facilitate biomolecular and cellular transports. However, freeze-drying is often plagued by variance in micropore architecture based on polymer choice. We hypothesized that water-polymer binding affinity plays a significant role in sizes and numbers of micropores formed through freeze-drying, influencing cell-derived tissue quality. Poly(ethylene glycol)diacrylate (PEGDA) hydrogels with alginate methacrylate (AM) were used due to AM's higher binding affinity for water than PEGDA. PEGDA-AM hydrogels with larger AM concentrations resulted in larger sizes and numbers of micropores than pure PEGDA hydrogels, attributed to the increased mass of water binding to the PEGDA-AM gel. Skeletal myoblasts loaded in microporous PEGDA-AM hydrogels were active to produce 3D muscle-like tissue, while those loaded in pure PEGDA gels were localized on the gel surface. We propose that this study will be broadly useful in designing and improving the performance of various microporous gels.

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

NASA Technical Reports Server (NTRS)

Tyson, Daniel S.; Ilhan, Faysal; Meador, Mary Ann B.; Smith, Dee Dee; Scheiman, Daniel A.; Meador, Michael A.

2004-01-01

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

A polycationic antimicrobial and biocompatible hydrogel with microbe membrane suctioning ability.

PubMed

Li, Peng; Poon, Yin Fun; Li, Weifeng; Zhu, Hong-Yuan; Yeap, Siew Hooi; Cao, Ye; Qi, Xiaobao; Zhou, Chuncai; Lamrani, Mouad; Beuerman, Roger W; Kang, En-Tang; Mu, Yuguang; Li, Chang Ming; Chang, Matthew W; Leong, Susanna Su Jan; Chan-Park, Mary B

2011-02-01

Despite advanced sterilization and aseptic techniques, infections associated with medical implants have not been eradicated. Most present coatings cannot simultaneously fulfil the requirements of antibacterial and antifungal activity as well as biocompatibility and reusability. Here, we report an antimicrobial hydrogel based on dimethyldecylammonium chitosan (with high quaternization)-graft-poly(ethylene glycol) methacrylate (DMDC-Q-g-EM) and poly(ethylene glycol) diacrylate, which has excellent antimicrobial efficacy against Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus and Fusarium solani. The proposed mechanism of the antimicrobial activity of the polycationic hydrogel is by attraction of sections of anionic microbial membrane into the internal nanopores of the hydrogel, like an 'anion sponge', leading to microbial membrane disruption and then microbe death. We have also demonstrated a thin uniform adherent coating of the hydrogel by simple ultraviolet immobilization. An animal study shows that DMDC-Q-g-EM hydrogel coating is biocompatible with rabbit conjunctiva and has no toxicity to the epithelial cells or the underlying stroma.

A polycationic antimicrobial and biocompatible hydrogel with microbe membrane suctioning ability

NASA Astrophysics Data System (ADS)

Li, Peng; Poon, Yin Fun; Li, Weifeng; Zhu, Hong-Yuan; Yeap, Siew Hooi; Cao, Ye; Qi, Xiaobao; Zhou, Chuncai; Lamrani, Mouad; Beuerman, Roger W.; Kang, En-Tang; Mu, Yuguang; Li, Chang Ming; Chang, Matthew W.; Jan Leong, Susanna Su; Chan-Park, Mary B.

2011-02-01

Despite advanced sterilization and aseptic techniques, infections associated with medical implants have not been eradicated. Most present coatings cannot simultaneously fulfil the requirements of antibacterial and antifungal activity as well as biocompatibility and reusability. Here, we report an antimicrobial hydrogel based on dimethyldecylammonium chitosan (with high quaternization)-graft-poly(ethylene glycol) methacrylate (DMDC-Q-g-EM) and poly(ethylene glycol) diacrylate, which has excellent antimicrobial efficacy against Pseudomonas aeruginosa, Escherichia coli, Staphylococcus aureus and Fusarium solani. The proposed mechanism of the antimicrobial activity of the polycationic hydrogel is by attraction of sections of anionic microbial membrane into the internal nanopores of the hydrogel, like an ‘anion sponge’, leading to microbial membrane disruption and then microbe death. We have also demonstrated a thin uniform adherent coating of the hydrogel by simple ultraviolet immobilization. An animal study shows that DMDC-Q-g-EM hydrogel coating is biocompatible with rabbit conjunctiva and has no toxicity to the epithelial cells or the underlying stroma.

Porous inorganic-organic shape memory polymers.

PubMed

Zhang, Dawei; Burkes, William L; Schoener, Cody A; Grunlan, Melissa A

2012-06-21

Thermoresponsive shape memory polymers (SMPs) are a type of stimuli-sensitive materials that switch from a temporary shape back to their permanent shape upon exposure to heat. While the majority of SMPs have been fabricated in the solid form, porous SMP foams exhibit distinct properties and are better suited for certain applications, including some in the biomedical field. Like solid SMPs, SMP foams have been restricted to a limited group of organic polymer systems. In this study, we prepared inorganic-organic SMP foams based on the photochemical cure of a macromer comprised of inorganic polydimethylsiloxane (PDMS) segments and organic poly(ε-caprolactone) (PCL) segments, diacrylated PCL(40)-block-PDMS(37)-block-PCL(40). To achieve tunable pore size with high interconnectivity, the SMP foams were prepared via a refined solvent-casting/particulate-leaching (SCPL) method. By varying design parameters such as degree of salt fusion, macromer concentration in the solvent and salt particle size, the SMP foams with excellent shape memory behavior and tunable pore size, pore morphology, and modulus were obtained.

On-chip self-assembly of cell embedded microstructures to vascular-like microtubes.

PubMed

Yue, Tao; Nakajima, Masahiro; Takeuchi, Masaru; Hu, Chengzhi; Huang, Qiang; Fukuda, Toshio

2014-03-21

Currently, research on the construction of vascular-like tubular structures is a hot area of tissue engineering, since it has potential applications in the building of artificial blood vessels. In this paper, we report a fluidic self-assembly method using cell embedded microstructures to construct vascular-like microtubes. A novel 4-layer microfluidic device was fabricated using polydimethylsiloxane (PDMS), which contains fabrication, self-assembly and extraction areas inside one channel. Cell embedded microstructures were directly fabricated using poly(ethylene glycol) diacrylate (PEGDA) in the fabrication area, namely on-chip fabrication. Self-assembly of the fabricated microstructures was performed in the assembly area which has a micro well. Assembled tubular structures (microtubes) were extracted outside the channel into culture dishes using a normally closed (NC) micro valve in the extraction area. The self-assembly mechanism was experimentally demonstrated. The performance of the NC micro valve and embedded cell concentration were both evaluated. Fibroblast (NIH/3T3) embedded vascular-like microtubes were constructed inside this reusable microfluidic device.

Temporal Control of Gelation and Polymerization Fronts Driven by an Autocatalytic Enzyme Reaction.

PubMed

Jee, Elizabeth; Bánsági, Tamás; Taylor, Annette F; Pojman, John A

2016-02-05

Chemical systems that remain kinetically dormant until activated have numerous applications in materials science. Herein we present a method for the control of gelation that exploits an inbuilt switch: the increase in pH after an induction period in the urease-catalyzed hydrolysis of urea was used to trigger the base-catalyzed Michael addition of a water-soluble trithiol to a polyethylene glycol diacrylate. The time to gelation (minutes to hours) was either preset through the initial concentrations or the reaction was initiated locally by a base, thus resulting in polymerization fronts that converted the mixture from a liquid into a gel (ca. 0.1 mm min -1 ). The rate of hydrolytic degradation of the hydrogel depended on the initial concentrations, thus resulting in a gel lifetime of hours to months. In this way, temporal programming of gelation was possible under mild conditions by using the output of an autocatalytic enzyme reaction to drive both the polymerization and subsequent degradation of a hydrogel.

Initial evaluation of vascular ingrowth into superporous hydrogels.

PubMed

Keskar, Vandana; Gandhi, Milind; Gemeinhart, Ernest J; Gemeinhart, Richard A

2009-08-01

There is a need for new materials and architectures for tissue engineering and regenerative medicine. Based upon our recent results developing novel scaffold architecture, we hypothesized that this new architecture would foster vascularization, a particular need for tissue engineering. We report on the potential of superporous hydrogel (SPH) scaffolds for in vivo cellular infiltration and vascularization. Poly(ethylene glycol) diacrylate (PEGDA) SPH scaffolds were implanted in the dorsum of severe combined immunodeficient (SCID) mice and harvested after 4 weeks of in vivo implantation. The SPHs were visibly red and vascularized, as apparent when compared to the non-porous hydrogel controls, which were macroscopically avascular. Host cell infiltration was observed throughout the SPHs. Blood cells and vascular structures, confirmed through staining for CD34 and smooth muscle alpha-actin, were observed throughout the scaffolds. This novel soft material may be utilized for cell transplantation, tissue engineering and in combination with cell therapies. The neovasularization and limited fibrotic response suggest that the architecture may be conducive to cell survival and rapid vessel development.

Microfluidic devices with permeable polymer barriers for capture and transport of biomolecules and cells.

PubMed

Lee, Ho Suk; Chu, Wai Keung; Zhang, Kun; Huang, Xiaohua

2013-09-07

We report a method for fabricating permeable polymer microstructure barriers in polydimethylsiloxane (PDMS) microfluidic devices and the use of the devices to capture and transport DNA and cells. The polymer microstructure in a desired location in a fluidic channel is formed in situ by the polymerization of acrylamide and polyethylene diacrylate cross-linker (PEG-DA) monomer in a solution which is trapped in the location using a pair of PDMS valves. The porous polymer microstructure provides a mechanical barrier to convective fluid flow in the channel or between two microfluidic chambers while it still conducts ions or small charged species under an electric field, allowing for the rapid capture and transport of biomolecules and cells by electrophoresis. We have demonstrated the application of the devices for the rapid capture and efficient release of bacteriophage λ genomic DNA, solution exchange and for the transport and capture of HeLa cells. Our devices will enable the multi-step processing of biomolecules and cells or individual cells within a single microfluidic chamber.

A novel surface modification technique for forming porous polymer monoliths in poly(dimethylsiloxane).

PubMed

Burke, Jeffrey M; Smela, Elisabeth

2012-03-01

A new method of surface modification is described for enabling the in situ formation of homogenous porous polymer monoliths (PPMs) within poly(dimethylsiloxane) (PDMS) microfluidic channels that uses 365 nm UV illumination for polymerization. Porous polymer monolith formation in PDMS can be challenging because PDMS readily absorbs the monomers and solvents, changing the final monolith morphology, and because PDMS absorbs oxygen, which inhibits free-radical polymerization. The new approach is based on sequentially absorbing a non-hydrogen-abstracting photoinitiator and the monomers methyl methacrylate and ethylene diacrylate within the walls of the microchannel, and then polymerizing the surface treatment polymer within the PDMS, entangled with it but not covalently bound. Four different monolith compositions were tested, all of which yielded monoliths that were securely anchored and could withstand pressures exceeding the bonding strength of PDMS (40 psi) without dislodging. One was a recipe that was optimized to give a larger average pore size, required for low back pressure. This monolith was used to concentrate and subsequently mechanical lyse B lymphocytes.

Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

PubMed

Lanzafame, Paola; Centi, Gabriele; Perathoner, Siglinda

2014-11-21

The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol.

Highly crosslinked polymeric monoliths for reversed-phase capillary liquid chromatography of small molecules.

PubMed

Liu, Kun; Tolley, H Dennis; Lee, Milton L

2012-03-02

Seven crosslinking monomers, i.e., 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA), neopentyl glycol dimethacrylate (NPGDMA), 1,5-pentanediol dimethacrylate (1,5-PDDMA), 1,6-hexanediol dimethacrylate (1,6-HDDMA), 1,10-decanediol dimethacrylate (1,10-DDDMA), and 1,12-dodecanediol dimethacrylate (1,12-DoDDMA), were used to synthesize highly cross-linked monolithic capillary columns for reversed-phase liquid chromatography (RPLC) of small molecules. Dodecanol and methanol were chosen as "good" and "poor" porogenic solvents, respectively, for these monoliths, and were investigated in detail to provide insight into the selection of porogen concentration using 1,12-DoDDMA. Isocratic elution of alkylbenzenes at a flow rate of 300 nL/min was conducted for all of the monoliths. Gradient elution of alkylbenzenes and alkylparabens provided high resolution separations. Optimized monoliths synthesized from all seven crosslinking monomers showed high permeability. Several of the monoliths demonstrated column efficiencies in excess of 50,000 plates/m. Monoliths with longer alkyl-bridging chains showed very little shrinking or swelling in solvents of different polarities. Column preparation was highly reproducible; the relative standard deviation (RSD) values (n=3) for run-to-run and column-to-column were less than 0.25% and 1.20%, respectively, based on retention times of alkylbenzenes. Copyright © 2012 Elsevier B.V. All rights reserved.

Spectrophotometric determination of boric acid in boron powder with curcumin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grotheer, E.W.

1979-12-01

A rapid and accurate method was needed to determine trace amounts of boric acid for quality control and specification testing of elemental boron. The reaction between boric acid and curcumin occurs at a measurable rate only when the curcumin molecule is protonated. Protonation takes place at the carbonyl groups in the presence of a strong acid and occurs completely and rapidly when sulfuric acid is added to a solution of curcumin in acetic acid. Spectrophotometric measurements were made. The extraction of boric acid from boron powder was found to be complete within 2h when either water or the diol solutionmore » was used. Whatman No. 40 cr 42 filter paper was used to obtain diol samples free of boron particles. The extraction efficiency of 2-ethyl-1,3-hexanediol was evaluated by adding 1 ml of 500 ppM aqueous boric acid and 1 drop of 10% NaOH to accurately weighed samples of boron powder. The water then was evaporated at room temperature and the samples were extracted with diol solution. The data obtained are included. The extraction efficiency also was evaluated by determining the boric acid content of boron which had been recovered from a previous extraction and boric acid determination. The determination of boric acid using curcumin is unaffected by the presence of other compounds, except for fluoride and nitrate ions. 2 tables. (DP)« less

K+-selective nanospheres: maximising response range and minimising response time.

PubMed

Ruedas-Rama, Maria Jose; Hall, Elizabeth A H

2006-12-01

Cross-linked K(+) ion-selective copolymer nanospheres have been prepared by free-radical photo-initiated polymerization of n-butyl acrylate (nBA) with hexanedioldiacrylate (HDDA). Nanospheres (<200 nm) containing H(+)-chromoionophore (ETH 5294) and lipophilic salt (KTClPB) for H(+)-sensors, or ETH 5294, a K(+)-selective ionophore (valinomycin) and anionic sites for K(+)-sensors were compared, and the effect of varying the normalised concentrations for beta (R(T)(-)/L(T)) and gamma (C(m)(T)/L(T)) was studied. Experimental data were fitted to theoretical curves for the dynamic response range, based on the effect of changes in the concentration of these lipophilic sensing components incorporated into the spheres, and conditions identified for maximising the response range. A complex valinomycin-K(+) formation constant, log K(IL) = 13.13 +/- 2.22, was obtained in the nBA matrix, and from the calibration curves the apparent acid-dissociation equilibrium constant (pK(a) = 12.92 +/- 0.03) was extracted for the H(+)-sensing system, and the equilibrium exchange constant (pK(exch) = 6.16 +/- 0.03, at pH 7) calculated for the K(+)-sensing nanospheres. A basis for establishing optimum performance was identified, whereby response range and response time were balanced with maximum fluorescence yield. Parameters for achieving nanospheres with a response time <5 minutes, covering 2-3 orders of magnitude change in activity were identified, demanding nanospheres with radius <300 nm and beta(crit) approximately 0.6. An RSD(%) approximately 3% was obtained in a study of the reproducibility of the response of the proposed nanospheres, and selectivity was also evaluated for a K(+)-selective nanosensor using several cations as interfering agents. In most cases, the fluorescent emission spectra showed no response to the cations tested, confirming the selectivity of nanospheres to potassium ion. The nanosensors were satisfactorily applied to the determination of K(+) in samples mimicking physiological conditions.

New Elastomeric Materials Based on Natural Rubber Obtained by Electron Beam Irradiation for Food and Pharmaceutical Use

PubMed Central

Craciun, Gabriela; Manaila, Elena; Stelescu, Maria Daniela

2016-01-01

The efficiency of polyfunctional monomers as cross-linking co-agents on the chemical properties of natural rubber vulcanized by electron beam irradiation was studied. The following polyfunctional monomers were used: trimethylolpropane-trimethacrylate, zinc-diacrylate, ethylene glycol dimethacrylate, triallylcyanurate and triallylisocyanurate. The electron beam treatment was done using irradiation doses in the range of 75 kGy–300 kGy. The gel fraction, crosslink density and effects of different aqueous solutions, by absorption tests, have been investigated as a function of polyfunctional monomers type and absorbed dose. The samples gel fraction and crosslink density were determined on the basis of equilibrium solvent-swelling measurements by applying the modified Flory–Rehner equation for tetra functional networks. The absorption tests were done in accordance with the SR ISI 1817:2015 using distilled water, acetic acid (10%), sodium hydroxide (1%), ethylic alcohol (96%), physiological serum (sodium chloride 0.9%) and glucose (glucose monohydrate 10%). The samples structure and morphology were investigated by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy techniques. PMID:28774150

3D Printing of Highly Stretchable, Shape-Memory, and Self-Healing Elastomer toward Novel 4D Printing.

PubMed

Kuang, Xiao; Chen, Kaijuan; Dunn, Conner K; Wu, Jiangtao; Li, Vincent C F; Qi, H Jerry

2018-02-28

The three-dimensional (3D) printing of flexible and stretchable materials with smart functions such as shape memory (SM) and self-healing (SH) is highly desirable for the development of future 4D printing technology for myriad applications, such as soft actuators, deployable smart medical devices, and flexible electronics. Here, we report a novel ink that can be used for the 3D printing of highly stretchable, SM, and SH elastomer via UV-light-assisted direct-ink-write printing. An ink containing urethane diacrylate and a linear semicrystalline polymer is developed for the 3D printing of a semi-interpenetrating polymer network elastomer that can be stretched by up to 600%. The 3D-printed complex structures show interesting functional properties, such as high strain SM and SM -assisted SH capability. We demonstrate that such a 3D-printed SM elastomer has the potential application for biomedical devices, such as vascular repair devices. This research paves a new way for the further development of novel 4D printing, soft robotics, and biomedical devices.

Flexible Nonstick Replica Mold for Transfer Printing of Ag Ink.

PubMed

Lee, Bong Kuk; Yu, Han Young; Kim, Yarkyeon; Yoon, Yong Sun; Jang, Won Ik; Do, Lee-Mi; Park, Ji-Ho; Park, Jaehoon

2016-03-01

We report the fabrication of flexible replica molds for transfer printing of Ag ink on a rigid glass substrate. As mold precursors, acrylic mixtures were prepared from silsesquioxane-based materials, silicone acrylate, poly(propylene glycol) diacrylate, 3,3,4,4,5,5,6,6,7,7,8,8, 9,9,10,10,10-heptadecafluorodecyl methacrylate, and photoinitiator. By using these materials, the replica molds were fabricated from a silicon master onto a flexible substrate by means of UV-assisted molding process at room temperature. The wettability of Ag ink decreased with increase in the water contact angle of replica molds. On the other hand, the transfer rate of Ag ink onto adhesive-modified substrates increased with increase in the water contact angle of replica molds. Transferred patterns were found to be thermally stable on the photocurable adhesive layer, whereas Ag-ink patterns transferred on non-photocurable adhesives were distorted by thermal treatment. We believe that these characteristics of replica molds and adhesives offer a new strategy for the development of the transfer printing of solution-based ink materials.

New Elastomeric Materials Based on Natural Rubber Obtained by Electron Beam Irradiation for Food and Pharmaceutical Use.

PubMed

Craciun, Gabriela; Manaila, Elena; Stelescu, Maria Daniela

2016-12-21

The efficiency of polyfunctional monomers as cross-linking co-agents on the chemical properties of natural rubber vulcanized by electron beam irradiation was studied. The following polyfunctional monomers were used: trimethylolpropane-trimethacrylate, zinc-diacrylate, ethylene glycol dimethacrylate, triallylcyanurate and triallylisocyanurate. The electron beam treatment was done using irradiation doses in the range of 75 kGy-300 kGy. The gel fraction, crosslink density and effects of different aqueous solutions, by absorption tests, have been investigated as a function of polyfunctional monomers type and absorbed dose. The samples gel fraction and crosslink density were determined on the basis of equilibrium solvent-swelling measurements by applying the modified Flory-Rehner equation for tetra functional networks. The absorption tests were done in accordance with the SR ISI 1817:2015 using distilled water, acetic acid (10%), sodium hydroxide (1%), ethylic alcohol (96%), physiological serum (sodium chloride 0.9%) and glucose (glucose monohydrate 10%). The samples structure and morphology were investigated by Fourier Transform Infrared Spectroscopy and Scanning Electron Microscopy techniques.

Fabrication of a Bioactive, PCL-based "Self-fitting" Shape Memory Polymer Scaffold.

PubMed

Nail, Lindsay N; Zhang, Dawei; Reinhard, Jessica L; Grunlan, Melissa A

2015-10-23

Tissue engineering has been explored as an alternative strategy for the treatment of critical-sized cranio-maxillofacial (CMF) bone defects. Essential to the success of this approach is a scaffold that is able to conformally fit within an irregular defect while also having the requisite biodegradability, pore interconnectivity and bioactivity. By nature of their shape recovery and fixity properties, shape memory polymer (SMP) scaffolds could achieve defect "self-fitting." In this way, following exposure to warm saline (~60 ºC), the SMP scaffold would become malleable, permitting it to be hand-pressed into an irregular defect. Subsequent cooling (~37 ºC) would return the scaffold to its relatively rigid state within the defect. To meet these requirements, this protocol describes the preparation of SMP scaffolds prepared via the photochemical cure of biodegradable polycaprolactone diacrylate (PCL-DA) using a solvent-casting particulate-leaching (SCPL) method. A fused salt template is utilized to achieve pore interconnectivity. To realize bioactivity, a polydopamine coating is applied to the surface of the scaffold pore walls. Characterization of self-fitting and shape memory behaviors, pore interconnectivity and in vitro bioactivity are also described.

Electric-Field-Directed Parallel Alignment Architecting 3D Lithium-Ion Pathways within Solid Composite Electrolyte.

PubMed

Liu, Xueqing; Peng, Sha; Gao, Shuyu; Cao, Yuancheng; You, Qingliang; Zhou, Liyong; Jin, Yongcheng; Liu, Zhihong; Liu, Jiyan

2018-05-09

It is of great significance to seek high-performance solid electrolytes via a facile chemistry and simple process for meeting the requirements of solid batteries. Previous reports revealed that ion conducting pathways within ceramic-polymer composite electrolytes mainly occur at ceramic particles and the ceramic-polymer interface. Herein, one facile strategy toward ceramic particles' alignment and assembly induced by an external alternating-current (AC) electric field is presented. It was manifested by an in situ optical microscope that Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 particles and poly(ethylene glycol) diacrylate in poly(dimethylsiloxane) (LATP@PEGDA@PDMS) assembled into three-dimensional connected networks on applying an external AC electric field. Scanning electron microscopy revealed that the ceramic LATP particles aligned into a necklacelike assembly. Electrochemical impedance spectroscopy confirmed that the ionic conductivity of this necklacelike alignment was significantly enhanced compared to that of the random one. It was demonstrated that this facile strategy of applying an AC electric field can be a very effective approach for architecting three-dimensional lithium-ion conductive networks within solid composite electrolyte.

Effect of aspect ratio and deformability on nanoparticle extravasation through nanopores.

PubMed

Kersey, Farrell R; Merkel, Timothy J; Perry, Jillian L; Napier, Mary E; DeSimone, Joseph M

2012-06-12

We describe the fabrication of filamentous hydrogel nanoparticles using a unique soft lithography based particle molding process referred to as PRINT (particle replication in nonwetting templates). The nanoparticles possess a constant width of 80 nm, and we varied their lengths ranging from 180 to 5000 nm. In addition to varying the aspect ratio of the particles, the deformability of the particles was tuned by varying the cross-link density within the particle matrix. Size characteristics such as hydrodynamic diameter and persistence length of the particles were analyzed using dynamic light scattering and electron microscopy techniques, respectively, while particle deformability was assessed by atomic force microscopy. Additionally, the ability of the particles to pass through membranes containing 0.2 μm pores was assessed by means of a simple filtration technique, and particle recovery was determined using fluorescence spectroscopy. The results show that particle recovery is mostly independent of aspect ratio at all cross-linker concentrations utilized, with the exception of 96 wt % PEG diacrylate 80 × 5000 nm particles, which showed the lowest percent recovery.

Highly Conductive, Stretchable, and Transparent Solid Polymer Electrolyte Membrane

NASA Astrophysics Data System (ADS)

He, Ruixuan; Echeverri, Mauricio; Kyu, Thein

2014-03-01

With the guidance of ternary phase diagrams, completely amorphous polymer electrolyte membranes (PEM) were successfully prepared by melt processing for lithium-ion battery. The PEM under consideration consisted of poly (ethylene glycol diacrylate) (PEGDA), succinonitrile (SCN) and Lithium bis(trifluoro-methane)sulfonamide (LiTFSI). After UV-crosslinking, the PEM is transparent and light-weight. Addition of SCN plastic crystal affords not only dissociation of the lithium salt, but also plasticization to the crosslinked PEGDA network. Of particular importance is the achievement of room-temperature ionic conductivity of ~10-3 S/cm, which is comparable to that of commercial liquid electrolyte. Higher ionic conductivities were achieved at elevated temperatures or with use of a moderately higher molecular weight of PEGDA. In terms of electrochemical and chemical stability, the PEM exhibited oxidative stability up to 5 V against lithium reference electrode. Stable interface behavior between the PEM and lithium electrode is also seen with ageing time. In the tensile tests, samples containing low molecular weight PEGDA are stiffer, whereas the high molecular weight PEGDA is stretchable up to 80% elongation. Supported by NSF-DMR 1161070.

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions.

PubMed

Avens, Heather J; Randle, Thomas James; Bowman, Christopher N

2008-10-17

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm(2)) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions

PubMed Central

Avens, Heather J.; Randle, Thomas James; Bowman, Christopher N.

2008-01-01

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm2) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities. PMID:19838291

Modulation of cultured neural networks using neurotrophin release from hydrogel-coated microelectrode arrays

NASA Astrophysics Data System (ADS)

Jun, Sang Beom; Hynd, Matthew R.; Dowell-Mesfin, Natalie M.; Al-Kofahi, Yousef; Roysam, Badrinath; Shain, William; Kim, Sung June

2008-06-01

Polyacrylamide and poly(ethylene glycol) diacrylate hydrogels were synthesized and characterized for use as drug release and substrates for neuron cell culture. Protein release kinetics was determined by incorporating bovine serum albumin (BSA) into hydrogels during polymerization. To determine if hydrogel incorporation and release affect bioactivity, alkaline phosphatase was incorporated into hydrogels and a released enzyme activity determined using the fluorescence-based ELF-97 assay. Hydrogels were then used to deliver a brain-derived neurotrophic factor (BDNF) from hydrogels polymerized over planar microelectrode arrays (MEAs). Primary hippocampal neurons were cultured on both control and neurotrophin-containing hydrogel-coated MEAs. The effect of released BDNF on neurite length and process arborization was investigated using automated image analysis. An increased spontaneous activity as a response to the released BDNF was recorded from the neurons cultured on the top of hydrogel layers. These results demonstrate that proteins of biological interest can be incorporated into hydrogels to modulate development and function of cultured neural networks. These results also set the stage for development of hydrogel-coated neural prosthetic devices for local delivery of various biologically active molecules.

Mechanomimetic hydrogels for vocal fold lamina propria regeneration.

PubMed

Kutty, Jaishankar K; Webb, Ken

2009-01-01

Vocal fold injury commonly leads to reduced vocal quality due to scarring-induced alterations in matrix composition and tissue biomechanics. The long-term hypothesis motivating our work is that rapid restoration of phonation and the associated dynamic mechanical environment will reduce scarring and promote regenerative healing. Toward this end, the objective of this study was to develop mechanomimetic, degradable hydrogels approximating the viscoelastic properties of the vocal ligament and mucosa that may be photopolymerized in situ to restore structural integrity to vocal fold tissues. The tensile and rheological properties of hydrogels (targeting the vocal ligament and mucosa, respectively) were varied as a function of macromer concentration. PEG diacrylate-based hydrogels exhibited linear stress-strain response and elastic modulus consistent with the properties of the vocal ligament at low strains (0-15%), but did not replicate the non-linear behavior observed in native tissue at higher strains. Methacrylated hyaluronic acid hydrogels displayed dynamic viscosity consistent with native vocal mucosa, while elastic shear moduli values were several-fold higher. Cell culture studies indicated that both hydrogels supported spreading, proliferation and collagen/proteoglycan matrix deposition by encapsulated fibroblasts throughout the 3D network.

Fast and easy enzyme immobilization by photoinitiated polymerization for efficient bioelectrochemical devices.

PubMed

Suraniti, Emmanuel; Studer, Vincent; Sojic, Neso; Mano, Nicolas

2011-04-01

Immobilization and electrical wiring of enzymes is of particular importance for the elaboration of efficient biosensors and can be cumbersome. Here, we report a fast and easy protocol for enzyme immobilization, and as a proof of concept, we applied it to the immobilization of bilirubin oxidase, a labile enzyme. In the first step, bilirubin oxidase is mixed with a redox hydrogel "wiring" the enzyme reaction centers to electrodes. Then, this adduct is covered by an outer layer of PEGDA made by photoinitiated polymerization of poly(ethylene-glycol) diacrylate (PEGDA) and a photoclivable precursor, DAROCUR. This two-step protocol is 18 times faster than the current state-of-the-art protocol and leads to currents 25% higher. In addition, the outer layer of PEGDA acts as a protective layer increasing the lifetime of the electrode by 100% when operating continuously for 2000 s and by 60% when kept in dry state for 24 h. This new protocol is particularly appropriate for labile enzymes that quickly denaturate. In addition, by tuning the ratio PEGDA/DAROCUR, it is possible to make the enzyme electrodes even more active or more stable.

Temporal Control of Gelation and Polymerization Fronts Driven by an Autocatalytic Enzyme Reaction.

PubMed

Jee, Elizabeth; Bánsági, Tamás; Taylor, Annette F; Pojman, John A

2016-02-05

Chemical systems that remain kinetically dormant until activated have numerous applications in materials science. Herein we present a method for the control of gelation that exploits an inbuilt switch: the increase in pH after an induction period in the urease-catalyzed hydrolysis of urea was used to trigger the base-catalyzed Michael addition of a water-soluble trithiol to a polyethylene glycol diacrylate. The time to gelation (minutes to hours) was either preset through the initial concentrations or the reaction was initiated locally by a base, thus resulting in polymerization fronts that converted the mixture from a liquid into a gel (ca. 0.1 mm min(-1)). The rate of hydrolytic degradation of the hydrogel depended on the initial concentrations, thus resulting in a gel lifetime of hours to months. In this way, temporal programming of gelation was possible under mild conditions by using the output of an autocatalytic enzyme reaction to drive both the polymerization and subsequent degradation of a hydrogel. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Synthesis and Characterization of Degradable Bioconjugated Hydrogels with Hyperbranched Multifunctional Crosslinkers

PubMed Central

Pedrón, Sara; Peinado, Carmen; Bosch, Paula; S.Anseth, Kristi

2010-01-01

Hyperbranched poly(ester amide) polymer (Hybrane™ S1200; Mn 1200 g/mol) was functionalized with maleic anhydride (MA) and propylene sulfide, to obtain multifunctional crosslinkers with fumaric and thiol-end groups, S1200MA and S1200SH, respectively. The degree of substitution of maleic acid groups (DS) was controlled by varying the molar ratio of MA to S1200 in the reaction mixture. Hydrogels were obtained by UV crosslinking of functionalized S1200 and poly(ethyleneglycol) diacrylate (PEGDA) in aqueous solutions. Compressive modulus increased with decreasing the S1200/PEG ratio and also depended on the DS of the multifunctional crosslinker (S1200). Also, heparin-based macromonomers together with functionalized hyperbranched polymers were used to construct novel functional hydrogels. The multivalent hyperbranched polymers allowed high crosslinking densities in heparin modified gels while introducing biodegradation sites. Both heparin presence and acrylate/thiol ratio have an impact on degradation profiles and morphologies. Hyperbranched crosslinked hydrogels showed no evidence of cell toxicity. Overall, the multifunctional crosslinkers afford hydrogels with promising properties that suggest that these may be suitable for tissue engineering applications. PMID:20561601

Formation of Heterogeneous Toroidal-Spiral Particles -- by Drop Sedimentation and Interaction

NASA Astrophysics Data System (ADS)

Liu, Ying; Nitsche, Ludwig; Gemeinhart, Richard; Sharma, Vishal; Szymusiak, Magdalena; Shen, Hao

2013-03-01

We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (TS) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form TS channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the TS shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. Within the critical separation distance, interaction of multiple drops generates similar structure with more flexibility. Furthermore, the understanding of multiple drop interaction is essential for mass production of TS particles by using parallel and sequential arrays of drops. This work was supported by NSF CBET Grant CBET-1039531.

4D printing smart biomedical scaffolds with novel soybean oil epoxidized acrylate

PubMed Central

Miao, Shida; Zhu, Wei; Castro, Nathan J.; Nowicki, Margaret; Zhou, Xuan; Cui, Haitao; Fisher, John P.; Zhang, Lijie Grace

2016-01-01

Photocurable, biocompatible liquid resins are highly desired for 3D stereolithography based bioprinting. Here we solidified a novel renewable soybean oil epoxidized acrylate, using a 3D laser printing technique, into smart and highly biocompatible scaffolds capable of supporting growth of multipotent human bone marrow mesenchymal stem cells (hMSCs). Porous scaffolds were readily fabricated by simply adjusting the printer infill density; superficial structures of the polymerized soybean oil epoxidized acrylate were significantly affected by laser frequency and printing speed. Shape memory tests confirmed that the scaffold fixed a temporary shape at −18 °C and fully recovered its original shape at human body temperature (37 °C), which indicated the great potential for 4D printing applications. Cytotoxicity analysis proved that the printed scaffolds had significant higher hMSC adhesion and proliferation than traditional polyethylene glycol diacrylate (PEGDA), and had no statistical difference from poly lactic acid (PLA) and polycaprolactone (PCL). This research is believed to significantly advance the development of biomedical scaffolds with renewable plant oils and advanced 3D fabrication techniques. PMID:27251982

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes.

PubMed

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang; Wang, Wei; Wang, Wenxin

2018-02-28

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via "A2 + B4" Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a "click" thiol-ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds - acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds.

Sensitization to reactive diluents and hardeners in epoxy resin systems. IVDK data 2002-2011. Part I: reaction frequencies.

PubMed

Geier, Johannes; Lessmann, Holger; Hillen, Uwe; Skudlik, Christoph; Jappe, Uta

2016-02-01

Epoxy resin systems (ERSs), consisting of resins, reactive diluents, and hardeners, are indispensable in many branches of industry. In order to develop less sensitizing ERS formulations, knowledge of the sensitizing properties of single components is mandatory. To analyse the frequency of sensitization in the patients concerned, as one integral part of a research project on the sensitizing potency of epoxy resin compounds (FP-0324). A retrospective analysis of data from the Information Network of Departments of Dermatology (IVDK), 2002-2011, and a comparison of reaction frequencies with (surrogate) exposure data, were performed. Almost half of the patients sensitized to epoxy resin were additionally sensitized to reactive diluents or hardeners. Among the reactive diluents, 1,6-hexanediol diglycidyl ether was the most frequent allergen, followed by 1,4-butanediol diglycidyl ether, phenyl glycidyl ether, and p-tert-butylphenyl glycidyl ether. Among the hardeners, m-xylylene diamine (MXDA) and isophorone diamine (IPDA) were the most frequent allergens. According to the calculated exposure-related frequency of sensitization, MXDA seems to be a far more important sensitizer than IPDA. Up to 60% of the patients sensitized to hardeners and 15-20% of those sensitized to reactive diluents do not react to epoxy resin. In cases of suspected contact allergy to an ERS, a complete epoxy resin series must be patch tested from the start. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Intralaboratory and interlaboratory evaluation of the EpiDerm 3D human reconstructed skin micronucleus (RSMN) assay.

PubMed

Hu, Ting; Kaluzhny, Yulia; Mun, Greg C; Barnett, Brenda; Karetsky, Viktor; Wilt, Nathan; Klausner, Mitchell; Curren, Rodger D; Aardema, Marilyn J

2009-03-17

A novel in vitro human reconstructed skin micronucleus (RSMN) assay has been developed using the EpiDerm 3D human skin model [R. D. Curren, G. C. Mun, D. P. Gibson, and M. J. Aardema, Development of a method for assessing micronucleus induction in a 3D human skin model EpiDerm, Mutat. Res. 607 (2006) 192-204]. The RSMN assay has potential use in genotoxicity assessments as a replacement for in vivo genotoxicity assays that will be banned starting in 2009 according to the EU 7th Amendment to the Cosmetics Directive. Utilizing EpiDerm tissues reconstructed with cells from four different donors, intralaboratory and interlaboratory reproducibility of the RSMN assay were examined. Seven chemicals were evaluated in three laboratories using a standard protocol. Each chemical was evaluated in at least two laboratories and in EpiDerm tissues from at least two different donors. Three model genotoxins, mitomycin C (MMC), vinblastine sulfate (VB) and methyl methanesulfonate (MMS) induced significant, dose-related increases in cytotoxicity and MN induction in EpiDerm tissues. Conversely, four dermal non-carcinogens, 4-nitrophenol (4-NP), trichloroethylene (TCE), 2-ethyl-1,3-hexanediol (EHD), and 1,2-epoxydodecane (EDD) were negative in the RSMN assay. Results between tissues reconstructed from different donors were comparable. These results indicate the RSMN assay using the EpiDerm 3D human skin model is a promising new in vitro genotoxicity assay that allows evaluation of chromosome damage following "in vivo-like" dermal exposures.

Anisotropic piezoresistivity characteristics of aligned carbon nanotube-polymer nanocomposites

NASA Astrophysics Data System (ADS)

Sengezer, Engin C.; Seidel, Gary D.; Bodnar, Robert J.

2017-09-01

Dielectrophoresis under the application of AC electric fields is one of the primary fabrication techniques for obtaining aligned carbon nanotube (CNT)-polymer nanocomposites, and is used here to generate long range alignment of CNTs at the structural level. The degree of alignment of CNTs within this long range architecture is observed via polarized Raman spectroscopy so that its influence on the electrical conductivity and piezoresistive response in both the alignment and transverse to alignment directions can be assessed. Nanocomposite samples consisting of randomly oriented, well dispersed single-wall carbon nanotubes (SWCNTs) and of long range electric field aligned SWCNTs in a photopolymerizable monomer blend (urethane dimethacrylate and 1,6-hexanediol dimethacrylate) are quantitatively and qualitatively evaluated. Piezoresistive sensitivities in form of gauge factors were measured for randomly oriented, well dispersed specimens with 0.03, 0.1 and 0.5 wt% SWCNTs and compared with gauge factors in both the axial and transverse to SWCNT alignment directions for electric field aligned 0.03 wt% specimens under both quasi-static monotonic and cyclic tensile loading. Gauge factors in the axial direction were observed to be on the order of 2, while gauge factors in the transverse direction demonstrated a 5 fold increase with values on the order of 10 for aligned specimens. Based on Raman analysis, it is believed the higher sensitivity of the transverse direction is related to architectural evolution of misaligned bridging structures which connect alignment structures under load due to Poisson’s contraction.

Determination of n-hexane metabolites by liquid chromatography/mass spectrometry. 2. Glucuronide-conjugated metabolites in untreated urine samples by electrospray ionization.

PubMed

Manini, P; Andreoli, R; Mutti, A; Bergamaschi, E; Niessen, W M

1998-01-01

A liquid chromatography atmospheric pressure electrospray mass spectrometry (ESI-LC/MS) system was evaluated for the identification and characterization of n-hexane conjugated metabolites (glucuronides) in untreated urine samples. Chromatography of glucuronides was obtained under ion-suppressed reversed-phase conditions, by using high-speed (3 cm, 3 microns) columns and formic acid (2 mM) as modifier in the mobile phase. The mass spectrometer was operated in negative ion (NI) mode. For the first time, four glucuronides were identified by ESI-LC/MS in untreated urine samples of rats exposed to n-hexane: 2-hexanol-glucuronide, 5-hydroxy-2-hexanone-glucuronide, 2,5-hexanediol-glucuronide and 4,5-dihydroxy-2-hexanone-glucuronide. Confirmation of the conjugated metabolites was obtained by LC/MS/MS experiments. Gas chromatography/mass spectrometry (GC/MS) and atmospheric pressure chemical ionization (APCI) LC/MS analyses were performed on the same samples. An integrated approach GC/MS-LC/MS for the semi-quantitative analysis of n-hexane glucuronides, whose standards are not commercially available, is discussed and proposed here. In order to understand the fate of the metabolites during sample pre-treatment, a study about the effects of enzymatic and acid hydrolysis on urine samples was conducted on glucuronides isolated by solid-phase extraction. Combined analyses by GC/MS and LC/MS enabled us to distinguish 'true' n-hexane metabolites from compounds resulting from sample treatment and handling (i.e. enzymatic and acid hydrolysis, extraction and GC injection).

New poly(ester urea) derived from L-leucine: electrospun scaffolds loaded with antibacterial drugs and enzymes.

PubMed

Díaz, Angélica; del Valle, Luis J; Tugushi, David; Katsarava, Ramaz; Puiggalí, Jordi

2015-01-01

Electrospun scaffolds from an amino acid containing poly(ester urea) (PEU) were developed as promising materials in the biomedical field and specifically in tissue engineering applications. The selected poly(ester urea) was obtained with a high yield and molecular weight by reaction of phosgene with a bis(α-aminoacyl)-α,ω-diol-diester monomer. The polymer having L-leucine, 1,6-hexanediol and carbonic acid units had a semicrystalline character and relatively high glass transition and melting temperatures. Furthermore it was highly soluble in most organic solvents, an interesting feature that facilitated the electrospinning process and the effective incorporation of drugs with bactericidal activity (e.g. biguanide derivatives such as clorhexidine and polyhexamethylenebiguanide) and enzymes (e.g. α-chymotrypsin) that accelerated the degradation process. Continuous micro/nanofibers were obtained under a wide range of processing conditions, being diameters of electrospun fibers dependent on the drug and solvent used. Poly(ester urea) samples were degradable in media containing lipases and proteinases but the degradation rate was highly dependent on the surface area, being specifically greater for scaffolds with respect to films. The high hydrophobicity of new scaffolds had repercussions on enzymatic degradability since different weight loss rates were found depending on how samples were exposed to the medium (e.g. forced or non-forced immersion). New scaffolds were biocompatible, as demonstrated by adhesion and proliferation assays performed with fibroblast and epithelial cells. Copyright © 2014 Elsevier B.V. All rights reserved.

Kinetics of monomer biodegradation in soil.

PubMed

Siotto, Michela; Sezenna, Elena; Saponaro, Sabrina; Innocenti, Francesco Degli; Tosin, Maurizio; Bonomo, Luca; Mezzanotte, Valeria

2012-01-01

In modern intensive agriculture, plastics are used in several applications (i.e. mulch films, drip irrigation tubes, string, clips, pots, etc.). Interest towards applying biodegradable plastics to replace the conventional plastics is promising. Ten monomers, which can be applied in the synthesis of potentially biodegradable polyesters, were tested according to ASTM 5988-96 (standard respirometric test to evaluate aerobic biodegradation in soil by measuring the carbon dioxide evolution): adipic acid, azelaic acid, 1,4-butanediol, 1,2-ethanediol, 1,6-hexanediol, lactic acid, glucose, sebacic acid, succinic acid and terephthalic acid. Eight replicates were carried out for each monomer for 27-45 days. The numerical code AQUASIM was applied to process the CO₂ experimental data in order to estimate values for the parameters describing the different mechanisms occurring to the monomers in soil: i) the first order solubilization kinetic constant, K(sol) (d⁻¹); ii) the first order biodegradation kinetic constant, K(b) (d⁻¹); iii) the lag time in biodegradation, t(lag) (d); and iv) the carbon fraction biodegraded but not transformed into CO₂, Y (-). The following range of values were obtained: [0.006 d⁻¹, 6.9 d⁻¹] for K(sol), [0.1 d⁻¹, 1.2 d⁻¹] for K(b), and [0.32-0.58] for Y; t(lag) was observed for azelaic acid, 1,2-ethanediol, and terephthalic acid, with estimated values between 3.0 e 4.9 d. Copyright © 2011 Elsevier Ltd. All rights reserved.

Design and synthesis of bio-based UV curable PU acrylate resin from itaconic acid for coating applications

PubMed Central

Patil, Deepak M.; Phalak, Ganesh A.; Mhaske, S. T.

2017-01-01

Abstract UV curable PUA resin was successfully synthesized from polyol based on sustainable resource originated from itaconic acid (IA), isophorone diisocyanate (IPDI) and 2-hydroxyethyl methacrylate (HEMA). A polyol was synthesized by condensation reaction of IA with 16-hexanediol in the presence of p-Toluenesulfonic acid (pTSA). The synthesized PUA resin was characterized for its structural elucidation by using Fourier Transform Infrared Spectrophotometer (FTIR), 1H and 13C NMR spectroscopy. The synthesized UV curable PUA resin was incorporated in varying concentrations in conventional PUA coating system. The effects of varying concentration of synthesized UV curable PUA resin on rheology, crystallinity, thermal and coating properties were evaluated. The rheological behavior of the resins were evaluated at variable stress and result showed decrease in viscosity of resin as concentration of synthesized UV curable PUA resin increases in conventional PUA resin. The cured coatings have been evaluated for glass transition temperature (T g) and thermal behavior by differential scanning calorimeter and thermogravimetric analysis respectively. The degree of crystallinity of the coatings was determined from X-ray diffraction patterns using the PFM program. It was found that increase in the mass proportion of IA based PUA in coatings, the coating becomes more rigid and crystalline. The synthesized UV curable PUA coatings showed interesting mechanical, chemical, solvent and thermal properties as compared to the conventional PUA. Further, cured coatings were also evaluated for gel content and water absorption. PMID:29491798

Multiple solvent crystal structures of ribonuclease A: An assessment of the method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dechene, Michelle; Wink, Glenna; Smith, Mychal

2010-11-12

The multiple solvent crystal structures (MSCS) method uses organic solvents to map the surfaces of proteins. It identifies binding sites and allows for a more thorough examination of protein plasticity and hydration than could be achieved by a single structure. The crystal structures of bovine pancreatic ribonuclease A (RNAse A) soaked in the following organic solvents are presented: 50% dioxane, 50% dimethylformamide, 70% dimethylsulfoxide, 70% 1,6-hexanediol, 70% isopropanol, 50% R,S,R-bisfuran alcohol, 70% t-butanol, 50% trifluoroethanol, or 1.0M trimethylamine-N-oxide. This set of structures is compared with four sets of crystal structures of RNAse A from the protein data bank (PDB) andmore » with the solution NMR structure to assess the validity of previously untested assumptions associated with MSCS analysis. Plasticity from MSCS is the same as from PDB structures obtained in the same crystal form and deviates only at crystal contacts when compared to structures from a diverse set of crystal environments. Furthermore, there is a good correlation between plasticity as observed by MSCS and the dynamic regions seen by NMR. Conserved water binding sites are identified by MSCS to be those that are conserved in the sets of structures taken from the PDB. Comparison of the MSCS structures with inhibitor-bound crystal structures of RNAse A reveals that the organic solvent molecules identify key interactions made by inhibitor molecules, highlighting ligand binding hot-spots in the active site. The present work firmly establishes the relevance of information obtained by MSCS.« less

Hygroscopic and phase separation properties of ammonium sulfate/organics/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-08-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead, they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR (Fourier transform infrared) spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance and, therefore, particles prepared in this study should mimic atmospheric mixed-phase aerosol particles. Some results of this study tend to be in agreement with previous microscopy experiments, but others, such as phase separation properties of 1,2,6-hexanetriol, do not agree with previous work. Because the particles studied in this experiment are of a smaller size than those used in microscopy studies, the discrepancies found could be a size-related effect.

PCL-based Shape Memory Polymers with Variable PDMS Soft Segment Lengths

PubMed Central

Zhang, Dawei; Giese, Melissa L.; Prukop, Stacy L.; Grunlan, Melissa A.

2012-01-01

Thermoresponsive shape memory polymers (SMPs) are stimuli-responsive materials that return to their permanent shape from a temporary shape in response to heating. The design of new SMPs which obtain a broader range of properties including mechanical behavior is critical to realize their potential in biomedical as well as industrial and aerospace applications. To tailor the properties of SMPs, “AB networks” comprised of two distinct polymer components have been investigated but are overwhelmingly limited to those in which both components are organic. In this present work, we prepared inorganic-organic SMPs comprised of inorganic polydimethyl-siloxane (PDMS) segments of varying lengths and organic poly(ε-caprolactone) (PCL) segments. PDMS has a particularly low Tg (−125 °C) which makes it a particularly effective soft segment to tailor the mechanical properties of PCL-based SMPs. The SMPs were prepared via the rapid photocure of solutions of diacrylated PCL40-block-PDMSm-block-PCL40 macromers (m = 20, 37, 66 and 130). The resulting inorganic-organic SMP networks exhibited excellent shape fixity and recovery. By changing the PDMS segment length, the thermal, mechanical, and surface properties were systematically altered. PMID:22904597

Angle selective backscattered electron contrast in the low-voltage scanning electron microscope: Simulation and experiment for polymers.

PubMed

Wan, Q; Masters, R C; Lidzey, D; Abrams, K J; Dapor, M; Plenderleith, R A; Rimmer, S; Claeyssens, F; Rodenburg, C

2016-12-01

Recently developed detectors can deliver high resolution and high contrast images of nanostructured carbon based materials in low voltage scanning electron microscopes (LVSEM) with beam deceleration. Monte Carlo Simulations are also used to predict under which exact imaging conditions purely compositional contrast can be obtained and optimised. This allows the prediction of the electron signal intensity in angle selective conditions for back-scattered electron (BSE) imaging in LVSEM and compares it to experimental signals. Angle selective detection with a concentric back scattered (CBS) detector is considered in the model in the absence and presence of a deceleration field, respectively. The validity of the model prediction for both cases was tested experimentally for amorphous C and Cu and applied to complex nanostructured carbon based materials, namely a Poly(N-isopropylacrylamide)/Poly(ethylene glycol) Diacrylate (PNIPAM/PEGDA) semi-interpenetration network (IPN) and a Poly(3-hexylthiophene-2,5-diyl) (P3HT) film, to map nano-scale composition and crystallinity distribution by avoiding experimental imaging conditions that lead to a mixed topographical and compositional contrast. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Stable Aqueous Foams from Cellulose Nanocrystals and Methyl Cellulose.

PubMed

Hu, Zhen; Xu, Richard; Cranston, Emily D; Pelton, Robert H

2016-12-12

The addition of cellulose nanocrystals (CNC) greatly enhanced the properties of methylcellulose (MC) stabilized aqueous foams. CNC addition decreased air bubble size, initial foam densities and drainage rates. Mixtures of 2 wt % CNC + 0.5 wt % MC gave the lowest density foams. This composition sits near the onset of nematic phase formation and also near the overlap concentration of methylcellulose. More than 94% of the added CNC particles remained in the foam phase, not leaving with the draining water. We propose that the nanoscale CNC particles bind to the larger MC coils both in solution and with MC at the air/water interface, forming weak gels that stabilize air bubbles. Wet CNC-MC foams were sufficiently robust to withstand high temperature (70 °C for 6 h) polymerization of water-soluble monomers giving macroporous CNC composite hydrogels based on acrylamide (AM), 2-hydroxyethyl methacrylate (HEMA), or polyethylene glycol diacrylate (PEGDA). At high temperatures, the MC was present as a fibrillar gel phase reinforced by CNC particles, explaining the very high foam stability. Finally, our CNC-MC foams are based on commercially available forms of CNC and MC, already approved for many applications. This is a "shovel-ready" technology.

Reduction of Non-Specific Protein Adsorption Using Poly(ethylene) Glycol (PEG) Modified Polyacrylate Hydrogels In Immunoassays for Staphylococcal Enterotoxin B Detection

PubMed Central

Charles, Paul T.; Stubbs, Veronte R.; Soto, Carissa M.; Martin, Brett D.; White, Brandy J.; Taitt, Chris R.

2009-01-01

Three PEG molecules (PEG-methacrylate, -diacrylate and -dimethacrylate) were incorporated into galactose-based polyacrylate hydrogels and their relative abilities to reduce non-specific protein adsorption in immunoassays were determined. Highly crosslinked hydrogels containing amine-terminated functionalities were formed and used to covalently attach antibodies specific for staphylococcal enterotoxin B (SEB). Patterned arrays of immobilized antibodies in the PEG-modified hydrogels were created with a PDMS template containing micro-channels for use in sandwich immunoassays to detect SEB. Different concentrations of the toxin were applied to the hydrogel arrays, followed with a Cy3-labeled tracer antibody specific for the two toxins. Fluorescence laser scanning confocal microscopy of the tracer molecules provided both qualitative and quantitative measurements on the detection sensitivity and the reduction in non-specific binding as a result of PEG incorporation. Results showed the PEG-modified hydrogel significantly reduced non-specific protein binding with a detection limit for SEB of 1 ng/mL. Fluorescence signals showed a 10-fold decrease in the non-specific binding and a 6-fold increase in specific binding of SEB. PMID:22389622

Hydrogel Film-Immobilized Lactobacillus brevis RK03 for γ-Aminobutyric Acid Production

PubMed Central

Hsueh, Yi-Huang; Liaw, Wen-Chang; Kuo, Jen-Min; Deng, Chi-Shin

2017-01-01

Hydrogels of 2-hydroxyethyl methacrylate/polyethylene glycol diacrylate (HEMA/PEGDA) have been extensively studied for their use in biomedical and pharmaceutical applications owing to their nontoxic and highly hydrophilic characteristics. Recently, cells immobilized by HEMA/PEGDA hydrogels have also been studied for enhanced production in fermentation. Hydrogel films of HEMA/PEGDA copolymer were generated by Ultraviolet (UV)-initiated photopolymerization. The hydrogel films were used to immobilize viable Lactobacillus brevis RK03 cells for the bioconversion of monosodium glutamate (MSG) to γ-aminobutyric acid (GABA). The mechanical properties and fermentation yields of the L. brevis RK03 cells immobilized on polyacrylate hydrogel films with different monomeric formulations were investigated. Fermentation was carried out in 75 mL de Man, Rogosa and Sharpe (MRS) medium containing various concentrations of MSG. We found that HEMA (93%)/PEGDA (3%) hydrogels (sample H) maximized GABA production. The conversion rate of MSG to GABA reached a maximum value of 98.4% after 240 h. Bioconversion activity gradually declined after 420 h to 83.8% after five cycles of semi-continuous fermentation. Our results suggest that HEMA (93%)/PEGDA (3%) hydrogels have great potential for use in GABA production via semi-continuous fermentation. PMID:29099794

PEGDA hydrogels as a replacement for animal tissues in mucoadhesion testing.

PubMed

Eshel-Green, Tal; Eliyahu, Shaked; Avidan-Shlomovich, Shlomit; Bianco-Peled, Havazelet

2016-06-15

Utilization of animal parts in ex-vivo mucoadhesion assays is a common approach that presents many difficulties due to animal rights issues and large variance between animals. This study examines the suitability of two PEGDA (poly(ethylene glycol) diacrylate) based hydrogels to serve as tissue mimetics for mucoadhesion evaluation. One hydrogel, termed PEGDA-QT, was composed of pentaerythritol tetrakis (3-mercaptopropionate) and PEG and contained free thiol groups mimicking those found in natural mucosa. The other hydrogel was formed by UV (ultraviolet) curing of PEGDA and mimicked the mechanical property of mucosa but not its chemical constitute. When ranking different first generation mucoadhesive polymers using a tensile assay, both hydrogels showed good agreement with the ranking achieved for porcine small intestine. However, only PEGDA-QT and porcine small intestine shared a similar displacement curve. The same ranking for PEGDA-QT and porcine small intestine was also observed when comparing a second-generation mucoadhesive polymer, thiolated alginate, to native alginate. Our findings suggest that PEGDA-QT could serve as a replacement for porcine small intestine in both mucoadhesion evaluations using a tensile machine and the flow-through method for first and second-generation mucoadhesive polymers. Copyright © 2016 Elsevier B.V. All rights reserved.

New design strategy for reversible plasticity shape memory polymers with deformable glassy aggregates.

PubMed

Lin, Tengfei; Tang, Zhenghai; Guo, Baochun

2014-12-10

Reversible plasticity shape memory (RPSM) is a new concept in the study of shape memory performance behavior and describes a phenomenon in which shape memory polymers (SMPs) can undergo a large plastic deformation at room temperature and subsequently recover their original shape upon heating. To date, RPSM behavior has been demonstrated in only a few polymers. In the present study, we implement a new design strategy, in which deformable glassy hindered phenol (AO-80) aggregates are incorporated into an amorphous network of epoxidized natural rubber (ENR) cured with zinc diacrylate (ZDA), in order to achieve RPSM properties. We propose that AO-80 continuously tunes the glass transition temperature (Tg) and improves the chain mobility of the SMP, providing traction and anchoring the ENR chains by intermolecular hydrogen bonding interactions. The RPSM behavior of the amorphous SMPs is characterized, and the results demonstrate good fixity at large deformations (up to 300%) and excellent recovery upon heating. Large energy storage capacities at Td in these RPSM materials are demonstrated compared with those achieved at elevated temperature in traditional SMPs. Interestingly, the further revealed self-healing properties of these materials are closely related to their RPSM behavior.

Holographic lithography for biomedical applications

NASA Astrophysics Data System (ADS)

Stankevicius, E.; Balciunas, E.; Malinauskas, M.; Raciukaitis, G.; Baltriukiene, D.; Bukelskiene, V.

2012-06-01

Fabrication of scaffolds for cell growth with appropriate mechanical characteristics is top-most important for successful creation of tissue. Due to ability of fast fabrication of periodic structures with a different period, the holographic lithography technique is a suitable tool for scaffolds fabrication. The scaffolds fabricated by holographic lithography can be used in various biomedical investigations such as the cellular adhesion, proliferation and viability. These investigations allow selection of the suitable material and geometry of scaffolds which can be used in creation of tissue. Scaffolds fabricated from di-acrylated poly(ethylene glycol) (PEG-DA-258) over a large area by holographic lithography technique are presented in this paper. The PEG-DA scaffolds fabricated by holographic lithography showed good cytocompatibility for rabbit myogenic stem cells. It was observed that adult rabbit muscle-derived myogenic stem cells grew onto PEG-DA scaffolds. They were attached to the pillars and formed cell-cell interactions. It demonstrates that the fabricated structures have potential to be an interconnection channel network for cell-to-cell interactions, flow transport of nutrients and metabolic waste as well as vascular capillary ingrowth. These results are encouraging for further development of holographic lithography by improving its efficiency for microstructuring three-dimensional scaffolds out of biodegradable hydrogels

Room-Temperature Performance of Poly(Ethylene Ether Carbonate)-Based Solid Polymer Electrolytes for All-Solid-State Lithium Batteries.

PubMed

Jung, Yun-Chae; Park, Myung-Soo; Kim, Duck-Hyun; Ue, Makoto; Eftekhari, Ali; Kim, Dong-Won

2017-12-13

Amorphous poly(ethylene ether carbonate) (PEEC), which is a copolymer of ethylene oxide and ethylene carbonate, was synthesized by ring-opening polymerization of ethylene carbonate. This route overcame the common issue of low conductivity of poly(ethylene oxide)(PEO)-based solid polymer electrolytes at low temperatures, and thus the solid polymer electrolyte could be successfully employed at the room temperature. Introducing the ethylene carbonate units into PEEC improved the ionic conductivity, electrochemical stability and lithium transference number compared with PEO. A cross-linked solid polymer electrolyte was synthesized by photo cross-linking reaction using PEEC and tetraethyleneglycol diacrylate as a cross-linking agent, in the form of a flexible thin film. The solid-state Li/LiNi 0.6 Co 0.2 Mn 0.2 O 2 cell assembled with solid polymer electrolyte based on cross-linked PEEC delivered a high initial discharge capacity of 141.4 mAh g -1 and exhibited good capacity retention at room temperature. These results demonstrate the feasibility of using this solid polymer electrolyte in all-solid-state lithium batteries that can operate at ambient temperatures.

A hydrophilic polymer based microfluidic system with planar patch clamp electrode array for electrophysiological measurement from cells.

PubMed

Xu, Baojian; Ye, WeiWei; Zhang, Yu; Shi, JingYu; Chan, ChunYu; Yao, XiaoQiang; Yang, Mo

2014-03-15

This paper presents a microfluidic planar patch clamp system based on a hydrophilic polymer poly(ethylene glycol) diacrylate (PEGDA) for whole cell current recording. The whole chip is fabricated by UV-assisted molding method for both microfluidic channel structure and planar electrode partition. This hydrophilic patch clamp chip has demonstrated a relatively high gigaseal success rate of 44% without surface modification compared with PDMS based patch clamp devices. This chip also shows a capability of rapid intracellular and extracellular solution exchange with high stability of gigaseals. The capillary flow kinetic experiments demonstrate that the flow rates of PEGDA microfluidic channels are around two orders of magnitude greater than those for PDMS-glass channels with the same channel dimensions. This hydrophilic polymer based patch clamp chips have significant advantages over current PDMS elastomer based systems such as no need for surface modification, much higher success rate of cell gigaseals and rapid solution exchange with stable cell gigaseals. Our results indicate the potential of these devices to serve as useful tools for pharmaceutical screening and biosensing tasks. © 2013 Elsevier B.V. All rights reserved.

Piezoelectric Nanoparticle-Polymer Composite Materials

NASA Astrophysics Data System (ADS)

McCall, William Ray

Herein we demonstrate that efficient piezoelectric nanoparticle-polymer composite materials can be synthesized and fabricated into complex microstructures using sugar-templating methods or optical printing techniques. Stretchable foams with excellent tunable piezoelectric properties are created by incorporating sugar grains directly into polydimethylsiloxane (PDMS) mixtures containing barium titanate (BaTiO3 -- BTO) nanoparticles and carbon nanotubes (CNTs), followed by removal of the sugar after polymer curing. Porosities and elasticity are tuned by simply adjusting the sugar/polymer mass ratio and the electrical performance of the foams showed a direct relationship between porosity and the piezoelectric outputs. User defined 2D and 3D optically printed piezoelectric microstructures are also fabricated by incorporating BTO nanoparticles into photoliable polymer solutions such as polyethylene glycol diacrylate (PEGDA) and exposing to digital optical masks that can be dynamically altered. Mechanical-to-electrical conversion efficiency of the optically printed composite is enhanced by chemically altering the surface of the BTO nanoparticles with acrylate groups which form direct covalent linkages with the polymer matrix under light exposure. Both of these novel materials should find exciting uses in a variety of applications including energy scavenging platforms, nano- and microelectromechanical systems (NEMS/MEMS), sensors, and acoustic actuators.

Noninvasive Assessment of Glycosaminoglycan Production in Injectable Tissue-Engineered Cartilage Constructs Using Magnetic Resonance Imaging

PubMed Central

Ramaswamy, Sharan; Uluer, Mehmet C.; Leen, Stephanie; Bajaj, Preeti; Fishbein, Kenneth W.

2008-01-01

Abstract The glycosaminoglycan (GAG) content of engineered cartilage is a determinant of biochemical and mechanical quality. The ability to measure the degree to which GAG content is maintained or increases in an implant is therefore of importance in cartilage repair procedures. The gadolinium exclusion magnetic resonance imaging (MRI) method for estimating matrix fixed charge density (FCD) is ideally suited to this. One promising approach to cartilage repair is use of seeded injectable hydrogels. Accordingly, we assess the reliability of measuring GAG content in such a system ex vivo using MRI. Samples of the photo-polymerizable hydrogel, poly(ethylene oxide) diacrylate, were seeded with bovine chondrocytes (∼2.4 million cells/sample). The FCD of the constructs was determined using MRI after 9, 16, 29, 36, 43, and 50 days of incubation. Values were correlated with the results of biochemical determination of GAG from the same samples. FCD and GAG were found to be statistically significantly correlated (R2 = 0.91, p <0.01). We conclude that MRI-derived FCD measurements of FCD in injectable hydrogels reflect tissue GAG content and that this methodology therefore has potential for in vivo monitoring of such constructs. PMID:18620483

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

PubMed Central

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Dual-Functional Hydrazide-Reactive and Anhydride-Containing Oligomeric Hydrogel Building Blocks.

PubMed

Kascholke, Christian; Loth, Tina; Kohn-Polster, Caroline; Möller, Stephanie; Bellstedt, Peter; Schulz-Siegmund, Michaela; Schnabelrauch, Matthias; Hacker, Michael C

2017-03-13

Biomimetic hydrogels are advanced biomaterials that have been developed following different synthetic routes. Covalent postfabrication functionalization is a promising strategy to achieve efficient matrix modification decoupled of general material properties. To this end, dual-functional macromers were synthesized by free radical polymerization of maleic anhydride with diacetone acrylamide (N-(1,1-dimethyl-3-oxobutyl)acrylamide) and pentaerythritol diacrylate monostearate. Amphiphilic oligomers (M n < 7.5 kDa) with anhydride contents of 7-20% offered cross-linking reactivity to yield rigid hydrogels with gelatinous peptides (E = 4-13 kPa) and good cell adhesion properties. Mildly reactive methyl ketones as second functionality remained intact during hydrogel formation and potential of covalent matrix modification was shown using hydrazide and hydrazine model compounds. Successful secondary dihydrazide cross-linking was demonstrated by an increase of hydrogel stiffness (>40%). Efficient hydrazide/hydrazine immobilization depending on solution pH, hydrogel ketone content as well as ligand concentration for bioconjugation was shown and reversibility of hydrazone formation was indicated by physiologically relevant hydrazide release over 7 days. Proof-of-concept experiments with hydrazido-functionalized hyaluronan demonstrated potential for covalent aECM immobilization. The presented dual-functional macromers have perspective as reactive hydrogel building blocks for various biomedical applications.

Hygroscopic and phase separation properties of ammonium sulfate/organic/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-03-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance, and therefore, particles prepared in this study should mimic atmospheric mixed phase aerosol particles. The results of this study tend to be in agreement with previous microscopy experiments, with several key differences, which possibly reveal a size-dependent effect on phase separation in organic/inorganic aerosol particles.

Preparation of poly(ethylene glycol) hydrogels with different network structures for the application of enzyme immobilization.

PubMed

Choi, Dongkil; Lee, Woojin; Park, Jinwon; Koh, Wongun

2008-01-01

In this study, poly(ethylene glycol) (PEG)-based hydrogels having different network structures were synthesized by UV-initiated photopolymerization and used for the enzyme immobilization. PEGs with different molecular weight were acrylated by derivatizing both ends with acryloyl chloride and photopolymerization of PEG-diacrylate (PEG-DA) yielded crosslinked hydrogel network within 5 seconds. Attachment of acrylate groups and gelation were confirmed by ATR/FT-IR and FT-Raman spectroscopy. Network structures of hydrogels could be easily controlled by changing the molecular weight (MW) of PEG-DA and characterized by calculating molecular weight between crosslinks and mesh size from the swelling measurement. Synthesis of hydrogels with higher MW of PEG produced less crosslinked hydrogels having higher water content, larger value of Mc and mesh size, which resulted in enhanced mass transfer but loss of mechanical properties. For the enzyme immobilization, glucose oxidase (GOX) was immobilized inside PEG hydrogels by means of physical entrapment and covalent immobilization. Encapsulated GOX were covalently bound to PEG backbone using acryloyl-PEG-N-hydroxysuccinimide and maintained their activity over a week period without leakage. Kinetic study indicated that immobilized enzyme inside hydrogel prepared from higher MW of PEG possessed lower apparent Km (Michaelis-Menten constant) and higher activity.

Electrospun Blends of Gelatin and Gelatin-dendrimer Conjugates as a Wound Dressing and Drug Delivery Platform

PubMed Central

Dongargaonkar, Alpana A.; Bowlin, Gary L.; Yang, Hu

2013-01-01

In this work, we report a new nanofiber construct based on electrospun blends of gelatin and gelatin-dendrimer conjugates. Highly branched star-shaped polyamidoamine (PAMAM) dendrimer G3.5 was covalently conjugated to gelatin via EDC/NHS chemistry. Blends of gelatin and gelatin-dendrimer conjugates mixed with various loading levels of silver acetate (0, 0.83, 1.65, and 3.30% w/w) were successfully electrospun into nanofiber constructs (NCs). The NCs were further converted into semi-interpenetrating networks (sIPNs) with photoreactive polyethylene glycol diacrylate (Mn=575 gmol-1) (PEG DA575). They were characterized in terms of fiber morphology, diameter, pore size, permeability, degradation, and mechanical properties. The resulting sIPN NCs retained nanofiber morphology, possessed similar fiber diameters to counterpart NCs, and gained improved structural stability. The sIPN NCs also showed good swelling capacity owing to porous structures and were permeable to aqueous solutions. Silvercontaining sIPN NCs allowed sustained silver release and showed antimicrobial activity against two common types of pathogens—Staphylococcus aureus and Pseudomonas aeruginosa. Incorporation of dendrimers into the gelatin nanofibers through covalent conjugation not only expands drug loading capacity of nanofiber constructs but provides tremendous flexibility for developing multifunctional electrospun dressing materials. PMID:24127747

Development of a microfabricated artificial limbus with micropockets for cell delivery to the cornea.

PubMed

Ortega, Ílida; Deshpande, Pallavi; Gill, Andrew A; MacNeil, Sheila; Claeyssens, Frederik

2013-06-01

The aim of this study was to develop a synthetic alternative to the human corneal limbus for use initially as an ex vivo model in which to study corneal stem cell function within a niche environment and ultimately to develop an implantable limbus for future clinical use. Microstereolithography was used for the fabrication of polyethylene glycol diacrylate (PEGDA) based rings on a macroscopic (1.2 cm) scale containing unique microfeatures (pockets) which were then modified with fibronectin to promote cell adhesion. These rings were designed to mimic the limbal area of the eye containing structures of the approximate size and shape of the stem cell microenvironments found in the palisades of Vogt. The attachment of rabbit limbal fibroblasts and rabbit limbal epithelial cells to the PEGDA rings was increased by pretreating the microfabricated structures with biotinylated fibronectin. Cell outgrowth from fibronectin coated microfabricated structures was 50% greater than from rings without structures or fibronectin coating. The cell loaded rings were then placed on an ex vivo wounded cornea model and the outgrowth of cells to form a multilayered epithelium was observed. We suggest this is a new approach to investigating limbal stem cells niches and the first steps towards a new approach for corneal regeneration.

Preparation and characterization of cellulose-based foams via microwave curing

PubMed Central

Demitri, Christian; Giuri, Antonella; Raucci, Maria Grazia; Giugliano, Daniela; Madaghiele, Marta; Sannino, Alessandro; Ambrosio, Luigi

2014-01-01

In this work, a mixture of a sodium salt of carboxymethylcellulose (CMCNa) and polyethylene glycol diacrylate (PEGDA700) was used for the preparation of a microporous structure by using the combination of two different procedures. First, physical foaming was induced using Pluronic as a blowing agent, followed by a chemical stabilization. This second step was carried out by means of an azobis(2-methylpropionamidine)dihydrochloride as the thermoinitiator (TI). This reaction was activated by heating the sample homogeneously using a microwave generator. Finally, the influence of different CMCNa and PEGDA700 ratios on the final properties of the foams was investigated. The viscosity, water absorption capacity, elastic modulus and porous structure were evaluated for each sample. In addition, preliminary biological characterization was carried out with the aim to prove the biocompatibility of the resulting material. The foam, including 20% of PEGDA700 in the mixture, demonstrated higher viscosity and stability before thermo-polymerization. In addition, increased water absorption capacity, mechanical resistance and a more uniform microporous structure were obtained for this sample. In particular, foam with 3% of CMCNa shows a hierarchical structure with open pores of different sizes. This morphology increased the properties of the foams. The full set of samples demonstrated an excellent biocompatibility profile with a good cell proliferation rate of more than 7 days. PMID:24501679

3D‐Bioprinted Osteoblast‐Laden Nanocomposite Hydrogel Constructs with Induced Microenvironments Promote Cell Viability, Differentiation, and Osteogenesis both In Vitro and In Vivo

PubMed Central

Zhai, Xinyun; Ma, Yufei; Cheng, Delin; Wu, Mingming; Liu, Wenguang; Zhao, Xiaoli

2017-01-01

Abstract An osteoblast‐laden nanocomposite hydrogel construct, based on polyethylene glycol diacrylate (PEGDA)/laponite XLG nanoclay ([Mg5.34Li0.66Si8O20(OH)4]Na0.66, clay)/hyaluronic acid sodium salt (HA) bio‐inks, is developed by a two‐channel 3D bioprinting method. The novel biodegradable bio‐ink A, comprised of a poly(ethylene glycol) (PEG)–clay nanocomposite crosslinked hydrogel, is used to facilitate 3D‐bioprinting and enables the efficient delivery of oxygen and nutrients to growing cells. HA with encapsulated primary rat osteoblasts (ROBs) is applied as bio‐ink B with a view to improving cell viability, distribution uniformity, and deposition efficiency. The cell‐laden PEG–clay constructs not only encapsulated osteoblasts with more than 95% viability in the short term but also exhibited excellent osteogenic ability in the long term, due to the release of bioactive ions (magnesium ions, Mg2+ and silicon ions, Si4+), which induces the suitable microenvironment to promote the differentiation of the loaded exogenous ROBs, both in vitro and in vivo. This 3D‐bioprinting method holds much promise for bone tissue regeneration in terms of cell engraftment, survival, and ultimately long‐term function. PMID:29593958

A Self-Folding Hydrogel In Vitro Model for Ductal Carcinoma

PubMed Central

Kwag, Hye Rin; Serbo, Janna V.; Korangath, Preethi; Sukumar, Saraswati

2016-01-01

A significant challenge in oncology is the need to develop in vitro models that accurately mimic the complex microenvironment within and around normal and diseased tissues. Here, we describe a self-folding approach to create curved hydrogel microstructures that more accurately mimic the geometry of ducts and acini within the mammary glands, as compared to existing three-dimensional block-like models or flat dishes. The microstructures are composed of photopatterned bilayers of poly (ethylene glycol) diacrylate (PEGDA), a hydrogel widely used in tissue engineering. The PEGDA bilayers of dissimilar molecular weights spontaneously curve when released from the underlying substrate due to differential swelling ratios. The photopatterns can be altered via AutoCAD-designed photomasks so that a variety of ductal and acinar mimetic structures can be mass-produced. In addition, by co-polymerizing methacrylated gelatin (methagel) with PEGDA, microstructures with increased cell adherence are synthesized. Biocompatibility and versatility of our approach is highlighted by culturing either SUM159 cells, which were seeded postfabrication, or MDA-MB-231 cells, which were encapsulated in hydrogels; cell viability is verified over 9 and 15 days, respectively. We believe that self-folding processes and associated tubular, curved, and folded constructs like the ones demonstrated here can facilitate the design of more accurate in vitro models for investigating ductal carcinoma. PMID:26831041

A Self-Folding Hydrogel In Vitro Model for Ductal Carcinoma.

PubMed

Kwag, Hye Rin; Serbo, Janna V; Korangath, Preethi; Sukumar, Saraswati; Romer, Lewis H; Gracias, David H

2016-04-01

A significant challenge in oncology is the need to develop in vitro models that accurately mimic the complex microenvironment within and around normal and diseased tissues. Here, we describe a self-folding approach to create curved hydrogel microstructures that more accurately mimic the geometry of ducts and acini within the mammary glands, as compared to existing three-dimensional block-like models or flat dishes. The microstructures are composed of photopatterned bilayers of poly (ethylene glycol) diacrylate (PEGDA), a hydrogel widely used in tissue engineering. The PEGDA bilayers of dissimilar molecular weights spontaneously curve when released from the underlying substrate due to differential swelling ratios. The photopatterns can be altered via AutoCAD-designed photomasks so that a variety of ductal and acinar mimetic structures can be mass-produced. In addition, by co-polymerizing methacrylated gelatin (methagel) with PEGDA, microstructures with increased cell adherence are synthesized. Biocompatibility and versatility of our approach is highlighted by culturing either SUM159 cells, which were seeded postfabrication, or MDA-MB-231 cells, which were encapsulated in hydrogels; cell viability is verified over 9 and 15 days, respectively. We believe that self-folding processes and associated tubular, curved, and folded constructs like the ones demonstrated here can facilitate the design of more accurate in vitro models for investigating ductal carcinoma.

Stabilization of miscible viscous fingering by a step-growth polymerization reaction

NASA Astrophysics Data System (ADS)

Bunton, Patrick; Stewart, Simone; Marin, Daniela; Tullier, Michael; Meiburg, Eckart; Pojman, John

2017-11-01

Viscous fingering is a hydrodynamic instability that occurs when a more mobile fluid displaces a fluid of lower mobility. Viscous fingering is often undesirable in industrial processes such as secondary petroleum recovery where it limits resource recovery. Linear stability analysis by Hejazi et al. (2010) has predicted that a non-monotonic viscosity profile at an otherwise unstable interface can in some instances stabilize the flow. We use step-growth polymerization at the interface between two miscible monomers as a model system. A dithiol monomer displacing a diacrylate react to form a linear polymer that behaves as a Newtonian fluid. Viscous fingering was imaged in a horizontal Hele-Shaw cell via Schlieren, which is sensitive to polymer conversion. By varying reaction rate via initiator concentration along with flow rate, we demonstrated increasing stabilization of the flow with increasing Damkohler number (ratio of the reaction rate to the flow rate). Results were compared with regions of predicted stability from the results of Hejazi et al. (2010). When the advection outran the reaction, viscous fingering occurred as usual. However, when the reaction was able to keep pace with the advection, the increased viscosity at the interface stabilized the flow. We acknowledge support from NSF CBET-1335739 and NSF CBET 1511653.

Effect of Molecular Weight on Mechanical and Electrochemical Performance of All Solid-State Polymer Electrolyte Membranes

NASA Astrophysics Data System (ADS)

He, Ruixuan; Ward, Daniel; Echeverri, Mauricio; Kyu, Thein

2015-03-01

Guided by ternary phase diagrams of polyethylene glycol diacrylate (PEGDA), succinonitrile plasticizer, and LiTFSI salt, completely amorphous solid-state transparent polymer electrolyte membranes (ss-PEM) were fabricated by UV irradiation in the isotropic melt state. Effects of PEGDA molecular weight (700 vs 6000 g/mol) on ss-PEM performance were investigated. These amorphous PEMs have superionic room temperature ionic conductivity of ~10-3 S/cm, whereby PEGDA6000-PEM outperforms its PEGDA700 counterpart, which may be ascribed to lower crosslinking density and greater segmental mobility. The longer chain between crosslinked points of PEGDA6000-PEM is responsible for greater extensibility of ~80% versus ~7% of PEGDA700-PEM. Besides, both PEMs exhibited thermal stability up to 120 °C and electrochemical stability versus Li+/Li up to 4.7V. LiFePO4/PEM/Li and Li4Ti5O12 /PEM/Li half-cells exhibited stable cyclic behavior up to 50 cycles tested with a capacity of ~140mAh/g, suggesting that LiFePO4/PEM/Li4Ti5O12 may be a promising full-cell for all solid-state lithium battery. We thank NSF-DMR 1161070 for providing funding of this project.

A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate

PubMed Central

Rwei, Syang-Peng; Chen, Yu-Ming; Chiang, Whe-Yi; Ting, Yi-Tien

2017-01-01

A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate), was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate) and HEA (2-hydroxy ethyl acrylate). DAPP was blended with regular bisphenol A epoxy acrylate (BAEA) in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer) results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI), reaching the saturated value of 26, and the heat release rate (HRR) measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases. PMID:28772562

Synthesis and electromechanical characterization of a new acrylic dielectric elastomer with high actuation strain and dielectric strength

NASA Astrophysics Data System (ADS)

Hu, Wei; Niu, Xiaofan; Yang, Xinguo; Zhang, Naifang; Pei, Qibing

2013-04-01

Dielectric Elastomers (DEs) can be actuated under high electric field to produce large strains. Most high-performing DE materials such as the 3M™ VHB™ membranes are commercial products designed for industrial pressure-sensitive adhesives. The limited knowledge of the exact chemical structures of these commercial materials has made it difficult to understand the relationship between molecular structures and electromechanical properties. In this work, new acrylic elastomers based on n-butyl acrylate and acrylic acid were synthesized from monomer solutions by UV-initiated bulk polymerization. The new acrylic copolymers have a potential to obtain high dielectric constant, actuation strain, dielectric strength, and a high energy density. Silicone and ester oligomer diacrylates were also added onto the copolymer structures to suppress crystallization and to crosslink the polymer chains. Four acrylic formulations were developed with different amounts of acrylic acid. This gives a tunable stiffness, while the dielectric constant is varied from 4.3 to 7.1. The figure-of-merit performance of the best formulation is 186 % area strain, 222 MV/m of dielectric strength, and 2.7 MJ/m3 of energy density. To overcome electromechanical instability, different prestrain ratios were investigated, and under the optimized prestrain, the material has a lifetime of thousands of cycles at 120 % area strain.

Feasibility of Crosslinked Acrylic Shape Memory Polymer for a Thrombectomy Device

PubMed Central

Muschenborn, Andrea D.; Hearon, Keith; Volk, Brent L.; Conway, Jordan W.; Maitland, Duncan J.

2014-01-01

Purpose To evaluate the feasibility of utilizing a system of SMP acrylates for a thrombectomy device by determining an optimal crosslink density that provides both adequate recovery stress for blood clot removal and sufficient strain capacity to enable catheter delivery. Methods Four thermoset acrylic copolymers containing benzylmethacrylate (BzMA) and bisphenol A ethoxylate diacrylate (Mn~512, BPA) were designed with differing thermomechanical properties. Finite element analysis (FEA) was performed to ensure that the materials were able to undergo the strains imposed by crimping, and fabricated devices were subjected to force-monitored crimping, constrained recovery, and bench-top thrombectomy. Results Devices with 25 and 35 mole% BPA exhibited the highest recovery stress and the highest brittle response as they broke upon constrained recovery. On the contrary, the 15 mole % BPA devices endured all testing and their recovery stress (5 kPa) enabled successful bench-top thrombectomy in 2/3 times, compared to 0/3 for the devices with the lowest BPA content. Conclusion While the 15 mole% BPA devices provided the best trade-off between device integrity and performance, other SMP systems that offer recovery stresses above 5 kPa without increasing brittleness to the point of causing device failure would be more suitable for this application. PMID:25414549

Functionalizable hydrogel microparticles of tunable size and stiffness for soft-tissue filler applications

PubMed Central

Chan, Ka Man Carmen; Li, Randolph H.; Chapman, Joseph W.; Trac, Eric M.; Kobler, James B.; Zeitels, Steven M.; Langer, Robert; Karajanagi, Sandeep S.

2014-01-01

Particle size, stiffness and surface functionality are important in determining the injection site, safety and efficacy of injectable soft-tissue fillers. Methods to produce soft injectable biomaterials with controlled particle characteristics are therefore desirable. Here we report a method based on suspension photopolymerization and semi-interpenetrating network (semi-IPN) to synthesize soft, functionalizable, spherical hydrogel microparticles (MP) of independently tunable size and stiffness. MP were prepared using acrylated forms of polyethylene glycol (PEG), gelatin and hyaluronic acid. Semi-IPN MP of PEG-diacrylate and PEG were used to study the effect of process parameters on particle characteristics. The process parameters were systematically varied to produce MP with size ranging from 115 to 515 μm and stiffness ranging from 190 to 1600 Pa. In vitro studies showed that the MP thus prepared were cytocompatible. The ratio and identity of the polymers used to make the semi-IPN MP were varied to control their stiffness and to introduce amine groups for potential functionalization. Slow-release polymeric particles loaded with Rhodamine or dexamethasone were incorporated in the MP as a proof-of-principle of drug incorporation and release from the MP. This work has implications in preparing injectable biomaterials of natural or synthetic polymers for applications as soft-tissue fillers. PMID:24561708

Hydrogel Bioprinted Microchannel Networks for Vascularization of Tissue Engineering Constructs

PubMed Central

Bertassoni, Luiz E.; Cecconi, Martina; Manoharan, Vijayan; Nikkhah, Mehdi; Hjortnaes, Jesper; Cristino, Ana Luiza; Barabaschi, Giada; Demarchi, Danilo; Dokmeci, Mehmet R.; Yang, Yunzhi; Khademhosseini, Ali

2014-01-01

Vascularization remains a critical challenge in tissue engineering. The development of vascular networks within densely populated and metabolically functional tissues facilitate transport of nutrients and removal of waste products, thus preserving cellular viability over a long period of time. Despite tremendous progress in fabricating complex tissue constructs in the past few years, approaches for controlled vascularization within hydrogel based engineered tissue constructs have remained limited. Here, we report a three dimensional (3D) micromolding technique utilizing bioprinted agarose template fibers to fabricate microchannel networks with various architectural features within photo cross linkable hydrogel constructs. Using the proposed approach, we were able to successfully embed functional and perfusable microchannels inside methacrylated gelatin (GelMA), star poly (ethylene glycol-co-lactide) acrylate (SPELA), poly (ethylene glycol) dimethacrylate (PEGDMA) and poly (ethylene glycol) diacrylate (PEGDA) hydrogels at different concentrations. In particular, GelMA hydrogels were used as a model to demonstrate the functionality of the fabricated vascular networks in improving mass transport, cellular viability and differentiation within the cell-laden tissue constructs. In addition, successful formation of endothelial monolayers within the fabricated channels was confirmed. Overall, our proposed strategy represents an effective technique for vascularization of hydrogel constructs with useful applications in tissue engineering and organs on a chip. PMID:24860845

Synthesis and characterization of gold nanoparticles in a self-assembled ionic liquid polymer nanocomposite

NASA Astrophysics Data System (ADS)

Magurudeniya, Harsha; Ringstrand, Bryan; Jungjohann, Katherine; Firestone, Millicent

Incorporation of nanoparticles(NPs) into polymer matrices has attracted interest, offering a means to create multi-functional materials combining the attributes of polymers (flexibility, processability, mechanical durability) with the opto-electrical properties of NPs. Synthesis of a self-supporting, hierarchically structured Au NP-network polymer was accomplished via a ``one-pot'' reaction employing a mesophase of AuCl3 and an imidazolium based-ionic liquid (IL) containing a acrylate group. In-situ generation of NPs was achieved by reduction of Au3+which in turn yields concomitant initiation of the polymerization of the mesophase. FT-IR and thermal analysis confirmed acrylate cross-linking. X-ray scattering confirms preservation of the mesophase within the NP composite. TEM showed a distribution of the NPs within the composite of primarily non-spherical morphologies. The co-integration of a macromer, PEG diacrylate, served as a reducing agent for the Au and the amount incorporated into the mesophase allowed for manipulation of the swelling factor of the resultant nanocomposite in a ethanol, providing means to modulate the plasmonic resonance of the NPs. This methodology provides means for organizing NPs within the structured regions of the poly(IL) matrix. Such composites may be of interest for photonic/sensing applications.

Biomimetic hydrogels for biosensor implant biocompatibility: electrochemical characterization using micro-disc electrode arrays (MDEAs).

PubMed

Justin, Gusphyl; Finley, Stephen; Abdur Rahman, Abdur Rub; Guiseppi-Elie, Anthony

2009-02-01

Our interest is in the development of engineered microdevices for continuous remote monitoring of intramuscular lactate, glucose, pH and temperature during post-traumatic hemorrhaging. Two important design considerations in the development of such devices for in vivo diagnostics are discussed; the utility of micro-disc electrode arrays (MDEAs) for electrochemical biosensing and the application of biomimetic, bioactive poly(HEMA)-based hydrogel composites for implant biocompatibility. A poly(HEMA)-based hydrogel membrane containing polyethylene glycol (PEG) was UV cross-linked with tetraethyleneglycol diacrylate following application to MDEAs (50 mum discs) and to 250 mum diameter gold electrodes within 8-well culture ware. Cyclic voltammetry (CV) of the MDEAs revealed a reduction in the apparent diffusion coefficient of ferrocenemonocarboxylic acid (FcCO(2)H), from 6.68 x 10(-5) to 6.74 x 10(-6) cm(2)/s for the uncoated and 6 mum thick hydrogel coated devices, respectively. Single frequency (4 kHz) temporal impedance measurements of the hydrogels in the 8-well culture ware showed a reversible 5% change in the absolute impedance of the hydrogels when exposed to a pH change between 6.1 to 7.2 and a 20% drop between pH 6.1 and 8.8.

Human cartilage tissue fabrication using three-dimensional inkjet printing technology.

PubMed

Cui, Xiaofeng; Gao, Guifang; Yonezawa, Tomo; Dai, Guohao

2014-06-10

Bioprinting, which is based on thermal inkjet printing, is one of the most attractive enabling technologies in the field of tissue engineering and regenerative medicine. With digital control cells, scaffolds, and growth factors can be precisely deposited to the desired two-dimensional (2D) and three-dimensional (3D) locations rapidly. Therefore, this technology is an ideal approach to fabricate tissues mimicking their native anatomic structures. In order to engineer cartilage with native zonal organization, extracellular matrix composition (ECM), and mechanical properties, we developed a bioprinting platform using a commercial inkjet printer with simultaneous photopolymerization capable for 3D cartilage tissue engineering. Human chondrocytes suspended in poly(ethylene glycol) diacrylate (PEGDA) were printed for 3D neocartilage construction via layer-by-layer assembly. The printed cells were fixed at their original deposited positions, supported by the surrounding scaffold in simultaneous photopolymerization. The mechanical properties of the printed tissue were similar to the native cartilage. Compared to conventional tissue fabrication, which requires longer UV exposure, the viability of the printed cells with simultaneous photopolymerization was significantly higher. Printed neocartilage demonstrated excellent glycosaminoglycan (GAG) and collagen type II production, which was consistent with gene expression. Therefore, this platform is ideal for accurate cell distribution and arrangement for anatomic tissue engineering.

Chromatic biosensor for detection of phosphinothricin acetyltransferase by use of polydiacetylene vesicles encapsulated within automatically generated immunohydrogel beads.

PubMed

Jung, Sung-Ho; Jang, Huisoo; Lim, Min-Cheol; Kim, Jae-Hwan; Shin, Kong-Sik; Kim, Sun Min; Kim, Hae-Yeong; Kim, Young-Rok; Jeon, Tae-Joon

2015-02-17

We developed a simple and sensitive colorimetric biosensor in the form of microparticles by using polydiacetylene (PDA) vesicles encapsulated within a hydrogel matrix for the detection of phosphinothricin acetyltransferase (PAT) protein, which is one of the most important marker proteins in genetically modified (GM) crops. Although PDA is commonly used as a sensing material due to its unique colorimetric properties, existing PDA biosensors are ineffective due to their low sensitivity as well as their lack of robustness. To overcome these disadvantages, we devised immunohydrogel beads made of anti-PAT-conjugated PDA vesicles embedded at high density within a poly(ethylene glycol) diacrylate (PEG-DA) hydrogel matrix. In addition, the construction of immunohydrogel beads was automated by use of a microfluidic device. In the immunoreaction, the sensitivity of antibody-conjugated PDA vesicles was significantly amplified, as monitored by the unaided eye. The limit of detection for target molecules reached as low as 20 nM, which is sufficiently low enough to detect target materials in GM organisms. Collectively, the results show that immunohydrogel beads constitute a promising colorimetric sensing platform for onsite testing in a number of fields, such as the food and medical industries, as well as warfare situations.

An Injectable Hydrogel as Bone Graft Material with Added Antimicrobial Properties.

PubMed

Tommasi, Giacomo; Perni, Stefano; Prokopovich, Polina

2016-06-01

Currently, the technique which provides the best chances for a successful bone graft, is the use of bone tissue from the same patient receiving it (autograft); the main limitations are the limited availability and the risks involved in removing living bone tissue, for example, explant site pain and morbidity. Allografts and xenografts may overcome these limitations; however, they increase the risk of rejection. For all these reasons the development of an artificial bone graft material is particularly important and hydrogels are a promising alternative for bone regeneration. Gels were prepared using 1,4-butanediol diacrylate as crosslinker and alpha tricalciumphosphate; ZnCl2 and SrCl2 were added to the aqueous phase. MTT results demonstrated that the addition of strontium had a beneficial effect on the osteoblast cells density on hydrogels, and zinc instead did not increase osteoblast proliferation. The amount of calcium produced by the osteoblast cells quantified through the Alizarin Red protocol revealed that both strontium and zinc positively influenced the formation of calcium; furthermore, their effect was synergistic. Rheology properties were used to mechanically characterize the hydrogels and especially the influence of crosslinker's concentration on them, showing the hydrogels presented had extremely good mechanical properties. Furthermore, the antimicrobial activity of strontium and zinc in the hydrogels against methicillin-resistant Staphylococcus aureus and Staphylococcus epidermidis was determined.

3D-PRINTING OF TRANSPARENT BIO-MICROFLUIDIC DEVICES IN PEG-DA

PubMed Central

Urrios, Arturo; Parra-Cabrera, Cesar; Bhattacharjee, Nirveek; Gonzalez-Suarez, Alan M.; Rigat-Brugarolas, Luis G.; Nallapatti, Umashree; Samitier, Josep; DeForest, Cole A.; Posas, Francesc; Garcia-Cordero, José L.; Folch, Albert

2016-01-01

The vast majority of microfluidic systems are molded in poly(dimethylsiloxane) (PDMS) by soft lithography due to the favorable properties of PDMS: biocompatible, elastomeric, transparent, gas-permeable, inexpensive, and copyright-free. However, PDMS molding involves tedious manual labor, which makes PDMS devices prone to assembly failures and difficult to disseminate to research and clinical settings. Furthermore, the fabrication procedures limit the 3D complexity of the devices to layered designs. Stereolithography (SL), a form of 3D-printing, has recently attracted attention as a way to customize the fabrication of biomedical devices due to its automated, assembly-free 3D fabrication, rapidly decreasing costs, and fast-improving resolution and throughput. However, existing SL resins are not biocompatible and patterning transparent resins at high resolution remains difficult. Here we report procedures for the preparation and patterning of a transparent resin based on low-MW poly(ethylene glycol) diacrylate (MW 250) (PEG-DA-250). The 3D-printed devices are highly transparent and cells can be cultured on PEG-DA-250 prints for several days. This biocompatible SL resin and printing process solves some of the main drawbacks of 3D-printed microfluidic devices: biocompatibility and transparency. In addition, it should also enable the production of non-microfluidic biomedical devices. PMID:27217203

Allergic contact dermatitis caused by acrylic-based medical dressings and adhesives.

PubMed

Mestach, Lien; Huygens, Sara; Goossens, An; Gilissen, Liesbeth

2018-06-11

Acrylates and methacrylates are acrylic resin monomers that are known to induce skin sensitization as a result of their presence in different materials, such as nail cosmetics, dental materials, printing inks, and adhesives. Allergic contact dermatitis resulting from the use of modern wound dressings containing them has only rarely been reported. To describe 2 patients who developed allergic contact dermatitis caused by acrylic-based modern medical dressings and/or adhesives. The medical charts of patients observed since 1990 were retrospectively reviewed for (meth)acrylate allergy resulting from contact with such materials, and their demographic characteristics and patch test results were analysed. Two patients were observed in 2014 and 2016 who had presented with positive patch test reactions to several acrylic-based dressings and/or adhesive materials, and to several (meth)acrylates, that is, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethyleneglycol dimethacrylate, bisphenol A-glycidyl methacrylate/epoxy-acrylate, urethane diacrylate, and/or penta-erythritol acrylate. Allergic contact dermatitis needs to be considered in patients with eczematous reactions or delayed healing following the use of acrylic-based modern dressings or adhesives. However, identification of the culprit allergen is hampered by poor cooperation from the producers, so adequate labelling of medical devices is an urgent necessity. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Injectable hyperbranched poly(β-amino ester) hydrogels with on-demand degradation profiles to match wound healing processes† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03913a

PubMed Central

Xu, Qian; Guo, Linru; A, Sigen; Gao, Yongsheng; Zhou, Dezhong; Greiser, Udo; Creagh-Flynn, Jack; Zhang, Hong; Dong, Yixiao; Cutlar, Lara; Wang, Fagang; Liu, Wenguang

2018-01-01

Adjusting biomaterial degradation profiles to match tissue regeneration is a challenging issue. Herein, biodegradable hyperbranched poly(β-amino ester)s (HP-PBAEs) were designed and synthesized via “A2 + B4” Michael addition polymerization, and displayed fast gelation with thiolated hyaluronic acid (HA-SH) via a “click” thiol–ene reaction. HP-PBAE/HA-SH hydrogels showed tunable degradation profiles both in vitro and in vivo using diamines with different alkyl chain lengths and poly(ethylene glycol) diacrylates with varied PEG spacers. The hydrogels with optimized degradation profiles encapsulating ADSCs were used as injectable hydrogels to treat two different types of humanized excisional wounds – acute wounds with faster healing rates and diabetic wounds with slower healing and neo-tissue formation. The fast-degrading hydrogel showed accelerated wound closure in acute wounds, while the slow-degrading hydrogel showed better wound healing for diabetic wounds. The results demonstrate that the new HP-PBAE-based hydrogel in combination with ADSCs can be used as a well-controlled biodegradable skin substitute, which demonstrates a promising approach in the treatment of various types of skin wounds. PMID:29719691

Poly(ethylene glycol)-grafted cyclic acetals based polymer networks with non-water-swellable, biodegradable and surface hydrophilic properties.

PubMed

Yin, Ruixue; Zhang, Nan; Wu, Wentao; Wang, Kemin

2016-05-01

Cyclic acetals based biomaterial without acidic products during hydrolytic degradation is a promising candidate for tissue engineering applications; however, low hydrophilicity is still one limitation for its biomedical application. In this work, we aim to achieve non-water-swellable cyclic acetal networks with improved hydrophilicity and surface wettability by copolymerization of cyclic acetal units based monomer, 5-ethyl-5-(hydroxymethyl)-β,β-dimethyl-1, 3-dioxane-2-ethanol diacrylate (EHD) and methoxy poly(ethylene glycol) monoacrylate (mPEGA) under UV irradiation, to avoid swelling of conventional hydrogels which could limit their applicability in particular of the mechanical properties and geometry integrity. Various EHD/mPEGA networks were fabricated with different concentrations of mPEGA from 0 to 30%, and the results showed photopolymerization behavior, mechanical property and thermal stability could not be significantly affected by addition of mPEGA, while the surface hydrophilicity was dramatically improved with the increase of mPEGA and could achieve a water contact angle of 37° with 30% mPEGA concentration. The obtained EHD/mPEGA network had comparative degradation rate to the PECA hydrogels reported previously, and MTT assay indicated it was biocompatible to L929 cells. Copyright © 2016 Elsevier B.V. All rights reserved.

3D printing of tablets using inkjet with UV photoinitiation.

PubMed

Clark, Elizabeth A; Alexander, Morgan R; Irvine, Derek J; Roberts, Clive J; Wallace, Martin J; Sharpe, Sonja; Yoo, Jae; Hague, Richard J M; Tuck, Chris J; Wildman, Ricky D

2017-08-30

Additive manufacturing (AM) offers significant potential benefits in the field of drug delivery and pharmaceutical/medical device manufacture. Of AM processes, 3D inkjet printing enables precise deposition of a formulation, whilst offering the potential for significant scale up or scale out as a manufacturing platform. This work hypothesizes that suitable solvent based ink formulations can be developed that allow the production of solid dosage forms that meet the standards required for pharmaceutical tablets, whilst offering a platform for flexible and personalized manufacture. We demonstrate this using piezo-activated inkjetting to 3D print ropinirole hydrochloride. The tablets produced consist of a cross-linked poly(ethylene glycol diacrylate) (PEGDA) hydrogel matrix containing the drug, photoinitiated in a low oxygen environment using an aqueous solution of Irgacure 2959. At a Ropinirole HCl loading of 0.41mg, drug release from the tablet is shown to be Fickian. Raman and IR spectroscopy indicate a high degree of cross-linking and formation of an amorphous solid dispersion. This is the first publication of a UV inkjet 3D printed tablet. Consequently, this work opens the possibility for the translation of scalable, high precision and bespoke ink-jet based additive manufacturing to the pharmaceutical sector. Copyright © 2017. Published by Elsevier B.V.

Multi-step Variable Height Photolithography for Valved Multilayer Microfluidic Devices.

PubMed

Brower, Kara; White, Adam K; Fordyce, Polly M

2017-01-27

Microfluidic systems have enabled powerful new approaches to high-throughput biochemical and biological analysis. However, there remains a barrier to entry for non-specialists who would benefit greatly from the ability to develop their own microfluidic devices to address research questions. Particularly lacking has been the open dissemination of protocols related to photolithography, a key step in the development of a replica mold for the manufacture of polydimethylsiloxane (PDMS) devices. While the fabrication of single height silicon masters has been explored extensively in literature, fabrication steps for more complicated photolithography features necessary for many interesting device functionalities (such as feature rounding to make valve structures, multi-height single-mold patterning, or high aspect ratio definition) are often not explicitly outlined. Here, we provide a complete protocol for making multilayer microfluidic devices with valves and complex multi-height geometries, tunable for any application. These fabrication procedures are presented in the context of a microfluidic hydrogel bead synthesizer and demonstrate the production of droplets containing polyethylene glycol (PEG diacrylate) and a photoinitiator that can be polymerized into solid beads. This protocol and accompanying discussion provide a foundation of design principles and fabrication methods that enables development of a wide variety of microfluidic devices. The details included here should allow non-specialists to design and fabricate novel devices, thereby bringing a host of recently developed technologies to their most exciting applications in biological laboratories.

Water-soluble photopolymerizable chitosan hydrogels for biofabrication via two-photon polymerization.

PubMed

Kufelt, Olga; El-Tamer, Ayman; Sehring, Camilla; Meißner, Marita; Schlie-Wolter, Sabrina; Chichkov, Boris N

2015-05-01

Fabrication of three-dimensional (3D) hydrogel microenvironments with predefined geometry and porosity can facilitate important requirements in tissue engineering and regenerative medicine. Chitosan (CH) is well known as a biocompatible hydrogel with prospective biological properties for biomedical aims. So far, microstructuring of this soft material presents a great limitation for its application as functional supporting material for guided tissue formation. Enabling photopolymerization, chemically modified CH can be applied for the biofabrication of reproducible 3D scaffolds using rapid prototyping techniques like two-photon polymerization (2PP) or others. The application of this technique allows precise serial fabrication of computer-designed microstructure geometries by scanning a femtosecond laser beam within a photosensitive material. This work explores a new synthesis of water-soluble photosensitive chitosan and the fabrication of well-defined microstructures from the generated materials. To modulate the mechanical and biochemical properties of the material, CH was combined and cross-linked with synthetic poly(ethylene glycol) diacrylate. For a biological adaption to the in vivo situation, CH was covalently crosslinked with a photosensitive modified vascular endothelial growth factor (VEGF). Performed in vitro studies reveal that modified CH is biocompatible. VEGF enhances CH bioactivity. Furthermore, a 3D CH scaffold can be successfully seeded with cells. Therefore, the established CH holds great promise for future applications in tissue engineering. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

End-Group Effects on the Properties of PEG-co-PGA Hydrogels

PubMed Central

Bencherif, Sidi A.; Srinivasan, Abiraman; Sheehan, Jeffrey A.; Walker, Lynn M.; Gayathri, Chakicherla; Gil, Roberto; Hollinger, Jeffrey O.; Matyjaszewski, Krzysztof; Washburn, Newell R.

2009-01-01

A series of resorbable poly(ethylene glycol)-co-poly(glycolic acid) macromonomers have been synthesized with the chemistries from three different photopolymerizable end-groups (acrylates, methacrylates, and urethane methacrylates). The aim of the study is to examine the effects of the chemistry of the cross-linker group on the properties of photocross-linkable hydrogels. PEG-co-PGA (4KG5) hydrogels were prepared by photopolymerization with high vinyl group conversion as confirmed by 1H NMR spectroscopy using DOSY 1D pulse sequence. Our study reveals that the nature of end-groups in a moderately amphiphilic polymer can adjust the distribution and size of the micellar configuration in water leading to changes in the macroscopic structure of hydrogels. By varying the chemistry of the cross-linker group (diacrylates; DA, dimethacrylates; DM, and urethane dimethacrylates; UDM), we determined that the hydrophobocity of a single core polymer consisting of poly(glycolic acid) could be fine-tuned leading to significant variations in the mechanical, swelling, and degradation properties of the gels. In addition, the effects of cross-linker chemistry on cytotoxicity and proliferation were examined. Cytotoxicity assays showed that all the three types of hydrogels (4KG5 DA, DM, and UDM) were biocompatible and the introduction of RGD ligand enhanced cell adhesion. However, differences in gel properties and stability differentially affected the spreading and proliferation of myoblast C2C12 cells. PMID:19328754

Development and Characterization of Mechanically Robust, 3D-Printable Photopolymers

NASA Astrophysics Data System (ADS)

Sycks, Dalton George

3D printing has seen an explosion of interest and growth in recent years, especially within the biomedical space. Prized for its efficiency, ability to produce complex geometries, and facile material processing, additive manufacturing is rapidly being used to create medical devices ranging from orthopedic implants to tissue scaffolds. However, 3D printing is currently limited to a select few material choices, especially when one considers soft tissue replacement or augmentation. To this end, my research focuses on developing material systems that are simultaneously 1) 3D printable, 2) biocompatible, and 3) mechanically robust with properties appropriate for soft-tissue replacement or augmentation applications. Two systems were developed toward this goal: an interpenetrating network (IPN) hydrogel consisting of covalently crosslinked poly (ethylene glycol) diacrylate (PEGDA) and ionically crosslinked brown sodium alginate, and semi-crystalline thiol-ene photopolymers containing spiroacetal molecules in the polymer main-chain backbone. In addition to successfully being incorporated into existing 3D printing systems (extrusion-deposition for the PEGDA-alginate hydrogel and digital light processing for the thiol-ene polymers) both systems exhibited biocompatibility and superior thermomechanical properties such as tensile modulus, failure strain, and toughness. This work offers two fully-developed, novel polymer platforms with outstanding performance; further, structure-property relationships are highlighted and discussed on a molecular and morphological level to provide material insights that are useful to researchers and engineers in the design of highly tuned and mechanically robust polymers.

Improved Human Bone Marrow Mesenchymal Stem Cell Osteogenesis in 3D Bioprinted Tissue Scaffolds with Low Intensity Pulsed Ultrasound Stimulation

PubMed Central

Zhou, Xuan; Castro, Nathan J.; Zhu, Wei; Cui, Haitao; Aliabouzar, Mitra; Sarkar, Kausik; Zhang, Lijie Grace

2016-01-01

3D printing and ultrasound techniques are showing great promise in the evolution of human musculoskeletal tissue repair and regeneration medicine. The uniqueness of the present study was to combine low intensity pulsed ultrasound (LIPUS) and advanced 3D printing techniques to synergistically improve growth and osteogenic differentiation of human mesenchymal stem cells (MSC). Specifically, polyethylene glycol diacrylate bioinks containing cell adhesive Arginine-Glycine-Aspartic acid-Serene (RGDS) peptide and/or nanocrystalline hydroxyapatite (nHA) were used to fabricate 3D scaffolds with different geometric patterns via novel table-top stereolithography 3D printer. The resultant scaffolds provide a highly porous and interconnected 3D environment to support cell proliferation. Scaffolds with small square pores were determined to be the optimal geometric pattern for MSC attachment and growth. The optimal LIPUS working parameters were determined to be 1.5 MHz, 20% duty cycle with 150 mW/cm2 intensity. Results demonstrated that RGDS peptide and nHA containing 3D printed scaffolds under LIPUS treatment can greatly promote MSC proliferation, alkaline phosphatase activity, calcium deposition and total protein content. These results illustrate the effectiveness of the combination of LIPUS and biomimetic 3D printing scaffolds as a valuable combinatorial tool for improved MSC function, thus make them promising for future clinical and various regenerative medicine application. PMID:27597635

Patch-test reactions to plastic and glue allergens.

PubMed

Kanerva, L; Jolanki, R; Alanko, K; Estlander, T

1999-07-01

Plastics and glues are common causes of occupational dermatoses, but only few reports have dealt with patch-test reactions caused by plastic and glue allergens. Patients exposed to plastics and remitted to an occupational dermatology clinic, were patch-tested with 50-53 plastic and glue allergens during a 6-year period. Conventional patch-test techniques were used. The most common causes of allergic patch-test reactions in 360 patients were novolac epoxy resin (5.1%), phenol formaldehyde resin (3.1%), 4-tert-butylcatechol (2.6%), phenyl glycidyl ether (2.6%), diaminodiphenyl methane (2.2%), benzoyl peroxide (2.2%), hexamethylene tetramine (2.0%) and o-cresyl glycidyl ether (1.6%). The allergens that most often elicited irritant patch-test reactions were: benzoyl peroxide (9.5%), abitol alcohol (3.6%), hydroquinone (3.1%), acid-catalyzed phenol formaldehyde resin (2.5%) and toluene diisocyanate (1.9%). Twenty-six out of 53 chemicals caused no allergic reaction during the 6-year period. Plastic allergens in the standard series provoked allergic reactions with formaldehyde (5.8%), diglycidyl ether of bisphenol A (3.2%), 4-tert-butylphenol-formaldehyde-resin (1.1%), toluene sulphonamide formaldehyde-resin (1.1%) and triethylenglycol diacrylate (0.4%). Although half of the plastic chemicals gave no allergic patch-test reactions during a 6-year period, with unusual allergens this low yield needs to be accepted, because otherwise rare allergies will not be detected. Also a negative reaction has diagnostic value.

Hand-Portable Gradient Capillary Liquid Chromatography Pumping System.

PubMed

Sharma, Sonika; Plistil, Alex; Barnett, Hal E; Tolley, H Dennis; Farnsworth, Paul B; Stearns, Stanley D; Lee, Milton L

2015-10-20

In this work, a novel splitless nanoflow gradient generator integrated with a stop-flow injector was developed and evaluated using an on-column UV-absorption detector. The gradient pumping system consisted of two nanoflow pumps controlled by micro stepper motors, a mixer connected to a serpentine tube, and a high-pressure valve. The gradient system weighed only 4 kg (9 lbs) and could generate up to 55 MPa (8000 psi) pressure. The system could operate using a 24 V DC battery and required 1.2 A for operation. The total volume capacity of the pump was 74 μL, and a sample volume of 60 nL could be injected. The system provided accurate nanoflow rates as low as 10 nL/min without employing a splitter, making it ideal for capillary column use. The gradient dwell volume was calculated to be 1.3 μL, which created a delay of approximately 4 min with a typical flow rate of 350 nL/min. Gradient performance was evaluated for gradient step accuracy, and excellent reproducibility was obtained in day-to-day experiments (RSD < 1.2%, n = 4). Linear gradient reproducibility was tested by separating a three-component pesticide mixture on a poly(ethylene glycol) diacrylate (PEGDA) monolithic column. The retention time reproducibility was very good in run-to-run experiments (RSD < 1.42%, n = 4). Finally, excellent separation of five phenols was demonstrated using the nanoflow gradient system.

The effect of glutathione as chain transfer agent in PNIPAAm-based thermo-responsive hydrogels for controlled release of proteins.

PubMed

Drapala, Pawel W; Jiang, Bin; Chiu, Yu-Chieh; Mieler, William F; Brey, Eric M; Kang-Mieler, Jennifer J; Pérez-Luna, Victor H

2014-03-01

To control degradation and protein release using thermo-responsive hydrogels for localized delivery of anti-angiogenic proteins. Thermo-responsive hydrogels derived from N-isopropylacrylamide (NIPAAm) and crosslinked with poly(ethylene glycol)-co-(L-lactic acid) diacrylate (Acry-PLLA-b-PEG-b-PLLA-Acry) were synthesized via free radical polymerization in the presence of glutathione, a chain transfer agent (CTA) added to modulate their degradation and release properties. Immunoglobulin G (IgG) and the recombinant proteins Avastin® and Lucentis® were encapsulated in these hydrogels and their release was studied. The encapsulation efficiency of IgG was high (75-87%) and decreased with CTA concentration. The transition temperature of these hydrogels was below physiological temperature, which is important for minimally invasive therapies involving these materials. The toxicity from unreacted monomers and free radical initiators was eliminated with a minimum of three buffer extractions. Addition of CTA accelerated degradation and resulted in complete protein release. Glutathione caused the degradation products to become solubilized even at 37°C. Hydrogels prepared without glutathione did not disintegrate nor released protein completely after 3 weeks at 37°C. PEGylation of IgG postponed the burst release effect. Avastin® and Lucentis® released from degraded hydrogels retained their biological activity. These systems offer a promising platform for the localized delivery of proteins.

Influence of macromer molecular weight and chemistry on poly(beta-amino ester) network properties and initial cell interactions.

PubMed

Brey, Darren M; Erickson, Isaac; Burdick, Jason A

2008-06-01

A library of photocrosslinkable poly(beta-amino ester)s (PBAEs) was recently synthesized to expand the number of degradable polymers that can be screened and developed for a variety of biological applications. In this work, the influence of variations in macromer chemistry and macromer molecular weight (MMW) on network reaction behavior, overall bulk properties, and cell interactions were investigated. The MMW was controlled through alterations in the initial diacrylate to amine ratio (> or =1) during synthesis and decreased with an increase in this ratio. Lower MMWs reacted more quickly and to higher double bond conversions than higher MMWs, potentially due to the higher concentration of reactive groups. Additionally, the lower MMWs led to networks with higher compressive and tensile moduli that degraded slower than networks formed from higher MMWs because of an increase in the crosslinking density and decrease in the number of degradable units per crosslink. The adhesion and spreading of osteoblast-like cells on polymer films was found to be dependent on both the macromer chemistry and the MMW. In general, the number of cells was similar on networks formed from a range of MMWs, but the spreading was dramatically influenced by MMW (higher spreading with lower MMWs). These results illustrate further diversity in photocrosslinkable PBAE properties and that the chemistry and macromer structure must be carefully selected for the desired application. Copyright 2007 Wiley Periodicals, Inc.

Human cartilage repair with a photoreactive adhesive-hydrogel composite.

PubMed

Sharma, Blanka; Fermanian, Sara; Gibson, Matthew; Unterman, Shimon; Herzka, Daniel A; Cascio, Brett; Coburn, Jeannine; Hui, Alexander Y; Marcus, Norman; Gold, Garry E; Elisseeff, Jennifer H

2013-01-09

Surgical options for cartilage resurfacing may be significantly improved by advances and application of biomaterials that direct tissue repair. A poly(ethylene glycol) diacrylate (PEGDA) hydrogel was designed to support cartilage matrix production, with easy surgical application. A model in vitro system demonstrated deposition of cartilage-specific extracellular matrix in the hydrogel biomaterial and stimulation of adjacent cartilage tissue development by mesenchymal stem cells. For translation to the joint environment, a chondroitin sulfate adhesive was applied to covalently bond and adhere the hydrogel to cartilage and bone tissue in articular defects. After preclinical testing in a caprine model, a pilot clinical study was initiated where the biomaterials system was combined with standard microfracture surgery in 15 patients with focal cartilage defects on the medial femoral condyle. Control patients were treated with microfracture alone. Magnetic resonance imaging showed that treated patients achieved significantly higher levels of tissue fill compared to controls. Magnetic resonance spin-spin relaxation times (T(2)) showed decreasing water content and increased tissue organization over time. Treated patients had less pain compared with controls, whereas knee function [International Knee Documentation Committee (IKDC)] scores increased to similar levels between the groups over the 6 months evaluated. No major adverse events were observed over the study period. With further clinical testing, this practical biomaterials strategy has the potential to improve the treatment of articular cartilage defects.

The effects of cross-linked thermo-responsive PNIPAAm-based hydrogel injection on retinal function.

PubMed

Turturro, Sanja B; Guthrie, Micah J; Appel, Alyssa A; Drapala, Pawel W; Brey, Eric M; Pérez-Luna, Victor H; Mieler, William F; Kang-Mieler, Jennifer J

2011-05-01

There is significant interest in biomaterials that provide sustained release of therapeutic molecules to the retina. Poly(N-isopropylacrylamide) (PNIPAAm)-based materials have received significant attention as injectable drug delivery platforms due to PNIPAAm's thermo-responsive properties at approximately 32 °C. While the drug delivery properties of PNIPAAm materials have been studied extensively, there is a need to evaluate the safety effects of hydrogel injection on retinal function. The purpose of this study was to examine the effect of poly(ethylene glycol) diacrylate (PEG-DA) crosslinked PNIPAAm hydrogel injection on retinal function. Utilizing scanning laser ophthalmoscopy (SLO), optical coherent tomography (OCT), and electroretinography (ERG), retinal function was assessed following hydrogel injection. In region near the hydrogel, there was a significant decrease in arterial and venous diameters (∼4%) and an increase in venous blood velocity (∼8%) 1 week post-injection. Retinal thickness decreased (∼6%) at 1 week and the maximum a- and b-wave amplitudes of ERG decreased (∼15%). All data returned to baseline values after week 1. These data suggest that the injection of PEG-DA crosslinked PNIPAAm hydrogel results in a small transient effect on retinal function without any long-term effects. These results further support the potential of PNIPAAm-based materials as an ocular drug delivery platform. Copyright © 2011 Elsevier Ltd. All rights reserved.

Paper-based immune-affinity arrays for detection of multiple mycotoxins in cereals.

PubMed

Li, Li; Chen, Hongpu; Lv, Xiaolan; Wang, Min; Jiang, Xizhi; Jiang, Yifei; Wang, Heye; Zhao, Yongfu; Xia, Liru

2018-03-01

Mycotoxins produced by different species of fungi may coexist in cereals and feedstuffs, and could be highly toxic for humans and animals. For quantification of multiple mycotoxins in cereals, we developed a paper-based mycotoxin immune-affinity array. First, paper-based microzone arrays were fabricated by photolithography. Then, monoclonal mycotoxin antibodies were added in a copolymerization reaction with a cross-linker to form an immune-affinity monolith on the paper-based microzone array. With use of a competitive immune-response format, paper-based mycotoxin immune-affinity arrays were successfully applied to detect mycotoxins in samples. The detection limits for deoxynivalenol, zearalenone, T-2 toxin, and HT-2 toxin were 62.7, 10.8, 0.36, and 0.23 μg·kg -1 , respectively, which meet relevant requirements for these compounds in food. The recovery rates were 81-86% for deoxynivalenol, 89-117% for zearalenone, 79-86% for T-2 toxin, and 78-83% for HT-2 toxin, and showed the paper-based immune-affinity arrays had good reproducibility. In summary, the paper-based mycotoxin immune-affinity array provides a sensitive, rapid, accurate, stable, and convenient platform for detection of multiple mycotoxins in agro-foods. Graphical abstract Paper-based immune-affinity monolithic array. DON deoxynivalenol, HT-2 HT-2 toxin, T-2 T-2 toxin, PEGDA polyethylene glycol diacrylate, ZEN zearalenone.

Continuous gradient scaffolds for rapid screening of cell-material interactions and interfacial tissue regeneration

PubMed Central

Bailey, Brennan M.; Nail, Lindsay N.; Grunlan, Melissa A.

2013-01-01

In tissue engineering, the physical and chemical properties of the scaffold mediates cell behavior including regeneration. Thus, a strategy that permits rapid screening of cell-scaffold interactions is critical. Herein, we have prepared eight “hybrid” hydrogel scaffolds in the form of continuous gradients such that a single scaffold contains spatially varied properties. These scaffolds are based on combining an inorganic macromer [methacrylated star polydimethylsiloxane, PDMSstar-MA] and organic macromer [poly(ethylene glycol)diacrylate, PEG-DA] as well both aqueous and organic fabrication solvents. Having previously demonstrated its bioactivity and osteoinductivity, PDMSstar-MA is a particularly powerful component to incorporate into instructive gradient scaffolds based on PEG-DA. The following parameters were varied to produce the different gradients or gradual transitions in: (1) the wt% ratio of PDMSstar-MA to PEG-DA macromers, (2) the total wt% macromer concentration, (3) the number average molecular weight (Mn) of PEG-DA and (4) the Mn of PDMSstar-MA. Upon dividing each scaffold into four “zones” perpendicular to the gradient, we were able to demonstrate the spatial variation in morphology, bioactivity, swelling and modulus. Among these gradient scaffolds are those in which swelling and modulus are conveniently decoupled. In addition to rapid screening of cell-material interactions, these scaffolds are well-suited for regeneration of interfacial tissues (e.g. osteochondral tissues) that transition from one tissue type to another. PMID:23707502

Experimental and theoretical distribution of electron density and thermopolimerization in crystals of Ph3Sb(O2CCH=CH2)2 complex

NASA Astrophysics Data System (ADS)

Fukin, Georgy K.; Samsonov, Maxim A.; Arapova, Alla V.; Mazur, Anton S.; Artamonova, Tatiana O.; Khodorkovskiy, Mikhail A.; Vasilyev, Aleksander V.

2017-10-01

In this paper we present the results of a high-resolution single crystal X-ray diffraction experiment of a triphenylantimony diacrylate (Ph3Sb(O2CCH=CH2)2 (1)) and a subsequent charge density study based on a topological analysis according to quantum theory of atoms in molecules (QTAIM) together with density functional theory (DFT) calculation of isolated molecule. The QTAIM was used to investigate nature of the chemical bonds and molecular graph of Ph3Sb(O2CCH=CH2)2 complex. The molecular graph shows that only in one acrylate group there is an evidence of bonding between antimony and carbonyl oxygen atom in terms of the presence of a bond path. Thus the molecular graph for this class of compounds does not provide a definitive picture of the chemical bonding and should be complemented with other descriptors, such as and a source function (SF), noncovalent interaction (NCI) index and delocalization index (DI). Moreover the realization of π…π interactions between double bonds of acrylate groups in adjacent molecules allowed us to carry out a thermopolimerization reaction in crystals of Ph3Sb(O2CCH=CH2)2 complex and to determine a probable structure of polymer by solid state CP/MAS 13C NMR.

Integrating valve-inspired design features into poly(ethylene glycol) hydrogel scaffolds for heart valve tissue engineering.

PubMed

Zhang, Xing; Xu, Bin; Puperi, Daniel S; Yonezawa, Aline L; Wu, Yan; Tseng, Hubert; Cuchiara, Maude L; West, Jennifer L; Grande-Allen, K Jane

2015-03-01

The development of advanced scaffolds that recapitulate the anisotropic mechanical behavior and biological functions of the extracellular matrix in leaflets would be transformative for heart valve tissue engineering. In this study, anisotropic mechanical properties were established in poly(ethylene glycol) (PEG) hydrogels by crosslinking stripes of 3.4 kDa PEG diacrylate (PEGDA) within 20 kDa PEGDA base hydrogels using a photolithographic patterning method. Varying the stripe width and spacing resulted in a tensile elastic modulus parallel to the stripes that was 4.1-6.8 times greater than that in the perpendicular direction, comparable to the degree of anisotropy between the circumferential and radial orientations in native valve leaflets. Biomimetic PEG-peptide hydrogels were prepared by tethering the cell-adhesive peptide RGDS and incorporating the collagenase-degradable peptide PQ (GGGPQG↓IWGQGK) into the polymer network. The specific amounts of RGDS and PEG-PQ within the resulting hydrogels influenced the elongation, de novo extracellular matrix deposition and hydrogel degradation behavior of encapsulated valvular interstitial cells (VICs). In addition, the morphology and activation of VICs grown atop PEG hydrogels could be modulated by controlling the concentration or micro-patterning profile of PEG-RGDS. These results are promising for the fabrication of PEG-based hydrogels using anatomically and biologically inspired scaffold design features for heart valve tissue engineering. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Electron beam initiated modification of acrylic elastomer in presence of polyfunctional monomers

NASA Astrophysics Data System (ADS)

Vijayabaskar, V.; Bhattacharya, S.; Tikku, V. K.; Bhowmick, Anil K.

2004-12-01

The structural changes of an acrylic rubber (ACM) in presence and absence of polyfunctional monomers like trimethylolpropane triacrylate, tripropyleneglycol diacrylate, trimethylolmethane tetraacrylate and trimethylolpropane trimethacrylate at different doses of electron beam (EB) irradiations were investigated with the help of FTIR spectroscopy (in the attenuated total reflectance mode) and sol-gel analysis. As the radiation dose increases, the concentration of carbonyl group increases in the ACM rubber due to aerial oxidation. This is corroborated from the increase in the absorbance values at 1734 and 1160 cm -1, which are due to carbonyl and C-O-C stretching frequencies, respectively. The increase in crosslinking is revealed by the increase in percentage gel content with radiation dose. The lifetime of spurs formed and the critical dose, an important criterion for overlapping of spurs have been determined for both grafted and ungrafted ACM rubber using a mathematical model. The predominance of crosslinking by electronic stopping with energetic EB projectile and the increase in effective radius of crosslinking have also been verified by this model. The doses at which the synergistic occurrence of both dislinking and endlinking steps originate have been calculated using linear energy transfer of EB. The ratio of scissioning to crosslinking for ACM rubber has been determined by using Charlesby-Pinner equation. The mechanical properties have been studied for different modified and unmodified systems and the tensile strength is found to increase with grafting of polyfunctional monomers.

Synthesis and Characterization of Poly(Ethylene Glycol) Based Thermo-Responsive Hydrogels for Cell Sheet Engineering.

PubMed

Son, Kuk Hui; Lee, Jin Woo

2016-10-20

The swelling properties and thermal transition of hydrogels can be tailored by changing the hydrophilic-hydrophobic balance of polymer networks. Especially, poly( N -isopropylacrylamide) (PNIPAm) has received attention as thermo-responsive hydrogels for tissue engineering because its hydrophobicity and swelling property are transited around body temperature (32 °C). In this study, we investigated the potential of poly(ethylene glycol) diacrylate (PEGDA) as a hydrophilic co-monomer and crosslinker of PNIPAm to enhance biological properties of PNIPAm hydrogels. The swelling ratios, lower critical solution temperature (LCST), and internal pore structure of the synthesized p(NIPAm- co -PEGDA) hydrogels could be varied with changes in the molecular weight of PEGDA and the co-monomer ratios (NIPAm to PEGDA). We found that increasing the molecular weight of PEGDA showed an increase of pore sizes and swelling ratios of the hydrogels. In contrast, increasing the weight ratio of PEGDA under the same molecular weight condition increased the crosslinking density and decreased the swelling ratios of the hydrogels. Further, to evaluate the potential of these hydrogels as cell sheets, we seeded bovine chondrocytes on the p(NIPAm- co -PEGDA) hydrogels and observed the proliferation of the seed cells and their detachment as a cell sheet upon a decrease in temperature. Based on our results, we confirmed that p(NIPAm- co -PEGDA) hydrogels could be utilized as cell sheets with enhanced cell proliferation performance.

Dual-degradable disulfide-containing PEI–Pluronic/DNA polyplexes: transfection efficiency and balancing protection and DNA release

PubMed Central

Zhang, Lifen; Chen, Zhenzhen; Li, Yanfeng

2013-01-01

Polymeric gene-delivery vectors to achieve lack of toxicity and a balance between protection and DNA release remains a formidable challenge. Incorporating intracellular environment-responsive degradable bonds is an appreciable step toward developing safer transfection agents. In this study, novel, dual-degradable polycation copolymers (Pluronic-diacrylate [PA]–polyethyleneimine [PEI]–SS) were synthesized through the addition of low molecular weight (800 Da) PEI cross-linked with SS (PEI-SS) to PA. Three PA-PEI-SS copolymers (PA-PEI-SS1, 2, and 3) with different PEI-SS to Pluronic molar ratios were investigated and found to strongly condense plasmid DNA into positively charged nanoparticles with an average particle size of approximately 200 nm and to possess higher stability against DNase I digestion and sodium heparin. Disulfide and ester bonds of the copolymers were susceptible to intracellular redox conditions. In vitro experiments demonstrated that the PA-PEI-SS copolymers had significantly lower cytotoxicity and higher transfection efficiency in both BGC-823 and 293T cell lines than the controls of degradable PEI-SS and nondegradable 25 kDa PEI. Transfection activity was influenced by the PEI-SS content in the polymers and PA-PEI-SS1 showed the highest efficiency of the three copolymers. These studies suggest that these dual-degradable copolymers could be used as potential biocompatible gene delivery carriers. PMID:24109182

Incorporation of Aggrecan in Interpenetrating Network Hydrogels to Improve Cellular Performance for Cartilage Tissue Engineering

PubMed Central

Ingavle, Ganesh C.; Frei, Anthony W.; Gehrke, Stevin H.

2013-01-01

Interpenetrating network (IPN) hydrogels were recently introduced to the cartilage tissue engineering literature, with the approach of encapsulating cells in thermally gelling agarose that is then soaked in a poly(ethylene glycol) diacrylate (PEGDA) solution, which is then photopolymerized. These IPNs possess significantly enhanced mechanical performance desirable for cartilage regeneration, potentially allowing patients to return to weight-bearing activities quickly after surgical implantation. In an effort to improve cell viability and performance, inspiration was drawn from previous studies that have elicited positive chondrogenic responses to aggrecan, the proteoglycan largely responsible for the compressive stiffness of cartilage. Aggrecan was incorporated into the IPNs in conservative concentrations (40 μg/mL), and its effect was contrasted with the incorporation of chondroitin sulfate (CS), the primary glycosaminoglycan associated with aggrecan. Aggrecan was incorporated by physical entrapment within agarose and methacrylated CS was incorporated by copolymerization with PEGDA. The IPNs incorporating aggrecan or CS exhibited over 50% viability with encapsulated chondrocytes after 6 weeks. Both aggrecan and CS improved cell viability by 15.6% and 20%, respectively, relative to pure IPNs at 6 weeks culture time. In summary, we have introduced the novel approach of including a raw material from cartilage, namely aggrecan, to serve as a bioactive signal to cells encapsulated in IPN hydrogels for cartilage tissue engineering, which led to improved performance of encapsulated chondrocytes. PMID:23379843

Characterization of photochemical-cured acrylates with calorimetric methods

NASA Astrophysics Data System (ADS)

Strehmel, Bernd; Anwand, Dirk; Wetzel, Henrik

1994-05-01

Radical polymerization kinetics of different kinds of diacrylates was investigated in linear polymers (binders) by using an isoperibolic calorimeter. For all experiments benzoin compounds were added as photoinitiator. The ester between acrylic acid and bisphenol-A-diglycidylether (DDGDA) and hexamethylenediacrylate were used as monomers. Both compounds have a high limiting conversion and a large polymerization rate in the binders investigated. Additionally, three kinds of termination reaction were observed: first order, second order, and primary radical termination. The last reaction was mainly found in the case of using the hexamethylenediacrylate monomer. The materials were investigated by DSC to determine the phase behavior. Both monomers form one phase with the binder (polymethylmethacrylate, PMMA). In contrast, a phase separation was observed between the crosslinked hexamethylenediacrylate and PMMA. Formations of semi- interpenetrating networks were found in the case of crosslinked DDGDA and PMMA. The glass transition temperatures were determined at different polymerization degrees also. The obtained results indicate that most of the network formation occurred in the glassy state. Fluorescence probe technique was applied to study changes in the mobility during network formation. The fluorescence probe crystal violet (CV) was used because this compound shows a strong free volume-dependent fluorescence. It was found that in the glassy state, where most of networks were formed, a large variation of the molecular mobility was observed during irradiation of the photopolymers. This result was in agreement with the observations during DSC experiments.

Crosslinked PEG and PEBAX Membranes for Concurrent Permeation of Water and Carbon Dioxide

PubMed Central

Scholes, Colin A.; Chen, George Q.; Lu, Hiep T.; Kentish, Sandra E.

2015-01-01

Membrane technology can be used for both post combustion carbon dioxide capture and acidic gas sweetening and dehydration of natural gas. These processes are especially suited for polymeric membranes with polyether functionality, because of the high affinity of this species for both H2O and CO2. Here, both crosslinked polyethylene glycol diacrylate and a polyether-polyamide block copolymer (PEBAX 2533©) are studied for their ability to separate CO2 from CH4 and N2 under single and mixed gas conditions, for both dry and wet feeds, as well as when 500 ppm H2S is present. The solubility of gases within these polymers is shown to be better correlated with the Lennard Jones well depth than with critical temperature. Under dry mixed gas conditions, CO2 permeability is reduced compared to the single gas measurement because of competitive sorption from CH4 or N2. However, selectivity for CO2 is retained in both polymers. The presence of water in the feed is observed to swell the PEG membrane resulting in a significant increase in CO2 permeability relative to the dry gas scenario. Importantly, the selectivity is again retained under wet feed gas conditions. The presence of H2S is observed to only slightly reduce CO2 permeability through both membranes. PMID:26703745

Photoinitiated chemical vapor deposition of cytocompatible poly(2-hydroxyethyl methacrylate) films.

PubMed

McMahon, Brian J; Pfluger, Courtney A; Sun, Bing; Ziemer, Katherine S; Burkey, Daniel D; Carrier, Rebecca L

2014-07-01

Poly(2-hydroxyethyl methacrylate) (pHEMA) is a widely utilized biomaterial due to lack of toxicity and suitable mechanical properties; conformal thin pHEMA films produced via chemical vapor deposition (CVD) would thus have broad biomedical applications. Thin films of pHEMA were deposited using photoinitiated CVD (piCVD). Incorporation of ethylene glycol diacrylate (EGDA) into the pHEMA polymer film as a crosslinker, confirmed via Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, resulted in varied swelling and degradation behavior. 2-Hydroxyethyl methacrylate-only films showed significant thickness loss (up to 40%), possibly due to extraction of low-molecular-weight species or erosion, after 24 h in aqueous solution, whereas films crosslinked with EGDA (9.25-12.4%) were stable for up to 21 days. These results differ significantly from those obtained with plasma-polymerized pHEMA, which degraded steadily over a 21-day period, even with crosslinking. This suggests that the piCVD films differ structurally from those fabricated via plasma polymerization (plasma-enhanced CVD). piCVD pHEMA coatings proved to be good cell culture materials, with Caco-2 cell attachment and viability comparable to results obtained on tissue-culture polystyrene. Thus, thin film CVD pHEMA offers the advantage of enabling conformal coating of a cell culture substrate with tunable properties depending on method of preparation and incorporation of crosslinking agents. © 2013 Wiley Periodicals, Inc.

An Injectable Hydrogel as Bone Graft Material with Added Antimicrobial Properties

PubMed Central

Tommasi, Giacomo; Perni, Stefano

2016-01-01

Currently, the technique which provides the best chances for a successful bone graft, is the use of bone tissue from the same patient receiving it (autograft); the main limitations are the limited availability and the risks involved in removing living bone tissue, for example, explant site pain and morbidity. Allografts and xenografts may overcome these limitations; however, they increase the risk of rejection. For all these reasons the development of an artificial bone graft material is particularly important and hydrogels are a promising alternative for bone regeneration. Gels were prepared using 1,4-butanediol diacrylate as crosslinker and alpha tricalciumphosphate; ZnCl2 and SrCl2 were added to the aqueous phase. MTT results demonstrated that the addition of strontium had a beneficial effect on the osteoblast cells density on hydrogels, and zinc instead did not increase osteoblast proliferation. The amount of calcium produced by the osteoblast cells quantified through the Alizarin Red protocol revealed that both strontium and zinc positively influenced the formation of calcium; furthermore, their effect was synergistic. Rheology properties were used to mechanically characterize the hydrogels and especially the influence of crosslinker's concentration on them, showing the hydrogels presented had extremely good mechanical properties. Furthermore, the antimicrobial activity of strontium and zinc in the hydrogels against methicillin-resistant Staphylococcus aureus and Staphylococcus epidermidis was determined. PMID:27174392

A simple and high-resolution stereolithography-based 3D bioprinting system using visible light crosslinkable bioinks.

PubMed

Wang, Zongjie; Abdulla, Raafa; Parker, Benjamin; Samanipour, Roya; Ghosh, Sanjoy; Kim, Keekyoung

2015-12-22

Bioprinting is a rapidly developing technique for biofabrication. Because of its high resolution and the ability to print living cells, bioprinting has been widely used in artificial tissue and organ generation as well as microscale living cell deposition. In this paper, we present a low-cost stereolithography-based bioprinting system that uses visible light crosslinkable bioinks. This low-cost stereolithography system was built around a commercial projector with a simple water filter to prevent harmful infrared radiation from the projector. The visible light crosslinking was achieved by using a mixture of polyethylene glycol diacrylate (PEGDA) and gelatin methacrylate (GelMA) hydrogel with eosin Y based photoinitiator. Three different concentrations of hydrogel mixtures (10% PEG, 5% PEG + 5% GelMA, and 2.5% PEG + 7.5% GelMA, all w/v) were studied with the presented systems. The mechanical properties and microstructure of the developed bioink were measured and discussed in detail. Several cell-free hydrogel patterns were generated to demonstrate the resolution of the solution. Experimental results with NIH 3T3 fibroblast cells show that this system can produce a highly vertical 3D structure with 50 μm resolution and 85% cell viability for at least five days. The developed system provides a low-cost visible light stereolithography solution and has the potential to be widely used in tissue engineering and bioengineering for microscale cell patterning.

Integrated electrokinetically driven microfluidic devices with pH-mediated solid-phase extraction coupled to microchip electrophoresis for preterm birth biomarkers.

PubMed

Sonker, Mukul; Knob, Radim; Sahore, Vishal; Woolley, Adam T

2017-07-01

Integration in microfluidics is important for achieving automation. Sample preconcentration integrated with separation in a microfluidic setup can have a substantial impact on rapid analysis of low-abundance disease biomarkers. Here, we have developed a microfluidic device that uses pH-mediated solid-phase extraction (SPE) for the enrichment and elution of preterm birth (PTB) biomarkers. Furthermore, this SPE module was integrated with microchip electrophoresis for combined enrichment and separation of multiple analytes, including a PTB peptide biomarker (P1). A reversed-phase octyl methacrylate monolith was polymerized as the SPE medium in polyethylene glycol diacrylate modified cyclic olefin copolymer microfluidic channels. Eluent for pH-mediated SPE of PTB biomarkers on the monolith was optimized using different pH values and ionic concentrations. Nearly 50-fold enrichment was observed in single channel SPE devices for a low nanomolar solution of P1, with great elution time reproducibility (<7% RSD). The monolith binding capacity was determined to be 400 pg (0.2 pmol). A mixture of a model peptide (FA) and a PTB biomarker (P1) was extracted, eluted, injected, and then separated by microchip electrophoresis in our integrated device with ∼15-fold enrichment. This device shows important progress towards an integrated electrokinetically operated platform for preconcentration and separation of biomarkers. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metabolic inactivation of five glycidyl ethers in lung and liver of humans, rats and mice in vitro.

PubMed

Boogaard, P J; de Kloe, K P; Bierau, J; Kuiken, G; Borkulo, P E; Watson, W P; van Sittert, N J

2000-05-01

1. Some glycidyl ethers (GE) have been shown to be direct mutagens in short-term in vitro tests and consequently GE are considered to be potentially mutagenic in vivo. However, GE may be metabolically inactivated in the body by two different enzymatic routes: conjugation of the epoxide moiety with the endogenous tripeptide glutathione (GSH) catalysed by glutathione S-transferase (GST) or hydrolysis of the epoxide moiety catalysed by epoxide hydrolase (EH). 2. The metabolic inactivation of five different GE, the diglycidyl ethers of bisphenol A (BADGE), 4,4'-dihydroxy-3,3',5,5'-tetramethylbiphenyl (Epikote YX4000) and 1,6-hexanediol (HDDGE) and the GE of 1-dodecanol (C12GE) and o-cresol (o-CGE), has been studied in subcellular fractions of human, C3H mouse and F344 rat liver and lung. 3. All GE were chemically very stable and resistant to aqueous hydrolysis, but were rapidly hydrolysed by EH in cytosolic and microsomal fractions of liver and lung. The aromatic GE were very good substrates for EH. In general, microsomal EH is more efficient than cytosolic EH in hydrolysis of GE, and human microsomes are more efficient than rodent microsomes. 4. The more water-soluble GE, o-CGE and HDDGE, were good substrates for GST whereas the more lipophilic GE, YX4000 and C12GE, were poor substrates for GST. In general, rodents are more efficient in GSH conjugation of GE than humans. 5. In general, the epoxide groups of YX4000 are the most and those of HDDGE the least efficiently inactivated of the five GE under study. For the other three GE no general trend was observed: the relative efficiency of inactivation varied with organ and species. 6. The large variation in metabolism observed with five representative GE indicate that GE have variable individual properties and should not be considered as a single, homogenous class of compounds.

Spatially localized recruitment of anti-inflammatory monocytes by SDF-1α-releasing hydrogels enhances microvascular network remodeling.

PubMed

Krieger, J R; Ogle, M E; McFaline-Figueroa, J; Segar, C E; Temenoff, J S; Botchwey, E A

2016-01-01

Tissue repair processes are characterized by the biphasic recruitment of distinct subpopulations of blood monocytes, including classical ("inflammatory") monocytes (IMs, Ly6C(hi)Gr1(+)CX3CR1(lo)) and non-classical anti-inflammatory monocytes (AMs, Ly6C(lo)Gr1(-)CX3CR1(hi)). Drug-eluting biomaterial implants can be used to tune the endogenous repair process by the preferential recruitment of pro-regenerative cells. To enhance recruitment of AMs during inflammatory injury, a novel N-desulfated heparin-containing poly(ethylene glycol) diacrylate (PEG-DA) hydrogel was engineered to deliver exogenous stromal derived factor-1α (SDF-1α), utilizing the natural capacity of heparin to sequester and release growth factors. SDF-1α released from the hydrogels maintained its bioactivity and stimulated chemotaxis of bone marrow cells in vitro. Intravital microscopy and flow cytometry demonstrated that SDF-1α hydrogels implanted in a murine dorsal skinfold window chamber promoted spatially-localized recruitment of AMs relative to unloaded internal control hydrogels. SDF-1α delivery stimulated arteriolar remodeling that was correlated with AM enrichment in the injury niche. SDF-1α, but not unloaded control hydrogels, supported sustained arteriogenesis and microvascular network growth through 7 days. The recruitment of AMs correlated with parameters of vascular remodeling suggesting that tuning the innate immune response by biomaterial SDF-1α release is a promising strategy for promoting vascular remodeling in a spatially controlled manner. Copyright © 2015 Elsevier Ltd. All rights reserved.

Improved resolution of 3D printed scaffolds by shrinking.

PubMed

Chia, Helena N; Wu, Benjamin M

2015-10-01

Three-dimensional printing (3DP) uses inkjet printheads to selectively deposit liquid binder to adjoin powder particles in a layer-by-layer fashion to create a computer-modeled 3D object. Two general approaches for 3DP have been described for biomedical applications (direct and indirect 3DP). The two approaches offer competing advantages, and both are limited by print resolution. This study describes a materials processing strategy to enhance 3DP resolution by controlled shrinking net-shape scaffolds. Briefly, porogen preforms are printed and infused with the desired monomer or polymer solution. After solidification or polymerization, the porogen is leached and the polymer is allowed to shrink by controlled drying. Heat treatment is performed to retain the dimensions against swelling forces. The main objective of this study is to determine the effects of polymer content and post-processing on dimension, microstructure, and thermomechanical properties of the scaffold. For polyethylene glycol diacrylate (PEG-DA), reducing polymer content corresponded with greater shrinkage with maximum shrinkage of ∼80 vol% at 20% vol% PEG-DA. The secondary heat treatment retains the microarchitecture and new dimensions of the scaffolds, even when the heat-treated scaffolds are immersed into water. To demonstrate shrinkage predictability, 3D components with interlocking positive and negative features were printed, processed, and fitted. This material processing strategy provides an alternative method to enhance the resolution of 3D scaffolds, for a wide range of polymers, without optimizing the binder-powder interaction physics to print each material combination. © 2014 Wiley Periodicals, Inc.

Encoding Hydrogel Mechanics via Network Cross-Linking Structure.

PubMed

Schweller, Ryan M; West, Jennifer L

2015-05-11

The effects of mechanical cues on cell behaviors in 3D remain difficult to characterize as the ability to tune hydrogel mechanics often requires changes in the polymer density, potentially altering the material's biochemical and physical characteristics. Additionally, with most PEG diacrylate (PEGDA) hydrogels, forming materials with compressive moduli less than ∼10 kPa has been virtually impossible. Here, we present a new method of controlling the mechanical properties of PEGDA hydrogels independent of polymer chain density through the incorporation of additional vinyl group moieties that interfere with the cross-linking of the network. This modification can tune hydrogel mechanics in a concentration dependent manner from <1 to 17 kPa, a more physiologically relevant range than previously possible with PEG-based hydrogels, without altering the hydrogel's degradation and permeability. Across this range of mechanical properties, endothelial cells (ECs) encapsulated within MMP-2/MMP-9 degradable hydrogels with RGDS adhesive peptides revealed increased cell spreading as hydrogel stiffness decreased in contrast to behavior typically observed for cells on 2D surfaces. EC-pericyte cocultures exhibited vessel-like networks within 3 days in highly compliant hydrogels as compared to a week in stiffer hydrogels. These vessel networks persisted for at least 4 weeks and deposited laminin and collagen IV perivascularly. These results indicate that EC morphogenesis can be regulated using mechanical cues in 3D. Furthermore, controlling hydrogel compliance independent of density allows for the attainment of highly compliant mechanical regimes in materials that can act as customizable cell microenvironments.

Immobilization of Cell-Adhesive Laminin Peptides in Degradable PEGDA Hydrogels Influences Endothelial Cell Tubulogenesis

PubMed Central

Ali, Saniya; Saik, Jennifer E.; Gould, Dan J.; Dickinson, Mary E.

2013-01-01

Abstract Attachment, spreading, and organization of endothelial cells into tubule networks are mediated by interactions between cells in the extracellular microenvironment. Laminins are key extracellular matrix components and regulators of cell adhesion, migration, and proliferation. In this study, laminin-derived peptides were conjugated to poly(ethylene glycol) (PEG) monoacrylate and covalently incorporated into degradable PEG diacrylate (PEGDA) hydrogels to investigate the influence of these peptides on endothelial cellular adhesion and function in organizing into tubule networks. Degradable PEGDA hydrogels were synthesized by incorporating a matrix metalloproteinase (MMP)–sensitive peptide, GGGPQGIWGQGK (abbreviated PQ), into the polymer backbone. The secretion of MMP-2 and MMP-9 by endothelial cells promotes polymer degradation and consequently cell migration. We demonstrate the formation of extensive networks of tubule-like structures by encapsulated human umbilical vein endothelial cells in hydrogels with immobilized synthetic peptides. The resulting structures were stabilized by pericyte precursor cells (10T1/2s) in vitro. During tubule formation and stabilization, extracellular matrix proteins such as collagen IV and laminin were deposited. Tubules formed in the matrix of metalloproteinase sensitive hydrogels were visualized from 7 days to 4 weeks in response to different combination of peptides. Moreover, hydrogels functionalized with laminin peptides and transplanted in a mouse cornea supported the ingrowth and attachment of endothelial cells to the hydrogel during angiogenesis. Results of this study illustrate the use of laminin-derived peptides as potential candidates for modification of biomaterials to support angiogenesis. PMID:23914330

Continuous gradient scaffolds for rapid screening of cell-material interactions and interfacial tissue regeneration.

PubMed

Bailey, Brennan M; Nail, Lindsay N; Grunlan, Melissa A

2013-09-01

In tissue engineering, the physical and chemical properties of the scaffold mediates cell behavior, including regeneration. Thus a strategy that permits rapid screening of cell-scaffold interactions is critical. Herein, we have prepared eight "hybrid" hydrogel scaffolds in the form of continuous gradients such that a single scaffold contains spatially varied properties. These scaffolds are based on combining an inorganic macromer (methacrylated star polydimethylsiloxane, PDMSstar-MA) and organic macromer (poly(ethylene glycol)diacrylate, PEG-DA) as well as both aqueous and organic fabrication solvents. Having previously demonstrated its bioactivity and osteoinductivity, PDMSstar-MA is a particularly powerful component to incorporate into instructive gradient scaffolds based on PEG-DA. The following parameters were varied to produce the different gradients or gradual transitions in: (1) the wt.% ratio of PDMSstar-MA to PEG-DA macromers, (2) the total wt.% macromer concentration, (3) the number average molecular weight (Mn) of PEG-DA and (4) the Mn of PDMSstar-MA. Upon dividing each scaffold into four "zones" perpendicular to the gradient, we were able to demonstrate the spatial variation in morphology, bioactivity, swelling and modulus. Among these gradient scaffolds are those in which swelling and modulus are conveniently decoupled. In addition to rapid screening of cell-material interactions, these scaffolds are well suited for regeneration of interfacial tissues (e.g. osteochondral tissues) that transition from one tissue type to another. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Lubricin is expressed in chondrocytes derived from osteoarthritic cartilage encapsulated in poly (ethylene glycol) diacrylate scaffold

PubMed Central

Musumeci, G.; Loreto, C.; Carnazza, M.L.; Coppolino, F.; Cardile, V.; Leonardi, R.

2011-01-01

Osteoarthritis (OA) is characterized by degenerative changes within joints that involved quantitative and/or qualitative alterations of cartilage and synovial fluid lubricin, a mucinous glycoprotein secreted by synovial fibroblasts and chondrocytes. Modern therapeutic methods, including tissue-engineering techniques, have been used to treat mechanical damage of the articular cartilage but to date there is no specific and effective treatment. This study aimed at investigating lubricin immunohistochemical expression in cartilage explant from normal and OA patients and in cartilage constructions formed by Poly (ethylene glycol) (PEG) based hydrogels (PEG-DA) encapsulated OA chondrocytes. The expression levels of lubricin were studied by immunohistochemistry: i) in tissue explanted from OA and normal human cartilage; ii) in chondrocytes encapsulated in hydrogel PEGDA from OA and normal human cartilage. Moreover, immunocytochemical and western blot analysis were performed in monolayer cells from OA and normal cartilage. The results showed an increased expression of lubricin in explanted tissue and in monolayer cells from normal cartilage, and a decreased expression of lubricin in OA cartilage. The chondrocytes from OA cartilage after 5 weeks of culture in hydrogels (PEGDA) showed an increased expression of lubricin compared with the control cartilage. The present study demonstrated that OA chondrocytes encapsulated in PEGDA, grown in the scaffold and were able to restore lubricin biosynthesis. Thus our results suggest the possibility of applying autologous cell transplantation in conjunction with scaffold materials for repairing cartilage lesions in patients with OA to reduce at least the progression of the disease. PMID:22073377

Formation of polymeric toroidal-spiral particles.

PubMed

Sharma, Vishal; Szymusiak, Magdalena; Shen, Hao; Nitsche, Ludwig C; Liu, Ying

2012-01-10

Compared to spherical matrices, particles with well-defined internal structure provide large surface to volume ratio and predictable release kinetics for the encapsulated payloads. We describe self-assembly of polymeric particles, whereby competitive kinetics of viscous sedimentation, diffusion, and cross-linking yield a controllable toroidal-spiral (T-S) structure. Precursor polymeric droplets are splashed through the surface of a less dense, miscible solution, after which viscous forces entrain the surrounding bulk solution into the sedimenting polymer drop to form T-S channels. The intricate structure forms because low interfacial tension between the two miscible solutions is dominated by viscous forces. The biocompatible polymer, poly(ethylene glycol) diacrylate (PEG-DA), is used to demonstrate the solidification of the T-S shapes at various configurational stages by UV-triggered cross-linking. The dimensions of the channels are controlled by Weber number during impact on the surface, and Reynolds number and viscosity ratio during subsequent sedimentation. We anticipate applications of the T-S particle in drug delivery, wherein diffusion through these T-S channels and the polymer matrix would offer parallel release pathways for molecules of different sizes. Polyphosphate, as a model macromolecule, is entrained in T-S particles during their formation. The in vitro release kinetics of polyphosphate from the T-S particles with various channel length and width is reported. In addition, self-assembly of T-S particles occurs in a single step under benign conditions for delicate macromolecules, and appears conducive to scaleup.

How do monomeric components of a polymer gel dosimeter respond to ionising radiation: A steady-state radiolysis towards preparation of a 3D polymer gel dosimeter

NASA Astrophysics Data System (ADS)

Kozicki, Marek

2011-12-01

Ionising radiation-induced reactions of aqueous single monomer solutions and mixtures of poly(ethylene glycol) diacrylate (PEGDA) and N, N'-methylenebisacrylamide (Bis) in a steady-state condition are presented below and above gelation doses in order to highlight reactions in irradiated 3D polymer gel dosimeters, which are assigned for radiotherapy dosimetry. Both monomers are shown to undergo radical polymerisation and cross-linking, which result in the measured increase in molecular weight and radius of gyration of the formed polydisperse polymer coils. The formation of nanogels was also observed for Bis solutions at a low concentration. In the case of PEGDA-Bis mixtures, co-polymerisation is suggested as well. At a sufficiently high radiation dose, the formation of a polymer network was observed for both monomers and their mixture. For this reason a sol-gel analysis for PEGDA and Bis was performed gravimetrically and a proposition of an alternative to this method employing a nuclear magnetic resonance technique is made. The two monomers were used for preparation of 3D polymer gel dosimeters having the acronyms PABIG and PABIG nx. The latter is presented for the first time in this work and is a type of the formerly established PABIG polymer gel dosimeter. The elementary characteristics of the new composition are presented, underlining the ease of its preparation, low dose threshold, and slightly increased sensitivity but lower quasi-linear range of dose response in comparison to PABIG.

Polymeric nanoparticles for nonviral gene therapy extend brain tumor survival in vivo.

PubMed

Mangraviti, Antonella; Tzeng, Stephany Yi; Kozielski, Kristen Lynn; Wang, Yuan; Jin, Yike; Gullotti, David; Pedone, Mariangela; Buaron, Nitsa; Liu, Ann; Wilson, David R; Hansen, Sarah K; Rodriguez, Fausto J; Gao, Guo-Dong; DiMeco, Francesco; Brem, Henry; Olivi, Alessandro; Tyler, Betty; Green, Jordan J

2015-02-24

Biodegradable polymeric nanoparticles have the potential to be safer alternatives to viruses for gene delivery; however, their use has been limited by poor efficacy in vivo. In this work, we synthesize and characterize polymeric gene delivery nanoparticles and evaluate their efficacy for DNA delivery of herpes simplex virus type I thymidine kinase (HSVtk) combined with the prodrug ganciclovir (GCV) in a malignant glioma model. We investigated polymer structure for gene delivery in two rat glioma cell lines, 9L and F98, to discover nanoparticle formulations more effective than the leading commercial reagent Lipofectamine 2000. The lead polymer structure, poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) end-modified with 1-(3-aminopropyl)-4-methylpiperazine, is a poly(β-amino ester) (PBAE) and formed nanoparticles with HSVtk DNA that were 138 ± 4 nm in size and 13 ± 1 mV in zeta potential. These nanoparticles containing HSVtk DNA showed 100% cancer cell killing in vitro in the two glioma cell lines when combined with GCV exposure, while control nanoparticles encoding GFP maintained robust cell viability. For in vivo evaluation, tumor-bearing rats were treated with PBAE/HSVtk infusion via convection-enhanced delivery (CED) in combination with systemic administration of GCV. These treated animals showed a significant benefit in survival (p = 0.0012 vs control). Moreover, following a single CED infusion, labeled PBAE nanoparticles spread completely throughout the tumor. This study highlights a nanomedicine approach that is highly promising for the treatment of malignant glioma.

Electroactive SWNT/PEGDA hybrid hydrogel coating for bio-electrode interface.

PubMed

He, Lei; Lin, Demeng; Wang, Yanping; Xiao, Yinghong; Che, Jianfei

2011-10-15

Electric interface between neural tissue and electrode plays a significant role in the development of implanted devices for continuous monitoring and functional stimulation of central nervous system in terms of electroactivity, biocompatibility and long-term stability. To engineer an interface that possesses these merits, a polymeric hydrogel based on poly(ethylene glycol) diacrylate (PEGDA) and single-walled carbon nanotubes (SWNTs) were employed to fabricate a hybrid hydrogel via covalent anchoring strategy, i.e., self-assembly of cysteamine (Cys) followed by Michael addition between Cys and PEGDA. XPS characterization proves that the Cys molecules are linked to gold surface via the strong S-Au bond and that the PEGDA macromers are covalently bonded to Cys. FTIR spectra indicate the formation of hybrid hydrogel coating during photopolymerization. Electrochemical measurements using cyclic voltammetry (CV) and impedance spectrum clearly show the enhancement of electric properties to the hydrogel by the SWNTs. The charge transfer of the hybrid hydrogel-based electrode is quasi-reversible and charge transfer resistance decreases to the tenth of that of the pure hydrogel due to electron hopping along the SWNTs. Additionally, this hybrid hydrogel provides a favorable biomimetic microenvironment for cell attachment and growth due to its inherent biocompatibility. Combination of these merits yields hybrid hydrogels that can be good candidates for application to biosensors and biomedical devices. More importantly, the hybrid hydrogel coatings fabricated via the current strategy have good adhesion to the electrode substrate which is highly desired for chronically implantable devices. Copyright © 2011 Elsevier B.V. All rights reserved.

Recent Developments in Thiolated Polymeric Hydrogels for Tissue Engineering Applications.

PubMed

Gajendiran, Mani; Rhee, Jae-Sung; Kim, Kyobum

2018-02-01

This review focuses on the recent strategy in the preparation of thiolated polymers and fabrication of their hydrogel matrices. The mechanism involved in the synthesis of thiolated polymers and fabrication of thiolated polymer hydrogels is exemplified with suitable schematic representations reported in the recent literature. The 2-iminothiolane namely "Traut's reagent" has been widely used for effectively thiolating the natural polymers such as collagen and gelatin, which contain free amino group in their backbone. The free carboxylic acid group containing polymers such as hyaluronic acid and heparin have been thiolated by using the bifunctional molecules such as cysteamine and L-cysteine via N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling reaction. The degree of thiolation in the polymer chain has been widely determined by using Ellman's assay method. The thiolated polymer hydrogels are prepared by disulfide bond formation (or) thiol-ene reaction (or) Michael-type addition reaction. The thiolated polymers such as thiolated gelatin are reacted with polyethylene glycol diacrylate for obtaining interpenetrating polymer network hydrogel scaffolds. Several in vitro cell culture experiments indicate that the developed thiolated polymer hydrogels exhibited biocompatibility and cellular mimicking properties. The developed hydrogel scaffolds efficiently support proliferation and differentiation of various cell types. In the present review article, the thiol-functionalized protein-based biopolymers, carbohydrate-based polymers, and some synthetic polymers have been covered with recently published research articles. In addition, the usage of new thiolated nanomaterials as a crosslinking agent for the preparation of three-dimensional tissue-engineered hydrogels is highlighted.

Micropatterned cell-cell interactions enable functional encapsulation of primary hepatocytes in hydrogel microtissues.

PubMed

Li, Cheri Y; Stevens, Kelly R; Schwartz, Robert E; Alejandro, Brian S; Huang, Joanne H; Bhatia, Sangeeta N

2014-08-01

Drug-induced liver injury is a major cause of drug development failures and postmarket withdrawals. In vitro models that incorporate primary hepatocytes have been shown to be more predictive than model systems which rely on liver microsomes or hepatocellular carcinoma cell lines. Methods to phenotypically stabilize primary hepatocytes ex vivo often rely on mimicry of hepatic microenvironmental cues such as cell-cell interactions and cell-matrix interactions. In this work, we sought to incorporate phenotypically stable hepatocytes into three-dimensional (3D) microtissues, which, in turn, could be deployed in drug-screening platforms such as multiwell plates and diverse organ-on-a-chip devices. We first utilize micropatterning on collagen I to specify cell-cell interactions in two-dimensions, followed by collagenase digestion to produce well-controlled aggregates for 3D encapsulation in polyethylene glycol (PEG) diacrylate. Using this approach, we examined the influence of homotypic hepatocyte interactions and composition of the encapsulating hydrogel, and achieved the maintenance of liver-specific function for over 50 days. Optimally preaggregated structures were subsequently encapsulated using a microfluidic droplet-generator to produce 3D microtissues. Interactions of engineered hepatic microtissues with drugs was characterized by flow cytometry, and yielded both induction of P450 enzymes in response to prototypic small molecules and drug-drug interactions that give rise to hepatotoxicity. Collectively, this study establishes a pipeline for the manufacturing of 3D hepatic microtissues that exhibit stabilized liver-specific functions and can be incorporated into a wide array of emerging drug development platforms.

Influence of the vehicle on elicitation of contact allergic reactions to acrylic compounds in the guinea pig.

PubMed

Björkner, B; Niklasson, B

1984-11-01

Many factors can influence the elicitation of hypersensitivity reactions in guinea pigs and humans. The effect which the vehicle might have on the test response in guinea pigs sensitized with various acrylic compounds, using the "guinea pig maximization test", has been investigated. A marked decrease in the number of positive animals was seen when acetone was used as test vehicle, compared to petrolatum. The same result was seen with alcohol as vehicle, when neopentyl glycol diacrylate (NPGDA) was used as an acrylic monomer model. The patch test locations on the guinea pig flank, also affected the test response. Half of the animals did not react when challenged near the abdomen, compared to a test site near the back. By means of HPLC-analysis, the possible adsorption of the acrylic monomer to the aluminium chamber or filter paper disc, was analysed. Our findings did not indicate that adsorption occurs. A decrease in the amount of acrylic monomer in the chamber with increasing time, was noted. There was a marked difference in the monomer residue between solutions with (darkness) and without (daylight) inhibitor. The monomer decrease was also more affected by an aluminium surface than a glass or filter paper surface. Aluminium oxide probably enhances the polymerization process. The discrepancy between the test results in this study, when petrolatum and acetone were used as test vehicles, is due to a polymerization process of the acrylic compounds. Thus, the petrolatum vehicle probably prevents polymerization of the acrylic monomer.

Flexible transparent displays based on core/shell upconversion nanophosphor-incorporated polymer waveguides

PubMed Central

Park, Bong Je; Hong, A-Ra; Park, Suntak; Kyung, Ki-Uk; Lee, Kwangyeol; Seong Jang, Ho

2017-01-01

Core/shell (C/S)-structured upconversion nanophosphor (UCNP)-incorporated polymer waveguide-based flexible transparent displays are demonstrated. Bright green- and blue-emitting Li(Gd,Y)F4:Yb,Er and Li(Gd,Y)F4:Yb,Tm UCNPs are synthesized via solution chemical route. Their upconversion luminescence (UCL) intensities are enhanced by the formation of C/S structure with LiYF4 shell. The Li(Gd,Y)F4:Yb,Er/LiYF4 and Li(Gd,Y)F4:Yb,Tm/LiYF4 C/S UCNPs exhibit 3.3 and 2.0 times higher UCL intensities than core counterparts, respectively. In addition, NaGdF4:Yb,Tm/NaGdF4:Eu C/S UCNPs are synthesized and they show red emission via energy transfer and migration of Yb3+ → Tm3+ → Gd3+ → Eu3+. The C/S UCNPs are incorporated into bisphenol A ethoxylate diacrylate which is used as a core material of polymer waveguides. The fabricated stripe-type polymer waveguides are highly flexible and transparent (transmittance > 90% in spectral range of 443–900 nm). The polymer waveguides exhibit bright blue, green, and red luminescence, depending on the incorporated UCNPs into the polymer core, under coupling with a near infrared (NIR) laser. Moreover, patterned polymer waveguide-based display devices are fabricated by reactive ion etching process and they realize bright blue-, green-, and red-colored characters under coupling with an NIR laser. PMID:28368021

Self-assembled pentablock copolymers for selective and sustained gene delivery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Bingqi

2011-05-15

The poly(diethylaminoethyl methacrylate) (PDEAEM) - Pluronic F127 - PDEAEM pentablock copolymer (PB) gene delivery vector system has been found to possess an inherent selectivity in transfecting cancer cells over non-cancer cells in vitro, without attaching any targeting ligands. In order to understand the mechanism of this selective transfection, three possible intracellular barriers to transfection were investigated in both cancer and non-cancer cells. We concluded that escape from the endocytic pathway served as the primary intracellular barrier for PB-mediated transfection. Most likely, PB vectors were entrapped and rendered non-functional in acidic lysosomes of non-cancer cells, but survived in less acidic lysosomesmore » of cancer cells. The work highlights the importance of identifying intracellular barriers for different gene delivery systems and provides a new paradigm for designing targeting vectors based on intracellular differences between cell types, rather than through the use of targeting ligands. The PB vector was further developed to simultaneously deliver anticancer drugs and genes, which showed a synergistic effect demonstrated by significantly enhanced gene expression in vitro. Due to the thermosensitive gelation behavior, the PB vector packaging both drug and gene was also investigated for its in vitro sustained release properties by using polyethylene glycol diacrylate as a barrier gel to mimic the tumor matrix in vivo. Overall, this work resulted in the development of a gene delivery vector for sustained and selective gene delivery to tumor cells for cancer therapy.« less

Two decades of occupational (meth)acrylate patch test results and focus on isobornyl acrylate.

PubMed

Christoffers, Wietske A; Coenraads, Pieter-Jan; Schuttelaar, Marie-Louise A

2013-08-01

Acrylates constitute an important cause of occupational contact dermatitis. Isobornyl acrylate sensitization has been reported in only 2 cases. We encountered an industrial process operator with occupational contact dermatitis caused by isobornyl acrylate. (i) To investigate whether it is relevant to add isobornyl acrylate to the (meth)acrylate test series. (ii) To report patients with (meth)acrylate contact allergy at an occupational dermatology clinic. Our patch test database was screened for positive reactions to (meth)acrylates between 1993 and 2012. A selected group of 14 patients was tested with an isobornyl acrylate dilution series: 0.3%, 0.1%, 0.033%, and 0.01%. Readings were performed on D2, D3, and D7. One hundred and fifty-one patients were tested with our (meth)acrylate series; 24 had positive reactions. Most positive reactions were to 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, and diethyleneglycol diacrylate. Hypothetical screening with 2-hydroxypropyl acrylate, ethyleneglycol dimethacrylate, ethoxylated bisphenol A glycol dimethacrylate and trimethylolpropane triacrylate identified 91.7% of the 24 patients. No positive reactions were observed in 14 acrylate-positive patients tested with the isobornyl acrylate dilution series. The 0.3% isobornyl acrylate concentration induced irritant reactions in 3 patients. We report a rare case of allergic contact dermatitis caused by isobornyl acrylate. However, this study provides insufficient support for isobornyl acrylate to be added to a (meth)acrylate series. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Projection-Based 3D Printing of Cell Patterning Scaffolds with Multiscale Channels.

PubMed

Xue, Dai; Wang, Yancheng; Zhang, Jiaxin; Mei, Deqing; Wang, Yue; Chen, Shaochen

2018-06-13

To fully actualize artificial, cell-laden biological models in tissue engineering, such as 3D organoids and organs-on-a-chip systems, cells need to be patterned such that they can precisely mimic natural microenvironments in vitro. Despite increasing interest in this area, patterning cells at multiscale (∼10 μm to 10 mm) remains a significant challenge in bioengineering. Here, we report a projection-based 3D printing system that achieves rapid and high-resolution fabrication of hydrogel scaffolds featuring intricate channels for multiscale cell patterning. Using this system, we were able to use biocompatible poly(ethylene glycol)diacrylate in fabricating a variety of scaffold architectures, ranging from regular geometries such as serpentine, spiral, and fractal-like to more irregular/intricate geometries, such as biomimetic arborescent and capillary networks. A red food dye solution was able to freely fill all channels in the scaffolds, from the trunk (>1100 μm in width) to the small branch (∼17 μm in width) without an external pump. The dimensions of the printed scaffolds remained stable over 3 days while being immersed in Dulbecco's phosphate-buffered saline at 37 °C, and a penetration analysis revealed that these scaffolds are suitable for metabolic and nutrient transport. Cell patterning experiments showed that red fluorescent protein-transfected A549 human nonsmall lung cancer cells adhered well in the scaffolds' channels, and showed further attachment and penetration during cell culture proliferation.

A novel pH-sensitive interferon-β (INF-β) oral delivery system for application in multiple sclerosis.

PubMed

Kondiah, Pierre P D; Tomar, Lomas K; Tyagi, Charu; Choonara, Yahya E; Modi, Girish; du Toit, Lisa C; Kumar, Pradeep; Pillay, Viness

2013-11-18

pH-sensitive microparticles were prepared using trimethyl-chitosan (TMC), poly(ethylene glycol)dimethacrylate (PEGDMA) and methacrylic acid (MAA) by free radical suspension polymerization, for the oral delivery of interferon-β (INF-β). The microparticles were subsequently compressed into a suitable oral tablet formulation. A Box-Behnken experimental design was employed for generating a series of formulations with varying concentrations of TMC (0.05-0.5 g/100 mL) and percentage crosslinker (polyethylene glycol diacrylate) (3-8%, w/w of monomers), for establishment of an optimized TMC-PEGDMA-MAA copolymeric microparticles. For pragmatism, insulin was initially employed as the model peptide for undertaking the preliminary experimentation and the optimized formulation was subsequently evaluated using INF-β. The prepared copolymeric microparticulate system was characterized for its morphological, porositometric and mucoadhesive properties. The optimized microparticles with 0.5 g/100 mL TMC and 3% crosslinker had an INF-β loading efficiency of 53.25%. The in vitro release of INF-β was recorded at 74% and 3% in intestinal (pH 6.8) and gastric (pH 1.2) pH from the oral tablet formulation, respectively. The tablet was further evaluated for plasma concentration of INF-β in the New Zealand White rabbit, and compared to a known subcutaneous formulation. The system showed an astounding effective release profile over 24h with higher INF-β plasma concentrations compared with the subcutaneous injection formulation. Copyright © 2013 Elsevier B.V. All rights reserved.

Flow lithography in ultraviolet-curable polydimethylsiloxane microfluidic chips

PubMed Central

Kim, Junbeom; An, Heseong; Seo, Yoojin; Jung, Youngmee; Lee, Jong Suk; Bong, Ki Wan

2017-01-01

Flow Lithography (FL) is the technique used for the synthesis of hydrogel microparticles with various complex shapes and distinct chemical compositions by combining microfluidics with photolithography. Although polydimethylsiloxane (PDMS) has been used most widely as almost the sole material for FL, PDMS microfluidic chips have limitations: (1) undesired shrinkage due to the thermal expansion of masters used for replica molding and (2) interfacial delamination between two thermally cured PDMS layers. Here, we propose the utilization of ultraviolet (UV)-curable PDMS (X-34-4184) for FL as an excellent alternative material of the conventional PDMS. Our proposed utilization of the UV-curable PDMS offers three key advantages, observed in our study: (1) UV-curable PDMS exhibited almost the same oxygen permeability as the conventional PDMS. (2) The almost complete absence of shrinkage facilitated the fabrication of more precise reverse duplication of microstructures. (3) UV-cured PDMS microfluidic chips were capable of much stronger interfacial bonding so that the burst pressure increased to ∼0.9 MPa. Owing to these benefits, we demonstrated a substantial improvement of productivity in synthesizing polyethylene glycol diacrylate microparticles via stop flow lithography, by applying a flow time (40 ms) an order of magnitude shorter. Our results suggest that UV-cured PDMS chips can be used as a general platform for various types of flow lithography and also be employed readily in other applications where very precise replication of structures on micro- or sub-micrometer scales and/or strong interfacial bonding are desirable. PMID:28469763

Pore Interconnectivity Influences Growth Factor-Mediated Vascularization in Sphere-Templated Hydrogels

PubMed Central

Somo, Sami I.; Akar, Banu; Bayrak, Elif S.; Larson, Jeffery C.; Appel, Alyssa A.; Mehdizadeh, Hamidreza; Cinar, Ali

2015-01-01

Rapid and controlled vascularization within biomaterials is essential for many applications in regenerative medicine. The extent of vascularization is influenced by a number of factors, including scaffold architecture. While properties such as pore size and total porosity have been studied extensively, the importance of controlling the interconnectivity of pores has received less attention. A sintering method was used to generate hydrogel scaffolds with controlled pore interconnectivity. Poly(methyl methacrylate) microspheres were used as a sacrificial agent to generate porous poly(ethylene glycol) diacrylate hydrogels with interconnectivity varying based on microsphere sintering conditions. Interconnectivity levels increased with sintering time and temperature with resultant hydrogel structure showing agreement with template structure. Porous hydrogels with a narrow pore size distribution (130–150 μm) and varying interconnectivity were investigated for their ability to influence vascularization in response to gradients of platelet-derived growth factor-BB (PDGF-BB). A rodent subcutaneous model was used to evaluate vascularized tissue formation in the hydrogels in vivo. Vascularized tissue invasion varied with interconnectivity. At week 3, higher interconnectivity hydrogels had completely vascularized with twice as much invasion. Interconnectivity also influenced PDGF-BB transport within the scaffolds. An agent-based model was used to explore the relative roles of steric and transport effects on the observed results. In conclusion, a technique for the preparation of hydrogels with controlled pore interconnectivity has been developed and evaluated. This method has been used to show that pore interconnectivity can independently influence vascularization of biomaterials. PMID:25603533

Oligo(ethylene glycol)-sidechain microgels prepared in absence of cross-linking agent: Polymerization, characterization and variation of particle deformability.

PubMed

Welsch, Nicole; Lyon, L Andrew

2017-01-01

We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties.

Oligo(ethylene glycol)-sidechain microgels prepared in absence of cross-linking agent: Polymerization, characterization and variation of particle deformability

PubMed Central

Lyon, L. Andrew

2017-01-01

We present a systematic study of self-cross-linked microgels formed by precipitation polymerization of oligo ethylene glycol methacrylates. The cross-linking density of these microgels and, thus, the network flexibility can be easily tuned through the modulation of the reaction temperature during polymerization. Microgels prepared in absence of any difunctional monomer, i.e. cross-linker, show enhanced deformability and particle spreading on solid surfaces as compared to microgels cross-linked with varying amounts of poly(ethylene glycol diacrylate) (PEG-DA) in addition to self-crosslinking. Particles prepared at low reaction temperatures exhibit the highest degree of spreading due to the lightly cross-linked and flexible polymer network. Moreover, AFM force spectroscopy studies suggest that cross-linker-free microgels constitute of a more homogeneous polymer network than PEG-DA cross-linked particles and have elastic moduli at the particle apex that are ~5 times smaller than the moduli of 5 mol-% PEG-DA cross-linked microgels. Resistive pulse sensing experiments demonstrate that microgels prepared at 75 and 80°C without PEG-DA are able to deform significantly to pass through nanopores that are smaller than the microgel size. Additionally, we found that polymer network flexibility of microgels is a useful tool to control the formation of particle dewetting patterns. This offers a promising new avenue for build-up of 2D self-assembled particle structures with patterned chemical and mechanical properties. PMID:28719648

A microfluidic device for evaluating the dynamics of the metabolism-dependent antioxidant activity of nutrients.

PubMed

Lee, Jungwoo; Choi, Jong-ryul; Ha, Sang Keun; Choi, Inwook; Lee, Seung Hwan; Kim, Donghyun; Choi, Nakwon; Sung, Jong Hwan

2014-08-21

Various food components are known for their health-promoting effects. However, their biochemical effects are generally evaluated in vitro, and their actual in vivo effect can vary significantly, depending on their metabolic profiles. To evaluate the effect of the liver metabolism on the antioxidant activity, we have developed a two-compartment microfluidic system that integrates the dynamics of liver metabolism and the subsequent antioxidant activity of food components. In the first compartment of the device, human liver enzyme fractions were immobilized inside a poly(ethylene glycol) diacrylate (PEGDA) hydrogel to mimic the liver metabolism. The radical scavenging activity was evaluated by the change of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) absorbance in the second compartment. Reaction engineering and fluid mechanics principles were used to develop a simplified analytical model and a more complex finite element model, which were used to design the chip and determine the optimal flow conditions. For real-time measurements of the reaction on a chip, we developed a custom-made photospectrometer system with an LED light source. The developed microfluidic system showed a linear and dose-dependent antioxidant activity in response to increasing concentration of flavonoid. We also compared the antioxidant activity of flavonoid after various liver metabolic reactions. This microfluidic system can serve as a novel in vitro platform for predicting the antioxidant activity of various food components in a more physiologically realistic manner, as well as for studying the mechanism of action of such food components.

Immobilizing enzymes onto electrode arrays by hydrogel photolithography to fabricate multi-analyte electrochemical biosensors.

PubMed

Yan, Jun; Pedrosa, Valber A; Simonian, Aleksandr L; Revzin, Alexander

2010-03-01

This paper describes a biomaterial microfabrication approach for interfacing functional biomolecules (enzymes) with electrode arrays. Poly (ethylene glycol) (PEG) hydrogel photopatterning was employed to integrate gold electrode arrays with the enzymes glucose oxidase (GOX) and lactate oxidase (LOX). In this process, PEG diacrylate (DA)-based prepolymer containing enzyme molecules as well as redox species (vinylferrocene) was spin-coated, registered, and UV cross-linked on top of an array of gold electrodes. As a result, enzyme-carrying circular hydrogel structures (600 microm diameter) were fabricated on top of 300 microm diameter gold electrodes. Importantly, when used with multiple masks, hydrogel photolithography allowed us to immobilize GOX and LOX molecules on adjacent electrodes within the same electrode array. Cyclic voltammetry and amperometry were used to characterize biosensor electrode arrays. The response of the biosensor array was linear for up to 20 mM glucose with sensitivity of 0.9 microA cm(-2) mM(-1) and 10 mM lactate with sensitivity of 1.1 microA cm(-2) mM(-1). Importantly, simultaneous detection of glucose and lactate from the same electrode array was demonstrated. A novel strategy for integrating biological and electrical components of a biosensor described in this paper provides the flexibility to spatially resolve and register different biorecognition elements with individual members of a miniature electrode array. Of particular interest to us are future applications of these miniature electrodes for real-time monitoring of metabolite fluxes in the vicinity of living cells.

Synthesis, Characterization, and Visible Light Curing Capacity of Polycaprolactone Acrylate

PubMed Central

Tzeng, Jy-Jiunn; Hsiao, Yi-Ting; Wu, Yun-Ching; Chen, Hsuan; Lee, Shyh-Yuan

2018-01-01

Polycaprolactone (PCL) is drawing increasing attention in the field of medical 3D printing and tissue engineering because of its biodegradability. This study developed polycaprolactone prepolymers that can be cured using visible light. Three PCL acrylates were synthesized: polycaprolactone-530 diacrylate (PCL530DA), glycerol-3 caprolactone triacrylate (Glycerol-3CL-TA), and glycerol-6 caprolactone triacrylate (Glycerol-6CL-TA). PCL530DA has two acrylates, whereas Glycerol-3CL-TA and Glycerol-6CL-TA have three acrylates. The Fourier transform infrared and nuclear magnetic resonance spectra suggested successful synthesis of all PCL acrylates. All are liquid at room temperature and can be photopolymerized into a transparent solid after exposure to 470 nm blue LED light using 1% camphorquinone as photoinitiator and 2% dimethylaminoethyl methacrylate as coinitiator. The degree of conversion for all PCL acrylates can reach more than 80% after 1 min of curing. The compressive modulus of PCL530DA, Glycerol-3CL-TA, and Glycerol-6CL-TA is 65.7 ± 12.7, 80.9 ± 6.1, and 32.1 ± 4.1 MPa, respectively, and their compressive strength is 5.3 ± 0.29, 8.3 ± 0.18, and 3.0 ± 0.53 MPa, respectively. Thus, all PCL acrylates synthesized in this study can be photopolymerized and because of their solid structure and low viscosity, they are applicable to soft tissue engineering and medical 3D printing. PMID:29854803

Flexible transparent displays based on core/shell upconversion nanophosphor-incorporated polymer waveguides

NASA Astrophysics Data System (ADS)

Park, Bong Je; Hong, A.-Ra; Park, Suntak; Kyung, Ki-Uk; Lee, Kwangyeol; Seong Jang, Ho

2017-04-01

Core/shell (C/S)-structured upconversion nanophosphor (UCNP)-incorporated polymer waveguide-based flexible transparent displays are demonstrated. Bright green- and blue-emitting Li(Gd,Y)F4:Yb,Er and Li(Gd,Y)F4:Yb,Tm UCNPs are synthesized via solution chemical route. Their upconversion luminescence (UCL) intensities are enhanced by the formation of C/S structure with LiYF4 shell. The Li(Gd,Y)F4:Yb,Er/LiYF4 and Li(Gd,Y)F4:Yb,Tm/LiYF4 C/S UCNPs exhibit 3.3 and 2.0 times higher UCL intensities than core counterparts, respectively. In addition, NaGdF4:Yb,Tm/NaGdF4:Eu C/S UCNPs are synthesized and they show red emission via energy transfer and migration of Yb3+ → Tm3+ → Gd3+ → Eu3+. The C/S UCNPs are incorporated into bisphenol A ethoxylate diacrylate which is used as a core material of polymer waveguides. The fabricated stripe-type polymer waveguides are highly flexible and transparent (transmittance > 90% in spectral range of 443-900 nm). The polymer waveguides exhibit bright blue, green, and red luminescence, depending on the incorporated UCNPs into the polymer core, under coupling with a near infrared (NIR) laser. Moreover, patterned polymer waveguide-based display devices are fabricated by reactive ion etching process and they realize bright blue-, green-, and red-colored characters under coupling with an NIR laser.

Role of the polymer phase in the mechanics of nacre-like composites

NASA Astrophysics Data System (ADS)

Niebel, Tobias P.; Bouville, Florian; Kokkinis, Dimitri; Studart, André R.

2016-11-01

Although strength and toughness are often mutually exclusive properties in man-made structural materials, nature is full of examples of composite materials that combine these properties in a remarkable way through sophisticated multiscale architectures. Understanding the contributions of the different constituents to the energy dissipating toughening mechanisms active in these natural materials is crucial for the development of strong artificial composites with a high resistance to fracture. Here, we systematically study the influence of the polymer properties on the mechanics of nacre-like composites containing an intermediate fraction of mineral phase (57 vol%). To this end, we infiltrate ceramic scaffolds prepared by magnetically assisted slip casting (MASC) with monomers that are subsequently cured to yield three drastically different polymers: (i) poly(lauryl methacrylate) (PLMA), a soft and weak elastomer; (ii) poly(methyl methacrylate) (PMMA), a strong, stiff and brittle thermoplastic; and (iii) polyether urethane diacrylate-co-poly(2-hydroxyethyl methacrylate) (PUA-PHEMA), a tough polymer of intermediate strength and stiffness. By combining our experimental data with finite element modeling, we find that stiffer polymers can increase the strength of the composite by reducing stress concentrations in the inorganic scaffold. Moreover, infiltrating the scaffolds with tough polymers leads to composites with high crack initiation toughness KIC. An organic phase with a minimum strength and toughness is also required to fully activate the mechanisms programmed within the ceramic structure for a rising R-curve behavior. Our results indicate that a high modulus of toughness is a key parameter for the selection of polymers leading to strong and tough bioinspired nacre-like composites.

Micropatterned Cell–Cell Interactions Enable Functional Encapsulation of Primary Hepatocytes in Hydrogel Microtissues

PubMed Central

Li, Cheri Y.; Stevens, Kelly R.; Schwartz, Robert E.; Alejandro, Brian S.; Huang, Joanne H.

2014-01-01

Drug-induced liver injury is a major cause of drug development failures and postmarket withdrawals. In vitro models that incorporate primary hepatocytes have been shown to be more predictive than model systems which rely on liver microsomes or hepatocellular carcinoma cell lines. Methods to phenotypically stabilize primary hepatocytes ex vivo often rely on mimicry of hepatic microenvironmental cues such as cell–cell interactions and cell–matrix interactions. In this work, we sought to incorporate phenotypically stable hepatocytes into three-dimensional (3D) microtissues, which, in turn, could be deployed in drug-screening platforms such as multiwell plates and diverse organ-on-a-chip devices. We first utilize micropatterning on collagen I to specify cell–cell interactions in two-dimensions, followed by collagenase digestion to produce well-controlled aggregates for 3D encapsulation in polyethylene glycol (PEG) diacrylate. Using this approach, we examined the influence of homotypic hepatocyte interactions and composition of the encapsulating hydrogel, and achieved the maintenance of liver-specific function for over 50 days. Optimally preaggregated structures were subsequently encapsulated using a microfluidic droplet-generator to produce 3D microtissues. Interactions of engineered hepatic microtissues with drugs was characterized by flow cytometry, and yielded both induction of P450 enzymes in response to prototypic small molecules and drug–drug interactions that give rise to hepatotoxicity. Collectively, this study establishes a pipeline for the manufacturing of 3D hepatic microtissues that exhibit stabilized liver-specific functions and can be incorporated into a wide array of emerging drug development platforms. PMID:24498910

Hydroxyapatite implants with designed internal architecture.

PubMed

Chu, T M; Halloran, J W; Hollister, S J; Feinberg, S E

2001-06-01

Porous hydroxyapatite (HA) has been used as a bone graft material in the clinics for decades. Traditionally, the pores in these HAs are either obtained from the coralline exoskeletal patterns or from the embedded organic particles in the starting HA powder. Both processes offer very limited control on the pore structure. A new method for manufacturing porous HA with designed pore channels has been developed. This method is essentially a lost-mold technique with negative molds made with Stereolithography and a highly loaded curable HA suspension as the ceramic carrier. Implants with designed channels and connection patterns were first generated from a Computer-Aided-Design (CAD) software and Computer Tomography (CT) data. The negative images of the designs were used to build the molds on a stereolithography apparatus with epoxy resins. A 40 vol% HA suspension in propoxylated neopentyl glycol diacrylate (PNPGDA) and iso-bornyl acrylate (IBA) was formulated. HA suspension was cast into the epoxy molds and cured into solid at 85 degrees C. The molds and acrylate binders were removed by pyrolysis, followed by HA green body sintering. With this method, implants with six different channel designs were built successfully and the designed channels were reproduced in the sintered HA implants. The channels created in the sintered HA implants were between 366 microm and 968 microm in diameter with standard deviations of 50 microm or less. The porosity created by the channels were between 26% and 52%. The results show that HA implants with designed connection pattern and well controlled channel size can be built with the technique developed in this study. Copyright 2001 Kluwer Academic Publishers

Self-initiation of UV photopolymerization reactions using tetrahalogenated bisphenol A (meth)acrylates.

PubMed

Pelras, Théophile; Knolle, Wolfgang; Naumov, Sergej; Heymann, Katja; Daikos, Olesya; Scherzer, Tom

2017-05-17

The potential of tetrachlorinated and tetrabrominated bisphenol A diacrylates and dimethacrylates for self-initiation of a radical photopolymerization was investigated. The kinetics of the photopolymerization of an acrylic model varnish containing halogenated monomers was studied by real-time FTIR spectroscopy, whereas the formation of reactive species and secondary products was elucidated by laser flash photolysis and product analysis by GC-MS after steady-state photolysis. The interpretation of the experimental data and the analysis of possible reaction pathways were assisted by quantum chemical calculations. It was shown that all halogenated monomers lead to a significant acceleration of the photopolymerization kinetics at a minimum concentration of 5 wt%. Steady-state and laser flash photolysis measurements as well as quantum chemical calculations showed that brominated and chlorinated samples do not follow the same pathway to generate radical species. Whereas chlorinated (meth)acrylates may cleave only at the C-O bonds of the carboxyl groups resulting in acrolein and oxyl radicals for initiation, brominated monomers may cleave either at the C-O bonds or at the C-Br bonds delivering aryl and bromine radicals. The quantum yields for the photolysis of the halogenated monomers were found to be in the order of 0.1 for acrylates and 0.2 for methacrylates (with an estimated error of 25%), independently of the attached Br and Cl halogens. Finally, the trihalogenated bisphenol A di(meth)acrylate radicals and the acrolein radicals were found to show the highest efficiencies for the reaction with another acrylic double bond leading to the formation of a polymer network.

CF4 plasma treatment of poly(dimethylsiloxane): effect of fillers and its application to high-aspect-ratio UV embossing.

PubMed

Yan, Y H; Chan-Park, M B; Yue, C Y

2005-09-13

Surface modification of poly(dimethylsiloxane) (PDMS) was carried out via CF4 plasma treatment. The test PDMS used contains significant amounts of quartz and silica fillers, while the control material is the same PDMS with quartz removed by centrifugation. Fluorination accompanied with roughening was produced on both PDMS surfaces. With short plasma times (15 min or less), a macromolecular fluorocarbon layer was formed on the PDMS surfaces because of the dominant fluorination, leading to significant increase in F concentration, decrease of surface energy, and some roughening. With intermediate plasma times (15-30 min), dynamic balance between fluorination and ablation was achieved, leading to a plateau of the surface roughness, fluorine content, and [F-Si]/[F-C] ratio. At our longest investigated plasma time of 45 min, the plasma ablated the fluorinated covering layer on the PDMS surfaces, leading to significant increase in roughness and [F-Si]/[F-C] ratio and decrease of surface F concentration. The effect of additional quartz in the test PDMS on surface F concentration, [F-Si]/[F-C] ratio, and roughness was dramatic only when ablation was significant (i.e., 45 min). The obtained Teflon-like surface displays long-term stability as opposed to hydrophobic recovery of other plasma-treated PDMS surfaces to increase hydrophilicity. On the basis of the optimized plasma treatment time of 15 min, a microstructured PDMS mold was plasma treated and successfully used for multiple high-aspect-ratio (about 8) UV embossing of nonpolar polypropylene glycol diacrylate (PPGDA) resin.

Photo-Patternable ZnO Thin Films Based on Cross-Linked Zinc Acrylate for Organic/Inorganic Hybrid Complementary Inverters.

PubMed

Jeong, Yong Jin; An, Tae Kyu; Yun, Dong-Jin; Kim, Lae Ho; Park, Seonuk; Kim, Yebyeol; Nam, Sooji; Lee, Keun Hyung; Kim, Se Hyun; Jang, Jaeyoung; Park, Chan Eon

2016-03-02

Complementary inverters consisting of p-type organic and n-type metal oxide semiconductors have received considerable attention as key elements for realizing low-cost and large-area future electronics. Solution-processed ZnO thin-film transistors (TFTs) have great potential for use in hybrid complementary inverters as n-type load transistors because of the low cost of their fabrication process and natural abundance of active materials. The integration of a single ZnO TFT into an inverter requires the development of a simple patterning method as an alternative to conventional time-consuming and complicated photolithography techniques. In this study, we used a photocurable polymer precursor, zinc acrylate (or zinc diacrylate, ZDA), to conveniently fabricate photopatternable ZnO thin films for use as the active layers of n-type ZnO TFTs. UV-irradiated ZDA thin films became insoluble in developing solvent as the acrylate moiety photo-cross-linked; therefore, we were able to successfully photopattern solution-processed ZDA thin films using UV light. We studied the effects of addition of a tiny amount of indium dopant on the transistor characteristics of the photopatterned ZnO thin films and demonstrated low-voltage operation of the ZnO TFTs within ±3 V by utilizing Al2O3/TiO2 laminate thin films or ion-gels as gate dielectrics. By combining the ZnO TFTs with p-type pentacene TFTs, we successfully fabricated organic/inorganic hybrid complementary inverters using solution-processed and photopatterned ZnO TFTs.

Microfabricated poly(ethylene glycol) templates enable rapid screening of triculture conditions for cardiac tissue engineering.

PubMed

Iyer, Rohin K; Chiu, Loraine L Y; Radisic, Milica

2009-06-01

The purpose of this study was to design a simple system for cultivation of micro-scale cardiac organoids and investigate the effects of cellular composition on the organoid function. We hypothesized that cultivation of cardiomyocytes (CM) on preformed networks of fibroblasts (FB) and endothelial cells (EC) would enhance the structural and functional properties of the organoids, compared to simultaneously seeding the three cell types or cultivating enriched CM alone. Microchannels for cell seeding were created by photopolymerization of poly(ethylene glycol) diacrylate. In the preculture group the channels were seeded with a mixture of NIH 3T3 FB and D4T EC, following by addition of neonatal rat CM after 2 days of FB/EC preculture. The control microchannels were seeded simultaneously with FB/EC/CM (simultaneous triculture) or with enriched CM alone (enriched CM). Preculture resulted in cylindrical, contractile, and compact cardiac organoids that contained elongated CM expressing connexin-43 and cardiac troponin I. In contrast, simultaneous triculture resulted in noncontractile organoids with clusters of CM growing separately from elongated FBs and ECs. The staining for Connexin-43 was absent in the simultaneous triculture group. When fixed or frozen FB/EC were utilized as a preculture substrate for CM, noncontractile organoids were obtained; while preculture on a single cell type (either FB or EC) resulted in contractile organoids but with inferior properties compared to preculture with both FB/EC. These results emphasize the importance of living cells, presence of both nonmyocyte cell types as well as sequential seeding approach for cultivation of functional multicell type cardiac organoids. 2008 Wiley Periodicals, Inc.

Process development for waveguide chemical sensors with integrated polymeric sensitive layers

NASA Astrophysics Data System (ADS)

Amberkar, Raghu; Gao, Zhan; Park, Jongwon; Henthorn, David B.; Kim, Chang-Soo

2008-02-01

Due to the proper optical property and flexibility in the process development, an epoxy-based, high-aspect ratio photoresist SU-8 is now attracting attention in optical sensing applications. Manipulation of the surface properties of SU-8 waveguides is critical to attach functional films such as chemically-sensitive layers. We describe a new integration process to immobilize fluorescence molecules on SU-8 waveguide surface for application to intensity-based optical chemical sensors. We use two polymers for this application. Spin-on, hydrophobic, photopatternable silicone is a convenient material to contain fluorophore molecules and to pattern a photolithographically defined thin layer on the surface of SU-8. We use fumed silica powders as an additive to uniformly disperse the fluorophores in the silicone precursor. In general, additional processes are not critically required to promote the adhesion between the SU-8 and silicone. The other material is polyethylene glycol diacrylate (PEGDA). Recently we demonstrated a novel photografting method to modify the surface of SU-8 using a surface bound initiator to control its wettability. The activated surface is then coated with a monomer precursor solution. Polymerization follows when the sample is exposed to UV irradiation, resulting in a grafted PEGDA layer incorporating fluorophores within the hydrogel matrix. Since this method is based the UV-based photografting reaction, it is possible to grow off photolithographically defined hydrogel patterns on the waveguide structures. The resulting films will be viable integrated components in optical bioanalytical sensors. This is a promising technique for integrated chemical sensors both for planar type waveguide and vertical type waveguide chemical sensors.

Probing vocal fold fibroblast response to hyaluronan in 3D contexts.

PubMed

Munoz-Pinto, Dany J; Jimenez-Vergara, Andrea Carolina; Gelves, L Marcela; McMahon, Rebecca E; Guiza-Arguello, Viviana; Hahn, Mariah S

2009-11-01

A number of treatments are being investigated for vocal fold (VF) scar, including designer implants. The aim of the present study was to validate a 3D model system for probing the effects of various bioactive moieties on VF fibroblast (VFF) behavior toward rational implant design. We selected poly(ethylene glycol) diacrylate (PEGDA) hydrogels as our base-scaffold due to their broadly tunable material properties. However, since cells encapsulated in PEGDA hydrogels are generally forced to take on rounded/stellate morphologies, validation of PEGDA gels as a 3D VFF model system required that the present work directly parallel previous studies involving more permissive scaffolds. We therefore chose to focus on hyaluronan (HA), a polysaccharide that has been a particular focus of the VF community. Toward this end, porcine VFFs were encapsulated in PEGDA hydrogels containing consistent levels of high Mw HA (HA(HMW)), intermediate Mw HA (HA(IMW)), or the control polysaccharide, alginate, and cultured for 7 and 21 days. HA(HMW) promoted sustained increases in active ERK1/2 relative to HA(IMW). Furthermore, VFFs in HA(IMW) gels displayed a more myofibroblast-like phenotype, higher elastin production, and greater protein kinase C (PkC) levels at day 21 than VFFs in HA(HMW) and alginate gels. The present results are in agreement with a previous 3D study of VFF responses to HA(IMW) relative to alginate in collagen-based scaffolds permissive of cell elongation, indicating that PEGDA hydrogels may serve as an effective 3D model system for probing at least certain aspects of VFF behavior. Copyright 2009 Wiley Periodicals, Inc.

Rapid 3D printing of anatomically accurate and mechanically heterogeneous aortic valve hydrogel scaffolds

PubMed Central

Hockaday, L A; Kang, K H; Colangelo, N W; Cheung, P Y C; Duan, B; Malone, E; Wu, J; Girardi, L N; Bonassar, L J; Lipson, H; Chu, C C; Butcher, J T

2013-01-01

The aortic valve exhibits complex three-dimensional (3D) anatomy and heterogeneity essential for long-term efficient biomechanical function. These are, however, challenging to mimic in de novo engineered living tissue valve strategies. We present a novel simultaneous 3D-printing/photocrosslinking technique for rapidly engineering complex, heterogeneous aortic valve scaffolds. Native anatomic and axisymmetric aortic valve geometries (root wall and tri-leaflets) with 12 to 22 mm inner diameters (ID) were 3D printed with poly-ethylene glycol-diacrylate (PEG-DA) hydrogels (700 or 8000 MW) supplemented with alginate. 3D printing geometric accuracy was quantified and compared using Micro-CT. Porcine aortic valve interstitial cells (PAVIC) seeded scaffolds were cultured for up to 21 days. Results showed that blended PEG-DA scaffolds could achieve over 10-fold range in elastic modulus (5.3±0.9 to 74.6±1.5 kPa). 3D printing times for valve conduits with mechanically contrasting hydrogels were optimized to 14 to 45 minutes, increasing linearly with conduit diameter. Larger printed valves had greater shape fidelity (93.3±2.6, 85.1±2.0, and 73.3±5.2% for 22, 17, and 12 mm ID porcine valves; 89.1±4.0, 84.1±5.6, and 66.6±5.2% for simplified valves). PAVIC seeded scaffolds maintained near 100% viability over 21 days. These results demonstrate that 3D hydrogel printing with controlled photocrosslinking can rapidly fabricate anatomical heterogeneous valve conduits that support cell engraftment. PMID:22914604

Upconversion Nanoparticles-Encoded Hydrogel Microbeads-Based Multiplexed Protein Detection

NASA Astrophysics Data System (ADS)

Shikha, Swati; Zheng, Xiang; Zhang, Yong

2018-06-01

Fluorescently encoded microbeads are in demand for multiplexed applications in different fields. Compared to organic dye-based commercially available Luminex's xMAP technology, upconversion nanoparticles (UCNPs) are better alternatives due to their large anti-Stokes shift, photostability, nil background, and single wavelength excitation. Here, we developed a new multiplexed detection system using UCNPs for encoding poly(ethylene glycol) diacrylate (PEGDA) microbeads as well as for labeling reporter antibody. However, to prepare UCNPs-encoded microbeads, currently used swelling-based encapsulation leads to non-uniformity, which is undesirable for fluorescence-based multiplexing. Hence, we utilized droplet microfluidics to obtain encoded microbeads of uniform size, shape, and UCNPs distribution inside. Additionally, PEGDA microbeads lack functionality for probe antibodies conjugation on their surface. Methods to functionalize the surface of PEGDA microbeads (acrylic acid incorporation, polydopamine coating) reported thus far quench the fluorescence of UCNPs. Here, PEGDA microbeads surface was coated with silica followed by carboxyl modification without compromising the fluorescence intensity of UCNPs. In this study, droplet microfluidics-assisted UCNPs-encoded microbeads of uniform shape, size, and fluorescence were prepared. Multiple color codes were generated by mixing UCNPs emitting red and green colors at different ratios prior to encapsulation. UCNPs emitting blue color were used to label the reporter antibody. Probe antibodies were covalently immobilized on red UCNPs-encoded microbeads for specific capture of human serum albumin (HSA) as a model protein. The system was also demonstrated for multiplexed detection of both human C-reactive protein (hCRP) and HSA protein by immobilizing anti-hCRP antibodies on green UCNPs.

Hydrogel Microencapsulated Insulin-Secreting Cells Increase Keratinocyte Migration, Epidermal Thickness, Collagen Fiber Density, and Wound Closure in a Diabetic Mouse Model of Wound Healing.

PubMed

Aijaz, Ayesha; Faulknor, Renea; Berthiaume, François; Olabisi, Ronke M

2015-11-01

Wound healing is a hierarchical process of intracellular and intercellular signaling. Insulin is a potent chemoattractant and mitogen for cells involved in wound healing. Insulin's potential to promote keratinocyte growth and stimulate collagen synthesis in fibroblasts is well described. However, there currently lacks an appropriate delivery mechanism capable of consistently supplying a wound environment with insulin; current approaches require repeated applications of insulin, which increase the chances of infecting the wound. In this study, we present a novel cell-based therapy that delivers insulin to the wound area in a constant or glucose-dependent manner by encapsulating insulin-secreting cells in nonimmunogenic poly(ethylene glycol) diacrylate (PEGDA) hydrogel microspheres. We evaluated cell viability and insulin secretory characteristics of microencapsulated cells. Glucose stimulation studies verified free diffusion of glucose and insulin through the microspheres, while no statistical difference in insulin secretion was observed between cells in microspheres and cells in monolayers. Scratch assays demonstrated accelerated keratinocyte migration in vitro when treated with microencapsulated cells. In excisional wounds on the dorsa of diabetic mice, microencapsulated RIN-m cells accelerated wound closure by postoperative day 7; a statistically significant increase over AtT-20ins-treated and control groups. Histological results indicated significantly greater epidermal thickness in both microencapsulated RIN-m and AtT-20ins-treated wounds. The results suggest that microencapsulation enables insulin-secreting cells to persist long enough at the wound site for a therapeutic effect and thereby functions as an effective delivery vehicle to accelerate wound healing.

Resin cements formulated with thio-urethanes can strengthen porcelain and increase bond strength to ceramics.

PubMed

Bacchi, Atais; Spazzin, Aloisio Oro; de Oliveira, Gabriel Rodrigues; Pfeifer, Carmem; Cesar, Paulo Francisco

2018-06-01

The use of thio-urethane oligomers has been shown to significantly improve the mechanical properties of resin cements (RCs). The aim of this study was to use thio-urethane-modified RC to potentially reinforce the porcelain-RC structure and to improve the bond strength to zirconia and lithium disilicate. Six oligomers were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP, P) or trimethylol-tris-3-mercaptopropionate (TMP, T) - with di-functional isocyanates - 1,6-Hexanediol-diissocyante (HDDI) (aliphatic, AL) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic, AR) or Dicyclohexylmethane 4,4'-Diisocyanate (HMDI) (cyclic, CC). Thio-urethanes (20 wt%) were added to a BisGMA/UDMA/TEGDMA organic matrix. Filler was introduced at 60 wt%. The microshear bond strength (μSBS), Weibull modulus (m), and failure pattern of RCs bonded to zirconia (ZR) and lithium disilicate (LD) ceramics was evaluated. Biaxial flexural test and fractographic analysis of porcelain discs bonded to RCs were also performed. The biaxial flexural strength (σ bf ) and m were calculated in the tensile surfaces of porcelain and RC structures (Z = 0 and Z = -t 2 , respectively). The μSBS was improved with RCs formulated with oligomers P_AL or T_AL bonded to LD and P_AL, P_AR or T_CC bonded to zirconia in comparison to controls. Mixed failures predominated in all groups. σ bf had superior values at Z = 0 with RCs formulated with oligomers P_AL, P_AR, T_AL, or T_CC in comparison to control; σ bf increased with all RCs composed by thio-urethanes at Z = -t 2 . Fractographic analysis revealed all fracture origins at Z = 0. The use of specific thio-urethane oligomers as components of RCs increased both the biaxial flexural strength of the porcelain-RC structure and the μSBS to LD and ZR. The current investigation suggests that it is possible to reinforce the porcelain-RC pair and obtain higher bond strength to LD and ZR with RCs formulated with selected types of thio-urethane oligomers. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of cationic side-chains on intracellular delivery and cytotoxicity of pH sensitive polymer-doxorubicin nanocarriers.

PubMed

Fang, Chen; Kievit, Forrest M; Cho, Yong-Chan; Mok, Hyejung; Press, Oliver W; Zhang, Miqin

2012-11-21

Fine-tuning the design of polymer-doxorubicin conjugates permits optimization of an efficient nanocarrier to greatly increase intracellular uptake and cytotoxicity. Here, we report synthesis of a family of self-assembled polymer-doxorubicin nanoparticles and an evaluation of the effects of various types of side-chains on intracellular uptake and cytotoxicity of the nanocarriers for lymphoma cells. Monomers with three different cationic side-chains (CA) and pK(a)'s, i.e., a guanidinium group (Ag), an imidazole group (Im), and a tertiary amine group (Dm), were comparatively investigated. The cationic monomer, poly(ethylene glycol) (PEG), and doxorubicin (Dox) were reacted with 1,4-(butanediol) diacrylate (BUDA) to prepare a poly(β-amino ester) (PBAE) polymer via Michael addition. All three polymer-Dox conjugates spontaneously formed nanoparticles (NP) through hydrophobic interactions between doxorubicin in aqueous solution, resulting in NP-Im/Dox, NP-Ag/Dox, and NP-Dm/Dox, with hydrodynamic sizes below 80 nm. Doxorubicin was linked to all 3 types of NPs with a hydrazone bond to assure selective release of doxorubicin only at acidic pH, as it occurs in the tumor microenvironment. Both NP-Im/Dox and NP-Ag/Dox exhibited much higher intracellular uptake by Ramos cells (Burkitt's lymphoma) than NP-Dm/Dox, suggesting that the type of side chain in the NPs determines the extent of intracellular uptake. As a result, NP-Im/Dox and NP-Ag/Dox showed cytotoxicity that was comparable to free Dox in vitro. Our findings suggest that the nature of surface cationic group on nanocarriers may profoundly influence their intracellular trafficking and resulting therapeutic efficacy. Thus, it is a crucial factor to be considered in the design of novel carriers for intracellular drug delivery.

Rare Earth Element Recovery from Low-Grade Feedstocks Using Engineered E. coli

NASA Astrophysics Data System (ADS)

Brewer, A. W.; Park, D.; Jiao, Y.

2017-12-01

Rare earth elements (REEs) are critical materials for emerging science and technology industries, especially in the field of clean energy. However, their supply is potentially at risk due to political and economic concerns. The exploitation of new, low-grade REE sources in the United States, such as geothermal brines and mine tailings, may help to mitigate that supply risk. To purify and concentrate REEs from these sources, we have developed a biosorption approach using engineered E. coli cells that express a lanthanide binding tag on the cell surface. This tag has a high selectivity for REEs that enhances the native cell wall adsorption properties; the terbium adsorption capacity was increased approximately 2-fold, and the REE surface affinity was increased compared to all non-REE metals except copper. This biosorption method offers advantages over conventional REE extraction methods as it is inexpensive, environmentally friendly, and effective with low-grade feedstocks. In order to expand this method to an industrial scale, the cells must be contained in a durable material that permits the cell surfaces to function in a variety of bioreactor systems and to be reused through multiple adsorption and desorption cycles. Polyethylene glycol diacrylate (PEGDA) beads, with diameters from 200-400 um, can be impregnated with high concentrations of cells, and show promise in the selective adsorption of REEs from solution. In the future, the application of the adsorptive qualities of these engineered cells may be expanded to include other valuable metals, such as indium and gallium, to further develop the economic potential of this approach. Prepared by LLNL under Contract DE-AC52-07NA27344. LLNL-ABS-736022.

3D bioprinting mesenchymal stem cell-laden construct with core-shell nanospheres for cartilage tissue engineering

NASA Astrophysics Data System (ADS)

Zhu, Wei; Cui, Haitao; Boualam, Benchaa; Masood, Fahed; Flynn, Erin; Rao, Raj D.; Zhang, Zhi-Yong; Zhang, Lijie Grace

2018-05-01

Cartilage tissue is prone to degradation and has little capacity for self-healing due to its avascularity. Tissue engineering, which provides artificial scaffolds to repair injured tissues, is a novel and promising strategy for cartilage repair. 3D bioprinting offers even greater potential for repairing degenerative tissue by simultaneously integrating living cells, biomaterials, and biological cues to provide a customized scaffold. With regard to cell selection, mesenchymal stem cells (MSCs) hold great capacity for differentiating into a variety of cell types, including chondrocytes, and could therefore be utilized as a cartilage cell source in 3D bioprinting. In the present study, we utilize a tabletop stereolithography-based 3D bioprinter for a novel cell-laden cartilage tissue construct fabrication. Printable resin is composed of 10% gelatin methacrylate (GelMA) base, various concentrations of polyethylene glycol diacrylate (PEGDA), biocompatible photoinitiator, and transforming growth factor beta 1 (TGF-β1) embedded nanospheres fabricated via a core-shell electrospraying technique. We find that the addition of PEGDA into GelMA hydrogel greatly improves the printing resolution. Compressive testing shows that modulus of the bioprinted scaffolds proportionally increases with the concentrations of PEGDA, while swelling ratio decreases with the increase of PEGDA concentration. Confocal microscopy images illustrate that the cells and nanospheres are evenly distributed throughout the entire bioprinted construct. Cells grown on 5%/10% (PEGDA/GelMA) hydrogel present the highest cell viability and proliferation rate. The TGF-β1 embedded in nanospheres can keep a sustained release up to 21 d and improve chondrogenic differentiation of encapsulated MSCs. The cell-laden bioprinted cartilage constructs with TGF-β1-containing nanospheres is a promising strategy for cartilage regeneration.

[Contact dermatitis from polyacrylate in TENS electrode].

PubMed

Weber-Muller, F; Reichert-Penetrat, S; Schmutz, J-L; Barbaud, A

2004-05-01

Transcutaneous electric nerve stimulation (TENS) is useful for many chronic pains. It induces few serious side effects, but skin reactions are not rare. We report on two cases of contact dermatitis due to TENS electrodes by sensitization to the acrylate in TENS conductive gel. A 50 year-old man suffered from post-traumatic lumbar pair. He developed eczematous lesions on the sites where the TENS electrodes were applied. Patch tests were positive with the TENS gel, with ethylene glycol dimethylacrylate (2 p. 100 petrolatum) and ethyl-acrylate (2 p. 100 petrolatum) on day 2 and 4 readings. A 54 Year-old man had a paralysis of the foot elevator following rupture of an aneurysm. After 2 months, he had an eczema on the sites where the TENS electrodes were applied. Patch tests were negative with the TENS electrodes but positive with 2-hydroxyethyl acrylate (0.1 p. 100 petrolatum), triethyleneglycol diacrylate (0.1 p. 100 petrolatum), 2-hydroxyethyl methacrylate (2 p. 100 petrolatum) and 2-hydroxypropyl methacrylate (2 p. 100 petrolatum) on day 2 and 4 readings. TENS transmits small electrical currents through the skin that induce the depolarization of the affected sensory nerve endings. They have few serious side effects but skin reactions such as irritation, burns or allergy to propylene glycol in the electrode gel, to the rubber of the electrodes (mercaptobenzothiazole) or to the metallic part of the electrodes, i.e. nickel, are not uncommon. To our knowledge, only one case of an allergy to the polyacrylates of TENS electrode gel has been previously reported in the literature. We emphasize that acrylate could be the main sensitizer in the more recently commercialized TENS electrodes and will propose alternative ways of treating patients sensitized to acrylate and who require treatment with TENS.

Differential polymer structure tunes mechanism of cellular uptake and transfection routes of poly(β-amino ester) polyplexes in human breast cancer cells.

PubMed

Kim, Jayoung; Sunshine, Joel C; Green, Jordan J

2014-01-15

Successful gene delivery with nonviral particles has several barriers, including cellular uptake, endosomal escape, and nuclear transport. Understanding the mechanisms behind these steps is critical to enhancing the effectiveness of gene delivery. Polyplexes formed with poly(β-amino ester)s (PBAEs) have been shown to effectively transfer DNA to various cell types, but the mechanism of their cellular uptake has not been identified. This is the first study to evaluate the uptake mechanism of PBAE polyplexes and the dependence of cellular uptake on the end group and molecular weight of the polymer. We synthesized three different analogues of PBAEs with the same base polymer poly(1,4-butanediol diacrylate-co-4-amino-1-butanol) (B4S4) but with small changes in the end group or molecular weight. We quantified the uptake and transfection efficiencies of the pDNA polyplexes formulated from these polymers in hard-to-transfect triple negative human breast cancer cells (MDA-MB 231). All polymers formed positively charged (10-17 mV) nanoparticles of ∼200 nm in size. Cellular internalization of all three formulations was inhibited the most (60-90% decrease in cellular uptake) by blocking caveolae-mediated endocytosis. Greater inhibition was shown with polymers that had a 1-(3-aminopropyl)-4-methylpiperazine end group (E7) than the others with a 2-(3-aminopropylamino)-ethanol end group (E6) or higher molecular weight. However, caveolae-mediated endocytosis was generally not as efficient as clathrin-mediated endocytosis in leading to transfection. These findings indicate that PBAE polyplexes can be used to transfect triple negative human breast cancer cells and that small changes to the same base polymer can modulate their cellular uptake and transfection routes.

Effect of oxygen, moisture and illumination on the stability and reliability of dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) OTFTs during operation and storage.

PubMed

Ding, Ziqian; Abbas, Gamal; Assender, Hazel E; Morrison, John J; Yeates, Stephen G; Patchett, Eifion R; Taylor, D Martin

2014-09-10

We report a systemic study of the stability of organic thin film transistors (OTFTs) both in storage and under operation. Apart from a thin polystyrene buffer layer spin-coated onto the gate dielectric, the constituent parts of the OTFTs were all prepared by vacuum evaporation. The OTFTs are based on the semiconducting small molecule dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) deposited onto the surface of a polystyrene-buffered in situ polymerized diacrylate gate insulator. Over a period of 9 months, no degradation of the hole mobility occurred in devices stored either in the dark in dry air or in uncontrolled air and normal laboratory fluorescent lighting conditions. In the latter case, rather than decreasing, the mobility actually increased almost 2-fold to 1.5 cm(2)/(V · s). The devices also showed good stability during repeat on/off cycles in the dark in dry air. Exposure to oxygen and light during the on/off cycles led to a positive shift of the transfer curves due to electron trapping when the DNTT was biased into depletion by the application of positive gate voltage. When operated in accumulation, negative gate voltage under the same conditions, the transfer curves were stable. When voltage cycling in moist air in the dark, the transfer curves shifted to negative voltages, thought to be due to the generation of hole traps either in the semiconductor or its interface with the dielectric layer. When subjected to gate bias stress in dry air in the dark for at least 144 h, the device characteristics remained stable.

Superhydrophobic Copper Surfaces with Anticorrosion Properties Fabricated by Solventless CVD Methods.

PubMed

Vilaró, Ignasi; Yagüe, Jose L; Borrós, Salvador

2017-01-11

Due to continuous miniaturization and increasing number of electrical components in electronics, copper interconnections have become critical for the design of 3D integrated circuits. However, corrosion attack on the copper metal can affect the electronic performance of the material. Superhydrophobic coatings are a commonly used strategy to prevent this undesired effect. In this work, a solventless two-steps process was developed to fabricate superhydrophobic copper surfaces using chemical vapor deposition (CVD) methods. The superhydrophobic state was achieved through the design of a hierarchical structure, combining micro-/nanoscale domains. In the first step, O 2 - and Ar-plasma etchings were performed on the copper substrate to generate microroughness. Afterward, a conformal copolymer, 1H,1H,2H,2H-perfluorodecyl acrylate-ethylene glycol diacrylate [p(PFDA-co-EGDA)], was deposited on top of the metal via initiated CVD (iCVD) to lower the surface energy of the surface. The copolymer topography exhibited a very characteristic and unique nanoworm-like structure. The combination of the nanofeatures of the polymer with the microroughness of the copper led to achievement of the superhydrophobic state. AFM, SEM, and XPS were used to characterize the evolution in topography and chemical composition during the CVD processes. The modified copper showed water contact angles as high as 163° and hysteresis as low as 1°. The coating withstood exposure to aggressive media for extended periods of time. Tafel analysis was used to compare the corrosion rates between bare and modified copper. Results indicated that iCVD-coated copper corrodes 3 orders of magnitude slower than untreated copper. The surface modification process yielded repeatable and robust superhydrophobic coatings with remarkable anticorrosion properties.

Tuning mechanical performance of poly(ethylene glycol) and agarose interpenetrating network hydrogels for cartilage tissue engineering.

PubMed

Rennerfeldt, Deena A; Renth, Amanda N; Talata, Zsolt; Gehrke, Stevin H; Detamore, Michael S

2013-11-01

Hydrogels are attractive for tissue engineering applications due to their incredible versatility, but they can be limited in cartilage tissue engineering applications due to inadequate mechanical performance. In an effort to address this limitation, our team previously reported the drastic improvement in the mechanical performance of interpenetrating networks (IPNs) of poly(ethylene glycol) diacrylate (PEG-DA) and agarose relative to pure PEG-DA and agarose networks. The goal of the current study was specifically to determine the relative importance of PEG-DA concentration, agarose concentration, and PEG-DA molecular weight in controlling mechanical performance, swelling characteristics, and network parameters. IPNs consistently had compressive and shear moduli greater than the additive sum of either single network when compared to pure PEG-DA gels with a similar PEG-DA content. IPNs withstood a maximum stress of up to 4.0 MPa in unconfined compression, with increased PEG-DA molecular weight being the greatest contributing factor to improved failure properties. However, aside from failure properties, PEG-DA concentration was the most influential factor for the large majority of properties. Increasing the agarose and PEG-DA concentrations as well as the PEG-DA molecular weight of agarose/PEG-DA IPNs and pure PEG-DA gels improved moduli and maximum stresses by as much as an order of magnitude or greater compared to pure PEG-DA gels in our previous studies. Although the viability of encapsulated chondrocytes was not significantly affected by IPN formulation, glycosaminoglycan (GAG) content was significantly influenced, with a 12-fold increase over a three-week period in gels with a lower PEG-DA concentration. These results suggest that mechanical performance of IPNs may be tuned with partial but not complete independence from biological performance of encapsulated cells. © 2013 Elsevier Ltd. All rights reserved.

Mechanical Properties, Cytocompatibility and Manufacturability of Chitosan:PEGDA Hybrid-Gel Scaffolds by Stereolithography.

PubMed

Morris, Viola B; Nimbalkar, Siddharth; Younesi, Mousa; McClellan, Phillip; Akkus, Ozan

2017-01-01

Extracellular matrix mimetic hydrogels which hybridize synthetic and natural polymers offer molecularly-tailored, bioactive properties and tunable mechanical strength. In addition, 3D bioprinting by stereolithography allows fabrication of internal pores and defined macroscopic shapes. In this study, we formulated a hybrid biocompatible resin using natural and synthetic polymers (chitosan and polyethylene glycol diacrylate (PEGDA), respectively) by controlling molecular weight of chitosan, feed-ratios, and photo-initiator concentration. Ear-shaped, hybrid scaffolds were fabricated by a stereolithographic method using a 405 nm laser. Hybrid hydrogel scaffolds of chitosan (50-190 kDa) and PEGDA (575 Da) were mixed at varying feed-ratios. Some of the cationic, amino groups of chitosan were neutralized by dialysis in acidic solution containing chitosan in excess of sodium acetate solution to inhibit quenching of newly formed photoradicals. A feed-ratio of 1:7.5 was found to be the most appropriate of the formulations considered in this study in terms of mechanical properties, cell adhesion, and printability. The biofabricated hybrid scaffold showed interconnected, homogeneous pores with a nominal pore size of 50 µm and an elastic modulus of ~400 kPa. Moreover, long-term cell viability and cell spreading was observed via actin filament staining. Printability of the biocompatible resin was confirmed by printing thresholded MR images of an ear and the feed ratio of 1:7.5 provided the most faithful reproduction of the shape. To the best of our knowledge, this is the first report of stereolithographic printing hybridizing cell-adhesive properties of chitosan with mechanical robustness of PEG in scaffolds suitable for repair of complex tissue geometries, such as those of the human ear.

Preconditioning of mesenchymal stromal cells toward nucleus pulposus-like cells by microcryogels-based 3D cell culture and syringe-based pressure loading system.

PubMed

Zeng, Yang; Feng, Siyu; Liu, Wei; Fu, Qinyouen; Li, Yaqian; Li, Xiaokang; Chen, Chun; Huang, Chenyu; Ge, Zigang; Du, Yanan

2017-04-01

To precondition mesenchymal stromal/stem cells (MSCs) with mechanical stimulation may enhance cell survival and functions following implantation in load bearing environment such as nucleus pulposus (NP) in intervertebral disc (IVD). In this study, preconditioning of MSCs toward NP-like cells was achieved in previously developed poly (ethylene glycol) diacrylate (PEGDA) microcryogels (PMs) within a syringe-based three-dimensional (3D) culture system which provided a facile and cost-effective pressure loading approach. PMs loaded with alginate and MSCs could be incubated in a sealable syringe which could be air-compressed to apply pressure loading through a programmable syringe pump. Expression levels of chondrogenic marker genes SOX9, COL II, and ACAN were significantly upregulated in MSCs when pressure loading of 0.2 MPa or 0.8 MPa was implemented. Expression levels of COL I and COL X were downregulated when pressure loading was applied. In a nude mouse model, MSCs loaded in PMs mechanically stimulated for three days were subcutaneously injected using the same culture syringe. Three weeks postinjection, more proteoglycans (PGs) were deposited and more SOX9 and COL II but less COL I and COL X were stained in 0.2 MPa group. Furthermore, injectable MSCs-loaded PMs were utilized in an ex vivo rabbit IVD organ culture model that demonstrated the leak-proof function and enhanced cell retention of PMs assisted cell delivery to a load bearing environment for potential NP regeneration. This microcryogels-based 3D cell culture and syringe-based pressure loading system represents a novel method for 3D cell culture with mechanical stimulation for better function. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 507-520, 2017. © 2015 Wiley Periodicals, Inc.

Effect of cationic side-chains on intracellular delivery and cytotoxicity of pH sensitive polymer-doxorubicin nanocarriers

NASA Astrophysics Data System (ADS)

Fang, Chen; Kievit, Forrest M.; Cho, Yong-Chan; Mok, Hyejung; Press, Oliver W.; Zhang, Miqin

2012-10-01

Fine-tuning the design of polymer-doxorubicin conjugates permits optimization of an efficient nanocarrier to greatly increase intracellular uptake and cytotoxicity. Here, we report synthesis of a family of self-assembled polymer-doxorubicin nanoparticles and an evaluation of the effects of various types of side-chains on intracellular uptake and cytotoxicity of the nanocarriers for lymphoma cells. Monomers with three different cationic side-chains (CA) and pKa's, i.e., a guanidinium group (Ag), an imidazole group (Im), and a tertiary amine group (Dm), were comparatively investigated. The cationic monomer, poly(ethylene glycol) (PEG), and doxorubicin (Dox) were reacted with 1,4-(butanediol) diacrylate (BUDA) to prepare a poly(β-amino ester) (PBAE) polymer via Michael addition. All three polymer-Dox conjugates spontaneously formed nanoparticles (NP) through hydrophobic interactions between doxorubicin in aqueous solution, resulting in NP-Im/Dox, NP-Ag/Dox, and NP-Dm/Dox, with hydrodynamic sizes below 80 nm. Doxorubicin was linked to all 3 types of NPs with a hydrazone bond to assure selective release of doxorubicin only at acidic pH, as it occurs in the tumor microenvironment. Both NP-Im/Dox and NP-Ag/Dox exhibited much higher intracellular uptake by Ramos cells (Burkitt's lymphoma) than NP-Dm/Dox, suggesting that the type of side chain in the NPs determines the extent of intracellular uptake. As a result, NP-Im/Dox and NP-Ag/Dox showed cytotoxicity that was comparable to free Dox in vitro. Our findings suggest that the nature of surface cationic group on nanocarriers may profoundly influence their intracellular trafficking and resulting therapeutic efficacy. Thus, it is a crucial factor to be considered in the design of novel carriers for intracellular drug delivery.

Synthesis of stiffness-tunable and cell-responsive Gelatin-poly(ethylene glycol) hydrogel for three-dimensional cell encapsulation.

PubMed

Cao, Ye; Lee, Bae Hoon; Peled, Havazelet Bianco; Venkatraman, Subbu S

2016-10-01

Biosynthetic poly(ethylene glycol) (PEG)-based hydrogels have been extensively investigated as extracellular matrix (ECM) mimicking gels as they retain the benefits of both ECM (biological cues) and synthetic hydrogels (tunable mechanical properties). In this article, we developed and characterized a new gelatin-PEG (GP) hydrogel that retains the benefits of gelatin and synthetic hydrogels. In this strategy, the thiolation of gelatin was accomplished by reacting with Traut's reagent; the thiolated gelatin was then conjugated to one end of PEG diacrylate (PEGDA) by Michael-type addition reaction. Two kinds of GP precursors, GP30 and GP60, were synthesized by changing the amount of Traut's reagent, while the weight ratio between thiolated-gelatin and PEGDA of GP30 and GP60 was 1.451:1 and 0.785:1, respectively. Finally, neonatal human dermal fibroblasts were encapsulated into the hydrogel by cross-linking the remaining double bonds of precursor under ultraviolet light. These GP hydrogels can encapsulate the fibroblasts in situ with high cell viability. Moreover, the behaviors of cells within the GP hydrogels can be modulated by varying the cross-linking density of GP hydrogel (storage modulus from 40 to 2000 Pa). In particular, this article showed that a minimum amount of cell-binding motifs (gelatin >2.30 wt/vol % and 44.0% dry weight percentage) are required for attachment; and appropriate initial rheological and structural properties (storage modulus <∼100 Pa and mesh size >∼150 nm) can accelerate the attachment of cells and improve cell viability. Hence, this mixed-hydrogel platform allows an easily control hydrogel structure and modulates cell behavior to reconstruct new tissue in the three-dimensional microenvironments. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2401-2411, 2016. © 2016 Wiley Periodicals, Inc.

Fabrication of poly(ethylene glycol) hydrogel microstructures using photolithography

NASA Technical Reports Server (NTRS)

Revzin, A.; Russell, R. J.; Yadavalli, V. K.; Koh, W. G.; Deister, C.; Hile, D. D.; Mellott, M. B.; Pishko, M. V.

2001-01-01

The fabrication of hydrogel microstructures based upon poly(ethylene glycol) diacrylates, dimethacrylates, and tetraacrylates patterned photolithographically on silicon or glass substrates is described. A silicon/silicon dioxide surface was treated with 3-(trichlorosilyl)propyl methacrylate to form a self-assembled monolayer (SAM) with pendant acrylate groups. The SAM presence on the surface was verified using ellipsometry and time-of-flight secondary ion mass spectrometry. A solution containing an acrylated or methacrylated poly(ethylene glycol) derivative and a photoinitiator (2,2-dimethoxy-2-phenylacetophenone) was spin-coated onto the treated substrate, exposed to 365 nm ultraviolet light through a photomask, and developed with either toluene, water, or supercritical CO2. As a result of this process, three-dimensional, cross-linked PEG hydrogel microstructures were immobilized on the surface. Diameters of cylindrical array members were varied from 600 to 7 micrometers by the use of different photomasks, while height varied from 3 to 12 micrometers, depending on the molecular weight of the PEG macromer. In the case of 7 micrometers diameter elements, as many as 400 elements were reproducibly generated in a 1 mm2 square pattern. The resultant hydrogel patterns were hydrated for as long as 3 weeks without delamination from the substrate. In addition, micropatterning of different molecular weights of PEG was demonstrated. Arrays of hydrogel disks containing an immobilized protein conjugated to a pH sensitive fluorophore were also prepared. The pH sensitivity of the gel-immobilized dye was similar to that in an aqueous buffer, and no leaching of the dye-labeled protein from the hydrogel microstructure was observed over a 1 week period. Changes in fluorescence were also observed for immobilized fluorophore labeled acetylcholine esterase upon the addition of acetyl acholine.

Self-Supporting Nanoclay as Internal Scaffold Material for Direct Printing of Soft Hydrogel Composite Structures in Air.

PubMed

Jin, Yifei; Liu, Chengcheng; Chai, Wenxuan; Compaan, Ashley; Huang, Yong

2017-05-24

Three dimensional (3D) bioprinting technology enables the freeform fabrication of complex constructs from various hydrogels and is receiving increasing attention in tissue engineering. The objective of this study is to develop a novel self-supporting direct hydrogel printing approach to extrude complex 3D hydrogel composite structures in air without the help of a support bath. Laponite, a member of the smectite mineral family, is investigated to serve as an internal scaffold material for the direct printing of hydrogel composite structures in air. In the proposed printing approach, due to its yield-stress property, Laponite nanoclay can be easily extruded through a nozzle as a liquid and self-supported after extrusion as a solid. Its unique crystal structure with positive and negative charges enables it to be mixed with many chemically and physically cross-linked hydrogels, which makes it an ideal internal scaffold material for the fabrication of various hydrogel structures. By mixing Laponite nanoclay with various hydrogel precursors, the hydrogel composites retain their self-supporting capacity and can be printed into 3D structures directly in air and retain their shapes before cross-linking. Then, the whole structures are solidified in situ by applying suitable cross-linking stimuli. The addition of Laponite nanoclay can effectively improve the mechanical and biological properties of hydrogel composites. Specifically, the addition of Laponite nanoclay results in a significant increase in the Young's modulus of each hydrogel-Laponite composite: 1.9-fold increase for the poly(ethylene glycol) diacrylate (PEGDA)-Laponite composite, 7.4-fold increase for the alginate-Laponite composite, and 3.3-fold increase for the gelatin-Laponite composite.

3D bioprinting mesenchymal stem cell-laden construct with core-shell nanospheres for cartilage tissue engineering.

PubMed

Zhu, Wei; Cui, Haitao; Boualam, Benchaa; Masood, Fahed; Flynn, Erin; Rao, Raj D; Zhang, Zhi-Yong; Zhang, Lijie Grace

2018-05-04

Cartilage tissue is prone to degradation and has little capacity for self-healing due to its avascularity. Tissue engineering, which provides artificial scaffolds to repair injured tissues, is a novel and promising strategy for cartilage repair. 3D bioprinting offers even greater potential for repairing degenerative tissue by simultaneously integrating living cells, biomaterials, and biological cues to provide a customized scaffold. With regard to cell selection, mesenchymal stem cells (MSCs) hold great capacity for differentiating into a variety of cell types, including chondrocytes, and could therefore be utilized as a cartilage cell source in 3D bioprinting. In the present study, we utilize a tabletop stereolithography-based 3D bioprinter for a novel cell-laden cartilage tissue construct fabrication. Printable resin is composed of 10% gelatin methacrylate (GelMA) base, various concentrations of polyethylene glycol diacrylate (PEGDA), biocompatible photoinitiator, and transforming growth factor beta 1 (TGF-β1) embedded nanospheres fabricated via a core-shell electrospraying technique. We find that the addition of PEGDA into GelMA hydrogel greatly improves the printing resolution. Compressive testing shows that modulus of the bioprinted scaffolds proportionally increases with the concentrations of PEGDA, while swelling ratio decreases with the increase of PEGDA concentration. Confocal microscopy images illustrate that the cells and nanospheres are evenly distributed throughout the entire bioprinted construct. Cells grown on 5%/10% (PEGDA/GelMA) hydrogel present the highest cell viability and proliferation rate. The TGF-β1 embedded in nanospheres can keep a sustained release up to 21 d and improve chondrogenic differentiation of encapsulated MSCs. The cell-laden bioprinted cartilage constructs with TGF-β1-containing nanospheres is a promising strategy for cartilage regeneration.

Involvement of the BLT2 receptor in the itch-associated scratching induced by 12-(S)-lipoxygenase products in ICR mice

PubMed Central

Kim, H J; Kim, D K; Kim, H; Koh, J Y; Kim, K M; Noh, M S; Lee, S; Kim, S; Park, S H; Kim, J J; Kim, S Y; Lee, C H

2008-01-01

Background and purpose: Recently, we reported that 12(S)-HPETE (12(S)-hydroperoxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid) induces scratching in ICR mice. We hypothesized that 12(S)-HPETE might act as an agonist of the low-affinity leukotriene B4 receptor BLT2. To confirm the involvement of the BLT2 receptor in 12(S)-HPETE-induced scratching, we studied the scratch response using the BLT2 receptor agonists compound A (4′-{[pentanoyl (phenyl) amino]methyl}-1,1′-biphenyl-2-carboxylic acid) and 12(S)-HETE (12(S)-hydroxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid). Experimental approach: A video recording was used to determine whether the BLT2 receptor agonists caused itch-associated scratching in ICR mice. Selective antagonists and several chemicals were used. Key results: Both 12(S)-HETE and compound A dose dependently induced scratching in the ICR mice. The dose–response curve for compound A showed peaks at around 0.005–0.015 nmol per site. Compound A- and 12(S)-HETE-induced scratching was suppressed by capsaicin and naltrexon. We examined the suppressive effects of U75302 (6-[6-(3-hydroxy-1E,5Z-undecadienyl)-2-pyridinyl]-1,5-hexanediol, the BLT1 receptor antagonist) and LY255283 (1-[5-ethyl-2-hydroxy-4-[[6-methyl-6-(1H-tetrazol-5-yl)heptyl]oxy]phenyl]-ethanone, the BLT2 receptor antagonist) on the BLT2 agonist-induced scratching. LY255283 suppressed compound A- and 12(S)-HETE-induced scratching, but U75302 did not. LY255283 required a higher dose to suppress the compound A-induced scratching than it did to suppress the 12(S)-HETE-induced scratching. One of the BLT2 receptor agonists, 12(R)-HETE (12(R)-hydroxyeicosa-5Z,8Z,10E,14Z-tetraenoic acid), also induced scratching in the ICR mice. Conclusions and implications: Our present results corroborate the hypothesis that the BLT2 receptor is involved in 12(S)-lipoxygenase-product-induced scratching in ICR mice. We also confirmed that this animal model could be a valuable means of evaluating the effects of BLT2 receptor antagonists. PMID:18536755

Catalytic Conversion of Renewable Resources into Bulk and Fine Chemicals.

PubMed

de Vries, Johannes G

2016-12-01

Several strategies can be chosen to convert renewable resources into chemicals. In this account, I exemplify the route that starts with so-called platform chemicals; these are relatively simple chemicals that can be produced in high yield, directly from renewable resources, either via fermentation or via chemical routes. They can be converted into the existing bulk chemicals in a very efficient manner using multistep catalytic conversions. Two examples are given of the conversion of sugars into nylon intermediates. 5-Hydroxymethylfurfural (HMF) can be prepared in good yield from fructose. Two hydrogenation steps convert HMF into 1,6-hexanediol. Oppenauer oxidation converts this product into caprolactone, which in the past, has been converted into caprolactam in a large-scale industrial process by reaction with ammonia. An even more interesting platform chemical is levulinic acid (LA), which can be obtained directly from lignocellulose in good yield by treatment with dilute sulfuric acid at 200°C. Hydrogenation converts LA into gamma-valerolactone, which is ring-opened and esterified in a gas-phase process to a mixture of isomeric methyl pentenoates in excellent selectivity. In a remarkable selective palladium-catalysed isomerising methoxycarbonylation, this mixture is converted in to dimethyl adipate, which is finally hydrolysed to adipic acid. Overall selectivities of both processes are extremely high. The conversion of lignin into chemicals is a much more complicated task in view of the complex nature of lignin. It was discovered that breakage of the most prevalent β-O-4 bond in lignin occurs not only via the well-documented C3 pathway, but also via a C2 pathway, leading to the formation of highly reactive phenylacetaldehydes. These compounds went largely unnoticed as they immediately recondense on lignin. We have now found that it is possible to prevent this by converting these aldehydes in a tandem reaction, as they are formed. For this purpose, we have used three different methods: acetalisation, hydrogenation, and decarbonylation. These reactions were first established in the tandem reactions of model compounds, but subsequently, we were able to show that this works equally well on organosolv lignin and even on lignocellulose. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anticorrosive organic/inorganic hybrid coatings

NASA Astrophysics Data System (ADS)

Gao, Tongzhai

Organic/inorganic hybrid coating system was developed for anticorrosion applications using polyurea, polyurethane or epoxide as the organic phase and polysiloxane, formed by sol-gel process, as the inorganic phase. Polyurea/polysiloxane hybrid coatings were formulated and moisture cured using HDI isocyanurate, alkoxysilane-functionalized HDI isocyanurate, and tetraethyl orthosilicate (TEOS) oligomers. Two urethanes were prepared using the same components as abovementioned in addition to the oligoesters derived from either cyclohexane diacids (CHDA) and 2-butyl-2-ethyl-1,3-propanediol (BEPD) or adipic acid (AA), isophthalic acid (IPA), 1,6-hexanediol (HD), and trimethylol propane (TMP). Accelerated weathering and outdoor exposure were performed to study the weatherability of the polyurethane/polysiloxane hybrid coating system. FTIR and solid-state 13C NMR revealed that the degradation of the hybrid coatings occurred at the urethane and ester functionalities of the organic phase. DMA and DSC analyses showed the glass transition temperature increased and broadened after weathering. SEM was employed to observe the change of morphology of the hybrid coatings and correlated with the gloss variation after weathering. Rutile TiO2 was formulated into polyurethane/polysiloxane hybrid coatings in order to investigate the effect of pigmentation on the coating properties and the sol-gel precursor. Chemical interaction between the TiO2 and the sol-gel precursor was investigated using solid-state 29Si NMR and XPS. The morphology, mechanical, viscoelastic, thermal properties of the pigmented coatings were evaluated as a function of pigmentation volume concentration (PVC). Using AFM and SEM, the pigment were observed to be well dispersed in the polymer matrix. The thermal stability, the tensile modulus and strength of the coatings were enhanced with increasing PVC, whereas the pull-off adhesion and flexibility were reduced with increasing PVC. Finally, the pigmented coatings were evaluated by electrochemical impedance spectroscopy (EIS) and the results showed that 10 wt% pigmentation improved the corrosion resistance of the entire coating system. The effect of pigmentation on epoxide/polysiloxane hybrid coatings was also investigated. The epoxide was successfully modified using 3-(triethoxysilyl) propyl isocyanate (TEOSPI) as indicated by FTIR and NMR. Good dispersion of the pigment particles was achieved as revealed by the SEM images. The tensile modulus, tensile strength, pencil hardness and thermal stability of the hybrid coatings were improved while the flexibility and pull-off adhesion were deteriorated when increasing PVC.

Integration of Stem Cell to Chondrocyte-Derived Cartilage Matrix in Healthy and Osteoarthritic States in the Presence of Hydroxyapatite Nanoparticles.

PubMed

Dua, Rupak; Comella, Kristin; Butler, Ryan; Castellanos, Glenda; Brazille, Bryn; Claude, Andrew; Agarwal, Arvind; Liao, Jun; Ramaswamy, Sharan

2016-01-01

We investigated the effectiveness of integrating tissue engineered cartilage derived from human bone marrow derived stem cells (HBMSCs) to healthy as well as osteoarthritic cartilage mimics using hydroxyapatite (HA) nanoparticles immersed within a hydrogel substrate. Healthy and diseased engineered cartilage from human chondrocytes (cultured in agar gels) were integrated with human bone marrow stem cell (HBMSC)-derived cartilaginous engineered matrix with and without HA, and evaluated after 28 days of growth. HBMSCs were seeded within photopolymerizable poly (ethylene glycol) diacrylate (PEGDA) hydrogels. In addition, we also conducted a preliminary in vivo evaluation of cartilage repair in rabbit knee chondral defects treated with subchondral bone microfracture and cell-free PEGDA with and without HA. Under in vitro conditions, the interfacial shear strength between tissue engineered cartilage derived from HBMSCs and osteoarthritic chondrocytes was significantly higher (p < 0.05) when HA nanoparticles were incorporated within the HBMSC culture system. Histological evidence confirmed a distinct spatial transition zone, rich in calcium phosphate deposits. Assessment of explanted rabbit knees by histology demonstrated that cellularity within the repair tissues that had filled the defects were of significantly higher number (p < 0.05) when HA was used. HA nanoparticles play an important role in treating chondral defects when osteoarthritis is a co-morbidity. We speculate that the calcified layer formation at the interface in the osteoarthritic environment in the presence of HA is likely to have attributed to higher interfacial strength found in vitro. From an in vivo standpoint, the presence of HA promoted cellularity in the tissues that subsequently filled the chondral defects. This higher presence of cells can be considered important in the context of accelerating long-term cartilage remodeling. We conclude that HA nanoparticles play an important role in engineered to native cartilage integration and cellular processes.

Folic acid conjugated cross-linked acrylic polymer (FA-CLAP) hydrogel for site specific delivery of hydrophobic drugs to cancer cells.

PubMed

Pillai, Jisha Jayadevan; Thulasidasan, Arun Kumar Theralikattu; Anto, Ruby John; Chithralekha, Devika Nandan; Narayanan, Ashwanikumar; Kumar, Gopalakrishnapillai Sankaramangalam Vinod

2014-07-15

The hydrogel based system is found to be rarely reported for the delivery of hydrophobic drug due to the incompatibility of hydrophilicity of the polymer network and the hydrophobicity of drug. This problem can be solved by preparing semi-interpenetrating network of cross-linked polymer for tuning the hydrophilicity so as to entrap the hydrophobic drugs. The current study is to develop a folic acid conjugated cross-linked pH sensitive, biocompatible polymeric hydrogel to achieve a site specific drug delivery. For that, we have synthesized a folic acid conjugated PEG cross-linked acrylic polymer (FA-CLAP) hydrogel and investigated its loading and release of curcumin. The formed polymer hydrogel was then conjugated with folic acid for the site specific delivery of curcumin to cancer cells and then further characterized and conducted the cell uptake and cytotoxicity studies on human cervical cancer cell lines (HeLa). In this study, we synthesized folic acid conjugated cross-linked acrylic hydrogel for the delivery of hydrophobic drugs to the cancer site. Poly (ethyleneglycol) (PEG) diacrylate cross-linked acrylic polymer (PAA) was prepared via inverse emulsion polymerization technique and later conjugated it with folic acid (FA-CLAP). Hydrophobic drug curcumin is entrapped into it and investigated the entrapment efficiency. Characterization of synthesized hydogel was done by using Fourier Transform-Infrared spectroscopy (FT-IR), Transmission Electron Microscopy (TEM), Differential Scanning Calorimetry (DSC). Polymerization and folate conjugation was confirmed by FT-IR spectroscopy. The release kinetics of drug from the entrapped form was studied which showed initial burst release followed by sustained release due to swelling and increased cross-linking. In vitro cytotoxicity and cell uptake studies were conducted in human cervical cancer (HeLa) cell lines. Results showed that curcumin entrapped folate conjugated cross-linked acrylic polymer (FA-CLAP) hydrogel showed higher cellular uptake than the non folate conjugated form. So this can be suggested as a better delivery system for site specific release of hydrophobic cancer drugs.

Electron-beam-initiated polymerization of poly(ethylene glycol)-based wood impregnants.

PubMed

Trey, Stacy M; Netrval, Julia; Berglund, Lars; Johansson, Mats

2010-11-01

The current study demonstrates that methacrylate and acrylate poly(ethylene glycol) (PEG) functional oligomers can be effectively impregnated into wood blocks, and cured efficiently to high conversions without catalyst by e-beam radiation, allowing for less susceptibility to leaching, and favorable properties including higher Brinell hardness values. PEG based monomers were chosen because there is a long history of this water-soluble monomer being able to penetrate the cell wall, thus bulking it and decreasing the uptake of water which further protects the wood from fungal attack. Diacrylate, dimethacrylate, and dihydroxyl functional PEG of M(w) 550-575, of concentrations 0, 30, 60, and 100 wt % in water, were vacuum pressure impregnated into Scots Pine blocks of 15 × 25 × 50 mm in an effort to bulk the cell wall. The samples were then irradiated and compared with nonirradiated samples. It was shown by IR, DSC that the acrylate polymers were fully cured to much higher conversions than can be reached with conventional methods. Leaching studies indicated a much lower amount of oligomer loss from the cured vinyl functional PEG chains in comparison to hydroxyl functional PEG indicating a high degree of fastening of the polymer in the wood. The Brinell hardness indicated a significant increase in hardness to hardwood levels in the modified samples compared to the samples of hydroxyl functional PEG and uncured vinyl PEG samples, which actually became softer than the untreated Scots Pine. By monitoring the dimensions of the sample it was found by weight percent gain calculations (WPG %) that water helps to swell the wood structure and allow better access of the oligomers into the cell wall. Further, the cure shrinkage of the wood samples demonstrated infiltration of the oligomers into the cell wall as this was not observed for methyl methacrylate which is well-documented to remain in the lumen. However, dimensional stability of the vinyl polymer modified blocks when placed in water was not observed to the same extent as PEG.

Electrospun meshes possessing region-wise differences in fiber orientation, diameter, chemistry and mechanical properties for engineering bone-ligament-bone tissues.

PubMed

Samavedi, Satyavrata; Vaidya, Prasad; Gaddam, Prudhvidhar; Whittington, Abby R; Goldstein, Aaron S

2014-12-01

Although bone-patellar tendon-bone (B-PT-B) autografts are the gold standard for repair of anterior cruciate ligament ruptures, they suffer from drawbacks such as donor site morbidity and limited supply. Engineered tissues modeled after B-PT-B autografts are promising alternatives because they have the potential to regenerate connective tissue and facilitate osseointegration. Towards the long-term goal of regenerating ligaments and their bony insertions, the objective of this study was to construct 2D meshes and 3D cylindrical composite scaffolds - possessing simultaneous region-wise differences in fiber orientation, diameter, chemistry and mechanical properties - by electrospinning two different polymers from off-set spinnerets. Using a dual drum collector, 2D meshes consisting of an aligned polycaprolactone (PCL) fiber region, randomly oriented poly(lactide-co-glycolide) (PLGA) fiber region and a transition region (comprised of both PCL and PLGA fibers) were prepared, and region-wise differences were confirmed by microscopy and tensile testing. Bone marrow stromal cells (BMSCs) cultured on these meshes exhibited random orientations and low aspect ratios on the random PLGA regions, and high aspect ratios and alignment on the aligned PCL regions. Next, meshes containing an aligned PCL region flanked by two transition regions and two randomly oriented PLGA regions were prepared and processed into 3D cylindrical composite scaffolds using an interpenetrating photo-crosslinkable polyethylene glycol diacrylate hydrogel to recapitulate the shape of B-PT-B autografts. Tensile testing indicated that cylindrical composites were mechanically robust, and eventually failed due to stress concentration in the aligned PCL region. In summary, this study demonstrates a process to fabricate electrospun meshes possessing region-wise differences in properties that can elicit region-dependent cell responses, and be readily processed into scaffolds with the shape of B-PT-B autografts. © 2014 Wiley Periodicals, Inc.

Tissue engineering approaches for studying the effect of biochemical and physiological stimuli on cell behavior

NASA Astrophysics Data System (ADS)

Jimenez Vergara, Andrea Carolina

Tissue engineering (TE) approaches have emerged as an alternative to traditional tissue and organ replacements. The aim of this work was to contribute to the understanding of the effects of cell-material and endothelial cell (EC) paracrine signaling on cell responses using poly(ethylene glycol) diacrylate (PEGDA) hydrogels as a material platform. Three TE applications were explored. First, the effect of glycosaminoglycan (GAG) identity was evaluated for vocal fold restoration. Second, the influence of GAG identity was explored and a novel approach for stable endothelialization was developed for vascular graft applications. Finally, EC paracrine signaling in the presence of cyclic stretch, and hydrophobicity and inorganic content were studied for osteogenic applications. In terms of vocal fold restoration, it was found that vocal fold fibroblast (VFF) phenotype and extracellular matrix (ECM) production were impacted by GAG identity. VFF phenotype was preserved in long-term cultured hydrogels containing high molecular weight hyaluronan (HAHMW). Furthermore, collagen I deposition, fibronectin production and smooth muscle α-actin (SM-α-actin) expression in PEG-HA, PEG-chondroitin sulfate C and PEG-heparan sulfate (HS) gels suggest that CSC and HS may be undesirable for vocal fold implants. Regarding vascular graft applications, the impact of GAG identity on smooth muscle cell (SMC) foam cell formation was explored. Results support the increasing body of literature that suggests a critical role for dermatan sulfate (DS)-bearing proteoglycans in early atherosclerosis. In addition, an approach for fabricating bi-layered tissue engineering vascular grafts (TEVGs) with stable endothelialization was validated using PEGDA as an intercellular “cementing” agent between adjacent endothelial cells (ECs). Finally, mesenchymal stem cell (MSC) differentiation toward osteogenic like cells was evaluated. ECM and cell phenotypic data showed that elevated scaffold inorganic content and hydrophobicity were indeed correlated with increased osteogenic differentiation. Moreover, the present results suggest that EC paracrine signaling enhances MSC osteogenesis in the presence of cyclic stretch.

Optimum 3D Matrix Stiffness for Maintenance of Cancer Stem Cells Is Dependent on Tissue Origin of Cancer Cells

PubMed Central

Jabbari, Esmaiel; Sarvestani, Samaneh K.; Daneshian, Leily; Moeinzadeh, Seyedsina

2015-01-01

Introduction The growth and expression of cancer stem cells (CSCs) depend on many factors in the tumor microenvironment. The objective of this work was to investigate the effect of cancer cells’ tissue origin on the optimum matrix stiffness for CSC growth and marker expression in a model polyethylene glycol diacrylate (PEGDA) hydrogel without the interference of other factors in the microenvironment. Methods Human MCF7 and MDA-MB-231 breast carcinoma, HCT116 colorectal and AGS gastric carcinoma, and U2OS osteosarcoma cells were used. The cells were encapsulated in PEGDA gels with compressive moduli in the 2-70 kPa range and optimized cell seeding density of 0.6x106 cells/mL. Micropatterning was used to optimize the growth of encapsulated cells with respect to average tumorsphere size. The CSC sub-population of the encapsulated cells was characterized by cell number, tumorsphere size and number density, and mRNA expression of CSC markers. Results The optimum matrix stiffness for growth and marker expression of CSC sub-population of cancer cells was 5 kPa for breast MCF7 and MDA231, 25 kPa for colorectal HCT116 and gastric AGS, and 50 kPa for bone U2OS cells. Conjugation of a CD44 binding peptide to the gel stopped tumorsphere formation by cancer cells from different tissue origin. The expression of YAP/TAZ transcription factors by the encapsulated cancer cells was highest at the optimum stiffness indicating a link between the Hippo transducers and CSC growth. The optimum average tumorsphere size for CSC growth and marker expression was 50 μm. Conclusion The marker expression results suggest that the CSC sub-population of cancer cells resides within a niche with optimum stiffness which depends on the cancer cells’ tissue origin. PMID:26168187

Antibody loaded collapsible hyaluronic acid hydrogels for intraocular delivery.

PubMed

Egbu, Raphael; Brocchini, Steve; Khaw, Peng T; Awwad, Sahar

2018-03-01

Injectable gels have the potential to encapsulate drugs for sustained release of protein therapeutics for use in the eye. Hyaluronic acid (HA) is a biodegradable clinically used material and poly N-isopropylacrylamide (pNIPAAM) is a stimuli responsive polymer that can display a lower critical solution temperature (LCST) at physiological conditions. Two gel systems incorporating HA were prepared in the presence of the antibody infliximab (INF): i) 1% and 5% tyramine-substituted HA (HA-Tyr) was enzymatically crosslinked in the presence of INF to form HA-Tyr-INF and ii) NIPAAM was chemically crosslinked in the presence of HA and INF with 1 and 3% poly(ethylene glycol) diacrylate (PEGDA) to form PEGDA-pNIPAAM-HA-INF. The PEGDA-pNIPAAM-HA-INF hydrogels displayed LCSTs at temperatures ranging from 31.4 ± 0.2 to 35.7 ± 0.3 °C. Although all the gels prepared were injectable, INF-loaded gels with lower crosslinking density (1% PEGDA-pNIPAAM-HA and 1% HA-Tyr) showed lower elastic (G') and viscous (G″) moduli compared to higher crosslinked gels (3% PEGDA-pNIPAAM-HA-INF and 5% HA-Tyr-INF) resulting in differences in swelling ratio (SR). Moduli may be correlated with overall stiffness of the gel. All hydrogels demonstrated sustained release of INF in a two-compartment in vitro outflow model of the human eye called the PK-Eye. The 1% PEGDA-pNIPAAM-HA-INF hydrogel displayed the slowest release (24.9 ± 0.4% INF release by day 9) in phosphate buffered saline (PBS, pH 7.4), which is a better release profile than the free drug alone (tested under the same conditions). These results suggest that PEGDA-pNIPAAM-HA has potential for the continued development of formulations to prolong the intraocular release of proteins. Copyright © 2017 Elsevier B.V. All rights reserved.

Biologically engineered protein-graft-poly(ethylene glycol) hydrogels: A cell-adhesive and plasmin-degradable biosynthetic material for tissue repair

NASA Astrophysics Data System (ADS)

Halstenberg, Sven

2002-01-01

The goal of the research presented in this dissertation was to create a biomimetic artificial material that exhibits functions of extracellular matrix relevant for improved nerve regeneration. Neural adhesion peptides were photoimmobilized on highly crosslinked poly(ethylene glycol)-based substrates that were otherwise non-adhesive. Neurons adhered in two-dimensional patterns for eleven hours, but no neurites extended. To enable neurite extension and nerve regeneration in three dimensions, and to address the need for specifically cell adhesive and cell degradable materials for clinical applications in tissue repair in general, an artificial protein was recombinantly expressed and purified that consisted of a repeating amino acid sequence based on fibrinogen and anti-thrombin III. The recombinant protein contained integrin-binding RGD sites, plasmin degradation sites, heparin binding sites, and six thiol-containing cysteine residues as grafting sites for poly(ethylene glycol) diacrylate via Michael-type conjugate addition. The resulting protein-graft-poly(ethylene glycol)acrylates were crosslinked by photopolymerization to form hydrogels. Although three-dimensional, RGD mediated and serine protease-dependent ingrowth of human fibroblasts into protein-graft-poly(ethylene glycol) hydrogels occurred, only surface neurite outgrowth was observed from chick dorsal root ganglia. Axonal outgrowth depended on the concentration of matrix-bound heparin, suggesting that improved mechanical strength of the hydrogels and possible immobilization of neuroactive factors due to the presence of heparin promoted neurite outgrowth. Together, the above results show that specific biological functions can be harnessed by protein-graft-poly(ethylene glycol) hydrogels to serve as matrices for tissue repair and regeneration. In particular, the two design objectives, specific cell adhesion and degradability by cell-associated proteases, were fulfilled by the material. In the future, this and similar artificial protein-graft-poly(ethylene glycol) materials with varying protein elements for improved wound healing might serve as biosynthetic implant materials or wound dressings that degrade in synchrony with the formation of a variety of target tissues.

ATR technique, an appropriate method for determining the degree of conversion in dental giomers

NASA Astrophysics Data System (ADS)

Prejmerean, Cristina; Prodan, Doina; Vlassa, Mihaela; Streza, Mihaela; Buruiana, Tinca; Colceriu, Loredana; Prejmerean, Vasile; Cuc, Stanca; Moldovan, Marioara

2016-12-01

Dental light-curing giomers were developed to combine the favourable properties of diacrylic resin composites (DRCs) and glass-ionomer cements (GICs) in a single material and to eliminate their inherent drawbacks. Giomers are characterized by their aesthetic appearance, high mechanical properties, adhesion to dental tissues as well as fluoride release and recharge abilities. The qualities of the giomers are greatly influenced by the level of conversion of the component resins. Infrared spectroscopy is one of the most largely used techniques for the determination of the degree of conversion in resin-based dental materials. However different results were obtained due to the performances of the used methods. The present work presents the determination of conversion degree in a series of dental copolymers and their corresponding giomers using transmission Fourier transform infrared spectroscopy (FTIR) and an attenuated total reflection technique (ATR) technique, respectively, the main aim being the study of the influence of the materials composition and of the light curing modes upon the achieved conversion in the cured giomers. Beautifil II commercial giomer was used as a control. A halogen lamp and a diode-blue LED lamp were used for the curing of the materials. The results showed that the composition of the resins greatly influenced the conversion. The highest conversions (up to 79%) were obtained in the case of the experimental giomers which contained the experimental Bis-GMA urethane analogue, followed by the Beautifil II giomer (61%) and experimental giomers based on commercial Bis-GMA (up to 50%), respectively. The resins light-cured by using the diode-blue LED lamp presented slightly higher conversions than the resins cured by halogen lamp. The study demonstrates the possibility to evaluate easily and reproducibly the conversion in light-curing composite materials with complex chemical composition and structure, particularly in the case of giomers by using the ATR technique.

A novel bioprinting method and system for forming hybrid tissue engineering constructs.

PubMed

Shanjani, Y; Pan, C C; Elomaa, L; Yang, Y

2015-12-18

Three dimensional (3D) bioprinting is a promising approach to form tissue engineering constructs (TECs) via positioning biomaterials, growth factors, and cells with controlled spatial distribution due to its layer-by-layer manufacturing nature. Hybrid TECs composed of relatively rigid porous scaffolds for structural and mechanical integrity and soft hydrogels for cell- and growth factor-loading have a tremendous potential to tissue regeneration under mechanical loading. However, despite excessive progress in the field, the current 3D bioprinting techniques and systems fall short in integration of such soft and rigid multifunctional components. Here we present a novel 3D hybrid bioprinting technology (Hybprinter) and its capability enabling integration of soft and rigid components for TECs. Hybprinter employs digital light processing-based stereolithography (DLP-SLA) and molten material extrusion techniques for soft and rigid materials, respectively. In this study, poly-ethylene glycol diacrylate (PEGDA) and poly-(ε-caprolactone) (PCL) were used as a model material for soft hydrogel and rigid scaffold, respectively. It was shown that geometrical accuracy, swelling ratio and mechanical properties of the hydrogel component can be tailored by DLP-SLA module. We have demonstrated the printability of variety of complex hybrid construct designs using Hybprinter technology and characterized the mechanical properties and functionality of such constructs. The compressive mechanical stiffness of a hybrid construct (90% hydrogel) was significantly higher than hydrogel itself (∼6 MPa versus 100 kPa). In addition, viability of cells incorporated within the bioprinted hybrid constructs was determined approximately 90%. Furthermore, a functionality of a hybrid construct composed of porous scaffold with an embedded hydrogel conduit was characterized for vascularized tissue engineering applications. High material diffusion and high cell viability in about 2.5 mm distance surrounding the conduit indicated that culture media effectively diffused through the conduit and fed the cells. The results suggest that the developed technology is potent to form functional TECs composed of rigid and soft biomaterials.

Novel system for pulse radiolysis with multi-angle light scattering detection (PR-MALLS) - concept, construction and first tests

NASA Astrophysics Data System (ADS)

Kadlubowski, S.; Sawicki, P.; Sowinski, S.; Rokita, B.; Bures, K. D.; Rosiak, J. M.; Ulanski, P.

2018-01-01

Time-resolved pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is an effective method for rapidly generating free radicals and other transient species in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. When used for polymer solutions, pulse radiolysis can be coupled with light-scattering detection, creating a powerful tool for kinetic and mechanistic analysis of processes like degradation or cross-linking of macromolecules. Changes in the light scattering intensity (LSI) of polymer solutions are indicative of alterations in the molecular weight and/or in the radius of gyration, i.e., the dimensions and shape of the macromolecules. In addition to other detection methods, LSI technique provides a convenient tool to study radiation-induced alterations in macromolecules as a function of time after the pulse. Pulse radiolysis systems employing this detection mode have been so far constructed to follow light scattered at a single angle (typically the right angle) to the incident light beam. Here we present an advanced pulse radiolysis & multi-angle light-scattering-intensity system (PR-MALLS) that has been built at IARC and is currently in the phase of optimization and testing. Idea of its design and operation is described and preliminary results for radiation-induced degradation of pullulan as well as polymerization and crosslinking of poly(ethylene glycol) diacrylate are presented. Implementation of the proposed system provides a novel research tool, which is expected to contribute to the expansion of knowledge on free-radical reactions in monomer- and polymer solutions, by delivering precise kinetic data on changes in molecular weight and size, and thus allowing to formulate or verify reaction mechanisms. The proposed method is universal and can be applied for studying both natural and synthetic polymers. The developed system can be also valuable in studies of the border of biology and medicine, especially on radical reactions of biopolymers and their conformational transitions. Furthermore, capability to follow fast changes in mass and dimensions of nanobjects may be of significant importance for nanoscience and nanotechnology.

3D scanning and 3D printing as innovative technologies for fabricating personalized topical drug delivery systems.

PubMed

Goyanes, Alvaro; Det-Amornrat, Usanee; Wang, Jie; Basit, Abdul W; Gaisford, Simon

2016-07-28

Acne is a multifactorial inflammatory skin disease with high prevalence. In this work, the potential of 3D printing to produce flexible personalised-shape anti-acne drug (salicylic acid) loaded devices was demonstrated by two different 3D printing (3DP) technologies: Fused Deposition Modelling (FDM) and stereolithography (SLA). 3D scanning technology was used to obtain a 3D model of a nose adapted to the morphology of an individual. In FDM 3DP, commercially produced Flex EcoPLA™ (FPLA) and polycaprolactone (PCL) filaments were loaded with salicylic acid by hot melt extrusion (HME) (theoretical drug loading - 2% w/w) and used as feedstock material for 3D printing. Drug loading in the FPLA-salicylic acid and PCL-salicylic acid 3D printed patches was 0.4% w/w and 1.2% w/w respectively, indicating significant thermal degradation of drug during HME and 3D printing. Diffusion testing in Franz cells using a synthetic membrane revealed that the drug loaded printed samples released <187μg/cm(2) within 3h. FPLA-salicylic acid filament was successfully printed as a nose-shape mask by FDM 3DP, but the PCL-salicylic acid filament was not. In the SLA printing process, the drug was dissolved in different mixtures of poly(ethylene glycol) diacrylate (PEGDA) and poly(ethylene glycol) (PEG) that were solidified by the action of a laser beam. SLA printing led to 3D printed devices (nose-shape) with higher resolution and higher drug loading (1.9% w/w) than FDM, with no drug degradation. The results of drug diffusion tests revealed that drug diffusion was faster than with the FDM devices, 229 and 291μg/cm(2) within 3h for the two formulations evaluated. In this study, SLA printing was the more appropriate 3D printing technology to manufacture anti-acne devices with salicylic acid. The combination of 3D scanning and 3D printing has the potential to offer solutions to produce personalised drug loaded devices, adapted in shape and size to individual patients. Copyright © 2016 Elsevier B.V. All rights reserved.

A dual electrochemical microsensor for simultaneous imaging of oxygen and pH over the rat kidney surface.

PubMed

Ha, Yejin; Myung, Dongshin; Shim, Jun Ho; Kim, Myung Hwa; Lee, Youngmi

2013-09-21

In this study, a dual microsensing electrochemical probe for measuring oxygen (O2) and pH levels was developed based on a dual recessed Pt disk electrode (each disk diameter, 10 μm) with the use of two Ag/AgCl reference electrodes (one for each disk of the dual electrode). One of the recessed Pt disks of the dual electrode was electrodeposited with a porous Pt layer and then coated with a hydrophobic photocured polymer (partially fluorinated epoxy diacrylate, abbreviated as FED). The Pt-FED covered disk was used as an amperometric O2 sensor and exhibited a linear current increase that was proportional to the PO2 level (partial O2 pressure) with high sensitivity (168.4 ± 33.8 pA mmHg(-1)) and fast response time (t90% = 0.17 ± 0.05 s). The other recessed Pt disk was electrodeposited with an IrO2 layer. The potential between the IrO2 deposited electrode and the Ag/AgCl reference electrode produced a reliable Nernstian response to pH changes (58.3 ± 1.5 mV pH(-1)) with a t90% of 0.43 ± 0.09 s. The sensor displayed high stability in the in vitro organ tissue measurements for at least 2.5 h. By using the developed dual O2/pH microsensor as a probe tip for scanning electrochemical microscopy, the two-dimensional images of the location-dependent PO2 and pH levels were simultaneously acquired and could be used to assess the surface of a rat kidney tissue slice. When compared to the corresponding medullary levels, both PO2 and pH were observed to be higher in the cortex area, while the modest level gradient was observed near the cortex-medulla border. This finding suggests that there is a direct relationship between the tissue O2 supply/consumption and pH, which is mainly determined by metabolite, such as CO2, production.

Polymeric nanoparticles as cancer-specific DNA delivery vectors to human hepatocellular carcinoma.

PubMed

Zamboni, Camila G; Kozielski, Kristen L; Vaughan, Hannah J; Nakata, Maisa M; Kim, Jayoung; Higgins, Luke J; Pomper, Martin G; Green, Jordan J

2017-10-10

Hepatocellular carcinoma (HCC) is the third most deadly cancer in the US, with a meager 5-year survival rate of <20%. Such unfavorable numbers are closely related to the heterogeneity of the disease and the unsatisfactory therapies currently used to manage patients with invasive HCC. Outside of the clinic, gene therapy research is evolving to overcome the poor responses and toxicity associated with standard treatments. The inadequacy of gene delivery vectors, including poor intracellular delivery and cell specificity, are major barriers in the gene therapy field. Herein, we described a non-viral strategy for effective and cancer-specific DNA delivery to human HCC using biodegradable poly(beta-amino ester) (PBAE) nanoparticles (NPs). Varied PBAE NP formulations were evaluated for transfection efficacy and cytotoxicity to a range of human HCC cells as well as healthy human hepatocytes. To address HCC heterogeneity, nine different sources of human HCC cells were utilized. The polymeric NPs composed of 2-((3-aminopropyl)amino) ethanol end-modified poly(1,5-pentanediol diacrylate-co-3-amino-1-propanol) ('536') at a 25 polymer-to-DNA weight-to-weight ratio led to high transfection efficacy to all of the liver cancer lines, but not to hepatocytes. Each individual HCC line had a significantly higher percentage of exogenous gene expression than the healthy liver cells (P<0.01). Notably, this biodegradable end-modified PBAE gene delivery vector was not cytotoxic and maintained the viability of hepatocytes above 80%. In a HCC/hepatocyte co-culture model, in which cancerous and healthy cells share the same micro-environment, 536 25 w/w NPs specifically transfected cancer cells. PBAE NP administration to a subcutaneous HCC mouse model, established with one of the human lines tested in vitro, confirmed effective DNA transfection in vivo. PBAE-based NPs enabled high and preferential DNA delivery to HCC cells, sparing healthy hepatocytes. These biodegradable and liver cancer-selective NPs are a promising technology to deliver therapeutic genes to liver cancer. Copyright © 2017 Elsevier B.V. All rights reserved.

Biomimetic hydrogels gate transport of calcium ions across cell culture inserts.

PubMed

Kotanen, Christian N; Wilson, A Nolan; Wilson, Ann M; Ishihara, Kazuhiko; Guiseppi-Elie, Anthony

2012-06-01

Control of the in vitro spatiotemporal availability of calcium ions is one means by which the microenvironments of hematopoietic stem cells grown in culture may be reproduced. The effects of cross-linking density on the diffusivity of calcium ions through cell culture compatible poly(2-hydroxyethyl methacrylate) [poly(HEMA)]-based bioactive hydrogels possessing 1.0 mol% 2-methacryloyloxyethyl phosphorylcholine (MPC), 5 mol% N,N-(dimethylamino)ethylmethacrylate (DMAEMA) and ca. 17 mol% n-butyl acrylate (n-BA) have been investigated to determine if varying cross-link density is a viable approach to controlling transport of calcium across hydrogel membranes. Cross-linking density was varied by changing the composition of cross-linker, tetraethyleneglycol diacrylate (TEGDA). The hydrogel membranes were formed by sandwich casting onto the external surface of track-etched polycarbonate membranes (T = 10 μm, φ = 0.4 μm pores) of cell culture inserts, polymerized in place by UV light irradiation and immersed in buffered (0.025 HEPES, pH 7.4) 0.10 M calcium chloride solution. The transport of calcium ions across the hydrogel membrane was monitored using a calcium ion selective electrode set within the insert. Degree of hydration (21.6 ± 1.0%) and void fraction were found to be constant across all cross-linking densities. Diffusion coefficients, determined using time-lag analysis, were shown to be strongly dependent on and to exponentially decrease with increasing cross-linking density. Compared to that found in buffer (2.0-2.5 × 10⁻⁶ cm²/s), diffusion coefficients ranged from 1.40 × 10⁻⁶ cm²/s to 1.80 × 10⁻⁷ cm²/s and tortuosity values ranged from 1.7 to 10.0 for the 1 and 12 mol% TEGDA cross-linked hydrogels respectively. Changes in tortuosity arising from variations in cross-link density were found to be the primary modality for controlling diffusivity through novel n-BA containing poly(HEMA)-based bioactive hydrogels.

Bioactive Hydrogels Made from Step-Growth Derived PEG-Peptide Macromers

PubMed Central

Miller, Jordan S.; Shen, Colette J.; Legant, Wesley R.; Baranski, Jan D.; Blakely, Brandon L.; Chen, Christopher S.

2010-01-01

Synthetic hydrogels based on poly(ethylene glycol) (PEG) have been used as biomaterials for cell biology and tissue engineering investigations. Bioactive PEG-based gels have largely relied on heterobifunctional or multi-arm PEG precursors that can be difficult to synthesize and characterize or expensive to obtain. Here, we report an alternative strategy, which instead uses inexpensive and readily available PEG precursors to simplify reactant sourcing. This new approach provides a robust system in which to probe cellular interactions with the microenvironment. We used the step-growth polymerization of PEG diacrylate (PEGDA, 3400 Da) with bis-cysteine matrix metalloproteinase (MMP)-sensitive peptides via Michael-type addition to form biodegradable photoactive macromers of the form acrylate-PEG-(peptide-PEG)m-acrylate. The molecular weight (MW) of these macromers is controlled by the stoichiometry of the reaction, with a high proportion of resultant macromer species greater than 500 kDa. In addition, the polydispersity of these materials was nearly identical for three different MMP-sensitive peptide sequences subjected to the same reaction conditions. When photopolymerized into hydrogels, these high MW materials exhibit increased swelling and sensitivity to collagenase-mediated degradation as compared to previously published PEG hydrogel systems. Cell-adhesive acrylate-PEG-CGRGDS was synthesized similarly and its immobilization and stability in solid hydrogels was characterized with a modified Lowry assay. To illustrate the functional utility of this approach in a biological setting, we applied this system to develop materials that promote angiogenesis in an ex vivo aortic arch explant assay. We demonstrate the formation and invasion of new sprouts mediated by endothelial cells into the hydrogels from embedded embryonic chick aortic arches. Furthermore, we show that this capillary sprouting and three-dimensional migration of endothelial cells can be tuned by engineering the MMP-susceptibility of the hydrogels and the presence of functional immobilized adhesive ligands (CGRGDS vs. CGRGES peptide). The facile chemistry described and significant cellular responses observed suggest the usefulness of these materials in a variety of in vitro and ex vivo biologic investigations, and may aid in the design or refinement of material systems for a range of tissue engineering approaches. PMID:20138664

3D patterned substrates for bioartificial blood vessels - The effect of hydrogels on aligned cells on a biomaterial surface.

PubMed

Zhao, Xinxin; Irvine, Scott Alexander; Agrawal, Animesh; Cao, Ye; Lim, Pei Qi; Tan, Si Ying; Venkatraman, Subbu S

2015-10-01

The optimal bio-artificial blood vessel construct is one that has a compliant tubular core with circumferentially aligned smooth muscle cells (SMCs). Obtaining this well-aligned pattern of SMCs on a scaffold is highly beneficial as this cellular orientation preserves the SMC contractile phenotype. We used 3D patterning to create channels on a polycaprolactone (PCL) scaffold; SMCs were then found to be aligned within the microchannels. To preserve this alignment, and to provide a protective coating that could further incorporate cells, we evaluated the use of two hydrogels, one based on poly(ethylene glycol) diacrylate (PEGDA) and the other based on gelatin. Hydrogels were either physically coated on the PCL surfaces or covalently linked via suitable surface modification of PCL. For covalent immobilization of PEGDA hydrogel, alkene groups were introduced on PCL, while for gelatin covalent linkage, serum proteins were introduced. It is, however, crucial that the hydrogel coating does not disrupt the cellular patterning and distribution. We show in this work that both the process of coating as well as the nature of the coating are critical to preservation of the aligned SMCs. The covalent coating methods involving the crosslinking of hydrogels with the surface of PCL films promoted hydrogel retention time on the film as compared with physical deposition. Furthermore, subsequent hydrogel degradation is affected by the components of the cell culture medium, hinting at a possible route to in vivo biodegradation. Surface features control cellular orientation and subsequently influence their functionality, a useful effect for cellularized biomedical devices. Such devices also can benefit from protective and cell friendly hydrogel coatings. However, literature is lacking on the fate of cells that have endured hydrogel coating whilst orientated on a biomaterial surface. In particular, elucidation of the cells ability to remain adherent and orientated post hydrogel addition. Coating requires two procedures that may be deleterious to the orientated cells: the surface pretreatment for gel binding and the hydrogel crosslinking reaction. We compare transglutaminase gelatin crosslinking and UV initiated PEGDA crosslinking, coated onto smooth muscle cells orientated on patterned PCL surfaces. This original study will be of considerable use to the wider biomaterials community. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Inorganic-organic shape memory polymers and foams for bone defect repairs

NASA Astrophysics Data System (ADS)

Zhang, Dawei

The ultimate goal of this research was to develop a "self-fitting" shape memory polymer (SMP) scaffold for the repair of craniomaxillofacial (CMF) bone defects. CMF defects may be caused by trauma, tumor removal or congenital abnormalities and represent a major class of bone defects. Their repair with autografts is limited by availability, donor site morbidity and complex surgical procedures. In addition, shaping and positioning of these rigid grafts into irregular defects is difficult. Herein, we have developed SMP scaffolds which soften at T > ˜56 °C, allowing them to conformally fit into a bone defect. Upon cooling to body temperature, the scaffold becomes rigid and mechanically locks in place. This research was comprised of four major studies. In the first study, photocrosslinkable acrylated (AcO) SMP macromers containing a poly(epsilon-caprolactone) (PCL) segment and polydimethylsiloxane (PDMS) segments were synthesized with the general formula: AcO-PCL40-block-PDMS m-block-PCL40-OAc. By varying the PDMS segment length (m), solid SMPs with highly tunable mechanical properties and excellent shape memory abilities were prepared. In the second study, porous SMP scaffolds were fabricated based on AcO-PCL 40-block-PDMS37-block-PCL 40-OAc via a revised solvent casting particulate leaching (SCPL) method. By tailoring scaffold parameters including salt fusion, macromer concentration and salt size, scaffold properties (e.g. pore features, compressive modulus and shape memory behavior) were tuned. In the third study, porous SMP scaffolds were produced from macromers with variable PDMS segment lengths (m = 0 -- 130) via an optimized SCPL method. The impact on pore features, thermal, mechanical, and shape memory properties as well as degradation rates were investigated. In the final study, a bioactive polydopamine coating was applied onto pore surfaces of the SMP scaffold prepared from PCL diacrylate. The thin coating did not affect intrinsic bulk properties of the scaffold. However, the coating significantly increased its bioactivity, giving rise to the formation of "bone-bonding" hydroxyapatite (HAp) when exposed to simulated body fluid (SBF). It was also shown that the coating largely enhanced the scaffold's capacities to support osteoblasts adhesion, proliferation and osteogenesis. Thus, the polydopamine coating should enhance the performance of the "self-fitting" SMP scaffolds for the repair of bone defects.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

Investigation on micro-patterned gold-plated polymer substrate for a micro hydraulic actuator

NASA Astrophysics Data System (ADS)

Sundaresan, Vishnu Baba; Akle, Barbar; Leo, Donald J.

2006-03-01

Plants have the ability to develop large mechanical force from chemical energy available with bio-fuels. The energy released by the cleavage of a terminal phosphate ion during the hydrolysis of a bio-fuel assists the transport of ions and fluids in cellular homeostasis. Materials that develop pressure and hence strain similar to the response of plants to an external stimuli are classified as nastic materials. This new class of actuators use protein transporters as functional units to move species and result in deformation [Leo et al 2005 (Proceedings of IMECE - 06)]. The ion transporters are hydrocarbons which are formed across the cellular membranes. The membranes that house the ion transporters are aggregates of phospholipids rigidized by cytoskeleton. Reconstituting these nano-machines on a harder matrix is quintessential to build a functional device. Artificial phospholipid membranes or Biliayer lipid membranes (BLM) have poor structural integrity and do not adhere to most surfaces. Patterned arrays of pores made on Poly-propylene glycol-diacrylate (PPG-DA) substrate, a photo curable polymer was made available to us for initial design iterations for an actuator. Hydrophobicity of PPG-DA posed initial problems to support a BLM. We modified the surface of micropatterned PPG-DA membrane by gold plating it. The surface of the porous PPG-DA membranes was plated with gold (Au). A 10nm seeding layer of Au was sputtered on the surface of the membrane. Further gold was reduced onto the sputtered gold surface [Supriya et al(Langmuir 2004, 20, 8870-8876)] by suspending the samples in a solution of hydroxylamine and Hydrogen tetrachloroaurate(III) trihydrate [HAuCl4.3H2O]. This reduction process increased the thickness of the gold, enhanced its adhesion to the PPG-DA substrate and improved the shapes of the pores. This surface modification of PPG-DA helped us form stable BLM with 1-Palmitoyl-2-Oleoyl-sn-Glycero-3- [Phospho-L-Serine] (Sodium Salt) (POPS), 1-Palmitoyl-2-Oleoyl-sn-Glycero- 3-Phosphoethanolamine (POPE) lipids. The observed ionic resistance of the BLM remained stable and sustained 4 mm water column for the the four hours observation period. This article describes the procedure we adopted to modify the PPG-DA substrate, form a BLM and the procedure to quantify the stability of the BLM formed with -amine and -thiol head groups in the lipids.

Study of pH-responsive microgels containing methacrylic acid: effects of particle composition and added calcium.

PubMed

Dalmont, Helene; Pinprayoon, Orawan; Saunders, Brian R

2008-03-18

pH-responsive microgel dispersions contain cross-linked polymer particles that swell when the pH approaches the pKa of the ionic monomer incorporated within the particles. In recent work from our group, it was demonstrated that the mechanical properties of degenerated intervertebral discs (IVDs) could be restored to normal values by injection of pH-responsive microgel dispersions (Saunders, J. M.; Tong, T.; LeMaitre, C.; Freemont, A. J.; Saunders, B. R. Soft Matter 2007, 3, 486). These dispersions change from a fluid to a gel with increasing pH. The present work investigates the pH-dependent properties of dispersions of microgel particles containing MAA (methacrylic acid) and also the effects of added Ca2+. Two microgels are discussed: microgel A is poly(EA/MAA/AM) (EA and AM are ethyl acrylate and allyl methacrylate), and microgel B is poly(EA/MAA/BDDA) (butanediol diacrylate). The pH-dependent particle properties investigated include hydrodynamic diameters and electrophoretic mobilities. The critical coagulation concentrations (CCC) of dilute dispersions and the elastic modulus (G') of concentrated, gelled microgel dispersions were also investigated. In the absence of added Ca2+, the particle swelling and G' were smallest and largest, respectively, for microgel A. The changes in hydrodynamic diameter and mobility with pH were explained in terms of a core-shell swelling mechanism. Added Ca2+ was found to significantly decrease the CCCs, extents of particle swelling, and magnitude of the electrophoretic mobility. This was attributed to the ionic cross-linking of neighboring RCOO- groups by Ca2+. It is suggested that the formation of ionic cross-links is inefficient within the microgel particles because of the presence of covalent cross-links that oppose the large-scale conformational rearrangement of neighboring RCOO- groups. The effect of Ca2+ on the properties of the gelled dispersions is important from the viewpoint of potential application in vivo. Rheological studies of the gelled microgel dispersions showed that added Ca2+ did not have a specific influence on G'. The differences observed in the presence of Ca2+ were attributed to ionic strength effects (screening). The key parameter that controls G' of the gelled microgel dispersions is pH. The results from this work suggest that the elasticity of the gels would be slightly reduced in vivo as a consequence of the high ionic strength present.

Nanoparticles as strengthening agents in polymer systems

NASA Astrophysics Data System (ADS)

Shahid, Naureen

2005-11-01

Carboxylate-substituted alumina nanoparticles are produced solvent free using mechanical shear. The general nature of this method has been demonstrated for L-lysine-, stearate, and p-hydroxybenzoate-derived materials. The reaction rate and particle size is controlled by a combination of temperature and shear rate. The nanoparticles are spectroscopically equivalent to those reported from aqueous syntheses, however, the average particle size can be decreased and the particle size distribution narrowed depending on the reaction conditions. Lysine and p-hydroxybenzoato alumoxanes have been introduced in carbon fiber reinforced epoxide resin composites. Different preparation conditions have been studied to obtain composite with enhanced performances that are ideal for the motor sports and aerospace industries. A new composite material has been fabricated utilizing surface-modified carboxylate alumoxane nanoparticles and the biodegradable polymer poly(propylene fumarate)/poly(propylene fumarate)-diacrylate (PPF/PPF-DA). For this study, composites were prepared using various functional groups including: a surfactant alumoxane to enhance nanoparticle dispersion into the polymer; an activated-alumoxane to enhance nanoparticle interaction with the polymer matrix; a mixed alumoxane containing both activated and surfactant groups. Nanocomposites prepared with all types of alumoxane, as well as blank polymer resin and unmodified boehmite, underwent mechanical testing and were characterized by SEM and microprobe analysis. A nanocomposite composed of mixed alumoxane nanoparticles dispersed in PPF/PPF-DA exhibited increased flexural modulus compared to polymer resin alone, and a significant enhancement over both the activated and surfacted alumoxanes. Boric acid is used as the cross-linking agent in oil well drilling industry even though the efficacy of the borate ion, [B(OH)4]- , as a cross-linking agent is poor. The reaction product of boric acid and the polysaccharide guaran (the major component of guar gum) has been investigated by 11B NMR spectroscopy. By comparison with the 11B NMR of boric acid and phenyl boronic acid complexes of 1,2-diols [HOCMe2CMe2OH, cis-C6H 10(OH)2, trans-C6H10(OH) 2, o-C6H4(OH)2], 1,3-diols (neol-H2), monosaccharides (L-fucose, mannose and galactose) and disaccharides (celloboise and sucrose) it is found that the guaran polymer is cross-linked via a borate complex of two 1,2-diols both forming chelate 5-membered ring cycles, this contrasts with previous proposals. (Abstract shortened by UMI.)

Region-Specific Effect of the Decellularized Meniscus Extracellular Matrix on Mesenchymal Stem Cell-Based Meniscus Tissue Engineering.

PubMed

Shimomura, Kazunori; Rothrauff, Benjamin B; Tuan, Rocky S

2017-03-01

The meniscus is the most commonly injured knee structure, and surgical repair is often ineffective. Tissue engineering-based repair or regeneration may provide a needed solution. Decellularized, tissue-derived extracellular matrices (ECMs) have received attention for their potential use as tissue-engineered scaffolds. In considering meniscus-derived ECMs (mECMs) for meniscus tissue engineering, it is noteworthy that the inner and outer regions of the meniscus have different structural and biochemical features, potentially directing the differentiation of cells toward region-specific phenotypes. To investigate the applicability of mECMs for meniscus tissue engineering by specifically comparing region-dependent effects of mECMs on 3-dimensional constructs seeded with human bone marrow mesenchymal stem cells (hBMSCs). Controlled laboratory study. Bovine menisci were divided into inner and outer halves and were minced, treated with Triton X-100 and DNase, and extracted with urea. Then, hBMSCs (1 × 10 6 cells/mL) were encapsulated in a photo-cross-linked 10% polyethylene glycol diacrylate scaffold containing mECMs (60 μg/mL) derived from either the inner or outer meniscus, with an ECM-free scaffold as a control. The cell-seeded constructs were cultured with chondrogenic medium containing recombinant human transforming growth factor β3 (TGF-β3) and were analyzed for expression of meniscus-associated genes as well as for the collagen (hydroxyproline) and glycosaminoglycan content as a function of time. Decellularization was verified by the absence of 4',6-diamidino-2-phenylindole (DAPI)-stained cell nuclei and a reduction in the DNA content. Quantitative real-time polymerase chain reaction showed that collagen type I expression was significantly higher in the outer mECM group than in the other groups, while collagen type II and aggrecan expression was highest in the inner mECM group. The collagen (hydroxyproline) content was highest in the outer mECM group, while the glycosaminoglycan content was higher in both the inner and outer mECM groups compared with the control group. These results showed that the inner mECM enhances the fibrocartilaginous differentiation of hBMSCs, while the outer mECM promotes a more fibroblastic phenotype. Our findings support the feasibility of fabricating bioactive scaffolds using region-specific mECM preparations for meniscus tissue engineering. This is the first report to demonstrate the feasibility of applying region-specific mECMs for the engineering of meniscus implants capable of reproducing the biphasic, anatomic, and biochemical characteristics of the meniscus, features that should contribute to the feasibility of their clinical application.

* A 3D Tissue-Printing Approach for Validation of Diffusion Tensor Imaging in Skeletal Muscle.

PubMed

Berry, David B; You, Shangting; Warner, John; Frank, Lawrence R; Chen, Shaochen; Ward, Samuel R

2017-09-01

The ability to noninvasively assess skeletal muscle microstructure, which predicts function and disease, would be of significant clinical value. One method that holds this promise is diffusion tensor magnetic resonance imaging (DT-MRI), which is sensitive to the microscopic diffusion of water within tissues and has become ubiquitous in neuroimaging as a way of assessing neuronal structure and damage. However, its application to the assessment of changes in muscle microstructure associated with injury, pathology, or age remains poorly defined, because it is difficult to precisely control muscle microstructural features in vivo. However, recent advances in additive manufacturing technologies allow precision-engineered diffusion phantoms with histology informed skeletal muscle geometry to be manufactured. Therefore, the goal of this study was to develop skeletal muscle phantoms at relevant size scales to relate microstructural features to MRI-based diffusion measurements. A digital light projection based rapid 3D printing method was used to fabricate polyethylene glycol diacrylate based diffusion phantoms with (1) idealized muscle geometry (no geometry; fiber sizes of 30, 50, or 70 μm or fiber size of 50 μm with 40% of walls randomly deleted) or (2) histology-based geometry (normal and after 30-days of denervation) containing 20% or 50% phosphate-buffered saline (PBS). Mean absolute percent error (8%) of the printed phantoms indicated high conformity to templates when "fibers" were >50 μm. A multiple spin-echo echo planar imaging diffusion sequence, capable of acquiring diffusion weighted data at several echo times, was used in an attempt to combine relaxometry and diffusion techniques with the goal of separating intracellular and extracellular diffusion signals. When fiber size increased (30-70 μm) in the 20% PBS phantom, fractional anisotropy (FA) decreased (0.32-0.26) and mean diffusivity (MD) increased (0.44 × 10 -3 mm 2 /s-0.70 × 10 -3 mm 2 /s). Similarly, when fiber size increased from 30 to 70 μm in the 50% PBS diffusion phantoms, a small change in FA was observed (0.18-0.22), but MD increased from 0.86 × 10 -3 mm 2 /s to 1.79 × 10 -3 mm 2 /s. This study demonstrates a novel application of tissue engineering to understand complex diffusion signals in skeletal muscle. Through this work, we have also demonstrated the feasibility of 3D printing for skeletal muscle with relevant matrix geometries and physiologically relevant tissue characteristics.

Adhesive complex coacervate inspired by the sandcastle worm as a sealant for fetoscopic defects

NASA Astrophysics Data System (ADS)

Kaur, Sarbjit

Inspired by the Sandcastle Worm, biomimetic of the water-borne adhesive was developed by complex coacervation of the synthetic copolyelectrolytes, mimicking the chemistries of the worm glue. The developed underwater adhesive was designed for sealing fetal membranes after fetoscopic surgery in twin-to-twin transfusion syndrome (TTTS) and sealing neural tissue of a fetus in aminiotic sac for spina bifida condition. Complex coacervate with increased bond strength was created by entrapping polyethylene glycol diacrylate (PEG-dA) monomer within the cross-linked coacervate network. Maximum shear bond strength of ~ 1.2 MPa on aluminum substrates was reached. The monomer-filled coacervate had complex flow behavior, thickening at low shear rates and then thinning suddenly with a 16-fold drop in viscosity at shear rates near 6 s-1. The microscale structure of the complex coacervates resembled a three-dimensional porous network of interconnected tubules. This complex coacervate adhesive was used in vitro studies to mimic the uterine wall-fetal membrane interface using a water column with one end and sealed with human fetal membranes and poultry breast, and a defect was created with an 11 French trocar. The coacervate adhesive in conjunction with the multiphase adhesive was used to seal the defect. The sealant withstood an additional traction of 12 g for 30-60 minutes and turbulence of the water column without leakage of fluid or slippage. The adhesive is nontoxic when in direct contact with human fetal membranes in an organ culture setting. A stable complex coacervate adhesive for long-term use in TTTS and spina bifida application was developed by methacrylating the copolyelectrolytes. The methacrylated coacervate was crosslinked chemically for TTTS and by photopolymerization for spina bifida. Tunable mechanical properties of the adhesive were achieved by varying the methacrylation of the polymers. Varying the amine to phosphate (A/P) ratio in the coacervate formation generated a range of viscosities. The chemically cured complex coacervate, with sodium (meta) periodate crosslinker, was tested in pig animal studies, showing promising results. The adhesive adhered to the fetal membrane tissue, with maximum strength of 473 +/- 82 KPa on aluminum substrates. The elastic modulus increased with increasing methacrylation on both the polyphosphate and polyamine within the coacervate. Photopolymerized complex coacervate adhesive was photocured using Eosin-Y and treiethanolamine photoinitiators, using a green laser diode. Soft substrate bond strength increased with increasing PEG-dA concentration to a maximum of ~90 kPa. The crosslinked complex coacervate adhesives with PEG networks swelled less than 5% over 30 days in physiological conditions. The sterile glue was nontoxic, deliverable through a fine cannula, and stable over a long time period. Preliminary animal studies show a novel innovative method to seal fetal membrane defects in humans, in utero.

Mechanics of biological polymer composites

NASA Astrophysics Data System (ADS)

Lomakin, Joseph

2009-12-01

Cartilage and cuticle are two natural materials capable of remarkable mechanical performance, especially considering the limitations on composition and processing conditions under which they are constructed. Their impressive properties are postulated to be a consequence of their complex multi-scale organization which has commonly been characterized by biochemical and microscopic methods. The objective of this dissertation is to overcome the limitations of such methods with mechanical analysis techniques generally reserved for the study of synthetic polymers. Methods for transient and dynamic mechanical analysis (DMA) of porcine TMJ disc sections and Tribolium castaneum and Tenebrio molitor elytral (modified forewing) cuticle were developed to characterize the mechanical performance of these biomaterials. The TMJ disc dynamic elastic modulus (E') was determined to be a strong function of disc orientation and pretension ranging from 700+/-240 kPa at (1g pretension) in the mediolateral direction to 73+/-8.5 MPa (150g preload) in the anteroposterior direction. Analogous mechanical testing was used to understand the relationship between composition and mechanical properties of beetle elytral cuticle at variable stages of maturation (tanning). Untanned elytra of both beetle species were ductile with a Young's modulus (E) of 44+/-8 MPa, but became brittle with an E of 2400+/-1100 MPa when fully tanned. Significantly, the E' of the TMJ disc and elytral cuticle exhibited a weak power law increase as a function of oscillation frequency. The exponent of the power law fit ( n) was determined to be a sensitive measure of molecular structure within these biomaterials. With increasing cuticular tanning, more so than with drying, the frequency dependence of cuticle E' diminished, suggesting cuticular cross-linking was an important component of tanning, as postulated by the quinone tanning hypothesis. The natural Black phenotype as well as TcADC iRNA suppressed Tribolium cuticle displayed a darker coloration and significantly increased n of 0.0470.004, suggesting both cuticles to be less cross-linked, a finding consistent with reduced beta-alanine metabolism. Suppression of the tanning enzyme laccase2 (TcLac2) resulted in a pale cuticle with an n of 0.043+/-0.005, implicating laccases in the formation of both pigments and cross-links during sclerotization. Cuticular cross-linking was increased and n decreased with decreased expression of structural proteins, CP10 and CP20. This work establishes n as an important novel parameter for confirming metabolic pathways within load bearing tissues and for understanding structure function relationships within biological polymer composites. Additionally, Tribolium castaneum elytral indentation modulus (800+/-200 MPa) was determined by nanoindentation and a 4nm regular hexagonal pattern on the dorsal side of elytra investigated via scanning, transmission and atomic microscopy. Based on studied biological materials, the combination of rigid macromolecules immersed in a ductile matrix was found to be significant in achieving exceptional mechanical performance. Inspired by this biological design principle, the synthesis, properties and structure of Poly(ethylene glycol) diacrylate/agarose semi-interpenetrating network hydrogels were explored. The resulting novel composite materials were 9x stiffer than agarose and 5x tougher than PEGDA alone and showed good biocompatibility, suggesting promise as a scaffold material for tissue engineering constructs for cartilage regeneration.

Novel bio-synthetic hybrid materials and coculture systems for musculoskeletal tissue engineering

NASA Astrophysics Data System (ADS)

Lee, Hyeseung Janice

Tissue Engineering is a truly exciting field of this age, trying to regenerate and repair impaired tissues. Unlike the old artificial implants, tissue engineering aims at making a long-term functional biological replacement. One strategy for such tissue engineering requires the following three components: cells, scaffolds, and soluble factors. Cells are cultured in a three-dimensional (3D) scaffold with medium containing various soluble factors. Once a tissue is developed in vitro, then it is implanted in vivo. The overall goal of this thesis was to develop novel bio-synthetic hybrid scaffolds and coculture system for musculoskeletal tissue engineering. The most abundant cartilage extracellular matrix (ECM) components are collagen and glycosaminoglycan (GAG), which are the natural scaffold for chondrocytes. As two different peptides, collagen mimetic peptide (CMP) and hyaluronic acid binding peptide (HABPep) were previously shown to bind to collagen and hyaluronic acid (HA) of GAG, respectively, it was hypothesized that immobilizing CMP and HABP on 3D scaffold would results in an interaction between ECM components and synthetic scaffolds via peptide-ECM bindings. CMP or HABPep-conjugated photopolymerizable poly(ethylene oxide) diacrylate (PEODA) hydrogels were synthesized and shown to retain encapsulated collagen or HA, respectively. This result supported that conjugated CMP and HABPep can interact with collagen and HA, respectively, and can serve as biological linkers in 3D synthetic hydrogels. When chondrocytes or mesenchymal stem cells (MSCs) were seeded, cells in CMP-conjugated scaffolds produced significantly more amount of type II collagen and GAG, compared to those in control scaffolds. Moreover, MSCs cultured in CMP-conjugated scaffolds exhibited lower level of hypertrophic markers, cbfa-1 and type X collagen. These results demonstrated that enhanced interaction between collagen and scaffold via CMP improves chondrogenesis of chondrocytes and MSCs and further reduces hypertrophy of differentiating MSCs. On the other hand, although cells in HABPep-conjugated scaffolds produced less ECM components, they survived and proliferated significantly more than those in control, resulting in overall increase in ECM contents per scaffold. Once implanted in vivo, HABPep-conjugated constructs increased GAG and type II collagen contents further, compared to those of the control hydrogel. These results showed that enhanced interaction between HA and scaffold via HABPep improved the in vitro culture expansion of MSCs and further ECM production in vivo. Effects of cell-secreted bioactive factors via cell-cell communication on stem cell differentiation were also investigated in 3D bilayer system. First, when mesenchymal progenitor cells (MPCs) were cocultured with ES-derived cells (ESDC), morphogenetic factors secreted by ESDCs showed a potential to improve MPC chondrogenesis in both control and chondrogenic medium by increasing not only MPC's chondrogenic gene expression, but also ECM production. Moreover, the effect of ESDC cell-mediated chondrogenesis of MSC could not be mimicked by chondrogenic medium supplemented with TGF-beta1 and dexamethasone. Secondly, coculturing hepatic cells enhanced specific chondrogenic differentiation of ES cells in the 3D bilayer system. These studies demonstrated that cell-secreted soluble factors can be used to guide stem cell differentiation.

Developing core-shell upconversion nanoparticles for optical encoding

NASA Astrophysics Data System (ADS)

Huang, Kai

Lanthanide-doped upconversion nanoparticles (UCNPs) are an emerging class of luminescent materials that emit UV or visible light under near infra-red (NIR) excitations, thereby possessing a large anti-Stokes shift property. Also considering their sharp emission bands, excellent photo- and chemical stability, and almost zero auto-fluorescence of their NIR excitation, UCNPs are advantageous for optical encoding. Fabricating core-shell structured UCNPs provides a promising strategy to tune and enhance their upconverting luminescence. However, the energy transfer between core and shell had been rarely studied. Moreover, this strategy had been limited by the difficulty of coating thick shells onto the large cores of UCNPs. To overcome these constraints, the overall aim of this project is to study the inter-layers energy transfer in core-shell UCNPs and to develop an approach for coating thicker shell onto the core UCNPs, in order to fabricate UCNPs with enhanced and tunable luminescence for optical encoding. The strategy for encapsulating UCNPs into hydrogel droplet to fabricate multi-color bead barcodes has also been developed. Firstly, to study the inter-layers energy transfer between the core and shell of coreshell UCNPs, the activator and sensitizer ions were separately doped in the core or shell by fabricating NaYF4:Er NaYF4:Yb and NaYF4:Yb NaYF4:Er UCNPs. This eliminated the intra-layer energy transfer, resulting in a luminescence that is solely based on the energy transfer between layers, which facilitated the study of inter-layers energy transfer. The results demonstrated that the NaYF4:Yb NaYF4:Er structure, with sensitizer ions doped in the core, was preferable because of the strong luminescence, through minimizing the cross relaxations between Er3+ and Yb3+ and the surface quenching. Based on these information, a strategy of enhancing and tuning upconversion luminescence of core-shell UCNPs by accumulating sensitizer in the core has been developed. Next, a strategy of coating a thick shell by lutetium doping has been developed. With a smaller ion radius compared to Y3+, when Lu3+ partially replace Y3+ in the NaYF4 UCNPs during nanoparticle synthesis, nucleation process is suppressed and the growth process is promoted, which are favorable for increasing the nanoparticle size and coating a thicker shell onto the core UCNPs. Through the rational doping of Lu3+, core UCNPs with bigger sizes and enhanced luminescence were produced. Using NaLuF4 as the shell material, shells with tremendous thickness were coated onto core UCNPs, with the shell/core ratio of up to 10:1. This led to the fabrication of multi-color UCNPs with well-designed core-shell structures with multiple layers and controllable thicknesses. Finally, a strategy of encapsulating these UCNPs to produce optically encoded micro-beads through high-throughput microfluidics has been developed. The hydrophobic UCNPs were first modified with Pluronic F127 to render them hydrophilic and uniformly distributed in the poly (ethylene glycol) diacrylate (PEGDA) hydrogel precursor. Droplets of the hydrogel precursor were formed in a microfluidic device and cross-linked into micro-beads under UV irradiation. Through encapsulation of multi-color UCNPs and by controlling their ratio, optically encoded multi-color micro-beads have been easily fabricated. These multi-color UCNPs and micro-bead barcodes have great potential for use in multiplexed bioimaging and detection.

Design and synthesis of multifunctional poly(ethylene glycol)s using enzymatic catalysis for multivalent cancer drug delivery

NASA Astrophysics Data System (ADS)

Seo, Kwang Su

The objective of this research was to design and synthesize multifunctional poly(ethylene glycol)s (PEG)s using enzyme-catalyzed reactions for multivalent targeted drug delivery. Based on computer simulation for optimum folate binding, a four-arm PEG star topology with Mn = 1000 g/mol was proposed. First, a four-functional core based on tetraethylene glycol (TEG) was designed and synthesized using transesterification and Michael addition reactions in the presence of Candida antarctica lipase B (CALB) as a biocatalyst. The four-functional core (HO)2-TEG-(OH)2 core was successfully prepared by the CALB-catalyzed transesterification of vinyl acrylate (VA) with TEG and then Michael addition of diethanolamine to the resulting TEG diacrylate with/without the use of solvent. The functional PEG arms with fluorescein isothiocyanate (FITC) and folic acid (FA) were prepared using both traditional organic chemistry and enzyme-catalyzed reactions. FITC was reacted with the amine group of H2N-PEG-OH in the presence of triethylamine via nucleophilic addition onto the isothiocyanate group. Then, divinyl adipate (DVA) was transesterified with the FITC-PEG-OH product in the presence of CALB to produce the FITC-PEG vinyl ester that will be attached to the four-functional core via CALC-catalyzed transesterification. For the synthesis of FA-PEG vinyl ester arm, DVA was first reacted with PEG-monobenzyl ether (BzPEG-OH) in bulk in the presence of CALB. The BzPEG vinyl ester was then transesterified with 12-bromo-1-dodecanol in the presence of CALB. Finally, BzPEG-Br was attached to FA exclusively in the gamma position using a new method. The thesis also discusses fundamental studies that were carried out in order to get better understanding of enzyme catalyzed transesterification and Michael addition reactions. First, in an effort to investigate the effects of reagent and enzyme concentrations in transesterification, vinyl methacrylate (VMA) was reacted with 2-(hydroxyethyl) acrylate (2HEA) in the presence of CALB. When the reaction was performed in tetrahydrofuran (THF) with a 2HEA concentration of 0.10 mol/L, only 19% conversion was observed within 4 hours, whereas complete conversion was achieved under solventless conditions. The effect of enzyme concentration in reactions with and without solvent was also studied. The effect of DVA concentration on the CALB-catalyzed transesterification with TEG was studied under solventless conditions. When 1.5 molar equivalent of DVA per OH in TEG was used, 42% divinyl-functionalized product was observed together with 56.5% oligomerized (di-, tri-, tetra- and pentamer) products. At 10 eq. of DVA, only 18.4% oligomerized products were obtained. The effect of diol molecular weight was also investigated. At 10.0 eq. DVA per OH only 2% dimer was observed with PEG Mn=1000 g/mol, and a single divinyl functionalized product was obtained with M n=2000 g/mol. The effects of polymer molecular weight and DVA concentration were also studied in the reaction of DVA with PEG monomethyl ether (MPEG-OH, Mn=1100 g/mol and 2000 g/mol). The extent of coupling decreased from 35% to 0.4% when the DVA concentration was increased from 1.5 to 10 per -OH in the MPEG-OH. No coupling was observed with MPEG-OH Mn=2000 g/mol at 5 eq. DVA per -OH. Following these fundamental studies, TEGs and PEGs were enzymatically functionalized. TEGs were transesterified with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 4 hours of reaction time. Benzyl protected TEG-OHs were also successfully functionalized with VMA and vinyl crotonate in the presence of CALB under solventless conditions within 2 hours. An eight-functional molecule was also synthesized from (HO)2-TEG-(OH) 2. First an alpha-vinyl-o-acrylate linker was prepared by the transesterification of DVA with 2HEA. This linker was then transesterified with (HO)-TEG-(OH)2, followed by Michael addition of DEA to the tetra-acrylated TEG. (Abstract shortened by UMI.)

Studies on Ionic Conductivity and Electrochemical Stability of Plasticized Photopolymerized Polymer Electrolyte Membranes for Solid State Lithium Ion Batteries

NASA Astrophysics Data System (ADS)

He, Ruixuan

In pursuit of safer and more flexible solid-state lithium ion batteries, solid polymer electrolytes have emerged as a promising candidate. The present dissertation entails exploration of solid plasticized, photopolymerized (i.e. ultraviolent-cured) polymer electrolyte membranes (PEM) for fulfilling the critical requirements of electrolytes, such as high ionic conductivity and good thermal and electrochemical stability, among others. Electrochemical performance of PEMs containing lithium ion half-cells was also investigated at different two temperatures. Phase diagram approach was adopted to guide the fabrication of two types of plasticized PEMs. Prepolymer poly (ethylene glycol) diacrylate (PEGDA) was used as a matrix for building an ionic conductive and mechanically sturdy network. Lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) was incorporated as a source of lithium ions, while a solid plasticizer succinonitrile (SCN) and a liquid plasticizer tetraethylene glycol dimethyl ether (TEGDME) were incorporated in the respective systems. The important role of plasticizer on the enhancement of ionic conductivity (sigma) to the superionic conductive level (10-3 S/cm) was revealed in both systems. It is worth noting that photopolymerization induced crystallization (PIC) occurred during UV-curing in the SCN-rich region of the ternary PEGDA/LiTFSI/SCN ternary mixtures. The PEM thus formed contained a plastic crystal phase, which showed lower σ relative to their amorphous PEGDA/LiTFSI/TEGDME counterpart. Comparisons on other thermal and electrochemical properties of the two types of PEMs are presented in Chapter IV. For the PEGDA/LiTFSI/SCN PEMs, fundamental study was carried out to clarify the relationship between σ and glass transition temperature (T g). In lithium salt/polymer binary PEMs, increase in Tg and reduction in σ were observed; these may be attributed to ion-dipole complexation between dissociated lithium cations and ether oxygen upon salt addition. Notably, above the threshold salt concentration of 7 mol %, dual loss tangent peaks were observed in dynamic mechanical studies. These might be ascribed to segmental relaxations of ion-dipole complexed networks and that of polymer chains surrounding the undissociated lithium salt acting like "fillers". Upon SCN incorporation, these two peaks merged into one that was further suppressed below the Tg of the pure network, whereas σ improved to the superionic conductor level. The role of SCN on the σ enhancement as both plasticizer for the polymer network and ionizer for the salt is discussed in Chapter V. In order to improve the mechanical toughness of the highly conductive PEGDA/LiTFSI/SCN PEM, effects of prepolymer molecular weight on mechanical and electrochemical properties of PEMs were further investigated. By increasing molecular weight of PEGDA from 700 to 6000 g/mol, toughness and elongation at break were enhanced as expected. Interestingly, improved ionic conductivity was achieved simultaneously. The dual improvement may be attributed to the less chemical crosslinked points and the more flexible chain motion in the looser network of PEGDA6000-PEM relative to its PEGDA700 counterpart. Subsequently, high thermal stability and electrochemical stability of both types of PEMs, as well as the satisfactory room temperature charge/discharge cycling performance of PEM containing lithium ion half-cells were observed. The pertinent information is documented in Chapter VI. Finally, the investigation of the charge/discharge cycling performance of solid-state LiFePO4 half-cells at an elevated temperature of 60°C is discussed in Chapter VII. In the half-cells, particularly, SCN plasticized PEMs with and without electrolyte modifier lithium bis(oxalato)borate (LiBOB) were respectively employed. Rapid decline of capacity and increase of cell resistance were found in the unmodified PEM containing cell; however, these deteriorations were greatly suppressed upon LiBOB modification. Electrochemical and thermal compatibility of PEMs towards different electrodes were examined in several symmetric cells and half-cells. Detailed characterization on LiFePO 4 electrodes and PEMs retrieved from these cells implied that the observed battery failure might be triggered by an amide-forming side reaction that took place at the interface of a SCN plasticized PEM and a lithium electrode at high temperature. Of particular importance is the fact that this detrimental side reaction was effectively suppressed upon LiBOB electrolyte modifier addition. Plausible mechanisms are discussed.