Visible Light Crosslinking of Methacrylated Hyaluronan Hydrogels for Injectable Tissue Repair

PubMed Central

Fenn, Spencer L.; Oldinski, Rachael A.

2015-01-01

Tissue engineering hydrogels are primarily cured in situ using ultraviolet (UV) radiation which limits the use of hydrogels as drug or cell carriers. Visible green light activated crosslinking systems are presented as a safe alternative to UV photocrosslinked hydrogels, without compromising material properties such as viscosity and stiffness. The objective of this study was to fabricate and characterize photocrosslinked hydrogels with well-regulated gelation kinetics and mechanical properties for the repair or replacement of soft tissue. An anhydrous methacrylation of hyaluronan (HA) was performed to control the degree of modification (DOM) of HA, verified by 1H-NMR spectroscopy. UV activated crosslinking was compared to visible green light activated crosslinking. While the different photocrosslinking techniques resulted in varied crosslinking times, comparable mechanical properties of UV and green light activated crosslinked hydrogels were achieved using each photocrosslinking method by adjusting time of light exposure. Methacrylated HA (HA-MA) hydrogels of varying molecular weight, DOM and concentration exhibited compressive moduli ranging from 1 kPa to 116 kPa, for UV crosslinking, and 3 kPa to 146 kPa, for green light crosslinking. HA-MA molecular weight and concentration were found to significantly influence moduli values. HA-MA hydrogels did not exhibit any significant cytotoxic affects towards human mesenchymal stem cells. Green light activated crosslinking systems are presented as a viable method to form natural-based hydrogels in situ. PMID:26097172

The use of gamma irradiation in preparation of polybutadiene rubber nanopowder; Its effect on particle size, morphology and crosslink structure of the powder

NASA Astrophysics Data System (ADS)

Rezaei Abadchi, Majid; Jalali-Arani, Azam

2014-02-01

The aim of this work was the preparation and characterization of polybutadiene rubber (BR) powder by irradiating of rubber lattices using 60Co radiation and spray-drying of them at the appropriate condition. The influences of absorbed dose on the volume swelling ratio, molecular weight between crosslinks, gel fraction, and glass transition temperature of obtained powder were studied. Morphology, size and size distribution of rubber particles were examined by using scanning electron microscopy (SEM) and laser particle size analyzer (LPSA) technique, respectively. Results obtained by LPSA revealed that radiation has no effect on particle size of rubber latex but after drying, adherence properties of rubber particle causes increase in particle size of rubber powder, as shown in SEM photograph. Fourier transform infrared spectroscopy of rubber powders confirmed that with increasing the irradiation dose, characteristic peak corresponds to the >Cdbnd C< double bands decreased. Also Charlesby-Pinner equation was used to evaluate radiation yield.

Influence of therapeutic radiation on polycaprolactone and polyurethane biomaterials.

PubMed

Cooke, Shelley L; Whittington, Abby R

2016-03-01

Biomedical polymers are exposed in vivo to ionizing radiation as implants, coatings and bystander materials. High levels of ionizing radiation (e.g. X-ray and gamma) have been reported to cause degradation and/or cross-linking in many polymers. This pilot study sought to determine causes of failure, by investigating how therapeutic radiation affects two different porous polymeric scaffolds: polycaprolactone (PCL) and polyurethane (PU). PCL is a bioresorbable material used in biomedical devices (e.g., dentistry, internal fixation devices and targeted drug delivery capsules). PU is commonly used in medical applications (e.g., coatings for pacemakers, tissue expanders, catheter tubing and wound dressings). PU was specifically fabricated to be a non-degradable polymer in this study. Porous scaffolds, fabricated using solvent casting and/or salt leeching techniques, were placed in phosphate buffered saline (PBS, pH=7.4) and exposed to typical cancer radiotherapy. A total dose of 50 Gy was broken into 25 doses over an eleven-week period. Collected PBS was tested for polymer leachants and degradation products using Gas Chromatography Mass Spectroscopy (GC-MS), results revealed no analyzable leachants from either polymer. Scaffolds were characterized using Environmental Scanning Electron Microscopy, Size-exclusion chromatography (SEC), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). No gross visual changes were observed in either polymer, however PU exhibited microstructure changes after irradiation. Increased number average molecular weight and weight average molecular weight in PCL and PU were observed after irradiation, indicating crosslinking. PU displayed an increase in intrinsic viscosity that further confirms increased crosslinking. PCL and PU showed decreases in crystallinity after irradiation, and PU crystallinity shifted from long-range-order hard segments to short-range-order hard segments after irradiation. Results from both PCL and PU suggest changes in polymer backbones. This preliminary study suggests that therapeutic radiation doses cause both degradation and crosslinking in PCL and PU. Copyright © 2015 Elsevier B.V. All rights reserved.

Chitosan-containing hydrogel wound dressings prepared by radiation technique

NASA Astrophysics Data System (ADS)

Mozalewska, Wiktoria; Czechowska-Biskup, Renata; Olejnik, Alicja K.; Wach, Radoslaw A.; Ulański, Piotr; Rosiak, Janusz M.

2017-05-01

The aim of the study was to develop an antimicrobial hydrogel wound dressing by means of radiation-initiated crosslinking of hydrophilic polymers, i.e. by well-established technology comprising gel manufacturing and its sterilization in one process. The approach included admixture of chitosan of relatively low molecular weight dissolved in lactic acid (LA) into the initial regular components of the conventional hydrogel dressing based on poly(N-vinyl pyrrolidone) (PVP) and agar. Molecular weight of chitosan was regulated by radiation-initiated degradation in the range of 39-132 kg mol-1. Optimum total concentration of LA in the resultant hydrogel dressing was evaluated as 0.05 mol dm-3, that is ca. 0.5%. Presence of LA in the system influenced essential radiation and technological parameters of hydrogel manufacturing. The setting temperature of the pre-hydrogel mixture, resulting from agar ability to congeal, was reduced with LA concentration, yet remained significantly above the room temperature. 0.5% of chitosan was effectively dissolved in aqueous solution of lactic acid due to its pH (lower than 5.5). Radiation parameters of PVP crosslinking in the presence of LA, as determined with generalized Charlesby-Pinner equation, were reflected in slight reduction of the maximum gel fraction and increase in gelation dose and in the factor comparing yields of scission to crosslinking. Nevertheless, essentially physical characteristics of the hydrogel was not affected, except for somewhat increased water uptake capacity, what in turn improves functionality of the dressing as extensive exudate for the wound can be efficiently absorbed. Preliminary microbiological studies showed antimicrobial character of the chitosan-containing hydrogel towards Gram-positive bacterial strain.

The radiation crosslinking process and new products

NASA Astrophysics Data System (ADS)

Ueno, Keiji

In 1988 there were over 90 EB accelerators for industrial use in Japan. The number one industrial application was Wire and Cable, the 2nd was PE foam and Curing, and the 3rd was Precure of tyre. R & D has a very high ration of EB accelerator use. Low energy industrial applications were coated steel (white board), plaster slab, coated paper, magnetic tape and floppy disks. As a new application of the radiation crosslinking process, we have studied radiation crosslinking of engineering plastics and succeeded in improving the hea tresistivity without using glass fibers. Many kinds of polyfunctional monomers used as crosslinking reagents of irradiated Nylon and PBT were studied.

Supercritical CO2 foaming of radiation crosslinked polypropylene/high-density polyethylene blend: Cell structure and tensile property

NASA Astrophysics Data System (ADS)

Yang, Chenguang; Xing, Zhe; Zhang, Mingxing; Zhao, Quan; Wang, Mouhua; Wu, Guozhong

2017-12-01

A blend of isotactic polypropylene (PP) with high-density polyethylene (HDPE) in different PP/HDPE ratios was irradiated by γ-ray to induce cross-linking and then foamed using supercritical carbon dioxide (scCO2) as a blowing agent. Radiation effect on the melting point and crystallinity were analyzed in detail. The average cell diameter and cell density were compared for PP/HDPE foams prepared under different conditions. The optimum absorbed dose for the scCO2 foaming of PP/HDPE in terms of foaming ability and cell structure was 20 kGy. Tensile measurements showed that the elongation at break and tensile strength at break of the crosslinked PP/HDPE foams were higher than the non-crosslinked ones. Of particular interest was the increase in the foaming temperature window from 4 ℃ for pristine PP to 8-12 ℃ for the radiation crosslinked PP/HDPE blends. This implies much easier handling of scCO2 foaming of crosslinked PP with the addition of HDPE.

Interaction of microwaves with carbon nanotubes to facilitate modification

NASA Technical Reports Server (NTRS)

Tour, James M. (Inventor); Dyke, Christopher A. (Inventor); Stephenson, Jason J. (Inventor); Yakobson, Boris I. (Inventor)

2011-01-01

The present invention is directed toward methods of crosslinking carbon nanotubes to each other using microwave radiation, articles of manufacture produced by such methods, compositions produced by such methods, and applications for such compositions and articles of manufacture. The present invention is also directed toward methods of radiatively modifying composites and/or blends comprising carbon nanotubes with microwaves, and to the compositions produced by such methods. In some embodiments, the modification comprises a crosslinking process, wherein the carbon nanotubes serve as a conduit for thermally and photolytically crosslinking the host matrix with microwave radiation.

The effect of radiation processing and filler morphology on the biomechanical stability of a thermoset polyester composite.

PubMed

Jayabalan, M; Shalumon, K T; Mitha, M K; Ganesan, K; Epple, M

2010-04-01

The effect of radiation processing and filler morphology on the biodegradation and biomechanical stability of a poly(propylene fumarate)/hydroxyapatite composite was investigated. Radiation processing influenced both cross-linking and biodegradation of the composites. Irradiation with a dose of 3 Mrad resulted in enhanced cross-linking, mechanical properties and a higher storage modulus which are favourable for dimensional stability of the implant. The particle morphology of the added hydroxyapatite in the highly cross-linked state significantly influenced the biomechanical and interfacial stability of the composites. Reorganization of agglomerated hydroxyapatite occurred in the cross-linked polymeric matrix under dynamic mechanical loading under simulated physiological conditions. Such a reorganization may increase the damping characteristics of the composite.

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

NASA Technical Reports Server (NTRS)

Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

1990-01-01

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

γ-H2AX formation in response to interstrand crosslinks requires XPF in human cells

PubMed Central

Mogi, Seiki; Oh, Dennis H.

2009-01-01

To further define the molecular mechanisms involved in processing interstrand crosslinks, we monitored the formation of phosphorylated histone H2AX (γ-H2AX), which is generated in chromatin near double strand break sites, following DNA damage in normal and repair-deficient human cells. Following treatment with a psoralen derivative and ultraviolet A radiation doses that produce significant numbers of crosslinks, γ-H2AX levels in nucleotide excision repair-deficient XP-A fibroblasts (XP12RO-SV) increased to levels that were twice those observed in normal control GM637 fibroblasts. A partial XPA revertant cell line (XP129) that is proficient in crosslink removal, exhibited reduced γ-H2AX levels that were intermediate between those of GM637 and XP-A cells. XP-F fibroblasts (XP2YO-SV and XP3YO) that are also repair-deficient exhibited γ-H2AX levels below even control fibroblasts following treatment with psoralen and ultraviolet A radiation. Similarly, another crosslinking agent, mitomycin C, did not induce γ-H2AX in XP-F cells, although it did induce equivalent levels of γ-H2AX in XPA and control GM637 cells. Ectopic expression of XPF in XP-F fibroblasts restored γ-H2AX induction following treatment with crosslinking agents. Angelicin, a furocoumarin which forms only monoadducts and not crosslinks following ultraviolet A radiation, as well as ultraviolet C radiation, resulted only in weak induction of γ-H2AX in all cells, suggesting that the double strand breaks observed with psoralen and ultraviolet A treatment result preferentially following crosslink formation. These results indicate that XPF is required to form γ-H2AX and likely double strand breaks in response to interstrand crosslinks in human cells. Furthermore, XPA may be important to allow psoralen interstrand crosslinks to be processed without forming a double strand break intermediate. PMID:16678501

Crosslinking of polysaccharides in room temperature ionic liquids by ionizing radiation

NASA Astrophysics Data System (ADS)

Kimura, Atsushi; Nagasawa, Naotsugu; Shimada, Akihiko; Taguchi, Mitsumasa

2016-07-01

Crosslinking of polysaccharides in room temperature ionic liquids (RTILs) by ionizing radiation were investigated by the scavenging method, fluorescent and X-ray photoelectron spectroscopy (XPS) analysis. Radiation chemical yields of hydroxyl radicals inducing the crosslinking of cellulose were estimated with phenol as a scavenger, and increased with water content in 1-ethyl-3-methylimidazolium acetate (EMI-acetate). Cellulose gel was also produced in fluorescent carboxylate-based RTILs, 1,3-dibutylimidazolium acetate (DBI-acetate). Light emission from DBI-acetate in cellulose gel was observed and 20-nm red shifted at a maximum wavelength of 415 nm when excited at 323 nm. Expected elements of carbon and oxygen were detected in neat cellulose by XPS, while additional nitrogen was detected in radiation-crosslinked cellulose gel produced in EMI-acetate. These results indicate that RTILs is incorporated in the cellulose gel. Chitin gel was first obtained in 1-butyl-3-methyimidazolium chloride by γ-ray irradiations, and its gel fraction increased with the dose and reached 86% at 60 kGy.

Effect of crosslinking UHMWPE on its tensile and compressive creep performance.

PubMed

Lewis, G; Carroll, M

2001-01-01

The in vitro quasi-static tensile and compressive creep properties of three sets of GUR 1050 ultra-high-molecular-weight polyethylene (UHMWPE) specimens were obtained. These sets were: control (as-received stock); "low-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 5 Mrad); and "high-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 15 Mrad). The % crystallinity (%C) and crosslink density (rho(x)) of the specimens in the three sets were also obtained. It was found that, in both tension and compression, crosslinking resulted in a significant depreciation in the creep properties, relative to control. The trend in the creep results is explained in terms of the impact of crosslinking on the polymer's %C and rho(x). The present results are in contrast to literature reports that show that crosslinking enhances the wear resistance of the polymer. The implications of the present results, taken together with the aforementioned literature results, are fully discussed vis-a-vis the use of crosslinked UHMWPE for fabricating articular components for arthroplasties.

Gamma radiation-induced synthesis and characterization of Polyvinylpyrrolidone nanogels

NASA Astrophysics Data System (ADS)

Ges, A. A.; Viltres, H.; Borja, R.; Rapado, M.; Aguilera, Y.

2017-01-01

Due to the importance of bioactive peptides, proteins and drug for pharmaceutical purpose, there is a growing interest for suitable delivery systems, able to increase their bioavailability and to target them to the desired location. Some of the most studied delivery systems involve encapsulation or entrapment of drugs into biocompatible polymeric devices. A multitude of techniques have been described for the synthesis of nanomaterials from polymers, however, the use of ionizing radiation (γ, e-), to obtain nano- and microgels polymer is characterized by the possibility of obtaining products with a high degree of purity. Although, in the world, electronic radiation is used for this purpose, gamma radiation has not been utilized for these purposes. In this paper is developed the formulation the formulation of Polyvinylpyrrolidone (PVP) nanogels synthesized by gamma radiation techniques, for their evaluation as potential system of drug delivery. Experiments were performed in absence of oxygen using aqueous solutions of PVP (0.05% -1%). Crosslinking reactions were carried out at 25° C in a gamma irradiation chamber with a 60Co source (MPX-γ 30). The Viscosimetry, Light Scattering, X-Ray Diffraction and Transmission Electron Microscopy (TEM), were used as characterization techniques.

Novel active stabilization technology in highly crosslinked UHMWPEs for superior stability

NASA Astrophysics Data System (ADS)

Oral, Ebru; Neils, Andrew L.; Wannomae, Keith K.; Muratoglu, Orhun K.

2014-12-01

Radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is the bearing of choice in joint arthroplasty. The demands on the longevity of this polymer are likely to increase with the recently advancing deterioration of the performance of alternative metal-on-metal implants. Vitamin E-stabilized, cross-linked UHMWPEs are considered the next generation of improved UHMWPE bearing surfaces for improving the oxidation resistance of the polymer. It was recently discovered that in the absence of radiation-induced free radicals, lipids absorbed into UHMWPE from the synovial fluid can initiate oxidation and result in new free radical-mediated oxidation mechanisms. In the presence of radiation-induced free radicals, it is possible for the polymer to oxidize through both existing free radicals at the time of implantation and through newly formed free radicals in vivo. Thus, we showed that reducing the radiation-induced free radicals in vitamin E-stabilized UHMWPE would increase its oxidative stability and presumably lead to improved longevity. We describe mechanical annealing and warm irradiation of irradiated vitamin E blends as novel methods to eliminate 99% of radiation-induced free radicals without sacrificing crystallinity. These are significant improvements in the processing of highly cross-linked UHMWPE for joint implants with improved longevity.

Study of crosslinking onset and hydrogen annealing of ultra-high molecular weight polyethylene irradiated with high-energy protons

NASA Astrophysics Data System (ADS)

Wilson, John Ford

1997-09-01

Ultra high molecular weight polyethylene (UHMW-PE) is used extensively in hip and knee endoprostheses. Radiation damage from the sterilization of these endoprostheses prior to surgical insertion results in polymer crosslinking and decreased oxidative stability. The motivation for this study was to determine if UHMW-PE could be crosslinked by low dose proton irradiation with minimal radiation damage and its subsequent deleterious effects. I found that low dose proton irradiation and post irradiation hydrogen annealing did crosslink UHMW-PE and limit post irradiation oxidation. Crosslinking onset was investigated for UHMW-PE irradiated with 2.6 and 30 MeV H+ ions at low doses from 5.7 × 1011-2.3 × 1014 ions/cm2. Crosslinking was determined from gel permeation chromatography (GPC) of 1,2,4 trichlorobenzene sol fractions and increased with dose. Fourier transform infrared spectroscopy (FTIR) showed irradiation resulted in increased free radicals confirmed from increased carbonyl groups. Radiation damage, especially at the highest doses observed, also showed up in carbon double bonds and increased methyl end groups. Hydrogen annealing after ion irradiation resulted in 40- 50% decrease in FTIR absorption associated with carbonyl. The hydrogen annealing prevented further oxidation after aging for 1024 hours at 80oC. Hydrogen annealing was successful in healing radiation damage through reacting with the free radicals generated during proton irradiation. Polyethylenes, polyesters, and polyamides are used in diverse applications by the medical profession in the treatment of orthopedic impairments and cardiovascular disease and for neural implants. These artificial implants are sterilized with gamma irradiation prior to surgery and the resulting radiation damage can lead to accelerated deterioration of the implant properties. The findings in this study will greatly impact the continued use of these materials through the elimination of many problems associated with radiation damage from sterilization. The higher energy transfer for proton compared to gamma irradiation greatly accelerated the radiation damage. Radiation damage increased linearly with dose over the range of doses examined. These results were consistent with findings from earlier researchers of gamma irradiation of polyethylene.

Influence of gamma irradiation on polymerization of pyrrole and glucose oxidase immobilization onto poly (pyrrole)/poly (vinyl alcohol) matrix

NASA Astrophysics Data System (ADS)

Idris, Sarada; A. Bakar, Ahmad Ashrif; Thevy Ratnam, Chantara; Kamaruddin, Nur Hasiba; Shaari, Sahbudin

2017-04-01

This paper describes the immobilization of glucose oxidase, GOx onto polymer matrix comprising of poly(pyrrole), PPy and poly(vinyl alcohol), PVA using gamma irradiation technique. Py/PVA-GOx film was prepared by spreading PVA:GOx, 1:1 solution onto dried pyrrole film and exposed to gamma irradiation from cobalt 60 source at doses ranging from 0 to 60 kGy. The films were subjected to structural and morphological analyses by using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Field emission scanning electron microscope (FESEM) and Atomic-force microscopy (AFM) techniques. Similar studies were also made on pristine pyrrole film which served as control. The SEM and FTIR spectra of Py/PVA-GOx film revealed that pyrrole has been successfully polymerized through irradiation-induced reactions. The results on the morphological properties of the samples characterize using FESEM, SEM and AFM further confirmed the occurrence of radiation-induced modification of Py/PVA-GOx film. The FTIR spectra showed the existence of intermolecular interaction between polymer matrix and GOx indicating that GOx had been successfully immobilized onto Ppy/PVA matrix by radiation-induced reactions. Results revealed that radiation induced reactions such as polymerization of pyrrole, crosslinking of PVA, grafting between the adjacent PVA and pyrrole molecules as well as immobilization of GOx onto Ppy/PVA matrix occurred simultaneously upon gamma irradiation. The optimum dose for GOx immobilization in the polymer matrix found to be 40 kGy. Therefore it is clear that this irradiation technique offered a simple single process to produce Py/PVA-GOx film without additional crosslinking and polymerization agents.

Synthesis of (azelaic-co-dodecanedioic) polyanhydride by microwave technique

NASA Astrophysics Data System (ADS)

Gutiérrez, M.; Sierra, C.; Acevedo Morantes, M.; Herrera, A. P.

2016-02-01

A polyanhydride was synthesized through microwave radiation using azelaic acid and dodecanedioic dicarboxylic acid at concentrations of 75:25, 50:50, and 25:75%w/w with acetic anhydride as crosslinking agent. Polymerization was carried out during 3 and 5 minutes. The copolymer with the highest molecular weight was selected using the intrinsic viscometry technique and by Huggin/Kraemer and Solomon/Ciuta methods. Based on these measurements, the 50:50 copolymer was selected with a polymerization time of 3 minutes in the microwave. This sample displayed the highest intrinsic viscosity (41.82cm3/g), demonstrating the relevance of the microwave technique for the synthesis of biopolymers.

Radiation crosslinking of highly plasticized PVC

NASA Astrophysics Data System (ADS)

Mendizabal, E.; Cruz, L.; Jasso, C. F.; Burillo, G.; Dakin, V. I.

1996-02-01

To improve the physical properties of highly plasticized PVC, the polymer was crosslinked by gamma irradiation using a dose rate of 91 kGy/h. The effect of plasticizer type was studied by using three different plasticizers, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), di(2-ethyl hexyl) phthalate (DOP), and di(2-ethylhexyl terephthalate) (DOTP), and varying irradiation doses. Gel content was determined by soxhlet extraction, tensile measurements were made on a universal testing machine and the mechano-dynamic measurements were made in a dynamic rheometer. It was found that a considerable bonding of plasticizer molecules to macromolelcules takes place along with crosslinking, so that the use of the solvent extraction method for measuring the degree of crosslinking can give erroneous information. Radiation-chemical crosslinking yield ( Gc) and molecular weight of interjunctions chains ( Mc), were calculated for different systems studied. Addition of ethylene glycol dimethacrylate (EGDM) as a crosslinking coagent and dioctyl tin oxide (DOTO) as a stabilizer was also studied. Plasticizers extraction resistance was increased by irradiation treatment.

Selective Permeability of PVA Membranes. I: Radiation-Crosslinked Membranes

NASA Technical Reports Server (NTRS)

Katz, Moshe G.; Wydeven, Theodore, Jr.

1981-01-01

The water and salt transport properties of ionizing radiation crosslinked poly(vinyl alcohol) (PVA) membranes were investigated. The studied membranes showed high permeabilities and low selectivities for both water and salt. The results were found to be in accord with a modified solution-diffusion model for transport across the membranes, in which pressure-dependent permeability coefficients are employed.

Selective permeability of PVA membranes. I - Radiation-crosslinked membranes

NASA Technical Reports Server (NTRS)

Katz, M. G.; Wydeven, T., Jr.

1981-01-01

The water and salt transport properties of ionizing radiation crosslinked poly(vinyl alcohol) (PVA) membranes were investigated. The studied membranes showed high permeabilities and low selectivities for both water and salt. The results were found to be in accord with a modified solution-diffusion model for transport across the membranes, in which pressure-dependent permeability coefficients are employed.

Gamma Irradiation and Oxidative Degradation of a Silica-Filled Silicone Elastomer

DOE PAGES

Labouriau, Andrea; Cady, Carl Mcelhinney; Gill, John T.; ...

2015-03-21

The radiation oxidative degradation of a commonly used silica-filled silicone elastomer DC745 was investigated by a series of experimental techniques. This elastomer is known to be chemically and thermally stable, but insufficient data exist on the radiation resistance. In the present work, gamma doses up to 200 kGy were applied under air at RT and 1Gy/s. Radiation chemical changes were investigated by NMR, FT-IR, Raman, and mass spectroscopy. DSC and TGA experiments probed thermal transitions and thermal stability changes with exposure dose. SEM probed variations on the surface of the elastomer, and solvent swelling methods were used to investigate changesmore » in the polymer network properties. Electron paramagnetic resonance was employed to detect and identify free radicals. Uniaxial compression load tests at variable temperatures were performed to assess changes in the material’s mechanical response as a function of radiation dose. Results demonstrate that, with increasing exposure, DC745 undergoes changes in chemistry that lead to an increase in thermal stability and cross-link density, formation of free radical species, decrease in heat of fusion and increase in stiffness at low temperatures. Taken together, these results indicate that oxidative cross-linking is the dominant radiolysis mechanism that occurs when this material is exposed to gamma irradiation in air at high dose rates.« less

Gamma Irradiation and Oxidative Degradation of a Silica-Filled Silicone Elastomer

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

Labouriau, Andrea; Cady, Carl Mcelhinney; Gill, John T.

The radiation oxidative degradation of a commonly used silica-filled silicone elastomer DC745 was investigated by a series of experimental techniques. This elastomer is known to be chemically and thermally stable, but insufficient data exist on the radiation resistance. In the present work, gamma doses up to 200 kGy were applied under air at RT and 1Gy/s. Radiation chemical changes were investigated by NMR, FT-IR, Raman, and mass spectroscopy. DSC and TGA experiments probed thermal transitions and thermal stability changes with exposure dose. SEM probed variations on the surface of the elastomer, and solvent swelling methods were used to investigate changesmore » in the polymer network properties. Electron paramagnetic resonance was employed to detect and identify free radicals. Uniaxial compression load tests at variable temperatures were performed to assess changes in the material’s mechanical response as a function of radiation dose. Results demonstrate that, with increasing exposure, DC745 undergoes changes in chemistry that lead to an increase in thermal stability and cross-link density, formation of free radical species, decrease in heat of fusion and increase in stiffness at low temperatures. Taken together, these results indicate that oxidative cross-linking is the dominant radiolysis mechanism that occurs when this material is exposed to gamma irradiation in air at high dose rates.« less

Photocrosslinking and Photodamage in Protein-Nucleic Acid Systems Resulting from UV and IR Radiation.

NASA Astrophysics Data System (ADS)

Kozub, John Andrew

1995-01-01

Photocrosslinking of protein-nucleic acid complexes with low intensity UV has frequently been used to study biological systems. We have investigated the photochemistry of protein-nucleic acid systems using nanosecond UV pulses from a Nd:YAG-pumped dye laser system, low-intensity continuous UV from a typical germicidal lamp, and high-intensity mid -IR pulses from the Vanderbilt Free Electron Laser. Quantum yields for UV-induced nucleic acid damage from laser pulses and the germicidal lamp were found to be nearly equivalent. We have demonstrated the general applicability of the laser to this technique by successfully crosslinking hnRNP protein to RNA, yeast TATA-binding protein to dsDNA, and gene 32 protein to ssDNA with UV laser pulses. Our results indicate that UV-crosslinking has an intrinsic specificity for nucleic acid sites containing thymidine (or uridine), forcing a distinction between preferred binding sites and favorable crosslinking sites. We have found in each system that protein and nucleic acid photodamage competes with crosslinking, limits the yield, and may interfere with subsequent analysis. The distribution of photoproducts in the gene 32 protein-ssDNA system was investigated as a function of the total dose of UV radiation and the intensity of UV laser pulses. It was found that laser pulses providing up to 50 photons per nucleic acid base induce a linear response from the system; the absolute and relative yields of photoproducts depend only on the total dose of UV and not on the rate of delivery. At higher intensities, the yield of crosslinks per incident photon was reduced. A single pulse at the optimum intensity (about 100-200 photons per nucleic acid base) induced roughly 80% of the maximum attainable yield of crosslinks in this system. The early results of our search for photochemistry induced by Free Electron Laser pulses indicate the potential to induce a unique photoreaction in the gene 32 protein -ssDNA system. The yield is apparently enhanced by simultaneous exposure to UV pulses. Future experiments will test the potential of IR and UV irradiations to increase the specificity for photocrosslinks.

Dependence of nanomechanical modification of polymers on plasma-induced cross-linking

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

Tajima, S.; Komvopoulos, K.

2007-01-01

The nanomechanical properties of low-density polyethylene (LDPE) modified by inductively coupled, radio-frequency Ar plasma were investigated by surface force microscopy. The polymer surface was modified under plasma conditions of different ion energy fluences and radiation intensities obtained by varying the sample distance from the plasma power source. Nanoindentation results of the surface stiffness versus maximum penetration depth did not reveal discernible differences between untreated and plasma-treated LDPE, presumably due to the small thickness of the modified surface layer that resulted in a substrate effect. On the contrary, nanoscratching experiments demonstrated a significant increase in the surface shear resistance of plasma-modifiedmore » LDPE due to chain cross-linking. These experiments revealed an enhancement of cross-linking with increasing ion energy fluence and radiation intensity, and a tip size effect on the friction force and dominant friction mechanisms (adhesion, plowing, and microcutting). In addition, LDPE samples with a LiF crystal shield were exposed to identical plasma conditions to determine the role of vacuum ultraviolet (VUV) and ultraviolet (UV) radiation in the cross-linking process. The cross-linked layer of plasma-treated LDPE exhibited much higher shear strength than that of VUV/UV-treated LDPE. Plasma-induced surface modification of the nanomechanical properties of LDPE is interpreted in the context of molecular models of the untreated and cross-linked polymer surfaces derived from experimental findings.« less

In vivo degradation in modern orthopaedic UHMWPE bearings and structural characterization of a novel alternative UHMWPE material

NASA Astrophysics Data System (ADS)

Reinitz, Steven D.

Ultra-high molecular weight polyethylene (UHMWPE) remains the most common bearing material for total joint arthroplasty. Advances in radiation cross-linking and other post-consolidation treatments have led to a rapid differentiation of polyethylene products on the market, with more than twenty unique materials currently being sold by the five largest orthopaedic manufacturers alone. Through oxidation, cross-link density, and free radical measurements, this work demonstrates for the first time that in vivo material degradation is occurring in cross-linked UHMWPE materials. Based on the rate of the reaction in certain materials, it is concluded that oxidative degradation may compromise the mechanical properties of the bearings in as few as ten years, potentially leading to early clinical failure of the devices. Using the knowledge gained from this work as well as previously published observations about UHMWPE oxidation, a two-mechanism model of oxidation is proposed that offers an explanation for the observed in vivo changes. From this model it is concluded that oxidative degradation is in part the result of in vivo chemical species. The two-mechanism model of oxidation suggests that different processing techniques for UHMWPE may reduce the risk of oxidative degradation. It is concluded that by avoiding any radiation cross-linking step, Equal Channel Angular Processing (ECAP) can produce UHMWPE materials with a reduced risk for in vivo oxidation while at the same time offering superior mechanical properties compared to commercially available UHMWPE materials, as well as similar wear behavior. Using dynamic mechanical analysis, the entanglement density in ECAP materials is quantified, and is related back to the ECAP processing parameters. The relationship between entanglement density and resultant material properties is established. The results will allow informed processing parameter selection for producing optimized materials for orthopaedics and other applications.

Crosslinking of aromatic polyamides via pendant propargyl groups

NASA Technical Reports Server (NTRS)

St.clair, A. K.; St.clair, T. L.; Barrick, J. D.; Campbell, F. J.

1980-01-01

Methods for crosslinking N-methyl substituted aromatic polyamides were investigated in an effort to improve the applicability of these polymers as matrix resins for Kavlar trademark fiber composites. High molecular weight polymers were prepared from isophthaloyl dichloride and 4,4'- bis(methylamino)diphenylmethane with varying proportions of the N,N'bispropargyl diamine incorporated as a crosslinking agent. The propargylcontaining diamines were crosslinked thermally and characterized by infrared spectroscopy, differential scanning calorimetry, and thermogravimetric analysis. Attempts were also made to crosslink polyamide films by exposure to ultraviolet light, electron beam, and gamma radiation.

Physicochemical characterizations of functional hybrid liposomal nanocarriers formed using photo-sensitive lipids

PubMed Central

Kumar Pramanik, Sumit; Losada-Pérez, Patricia; Reekmans, Gunter; Carleer, Robert; D’Olieslaeger, Marc; Vanderzande, Dirk; Adriaensens, Peter; Ethirajan, Anitha

2017-01-01

With recent advances in the field of diagnostics and theranostics, liposomal technology has secured a fortified position as a potential nanocarrier. Specifically, radiation/photo-sensitive liposomes containing photo-polymerizable cross-linking lipids are intriguing as they can impart the vesicles with highly interesting properties such as response to stimulus and improved shell stability. In this work, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphoethanolamine (DTPE) is used as a photo-polymerizable lipid to form functional hybrid-liposomes as it can form intermolecular cross-linking through the diacetylenic groups. Hybrid-liposomes were formulated using mixtures of DTPE and saturated lipids of different chain lengths (dipalmitoylphosphatidylcholine (DPPC) and dimirystoilphosphatidylcholine (DMPC)) at different molar ratios. The physico-chemical characteristics of the liposomes has been studied before and after UV irradiation using a combination of techniques: DSC, QCM-D and solid-state NMR. The results signify the importance of a subtle modification in alkyl chain length on the phase behavior of the hybrid-liposomes and on the degree of crosslinking in the shell. PMID:28406235

Tunable photonic multilayer sensors from photo-crosslinkable polymers

NASA Astrophysics Data System (ADS)

Chiappelli, Maria; Hayward, Ryan

2014-03-01

The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

Progress in radiation processing of polymers

NASA Astrophysics Data System (ADS)

Chmielewski, Andrzej G.; Haji-Saeid, Mohammad; Ahmed, Shamshad

2005-07-01

Modification in polymeric structure of plastic material can be brought either by conventional chemical means or by exposure to ionization radiation from ether radioactive sources or highly accelerated electrons. The prominent drawbacks of chemical cross-linking typically involve the generation of noxious fumes and by products of peroxide degradation. Both the irradiation sources have their merits and limitations. Increased utilization of electron beams for modification and enhancement of polymer materials has been in particular witnessed over the past 40 years. The paper highlights several recent cases of EB utilization to improve key properties of selected plastic products. In paper is provided a survey of radiation processing methods of industrial interest, encompassing technologies which are already commercially well established, through developments in the active R&D stage which show pronounced promise for future commercial use. Radiation cross-linking technologies discussed include: application in cable and wire, application in rubber tyres, radiation vulcanization of rubber latex, development of radiation crosslinked SiC fiber, polymer recycling, development of gamma compatible pp, hydrogels etc. Over the years, remarkable advancement has been achieved in radiation processing of natural polymers. Role of radiation in improving the processing of temperature of PCL for use as biodegradable polymer, in accelerated breakdown of cellulose into viscose and enhancement in yields of chitin/chitosan from sea-food waste, is described.

Spectroscopic analysis of radiation-generated changes in tensile properties of a polyetherimide film

NASA Technical Reports Server (NTRS)

Long, E. R., Jr.; Long, S. A. T.

1985-01-01

The effects of electron radiation on Ultem, a polyetherimide were studied for doses from 2 x 10 to the 9th power to 6 x 10 to the 9th power rad. Specimens were studied for tensile property testing and for electron paramagnetic resonance and infrared spectroscopic measurements of molecular structure. A Faraday cup design and a method for remote temperature measurement were developed. The spectroscopic data show that radiation caused dehydrogenation of methyl groups, rupture of main-chain ether linkage, and opening of imide rings, all to form radicals and indicate that the so-formed atomic hydrogen attached to phenyl radicals, but not to phenoxyl radicals, which would have formed hydroxyls. The observed decays of the radiation-generated phenoxyl, gem-dimethyl, and carbonyl radicals were interpreted as a combining of the radicals to form crosslinking. This crosslinking is the probable cause of the major reduction in the elongation of the tensile specimens after irradiation. Subsequent classical solubility tests indicate that the irradiation caused massive crosslinking.

A novel mechanism of UV-A and riboflavin-mediated corneal cross-linking through induction of tissue transglutaminases.

PubMed

Kopsachilis, Nikolaos; Tsaousis, Konstantinos T; Tsinopoulos, Ioannis T; Kruse, Friedrich E; Welge-Luessen, Ulrich

2013-07-01

Collagen cross-linking using UV-A irradiation combined with the photosensitizer riboflavin is a new technique for treating progressive keratoconus. The purposes of this study were to examine whether primary human corneal keratocytes (HCKs) are capable of expressing and secreting fibronectin and tissue transglutaminase (tTgase), an enzyme cross-linking extracellular matrix protein, and to examine whether fibronectin and tTgase are increased after the treatment of HCK cells with UV-A irradiation combined with riboflavin (RFUV-A), thus providing another possible physiological mechanism of the cross-linking pathway. Cell cultures established from HCKs were treated with 0.025% riboflavin solution and UV-A (370 nm) irradiance 3 mW/cm2 for 30 minutes. Induction of fibronectin and tTgase was investigated by immunohistochemistry, real-time polymerase chain reaction, and Western blot analysis. Cell viability was quantified by a microscopic live-dead assay. External tTgase activity was measured by the ability to form polymerized fibronectin and the incorporation of biotinylated cadaverine into fibronectin. Treatment of cultured HCK cells with RFUV-A increased the fibronectin and tTgase messenger RNA and protein levels. This effect was not observed in cells treated with riboflavin or UV-A radiation alone. Incorporation of biotinylated cadaverine was significantly increased when HCK cells were treated with RFUV-A. The enzymes tTgase and fibronectin are expressed by RFUV-A treatment in cultured HCK cells. This mechanism provides more information about the physiology of corneal cross-linking.

Radiation processed polychloroprene-co-ethylene-propene diene terpolymer blends: Effect of radiation vulcanization on solvent transport kinetics

NASA Astrophysics Data System (ADS)

Dubey, K. A.; Bhardwaj, Y. K.; Chaudhari, C. V.; Kumar, Virendra; Goel, N. K.; Sabharwal, S.

2009-03-01

Blends of polychloroprene rubber (PCR) and ethylene propylene diene terpolymer rubber (EPDM) of different compositions were made and exposed to different gamma radiation doses. The radiation sensitivity and radiation vulcanization efficiency of blends was estimated by gel-content analysis, Charlesby-Pinner parameter determination and crosslinking density measurements. Gamma radiation induced crosslinking was most efficient for EPDM ( p0/ q0 ˜ 0.08), whereas it was the lowest for blends containing 40% PCR ( p0/ q0 ˜ 0.34). The vulcanized blends were characterized for solvent diffusion characteristics by following the swelling dynamics. Blends with higher PCR content showed anomalous swelling. The sorption and permeability of the solvent were not strictly in accordance with each other and the extent of variation in two parameters was found to be a function of blend composition. The Δ G values for solvent diffusion were in the range -2.97 to -9.58 kJ/mol and indicated thermodynamically favorable sorption for all blends. These results were corroborated by dynamic swelling, experimental as well as simulated profiles and have been explained on the basis of correlation between crosslinking density, diffusion kinetics, thermodynamic parameters and polymer-polymer interaction parameter.

Synthesis of fast response crosslinked PVA-g-NIPAAm nanohydrogels by very low radiation dose in dilute aqueous solution

NASA Astrophysics Data System (ADS)

Fathi, Marziyeh; Reza Farajollahi, Ali; Akbar Entezami, Ali

2013-05-01

Nanohydrogels of poly(vinyl alcohol)-g-N-isopropylacrylamide (PVA-g-NIPAAm) are synthesized by PVA and NIPAAm dilute aqueous solution using much less radiation dose of 1-20 Gy via intramolecular crosslinking at ambient temperature. The radiation synthesis of nanohydrogels is performed in the presence of tetrakis (hydroxymethyl) phosphonium chloride (THPC) due to its rapid oxygen scavenging abilities and hydrogen peroxide (H2O2) as a source of hydroxyl radicals. The effect of radiation dose, feed composition ratio of PVA and H2O2 is investigated on swelling properties such as temperature and pH dependence of equilibrium swelling ratio as well as deswelling kinetics. Experimental data exhibit high equilibrium swelling ratio and fast response time for the synthesized nanohydrogels. The average molecular weight between crosslinks (Mc) and crosslinking density (ρx) of the obtained nanohydrogels are calculated from swelling data as a function of radiation dose, H2O2 and PVA amount. Fourier transform infrared spectroscopy (FT-IR), elemental analysis of nitrogen content and thermogravimetric analysis (TGA) are used to confirm the grafting reaction. Lower critical solution temperature (LCST) is measured around 33 °C by differential scanning calorimetry (DSC) for PVA-g-NIPAAm nanohydrogels. Dynamic light scattering (DLS) data demonstrate that the increase of radiation dose leads to the decreasing in dimension of nanohydrogels. Also, rheological studies are confirmed an improvement in the mechanical properties of the nanohydrogels with increasing the radiation dose. A cytotoxicity study exhibits a good biocompatibility for the obtained nanohydrogels. The prepared nanohydrogels show fast swelling/deswelling behavior, high swelling ratio, dual sensitivity and good cytocompatibility, which may find potential applications as biomaterial.

Remarkably enhanced thermal stability of an irradiation-crosslinked ethylene-octene copolymer by incorporation of a novel organic/inorganic hybrid nano-sensitizer

NASA Astrophysics Data System (ADS)

Zhang, Sideng; Sun, Bin; Jiang, Xiaoze; Li, Lili; Meng, Zhouqi; Zhu, Meifang

2015-01-01

We report a novel method to improve the anti-thermal-deformation performance of an ethylene-octene copolymer (POE) using vinyl functionalized silica nanoparticles (M-SiO2) as a sensitizer to enhance radiation-induced crosslinking. The M-SiO2 nanoparticles were prepared by coupling commercially available silica nanoparticles with KH570 (γ-methacryloxypropyl-trimethoxysilane, γ-MPS) and were blended with POE by melt blending. Then, the mixture was irradiated with γ-rays under a nitrogen atmosphere to form the crosslinked POE/M-SiO2 nanocomposite. The novel nanocomposites were characterized, and the results showed that the gel fraction was proportional to the content of M-SiO2 in the loading range studied in this work. When the content of M-SiO2 was 10 wt%, the gel fraction of POE was increased by approximately 50%, and the softening temperature (T0.5D) increased from 104.4 °C to 224.6 °C after a 120 kGy dose of radiation. The tensile strength of the POE/M-SiO2-10 nanocomposite was better than that of the neat POE copolymer irradiated with an absorption dose up to 100 kGy. In contrast, the elongation of the POE/M-SiO2-10 nanocomposite was lower than that of the neat POE irradiated under the same conditions, due to the increased degree of crosslinking by radiation. These results clearly demonstrated that the use of M-SiO2 as an irradiation sensitizer effectively enhanced the radiation-induced crosslinking of POE.

Radiation crosslinking of styrene-butadiene rubber containing waste tire rubber and polyfunctional monomers

NASA Astrophysics Data System (ADS)

Yasin, Tariq; Khan, Sara; Shafiq, Muhammad; Gill, Rohama

2015-01-01

The objective of this study was to investigate the influence of polyfunctional monomers (PFMs) and absorbed dose on the final characteristics of styrene-butadiene rubber (SBR) mixed with waste tire rubber (WTR). A series of SBR/WTR blends were prepared by varying the ratios of WTR in the presence of PFMs, namely trimethylolpropane trimethacrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA) and crosslinked using gamma rays. The physicochemical characteristics of the prepared blends were investigated. It was observed that tensile strength, hardness and gel content of the blends increased with absorbed dose while the blends containing TMPTA showed higher tensile strength, gel content and thermal stability as compared to the blends containing TMPTMA. Higher thermal stability was observed in the blends which were crosslinked by radiation as compared to the blends crosslinked by sulfur. These blends exhibited higher rate of swelling in organic solvents, whereas negligible swelling was observed in acidic and basic environment.

Rheological analysis of irradiated crosslinkable and scissionable polymers used for medical devices under different radiation conditions

NASA Astrophysics Data System (ADS)

Satti, A. J.; Ressia, J. A.; Cerrada, M. L.; Andreucetti, N. A.; Vallés, E. M.

2018-03-01

The effects on different synthetic polymers of distinct types of radiation, gamma rays and electron beam, under different atmospheres are followed by changes in their viscoelastic behavior. Taking into account the two main radioinduced reactions, crosslinking and scissioning of polymeric chains, liquid polydimethylsiloxane has been used as example of crosslinkable polymer and semi crystalline polypropylene as example of scissionable polymer. Propylene - 1-hexene copolymers have been also evaluated, and the effects of both reactions were clearly noticed. Accordingly, samples of those aforementioned polymers have been irradiated with 60Co gamma irradiation in air and under vacuum, and also with electron beam, at similar doses. Sinusoidal dynamic oscillation experiments showed a significant increase in branching and crosslinking reactions when specimens are irradiated under vacuum, while scissioning reactions were observed for the different polymers when irradiation takes place under air with either gamma irradiation or electron beam.

Preparation of redox polymer cathodes for thin film rechargeable batteries

DOEpatents

Skotheim, T.A.; Lee, H.S.; Okamoto, Yoshiyuki.

1994-11-08

The present invention relates to the manufacture of thin film solid state electrochemical devices using composite cathodes comprising a redox polymer capable of undergoing oxidation and reduction, a polymer solid electrolyte and conducting carbon. The polymeric cathode material is formed as a composite of radiation crosslinked polymer electrolytes and radiation crosslinked redox polymers based on polysiloxane backbones with attached organosulfur side groups capable of forming sulfur-sulfur bonds during electrochemical oxidation.

Natural polyphenols enhance stability of crosslinked UHMWPE for joint implants.

PubMed

Shen, Jie; Gao, Guorong; Liu, Xincai; Fu, Jun

2015-03-01

Radiation-crosslinked UHMWPE has been used for joint implants since the 1990s. Postirradiation remelting enhances oxidative stability, but with some loss in strength and toughness. Vitamin E-stabilized crosslinked UHMWPE has shown improved strength and stability as compared with irradiated and remelted UHMWPE. With more active phenolic hydroxyl groups, natural polyphenols are widely used in the food and pharmaceutical industries as potent stabilizers and could be useful for oxidative stability in crosslinked UHMWPE. We asked whether UHMWPE blended with polyphenols would (1) show higher oxidation resistance after radiation crosslinking; (2) preserve the mechanical properties of UHMWPE after accelerated aging; and (3) alter the wear resistance of radiation-crosslinked UHMWPE. The polyphenols, gallic acid and dodecyl gallate, were blended with medical-grade UHMWPE followed by consolidation and electron beam irradiation at 100 kGy. Radiation-crosslinked virgin and vitamin E-blended UHMWPEs were used as reference materials. The UHMWPEs were aged at 120 °C in air with oxidation levels analyzed by infrared spectroscopy. Tensile (n = 5 per group) and impact (n = 3 per group) properties before and after aging as per ASTM F2003 were evaluated. The wear rates were examined by pin-on-disc testing (n = 3 per group). The data were reported as mean ± SDs. Statistical analysis was performed by using Student's t-test for a two-tailed distribution with unequal variance for tensile and impact data obtained with n ≥ 3. A significant difference is defined with p < 0.05. The oxidation induction time of 100 kGy UHMWPE was prolonged to 144 hours with 0.05 wt% dodecyl gallate and 192 hours with 0.05 wt% gallic acid compared with 48 hours for 0.05 wt% vitamin E-blended UHMWPE. Accelerated aging of these polyphenol-blended UHMWPEs resulted in ultimate tensile strength of 50.4 ± 1.4 MPa and impact strength of 53 ± 5 kJ/m(2) for 100 kGy-irradiated UHMWPE with 0.05 wt% dodecyl gallate, for example, in comparison to 51.2 ± 0.7 MPa (p = 0.75) and 58 ± 5 kJ/m(2) (p = 0.29) before aging. The pin-on-disc wear rates of 100 kGy-irradiated UHMWPE with 0.05 wt% dodecyl gallate and 0.05 wt% gallic acid were 2.29 ± 0.31 and 1.65 ± 0.32 mg/million cycles, comparable to 1.68 ± 0.25 and 2.05 ± 0.22 mg/million cycles for 100 kGy-irradiated virgin and 0.05 wt% vitamin E-blended UHMWPE. Based on the sample numbers tested in this study, polyphenols appear to effectively enhance the oxidation stability without altering the mechanical properties or pin-on-disc wear rate of radiation-crosslinked UHMWPE. Crosslinked UHMWPE with natural polyphenols with improved oxidative stability and low wear may find clinical application in joint implants.

Design of polymeric immunomicrospheres for cell labelling and cell separation

NASA Technical Reports Server (NTRS)

Rembaum, A.; Margel, S.

1978-01-01

Synthesis of several classes of hydrophylic microspheres applied to cell labeling and cell separation is described. Five classes of cross-linked microspheres with functional groups such as carboxyl, hydroxyl, amide and/or pyridine groups were synthesized. These functional groups were used to bind covalently antibodies and other proteins to the surface of the microspheres. To optimize the derivatisation technique, polyglutaraldehyde immunomicrospheres were prepared and utilized. Specific populations of human and murine lymphocytes were labelled with microspheres synthesized by the emulsion of the ionizing radiation technique. The labelling of the cells by means of microspheres containing an iron core produced successful separation of B from T lymphocytes by means of a magnetic field.

Effects of near-UV radiation on the protein of the grey squirrel lens.

PubMed

Zigman, S; Paxhia, T; Waldron, W

1988-06-01

In vivo exposure of grey squirrels to 40W BLB illumination resulted in alterations in the state of the lens crystallins, mainly in the outer layer of the lens. HPLC revealed an increase of the void volume or crosslinked crystallins and an increase in peptides with molecular weights lower than 20,000 d. In vitro exposure of squirrel lens aqueous extracts to Woods lamp radiation (predominantly 365 nm) led to similar but more exaggerated changes as viewed by high performance liquid chromatography. When viewed by polyacrylamide gel electrophoresis (PAGE), soluble protein crosslinking was also observed. The near-UV absorbing chromophores of low molecular weight present in the lens served as photosensitizers that enhanced the protein changes. Sodium azide inhibited the changes, indicating a role for singlet oxygen in the crosslinking.

A comparison between the effects of gamma radiation and sulfur cure system on the microstructure and crosslink network of (styrene butadiene rubber/ethylene propylene diene monomer) blends in presence of nanoclay

NASA Astrophysics Data System (ADS)

Shoushtari Zadeh Naseri, Aida; Jalali-Arani, Azam

2015-10-01

Rubber blends based on (styrene-butadiene rubber (SBR)/ethylene-propylene-diene monomer (EPDM)) with and without organoclay (OC) were prepared through a melt mixing process. The concentration ratio of the rubber phases (EPDM/SBR; 50/50 wt%) and the amount of the OC were kept constant. The samples were then vulcanized by means of gamma radiation using a Co-60 gamma source as well as sulfur cure system. The effect of absorbed dose on the formation of the crosslinks was confirmed by the Fourier transform infrared spectroscopy (FTIR). The effects of absorbed dose, sulfur cure system and OC on the gel content, and crosslink density were evaluated by the chemical tests. Applying the Charlesby-Pinner equation to estimate the radiation chemical yield, revealed that the use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. Employing the swelling test data, some thermodynamic parameters were determined. Using field emission scanning electron microscopy (FE-SEM) to investigate microstructure of the samples revealed a more homogeneous structure and also an increase in compatibility of the blend components in the sample cured by the irradiation in comparison to that cured by the sulfur curing system.

Gamma radiation effects on siloxane-based additive manufactured structures

NASA Astrophysics Data System (ADS)

Schmalzer, Andrew M.; Cady, Carl M.; Geller, Drew; Ortiz-Acosta, Denisse; Zocco, Adam T.; Stull, Jamie; Labouriau, Andrea

2017-01-01

Siloxane-basedadditive manufactured structures prepared by the direct ink write (DIW) technology were exposed to ionizing irradiation in order to gauge radiolysis effects on structure-property relationships. These well-defined 3-D structures were subjected to moderate doses of gamma irradiation in an inert atmosphere and characterized by a suite of experimental methods. Changes in thermal, chemical, microstructure, and mechanical properties were evaluated by DSC, TGA, FT-IR, mass spectroscopy, EPR, solvent swelling, SEM, and uniaxial compressive load techniques. Our results demonstrated that 3-D structures made from aromatic-free siloxane resins exhibited hardening after being exposed to gamma radiation. This effect was accompanied by gas evolution, decreasing in crystallization levels, decreasing in solvent swelling and damage to the microstructure. Furthermore, long-lived radiation-induced radicals were not detected by EPR methods. Our results are consistent with cross-link formation being the dominant degradation mechanism over chain scission reactions. On the other hand, 3-D structures made from high phenyl content siloxane resins showed little radiation damage as evidenced by low off gassing.

Spectroscopic comparison of effects of electron radiation on mechanical properties of two polyimides

NASA Technical Reports Server (NTRS)

Long, Edward R., Jr.; Long, Sheila Ann T.

1987-01-01

The differences in the radiation durabilities of two polyimide materials, Du Pont Kapton and General Electric Ultem, are compared. An explanation of the basic mechanisms which occur during exposure to electron radiation from analyses of infrared (IR) and electron paramagnetic resonance (EPR) spectroscopic data for each material is provided. The molecular model for Kapton was, in part, established from earlier modeling for Ultem (pp. 1293-1298 of IEEE Transactions on Nuclear Science, December 1984). Techniques for understanding the durability of one complex polymer based on the understanding of a different and equally complex polymer are demonstrated. The spectroscopic data showed that the primary radiation-generated change in the tensile properties of Ultem (a large reduction in tensile elongation) was due to crosslinking, which followed the capture by phenyl radicals of hydrogen atoms removed from gem-dimethyl groups. In contrast, the tensile properties of Kapton remained unchanged because radical-radical recombination, a self-mending process, took place.

An investigation of the role of water on retrograde/condensation reactions and enhanced liquefaction yields. Quarterly progress report, January 1, 1994--March 31, 1994

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

Miknis, F.P.; Netzel, D.A.

The results of coal swelling measurements using 1,4-dioxane as the swelling reagent for premoisturized coals (raw) and coal dried thermally, chemically, and with microwave radiation are presented. An increase in the swelling ratio relative to raw coal indicates a decrease in the amount of cross-linking in the coal. Conversely, a decrease in the ratio indicates an increase in cross-linking. The extent of cross-linking (as measured by 1,4-dioxane) for Texas, Black Thunder, and Eagle Butte Coals are about the same. Illinois {number_sign}6 coal appears to have less cross-linking relative to the other three coals. These results are expected on the basismore » of coal rank. The increase in cross linking is most pronounced for coals dried thermally and with microwave radiation. A decrease in the swelling ratios for all four coals suggests that cross-linking had occurred possibly due to partial devolatilization process. However, low temperature, chemical dehydration of the coals causes only a small or no change in the internal structure for Texas and Illinois {number_sign}6 coals whereas a significant decrease in the cross-linking structure for the Black Thunder and Eagle Butte coals is observed. It is possible that the solvent (CH{sub 3}OH) and products resulting from the chemical dehydrating (acetone and methanol) occupy the surface sites that water had before the reaction and thus preventing cross-linking to occur. These reagents can also promote swelling of coals and may account for some of the decrease in the cross-linking of the coal structure observed for the chemically dried coals.« less

A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems

PubMed Central

Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T.; Ware, Taylor; Voit, Walter E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

2014-01-01

The synthetic design and thermomechanical characterization of shape memory polymers (SMPs) built from a new polyurethane chemistry that enables facile, bulk and tunable cross-linking of low-molecular weight thermoplastics by electron beam irradiation is reported in this study. SMPs exhibit stimuli-induced geometry changes and are being proposed for applications in numerous fields. We have previously reported a polyurethane SMP system that exhibits the complex processing capabilities of thermoplastic polymers and the mechanical robustness and tunability of thermomechanical properties that are often characteristic of thermoset materials. These previously reported polyurethanes suffer practically because the thermoplastic molecular weights needed to achieve target cross-link densities severely limit high-throughput thermoplastic processing and because thermally unstable radiation-sensitizing additives must be used to achieve high enough cross-link densities to enable desired tunable shape memory behavior. In this study, we demonstrate the ability to manipulate cross-link density in low-molecular weight aliphatic thermoplastic polyurethane SMPs (Mw as low as ~1.5 kDa) without radiation-sensitizing additives by incorporating specific structural motifs into the thermoplastic polymer side chains that we hypothesized would significantly enhance susceptibility to e-beam cross-linking. A custom diol monomer was first synthesized and then implemented in the synthesis of neat thermoplastic polyurethane SMPs that were irradiated at doses ranging from 1 to 500 kGy. Dynamic mechanical analysis (DMA) demonstrated rubbery moduli to be tailorable between 0.1 and 55 MPa, and both DMA and sol/gel analysis results provided fundamental insight into our hypothesized mechanism of electron beam cross-linking, which enables controllable bulk cross-linking to be achieved in highly processable, low-molecular weight thermoplastic shape memory polymers without sensitizing additives. PMID:25411511

Towards aging mechanisms of cross-linked polyethylene (XLPE) cable insulation materials in nuclear power plants

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

Liu, Shuaishuai; Fifield, Leonard S.; Bowler, Nicola

Cross-linked polyethylene (XLPE) cable insulation material undergoes simultaneous, accelerated thermal and gamma-radiation aging to simulate the long-term aging environment within nuclear power plants (NPPs). A variety of materials characterization tests, including scanning electron microscopy, thermo-gravimetric analysis, differential scanning calorimetry, oxidation induction time, gel-fraction and dielectric properties measurement, are conducted on pristine and differently aged XLPE samples. A preliminary model of one possible aging mechanism of XLPE cable insulation material under gamma radiation at elevated temperature of 115 °C is suggested.

Preparation of well-defined erythromycin imprinted non-woven fabrics via radiation-induced RAFT-mediated grafting

NASA Astrophysics Data System (ADS)

Söylemez, Meshude Akbulut; Barsbay, Murat; Güven, Olgun

2018-01-01

Radiation-induced RAFT polymerization technique was applied to synthesize well-defined molecularly imprinted polymers (MIPs) of erythromycin (ERY). Methacrylic acid (MAA) was grafted onto porous polyethylene (PE)/polypropylene (PP) nonwoven fabrics, under γ-irradiation by employing 2-pheny-2-propyl benzodithioate as the RAFT agent and ethylene glycol dimethacrylate (EGDMA) as the crosslinker. MAA/erythromycin ratios of 2/1, 4/1, 6/1 were tested to optimize the synthesis of MIPs. The highest binding capacity was encountered at a MAA/ERY ratio of 4/1. Non-imprinted polymers (NIPs) were also synthesized in the absence of ERY. The MIPs synthesized by RAFT method presented a better binding capacity compared to those prepared by conventional method where no RAFT agent was employed.

Oxidation resistant peroxide cross-linked UHMWPE produced by blending and surface diffusion

NASA Astrophysics Data System (ADS)

Gul, Rizwan M.; Oral, Ebru; Muratoglu, Orhun K.

2014-06-01

Ultra-high molecular weight polyethylene (UHMWPE) has been widely used as acetabular cup in total hip replacement (THR) and tibial component in total knee replacement (TKR). Crosslinking of UHMWPE has been successful used to improve its wear performance leading to longer life of orthopedic implants. Crosslinking can be performed by radiation or organic peroxides. Peroxide crosslinking is a convenient process as it does not require specialized equipment and the level of crosslinking can be manipulated by changing the amount of peroxide added. However, there is concern about the long-term stability of these materials due to possible presence of by-products. Vitamin E has been successfully used to promote long-term oxidative stability of UHMWPE. In this study, UHMWPE has been crosslinked using organic peroxide in the presence of Vitamin E to produce an oxidation resistant peroxide crosslinked material. Crosslinking was performed both in bulk by mixing peroxide and resin, and only on the surface using diffusion of peroxides.The results show that UHMWPE can be crosslinked using organic peroxides in the presence of vitamin E by both methods. However, the level of crosslinking decreases with the increase in vitamin E content. The wear resistance increases with the increase in crosslink density, and oxidation resistance significantly increases due to the presence of vitamin E.

Microgel Modified UV-Cured Methacrylic-Silica Hybrid: Synthesis and Characterization

PubMed Central

Corcione, Carola Esposito; Striani, Raffaella; Frigione, Mariaenrica

2013-01-01

An innovative photopolymerizable microgel modified UV-cured acrylic-silica hybrid formulation was developed and characterized for possible use as protective coating for different substrates. A deep investigation, aiming at providing a strong scientific basis for the production of organic-inorganic (O-I) hybrids exhibiting phase co-continuity, was firstly carried out. The O-I hybrid first proposed in this study was obtained from organic precursors with a high siloxane content, which are mixed with tetraethoxysilane (TEOS) in such a way to produce co-continuous silica nanodomains dispersed within the crosslinked organic phase, as a result of the sol-gel process. The first part of the research deals with the selection and optimization of suitable systems through appropriate chemical modifications, in order to ensure that curing reactions can be carried out at room temperature and in the presence of UV radiation. Firstly, the silica domains are formed, followed by crosslinking reactions of the acrylic groups in the oligomer via a free radical polymerization. The crosslinking reaction was controlled with the use of a suitable photoinitiator. Most of the experimental work was devoted to understanding the morphology of the hybrid system, both in uncured and cured states, and to assess its final thermal and optical properties, using different experiential techniques. PMID:28788307

Altered Cross-Linking of HSP27 by Zerumbone as a Novel Strategy for Overcoming HSP27-Mediated Radioresistance

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

Choi, Seo-Hyun; School of Life Sciences and Biotechnology, Korea University, Seoul; Lee, Yoon-Jin

Purpose: HSP27 or HSP25 negatively regulates apoptosis pathways after radiation or chemotherapeutic agents. Abrogation of HSP27 function may be a candidate target for overcoming radio- and chemoresistance. Methods and Materials: Zerumbone (ZER), a cytotoxic component isolated from Zingiber zerumbet smith. Clonogenic survival assay and flow cytometry after Annexin V staining were performed to determine in vitro sensitization effects of ZER with ionizing radiation. A nude mouse xenografting system was also applied to detect in vivo radiosensitizing effects of ZER. Results: ZER produced cross-linking of HSP27, which was dependent on inhibition of the monomeric form of HSP27. ZER was directly insertedmore » between the disulfide bond in the HSP27 dimer and modified normal HSP27 dimerization. Pretreatment with ZER before radiation inhibited the binding affinity between HSP27 and apoptotic molecules, such as cytochrome c and PKC{delta}, and induced sensitization in vitro and in an in vivo xenografted nude mouse system. Structural analogs lacking only the carbonyl group in ZER, such as {alpha}-humulene (HUM) and 8-hydroxy-humulen (8-OH-HUM), did not affect normal cross-linking of HSP27 and did not induce radiosensitization. Conclusions: We suggest that altered cross-linking of HSP27 by ZER is a good strategy for abolishing HSP27-mediated resistance.« less

Altered cross-linking of HSP27 by zerumbone as a novel strategy for overcoming HSP27-mediated radioresistance.

PubMed

Choi, Seo-Hyun; Lee, Yoon-Jin; Seo, Woo Duck; Lee, Hae-June; Nam, Joo-Won; Lee, Yoo Jin; Kim, Joon; Seo, Eun-Kyoung; Lee, Yun-Sil

2011-03-15

HSP27 or HSP25 negatively regulates apoptosis pathways after radiation or chemotherapeutic agents. Abrogation of HSP27 function may be a candidate target for overcoming radio- and chemoresistance. Zerumbone (ZER), a cytotoxic component isolated from Zingiber zerumbet smith. Clonogenic survival assay and flow cytometry after Annexin V staining were performed to determine in vitro sensitization effects of ZER with ionizing radiation. A nude mouse xenografting system was also applied to detect in vivo radiosensitizing effects of ZER. ZER produced cross-linking of HSP27, which was dependent on inhibition of the monomeric form of HSP27. ZER was directly inserted between the disulfide bond in the HSP27 dimer and modified normal HSP27 dimerization. Pretreatment with ZER before radiation inhibited the binding affinity between HSP27 and apoptotic molecules, such as cytochrome c and PKCδ, and induced sensitization in vitro and in an in vivo xenografted nude mouse system. Structural analogs lacking only the carbonyl group in ZER, such as α-humulene (HUM) and 8-hydroxy-humulen (8-OH-HUM), did not affect normal cross-linking of HSP27 and did not induce radiosensitization. We suggest that altered cross-linking of HSP27 by ZER is a good strategy for abolishing HSP27-mediated resistance. Copyright © 2011 Elsevier Inc. All rights reserved.

Protection effects of condensed bromoacenaphthylene on radiation deterioration of ethylene-propylene-diene rubber. [Gamma radiation

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

Morita, Y.; Hagiwara, M.; Kasai, N.

1982-09-01

As a continuation of a series of the studies on the flame and ..gamma..-radiation resistant modification of ethylene-propylene-diene rubber (EPDM), condensed bromoacenaphthylene (con-BACN) as a newly developed flame retardant was synthesized and its effects on the radiation resistance of EPDM were investigated. The radiation resistance evaluated by measuring tensile properties of irradiated sheets of 2 mm thick was found improved greatly by adding con-BACN together with ordinary rubber ingredients but decreased by decabromodiphenylether (DBDPE) that has bromins in aromatic rings as con-BACN. When EPDM sheets of 1 mm thick were irradiated in oxygen at a dose rate of 1 Xmore » 10/sup 5/ rad/h, the weight swelling ratio increased with increasing dose, indicating that oxidative main chain scission is predominant under the irradiation conditions. On the other hand, crosslinking was shown to be predominant in nitrogen. From the results of the swelling experiments with different additives, it was concluded that DBDPE accelerates both the main chain scission in oxygen and the crosslinking in nitrogen. In contrast to this, con-BACN reduced the chain scission in oxygen. This observation was accounted by the assumption that the influence of the oxidative chain scission is partly compensated by the concurrent crosslinking which takes place through additions of con-BACN to substrate polymers even in the presence of oxygen.« less

Wear of a 5 megarad cross-linked polyethylene liner: a 6-year RSA study.

PubMed

Callary, Stuart A; Campbell, David G; Mercer, Graham; Nilsson, Kjell G; Field, John R

2013-07-01

One cross-linked polyethylene (XLPE) liner is manufactured using a lower dose of radiation, 5 Mrad, which may result in less cross-linking. The reported in vivo wear rate of this XLPE liner in patients undergoing THA has varied, and has included some patients in each reported cohort who had greater than 0.1 mm/year of wear, which is an historical threshold for osteolysis. Previous studies have measured wear on plain radiographs, an approach that has limited sensitivity. We therefore measured the amount and direction of wear at 6 years using Radiostereometric analysis (RSA) in patients who had THAs that included a cross-linked polyethylene liner manufactured using 5 Mrad radiation. We prospectively reviewed wear in 30 patients who underwent primary THAs with the same design of cross-linked acetabular liner and a 28-mm articulation. Tantalum markers were inserted during surgery and all patients had RSA radiographic examinations at 1 week, 6 months, 1, 2, and 6 years postoperatively. The mean proximal, two-dimensional (2-D) and three-dimensional (3-D) wear rates calculated between 1 year and 6 years were 0.014, 0.014, and 0.018 mm/per year, respectively. The direction of the head penetration recorded between 1 week and 6 years was in a proximal direction for all patients, proximolateral for 16 of 24 patients, and proximomedial for eight of 24 patients. The proximal, 2-D and 3-D wear of a XLPE liner produced using 5 Mrad of radiation was low but measurable by RSA after 6 years. No patients had proximal 2-D or 3-D wear rates exceeding 0.1 mm/year. Further followup is needed to evaluate the effect of XLPE wear particles on the development of long-term osteolysis.

Evaluating the Effects of Riboflavin/UV-A and Rose-Bengal/Green Light Cross-Linking of the Rabbit Cornea by Noncontact Optical Coherence Elastography

PubMed Central

Singh, Manmohan; Li, Jiasong; Han, Zhaolong; Vantipalli, Srilatha; Liu, Chih-Hao; Wu, Chen; Raghunathan, Raksha; Aglyamov, Salavat R.; Twa, Michael D.; Larin, Kirill V.

2016-01-01

Purpose The purpose of this study was to use noncontact optical coherence elastography (OCE) to evaluate and compare changes in biomechanical properties that occurred in rabbit cornea in situ after corneal collagen cross-linking by either of two techniques: ultraviolet-A (UV-A)/riboflavin or rose-Bengal/green light. Methods Low-amplitude (≤10 μm) elastic waves were induced in mature rabbit corneas by a focused air pulse. Elastic wave propagation was imaged by a phase-stabilized swept source OCE (PhS-SSOCE) system. Corneas were then cross-linked by either of two methods: UV-A/riboflavin (UV-CXL) or rose-Bengal/green light (RGX). Phase velocities of the elastic waves were fitted to a previously developed modified Rayleigh-Lamb frequency equation to obtain the viscoelasticity of the corneas before and after the cross-linking treatments. Micro-scale depth-resolved phase velocity distribution revealed the depth-wise heterogeneity of both cross-linking techniques. Results Under standard treatment settings, UV-CXL significantly increased the stiffness of the corneas by ∼47% (P < 0.05), but RGX did not produce statistically significant increases. The shear viscosities were unaffected by either cross-linking technique. The depth-wise phase velocities showed that UV-CXL affected the anterior ∼34% of the corneas, whereas RGX affected only the anterior ∼16% of the corneas. Conclusions UV-CXL significantly strengthens the cornea, whereas RGX does not, and the effects of cross-linking by UV-CXL reach deeper into the cornea than cross-linking effects of RGX under similar conditions. PMID:27409461

Biodegradable organic acid-crosslinked alkali-treated gelatins with anti-thrombogenic and endothelialization properties

PubMed Central

Inoue, Motoki; Sasaki, Makoto; Taguchi, Tetsushi

2012-01-01

Gelatins were crosslinked with organic acids and treated with alkali to impart to them endothelialization and anti-thrombogenic properties. These matrices were characterized by biochemical and physicochemical techniques. The amounts of residual amino groups in the matrices decreased with increasing crosslinker concentration. The matrices with the highest crosslinking densities showed excellent endothelial cell adhesion and proliferation. In addition, the adhesion of platelets and formation of fibrin networks on the matrices were suppressed with increasing crosslinker concentration. The matrices also exhibited excellent biodegradability, and the degradation rate decreased with increasing crosslinking density. All the organic acid-crosslinked alkali-treated gelatins showed excellent anti-thrombogenic and endothelialization properties, superior to those of glutaraldehyde-crosslinked alkali-treated gelatins. PMID:27877542

Swelling of radiation crosslinked acrylamide-based microgels and their potential applications

NASA Astrophysics Data System (ADS)

Abd El-Rehim, H. A.

2005-10-01

Crosslinked polyacrylamide PAAm and acrylamide-Na-acrylate P(AAm-Na-AAc) microgels were prepared by electron beam irradiation. It was found that the dose required for crosslinking depends on the polymer moisture content, so that the dose to obtain PAAm of maximum gel fraction was over 40 and 20 kGy for dry and moist PAAm, respectively. The structural changes in irradiated PAAm were investigated using FTIR and SEM. The swelling property of such microgels in distilled water and real urine solution was determined and crosslinked polymers reached their equilibrium swelling state in a few minutes. As the gel content and crosslinking density decrease, the swelling of the microgels increases. The ability of the microgels to absorb and retain large amount of solutions suggested their possible uses in horticulture and in hygienic products such as disposable diapers.

Radiation-induced DNA-protein cross-links: Mechanisms and biological significance.

PubMed

Nakano, Toshiaki; Xu, Xu; Salem, Amir M H; Shoulkamy, Mahmoud I; Ide, Hiroshi

2017-06-01

Ionizing radiation produces various DNA lesions such as base damage, DNA single-strand breaks (SSBs), DNA double-strand breaks (DSBs), and DNA-protein cross-links (DPCs). Of these, the biological significance of DPCs remains elusive. In this article, we focus on radiation-induced DPCs and review the current understanding of their induction, properties, repair, and biological consequences. When cells are irradiated, the formation of base damage, SSBs, and DSBs are promoted in the presence of oxygen. Conversely, that of DPCs is promoted in the absence of oxygen, suggesting their importance in hypoxic cells, such as those present in tumors. DNA and protein radicals generated by hydroxyl radicals (i.e., indirect effect) are responsible for DPC formation. In addition, DPCs can also be formed from guanine radical cations generated by the direct effect. Actin, histones, and other proteins have been identified as cross-linked proteins. Also, covalent linkages between DNA and protein constituents such as thymine-lysine and guanine-lysine have been identified and their structures are proposed. In irradiated cells and tissues, DPCs are repaired in a biphasic manner, consisting of fast and slow components. The half-time for the fast component is 20min-2h and that for the slow component is 2-70h. Notably, radiation-induced DPCs are repaired more slowly than DSBs. Homologous recombination plays a pivotal role in the repair of radiation-induced DPCs as well as DSBs. Recently, a novel mechanism of DPC repair mediated by a DPC protease was reported, wherein the resulting DNA-peptide cross-links were bypassed by translesion synthesis. The replication and transcription of DPC-bearing reporter plasmids are inhibited in cells, suggesting that DPCs are potentially lethal lesions. However, whether DPCs are mutagenic and induce gross chromosomal alterations remains to be determined. Copyright © 2017 Elsevier Inc. All rights reserved.

Femtosecond UV-laser pulses to unveil protein-protein interactions in living cells.

PubMed

Itri, Francesco; Monti, Daria M; Della Ventura, Bartolomeo; Vinciguerra, Roberto; Chino, Marco; Gesuele, Felice; Lombardi, Angelina; Velotta, Raffaele; Altucci, Carlo; Birolo, Leila; Piccoli, Renata; Arciello, Angela

2016-02-01

A hallmark to decipher bioprocesses is to characterize protein-protein interactions in living cells. To do this, the development of innovative methodologies, which do not alter proteins and their natural environment, is particularly needed. Here, we report a method (LUCK, Laser UV Cross-linKing) to in vivo cross-link proteins by UV-laser irradiation of living cells. Upon irradiation of HeLa cells under controlled conditions, cross-linked products of glyceraldehyde-3-phosphate dehydrogenase (GAPDH) were detected, whose yield was found to be a linear function of the total irradiation energy. We demonstrated that stable dimers of GAPDH were formed through intersubunit cross-linking, as also observed when the pure protein was irradiated by UV-laser in vitro. We proposed a defined patch of aromatic residues located at the enzyme subunit interface as the cross-linking sites involved in dimer formation. Hence, by this technique, UV-laser is able to photofix protein surfaces that come in direct contact. Due to the ultra-short time scale of UV-laser-induced cross-linking, this technique could be extended to weld even transient protein interactions in their native context.

The effect of collagen crosslinking on the biphasic poroviscoelastic cartilage properties determined from a semi-automated microindentation protocol for stress relaxation.

PubMed

McGann, Megan E; Bonitsky, Craig M; Ovaert, Timothy C; Wagner, Diane R

2014-06-01

Given the important role of the collagenous structure in cartilage mechanics, there is considerable interest in the relationship between collagen crosslinking and the mechanical behavior of the cartilage matrix. While crosslink-induced alterations to the elastic modulus of cartilage have been described, changes to time-dependent behavior have not yet been determined. The objective of the study was to quantify changes to cartilage material properties, including viscoelastic coefficients, with crosslinking via indentation. To accomplish this, a semi-autonomous microindentation stress relaxation protocol was first developed, validated and then applied to cartilage specimens before and after crosslinking. The change in mechanical properties with crosslinking was analyzed both in the unloading portions of the test via the Oliver-Pharr method and in the holding portion with an inverse iterative finite element model that represented cartilage as a biphasic poroviscoelastic material. Although both techniques suggested a similar increase in equilibrium modulus in the crosslinked specimens as compared to the controls, distinct differences in the control specimens were apparent, suggesting that the two different techniques may be capturing different aspects of the material behavior. No differences in time-dependent properties were observed between the crosslinked and the control specimens. These results give further insight into the effects of crosslinking in cartilage mechanical behavior. Additionally, the microindentation stress relaxation protocol may enable increased automation for high-throughput testing. Copyright © 2014 Elsevier Ltd. All rights reserved.

The elimination of free radicals in irradiated UHMWPEs with and without vitamin E stabilization by annealing under pressure.

PubMed

Oral, Ebru; Ghali, Bassem W; Muratoglu, Orhun K

2011-04-01

Radiation crosslinking of ultrahigh molecular weight polyethylene (UHMWPE) has been used to decrease the wear of joint implant bearing surfaces. While radiation crosslinking has been successful in decreasing femoral head penetration into UHMWPE acetabular liners in vivo, postirradiation thermal treatment of the polymer is required to ensure the oxidative stability of joint implants in the long term. Two types of thermal treatment have been used: (i) annealing below the melting point preserves the mechanical properties but the residual free radicals trapped in the crystalline regions are not completely eliminated, leading to oxidation in the long-term and (ii) annealing above the melting point (melting) eliminates the free radicals but leads to a decrease in mechanical properties through loss of crystallinity during the melting process. In this study, we hypothesized that free radicals could be reduced by annealing below the melting point under pressure effectively without melting due to the elevation of the melting point. By avoiding the complete melting of UHMWPE, mechanical properties would be preserved. Our hypothesis tested positive in that we found the radiation-induced free radicals to be markedly reduced (below the detection limit of state-of-the-art electron spin resonance) by thermal annealing under pressure in radiation crosslinked virgin UHMWPE and UHMWPE/vitamin-E blends without loss of mechanical properties. Copyright © 2011 Wiley Periodicals, Inc.

Variation of mechanical properties and oxidation with radiation dose and source in highly crosslinked remelted UHMWPE.

PubMed

Fung, Mitchell; Bowsher, John G; Van Citters, Douglas W

2018-06-01

Ultra-high molecular weight polyethylene (UHMWPE) is the current gold standard for bearing materials used in total joint arthroplasty. High-dose radiation is commonly used to crosslink UHMWPE, thereby improving its wear resistance. A subsequent remelting step eliminates trapped residual free radicals to promote oxidative stability on the shelf, and to prevent material degradation over the long term. Assessment of clinically retrieved, highly crosslinked UHMWPE devices shows signs of unanticipated oxidation occurring in vivo, despite the absence of free radicals prior to implantation. These findings warrant further investigation into possible factors impacting this phenomenon along with its clinical implications. The overall objective of this work is to quantify the influence of irradiation dose and source on UHMWPE's oxidative stability, along with the effects of oxidation on the ultimate mechanical properties, including strength, ductility, and toughness. The results showed a strong positive correlation between maximum oxidation and initial transvinylene content. Critical oxidation levels in the context of mechanical property loss were determined for e-beam and gamma treatments at various radiation doses. Further, it was shown that critical oxidation was more dependent on radiation dose and less dependent on source. If in vivo oxidation persists in these devices, this can potentially lead to mechanical failure (e.g. fatigue damage) as observed in terminally gamma-sterilized devices. Copyright © 2018 Elsevier Ltd. All rights reserved.

Detection of DNA–protein crosslinks (DPCs) by novel direct fluorescence labeling methods: distinct stabilities of aldehyde and radiation-induced DPCs

PubMed Central

Shoulkamy, Mahmoud I.; Nakano, Toshiaki; Ohshima, Makiko; Hirayama, Ryoichi; Uzawa, Akiko; Furusawa, Yoshiya; Ide, Hiroshi

2012-01-01

Proteins are covalently trapped on DNA to form DNA–protein crosslinks (DPCs) when cells are exposed to DNA-damaging agents. DPCs interfere with many aspects of DNA transactions. The current DPC detection methods indirectly measure crosslinked proteins (CLPs) through DNA tethered to proteins. However, a major drawback of such methods is the non-linear relationship between the amounts of DNA and CLPs, which makes quantitative data interpretation difficult. Here we developed novel methods of DPC detection based on direct CLP measurement, whereby CLPs in DNA isolated from cells are labeled with fluorescein isothiocyanate (FITC) and quantified by fluorometry or western blotting using anti-FITC antibodies. Both formats successfully monitored the induction and elimination of DPCs in cultured cells exposed to aldehydes and mouse tumors exposed to ionizing radiation (carbon-ion beams). The fluorometric and western blotting formats require 30 and 0.3 μg of DNA, respectively. Analyses of the isolated genomic DPCs revealed that both aldehydes and ionizing radiation produce two types of DPC with distinct stabilities. The stable components of aldehyde-induced DPCs have half-lives of up to days. Interestingly, that of radiation-induced DPCs has an infinite half-life, suggesting that the stable DPC component exerts a profound effect on DNA transactions over many cell cycles. PMID:22730301

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.

Acrolein Microspheres Are Bonded To Large-Area Substrates

NASA Technical Reports Server (NTRS)

Rembaum, Alan; Yen, Richard C. K.

1988-01-01

Reactive cross-linked microspheres produced under influence of ionizing radiation in aqueous solutions of unsaturated aldehydes, such as acrolein, with sodium dodecyl sulfate. Diameters of spheres depend on concentrations of ingredients. If polystyrene, polymethylmethacrylate, or polypropylene object immersed in solution during irradiation, microspheres become attached to surface. Resulting modified surface has grainy coating with reactivity similar to free microspheres. Aldehyde-substituted-functional microspheres react under mild conditions with number of organic reagents and with most proteins. Microsphere-coated macrospheres or films used to immobilize high concentrations of proteins, enzymes, hormones, viruses, cells, and large number of organic compounds. Applications include separation techniques, clinical diagnostic tests, catalytic processes, and battery separators.

Cured composite materials for reactive metal battery electrolytes

DOEpatents

Harrup, Mason K.; Stewart, Frederick F.; Peterson, Eric S.

2006-03-07

A solid molecular composite polymer-based electrolyte is made for batteries, wherein silicate compositing produces a electrolytic polymer with a semi-rigid silicate condensate framework, and then mechanical-stabilization by radiation of the outer surface of the composited material is done to form a durable and non-tacky texture on the electrolyte. The preferred ultraviolet radiation produces this desirable outer surface by creating a thin, shallow skin of crosslinked polymer on the composite material. Preferably, a short-duration of low-medium range ultraviolet radiation is used to crosslink the polymers only a short distance into the polymer, so that the properties of the bulk of the polymer and the bulk of the molecular composite material remain unchanged, but the tough and stable skin formed on the outer surface lends durability and processability to the entire composite material product.

Radiation grafted and sulfonated (FEP-g-polysterene) - An alternative to perfluorinated membranes for PEM fuel cells?

NASA Astrophysics Data System (ADS)

Buechi, F. N.; Gupta, B.; Rouilly, M.; Hauser, P. C.; Chapiro, A.; Scherer, G. G.

Partially fluorinated proton exchange membranes (PEMs) were synthesized for fuel cell applications by simultaneous radiation grafting of styrene on FEP films followed by sulfonation. Properties of the synthesized membranes can be tailored by varying the degree of grafting and crosslinking. The performance of these membranes was tested in H2/O2 fuel cells. Long time testing showed steady performance for high grafted membranes over periods of more than 300 h at a cell temperature of 60 C. Low grafted membranes and the Morgane CDS membrane showed considerable decay of cell power on the same time scale. A fast degradation of all membranes occurred at a cell temperature of 80 C. It is noted that grafting in film form makes this process a potentially cheap and easy technique for the preparation of solid polymer fuel cell electrolytes.

Radiation synthesis of biocompatible hydrogels of dextran methacrylate

NASA Astrophysics Data System (ADS)

Szafulera, Kamila; Wach, Radosław A.; Olejnik, Alicja K.; Rosiak, Janusz M.; Ulański, Piotr

2018-01-01

The aim of this work was to synthesize biocompatible dextran-based hydrogels through crosslinking initiated by ionizing radiation. A series of derivatives of dextran has been synthesized by coupling of methacrylated glycidyl to the structure of this polysaccharide, yielding dextran methacrylate (Dex-MA) of the degree of methacrylate substitution (DS) up to 1.13 as characterised by FTIR and NMR spectroscopy. Chemically crosslinked hydrogels were formed by electron-beam irradiation of Dex-MA in aqueous solution in the absence of low-molecular-weight additives such as catalysts, monomers or crosslinking agents. Crosslinking of Dex-MA in aqueous solutions of 20 g/l and above was an efficient process, the gels were formed at doses as low as 0.5 kGy (experiments conducted up to 100 kGy) and were characterised by high content of insoluble fraction (70-100%). Due to high crosslinking density the equilibrium degree of swelling of fabricated gels was controlled principally by the initial concentration of Dex-MA solution subjected to irradiation, and it was in the range of 20 to over 100 g of water absorbed by gram of gel. Cytocompatibility of hydrogels was examined using XTT assay through evaluation of the cell viability being in indirect contact with hydrogels. The results indicated that hydrogels of Dex-MA of the average DS below 1 were not cytotoxic. Altogether, our data demonstrate that irradiation of methacrylated dextran in aqueous solution is an efficient method of fabrication of biocompatible hydrogels, which applications in regeneration medicine are anticipated.

Efficacy and safety of newly developed cross-linked dextran gel injection for glans penis augmentation with a novel technique

PubMed Central

Yang, Dae Yul; Ko, Kyungtae; Lee, Seong Ho; Moon, Du Geon; Kim, Jong Wook; Lee, Won Ki

2018-01-01

There is no safe and effective standard method for glans penis augmentation. Furthermore, there has been scant research on glans penis augmentation due to a poor understanding of glans anatomy, technical difficulty, and a lack of suitable substances for augmentation. Cross-linked dextran gel is a newly developed filler for soft-tissue augmentation. We evaluated the efficacy and safety of using a novel technique to inject cross-linked dextran gel for glans penis augmentation during a 24-week follow-up study. This prospective, single-arm, multicenter study enrolled twenty healthy adult men who underwent glans penis augmentation between June and August 2013. Cross-linked dextran gel was injected into the glans penis using a simple and easy technique. The sizes of the glans penis and individual satisfaction were assessed. Any adverse event was also reported. A total of 18 individuals were analyzed; two of them were lost to follow-up. The mean procedure time and injected volume were about 30 min and 6.6 ± 0.9 ml, respectively. The mean surface areas of the glans at baseline and 24 weeks were 20.0 ± 3.5 cm2 and 33.6 ± 5.4 cm2, respectively, representing a mean increase of 68.7% ± 14.0% (P < 0.001). Sixteen individuals (88.9%) were satisfied with the outcomes, and none were dissatisfied. There were no serious adverse events during the study. Cross-linked dextran gel injection for glans penis augmentation was easy and showed a significant augmentative effect on the glans penis, good durability, and was well tolerated without serious adverse events. Therefore, cross-linked dextran gel injection may be an effective, new technique for glans penis augmentation. PMID:28303807

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

Mahmud, Maznah; Radiation Processing Technology Division, Malaysian Nuclear Agency, 43000 Kajang, Selangor; Daik, Rusli

Poly(vinylpyrrolidone) (PVP)-crosslinked chitosan hydrogels were prepared by gamma radiation at various doses; 1, 3 5, 7, 10, 15, 20, 25 and 30kGy. Gamma radiation was used as a crosslinking tool which requires no chemical initiator, no heating process and need no purification step on the end products obtained. The hydrogel formulations were composed of 6% chitosan with average molecular weight (Mw) = 48 800 g/mol and 14% PVP with Mw = 10 000 g/mol in 2% lactic acid. Physical properties of hydrogels such as gel fraction and swelling property at pH 5.5 and pH 7.0 as well as syneresis activitymore » were determined. It was found that different radiation dose induces different effect on hydrogels’ network formed. Morphological study of hydrogels has been carried out by scanning electron microscope (SEM). From these preliminary evaluations, it can be concluded that gamma radiation is an effective tool for network development of hydrogels and it also induces enhancement on characteristics of hydrogels synthesized.« less

Cross-linked polyvinyl pyridine coated glass particle catalyst support and aqueous composition or polyvinyl pyridine adducted microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1981-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Ultraviolet-B radiation induced cross-linking improves physical properties of cold- and warm-water fish gelatin gels and films.

PubMed

Otoni, Caio G; Avena-Bustillos, Roberto J; Chiou, Bor-Sen; Bilbao-Sainz, Cristina; Bechtel, Peter J; McHugh, Tara H

2012-09-01

Cold- and warm-water fish gelatin granules were exposed to ultraviolet-B radiation for doses up to 29.7 J/cm(2). Solutions and films were prepared from the granules. Gel electrophoresis and refractive index were used to examine changes in molecular weight of the samples. Also, the gel strength and rheological properties of the solutions as well as the tensile and water vapor barrier properties of the films were characterized. SDS-PAGE and refractive index results indicated cross-linking of gelatin chains after exposure to radiation. Interestingly, UV-B treated samples displayed higher gel strengths, with cold- and warm-water fish gelatin having gel strength increases from 1.39 to 2.11 N and from 7.15 to 8.34 N, respectively. In addition, both gelatin samples exhibited an increase in viscosity for higher UV doses. For gelatin films, the cold-water fish gelatin samples made from irradiated granules showed greater tensile strength. In comparison, the warm-water gelatin films made from irradiated granules had lower tensile strength, but better water vapor barrier properties. This might be due to the UV induced cross-linking in warm-water gelatin that disrupted helical structures. Journal of Food Science copy; 2012 Institute of Food Technologists® No claim to original US government works.

Electron beam curing of EPDM

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

Vroomen, G.L.M.; Visser, G.W.; Gehring, J.

1991-11-01

Normally EPDM rubbers are vulcanized by systems based on sulphur, resin or peroxide. The common feature of these systems is that they all require activator energy in the form of heat. The (extremely) high temperatures (approximately 180C) have the disadvantage that the final properties of the finished product may be affected in one way or another by a variety of uncontrolled side reactions which may occur. Radiation curing, on the other hand, is a process which differs from those mentioned above in that the final curing is carried out at about 20C under closely controlled conditions (such as radiation dose,more » penetration depth, etc.), and this form of curing ultimately results in a more well-defined end product. In the rubber industry, this technique is used by large rubber processors (for example, in roof sheeting and cable production). Its widespread use is, however, impeded by the high investment costs. One way of avoiding these high costs is to arrange for the products to be irradiated by contractors. The optimum radiation dose for EPDM is determined by the required pattern of properties. From this study it may be concluded that the network is primarily built up at a radiation dose of up to approximately 100 kGy. The degree to which it is built up depends partly on the coactivator used and the EPDM type used. In choosing the coactivator, allowance has to be made for its solubility in EPDM. The type of oil chosen and any stabilizer additions will affect the crosslinking efficiency. Contrary to studies published earlier, in this study it was found that when EDMA is used as a coactivator, no difference can be detected between a DCPD type (4%) and an ENB type (4%), provided both have an identical molecular weight distribution. Increasing the ENB content has less effect on the final crosslink density than using a type having a broader molecular weight distribution.« less

ICC-CLASS: isotopically-coded cleavable crosslinking analysis software suite

PubMed Central

2010-01-01

Background Successful application of crosslinking combined with mass spectrometry for studying proteins and protein complexes requires specifically-designed crosslinking reagents, experimental techniques, and data analysis software. Using isotopically-coded ("heavy and light") versions of the crosslinker and cleavable crosslinking reagents is analytically advantageous for mass spectrometric applications and provides a "handle" that can be used to distinguish crosslinked peptides of different types, and to increase the confidence of the identification of the crosslinks. Results Here, we describe a program suite designed for the analysis of mass spectrometric data obtained with isotopically-coded cleavable crosslinkers. The suite contains three programs called: DX, DXDX, and DXMSMS. DX searches the mass spectra for the presence of ion signal doublets resulting from the light and heavy isotopic forms of the isotopically-coded crosslinking reagent used. DXDX searches for possible mass matches between cleaved and uncleaved isotopically-coded crosslinks based on the established chemistry of the cleavage reaction for a given crosslinking reagent. DXMSMS assigns the crosslinks to the known protein sequences, based on the isotopically-coded and un-coded MS/MS fragmentation data of uncleaved and cleaved peptide crosslinks. Conclusion The combination of these three programs, which are tailored to the analytical features of the specific isotopically-coded cleavable crosslinking reagents used, represents a powerful software tool for automated high-accuracy peptide crosslink identification. See: http://www.creativemolecules.com/CM_Software.htm PMID:20109223

Influence of gamma irradiation on carbon nanotube-reinforced polypropylene.

PubMed

Castell, P; Medel, F J; Martinez, M T; Puértolas, J A

2009-10-01

Single walled carbon nanotubes (SWNT) have been incorporated into a polypropylene (PP) matrix in different concentrations (range: 0.25-2.5 wt%). The nanotubes were blended with PP particles (approximately 500 microm in size) before mixing in an extruder. Finally, rectangular plates were obtained by compression moulding. PP-SWNT composites were gamma irradiated at different doses, 10 and 20 kGy, to promote crosslinking in the matrix and potentially enhance the interaction between nanotubes and PP. Extensive thermal, structural and mechanical characterization was conducted by means of DSC, X-ray diffraction, Raman spectroscopy, uniaxial tensile tests and dynamic mechanical thermal (DMTA) techniques. DSC thermograms reflected higher crystallinity with increasing nanotube concentration. XRD analysis confirmed the only presence of a monoclinic crystals and proved unambiguously that CNTs generated a preferred orientation. Raman spectroscopy confirmed that the intercalation of the polymer between bundles is favored at low CNTs contents. Elastic modulus results confirmed the reinforcement of the polypropylene matrix with increasing SWNT concentration, although stiffness saturation was observed at the highest concentration. Loss tangent DMTA curves showed three transitions for raw polypropylene. While gamma relaxation remained practically unchanged in all the samples, beta relaxation temperatures showed an increase with increasing CNT content due to the reduced mobility of the system. Gamma-irradiated PP exhibited an increase in the beta relaxation temperature, associated with changes in glass transition due to radiation-induced crosslinking. On the contrary, gamma-irradiated nanocomposites did not show this effect probably due to the reaction of radiative free radicals with CNTs.

Crosslinked polyethylene foams, via EB radiation

NASA Astrophysics Data System (ADS)

Cardoso, E. C. L.; Lugão, A. B.; Andrade E. Silva, L. G.

1998-06-01

Polyethylene foams, produced by radio-induced crosslinking, show a smooth and homogeneous surface, when compared to chemical crosslinking method using peroxide as crosslinking agent. This process fosters excellent adhesive and printability properties. Besides that, closed cells, intrinsic to theses foams, imparts opitmum mechanical, shocks and insulation resistance, indicating these foams to some markets segments as: automotive and transport; buoyancy, flotation and marine: building and insulation: packaging: domestic sports and leisure goods. We were in search of an ideal foam, by adding 5 to 15% of blowing agent in LDPE. A series of preliminary trials defined 203° C as the right blowing agent decomposition temperature. At a 22.7 kGy/dose ratio, the lowest dose for providing an efficient foam was 30 kGy, for a formulation comprising 10% of azodicarbonamide in LDPE, within a 10 minutes foaming time.

Are the surgeons safe during UV-A radiation exposure in collagen cross-linking procedure?

PubMed

Shetty, Rashmi; Shetty, Rohit; Mahendradas, Padmamalini; Shetty, Bhujang K

2012-02-01

To quantify the effect of scattered UV-A radiation used in the collagen cross-linking (CXL) procedure and the amount of radiation reaching the surgeon and the surrounding area and to estimate the dampening effect by various protective devices. In this case series, 3 patients [aged 25-30 (±2.5) years] with keratoconus underwent a CXL procedure with UV-A light and riboflavin. Irradiance was measured using a spectrometer (Model USB2000; Ocean Optics, Inc) for various distances from the source, at various angles, and for different durations of radiation. The spectrometer was also used to measure the dampening effect produced by gown, latex gloves, and UV-protective glasses. Maximum UV-A radiation (1.4 × 10(-9) mW/cm(2)) was measured at 2 cm from the limbus, when the probe was held at a 45-degree angle to the floor. UV-A radiation reaching the surgeon's eye and the abdomen was 3.403 × 10(-11) and 2.36 × 10(-11) mW/cm(2), respectively. Gown, latex gloves, and UV-protective glasses showed dampening effects of 99.58%, 95.01%, and 99.73%, respectively. CXL appears to be a safe procedure with respect to UV-A radiation exposure to the surgeon. Further safety can be ensured by UV-protective devices.

Preparation, Characterization and Utilization of Electrodes Coated with Polymeric Networks Formed by Gamma Radiation Crosslinking.

DTIC Science & Technology

1987-04-01

polymers such as poly[ diallyl dimethyl ammonium chloride] , poly [vinylbenzyl trimethyl ammonium chloride], poly[styrene sulfonic acid , sodium salt] and...poly[acrylic acid ], which would ordinarily dissolve from the electrode surface in aqueous solution unless crosslinked into a network, and several...Irradiation on a Water-Soluble Polymer: DDAC 8 E. Electrochemistry of DDAC Networks on Platinum and Graphite 10 F. Poly [acrylic acid ] Films on Graphite

Assessment of UVA-Riboflavin Corneal Cross-Linking Using Small Amplitude Oscillatory Shear Measurements.

PubMed

Aslanides, Ioannis M; Dessi, Claudia; Georgoudis, Panagiotis; Charalambidis, Georgios; Vlassopoulos, Dimitris; Coutsolelos, Athanassios G; Kymionis, George; Mukherjee, Achyut; Kitsopoulos, Theofanis N

2016-04-01

The effect of ultraviolet (UV)-riboflavin cross-linking (CXL) has been measured primarily using the strip extensometry technique. We propose a simple and reliable methodology for the assessment of CXL treatment by using an established rheologic protocol based on small amplitude oscillatory shear (SAOS) measurements. It provides information on the average cross-link density and the elastic modulus of treated cornea samples. Three fresh postmortem porcine corneas were used to study the feasibility of the technique, one serving as control and two receiving corneal collagen cross-linking treatment. Subsequently, five pairs of fresh postmortem porcine corneas received corneal collagen cross-linking treatment with riboflavin and UVA-irradiation (370 nm; irradiance of 3 mW/cm2) for 30 minutes (Dresden protocol); the contralateral porcine corneas were used as control samples. After the treatment, the linear viscoelastic moduli of the corneal samples were measured using SAOS measurements and the average cross-linking densities extracted. For all cases investigated, the dynamic moduli of the cross-linked corneas were higher compared to those of the corresponding control samples. The increase of the elastic modulus of the treated samples was between 122% and 1750%. The difference was statistically significant for all tested samples (P = 0.018, 2-tailed t-test). We report a simple and accurate methodology for quantifying the effects of cross-linking on porcine corneas treated with the Dresden protocol by means of SAOS measurements in the linear regime. The measured dynamic moduli, elastic and viscous modulus, represent the energy storage and energy dissipation, respectively. Hence, they provide a means to assess the changing physical properties of the cross-linked collagen networks after CXL treatment.

Study on the PTC/NTC effect of carbon black-filled polymer composites

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

Tang, Hao; Chen, Xinfang; Luo, Yunxia

1995-12-01

In this work, the effect of processing condition and radiation-crosslinking on the electrical and dynamic behaviors of carbon black filled low density polyethylene (LDPE) composites were investigated. Compared with the solution counterpart, the mechanical composites have a strong PTC effect and a great dynamic elastic mold, which results from the strong interaction between carbon black and LDPE. The experiment result shows that the NTC effect is caused by the decrease of elastic mold of LDPE at high temperature, and it can be declined significantly by radiation-crosslinking. We conclude that the strong interaction between polymer and carbon black is essentially importantmore » for composites to have a great PTC intensity good electrical reproducibility and high dynamic elastic sold.« less

A General Method for Targeted Quantitative Cross-Linking Mass Spectrometry.

PubMed

Chavez, Juan D; Eng, Jimmy K; Schweppe, Devin K; Cilia, Michelle; Rivera, Keith; Zhong, Xuefei; Wu, Xia; Allen, Terrence; Khurgel, Moshe; Kumar, Akhilesh; Lampropoulos, Athanasios; Larsson, Mårten; Maity, Shuvadeep; Morozov, Yaroslav; Pathmasiri, Wimal; Perez-Neut, Mathew; Pineyro-Ruiz, Coriness; Polina, Elizabeth; Post, Stephanie; Rider, Mark; Tokmina-Roszyk, Dorota; Tyson, Katherine; Vieira Parrine Sant'Ana, Debora; Bruce, James E

2016-01-01

Chemical cross-linking mass spectrometry (XL-MS) provides protein structural information by identifying covalently linked proximal amino acid residues on protein surfaces. The information gained by this technique is complementary to other structural biology methods such as x-ray crystallography, NMR and cryo-electron microscopy[1]. The extension of traditional quantitative proteomics methods with chemical cross-linking can provide information on the structural dynamics of protein structures and protein complexes. The identification and quantitation of cross-linked peptides remains challenging for the general community, requiring specialized expertise ultimately limiting more widespread adoption of the technique. We describe a general method for targeted quantitative mass spectrometric analysis of cross-linked peptide pairs. We report the adaptation of the widely used, open source software package Skyline, for the analysis of quantitative XL-MS data as a means for data analysis and sharing of methods. We demonstrate the utility and robustness of the method with a cross-laboratory study and present data that is supported by and validates previously published data on quantified cross-linked peptide pairs. This advance provides an easy to use resource so that any lab with access to a LC-MS system capable of performing targeted quantitative analysis can quickly and accurately measure dynamic changes in protein structure and protein interactions.

New trend of radiation application to polymer modification — irradiation in oxygen free atmosphere and at elevated temperature

NASA Astrophysics Data System (ADS)

Seguchi, Tadao

2000-03-01

Polycarbosilane (PCS) fiber as a precursor for ceramic fiber of silicon carbide was cured by electron beam (EB) irradiation under oxygen free atmosphere. Oxygen content in the cured PCS fiber was scarce and the obtained silicon carbide (SiC) fiber with low oxygen content showed high heat resistance up to 1973 K and tensile strength of 3 GPa. Also, the EB cured PCS fiber with very low oxygen content could be converted to silicon nitride (Si 3N 4) fiber by the pyrolysis in NH 3 gas atmosphere, which was the new processing to produce Si 3N 4 fiber. The process of SiC fiber synthesis was developed to the commercial plant. The other application was the crosslinking of polytetrafluoroethylene (PTFE). PTFE, which had been recognized to be a typical chain scission polymer, could be induced to crosslinking by irradiation at the molten state in oxygen free atmosphere. The physical properties such as crystallinity, mechanical properties, etc. changed much by crosslinking, and the radiation resistance was much improved.

Preparation and evaluation of β-glucan hydrogel prepared by the radiation technique for drug carrier applications.

PubMed

Park, Jong-Seok; Lim, Youn-Mook; Baik, Jae; Jeong, Jin-Oh; An, Sung-Jun; Jeong, Sung-In; Gwon, Hui-Jeong; Khil, Myung-Seob

2018-06-14

β-Glucan can provide excellent environment to apply to drug carrier due to its immunological and anti-inflammatory effect. Minocycline hydrochloride (MH) has excellent oral bioavailability pharmacological properties. Specifically, MH is effectively absorbed into the gingiva for periodontal disease treatment. In this study, we attempt to develop MH loaded β-glucan hydrogel for periodontal disease treatment through radiation-crosslinking technique. In addition, MH loaded β-glucan hydrogels were tested for their cytotoxicity and antibacterial activity. Finally, we conducted an in vivo study to demonstrate the potential to prevent the invasion of bacteria to treat periodontal disease. The gel content and compressive strength of the β-glucan hydrogels increased as the β-glucan content and the absorbed dose (up to 7 kGy) increased. For a radiation dose of 7 kGy, the gelation and the compressive strength of a 6 wt% β-glucan hydrogel were approximately 92% and 270 kPa, respectively. As a drug, MH was consistently released from β-glucan hydrogels, reaching 80% at approximately 90 min. Furthermore, the MH loaded β-glucan hydrogels showed no cytotoxicity. The MH loaded β-glucan hydrogels exhibited good antibacterial activity against Porphyromonas gingivalis. In addition, MH loaded β-glucan hydrogel demonstrated the potential of a good capability to prevent the invasion of bacteria and to treat wounds. Copyright © 2017. Published by Elsevier B.V.

Radiation-grafted proton exchange membranes based on co-grafting from binary monomer mixtures into poly(ethylene-co-tetrafluoroethylene) (ETFE) film

NASA Astrophysics Data System (ADS)

Sohn, Joon-Yong; Sung, Hae-Jun; Song, Joo-Myung; Shin, Junhwa; Nho, Young-Chang

2012-08-01

In this study, proton exchange membranes (PEMs) based on a poly(ethylene-co-tetrafluoroethylene) (ETFE) film were synthesized through the graft copolymerization of styrene and VTMS (vinyltrimethoxysilane), or styrene and TMSPM (3-(trimethoxysilyl) propyl methacrylate) binary monomer systems using a simultaneous irradiation method. The prepared membranes with the similar degrees of grafting were investigated by measuring ion exchange capacity, proton conductivity, water uptake, chemical stability, and dimensional stability. The results indicate that the silane-crosslinked proton exchange membrane (PEM) has not only lower water uptake and dimensional change but also high proton conductivity at low humidity condition compared to non-crosslinked poly(ethylene-co-tetrafluoroethylene)-g-poly(styrene sulfonic acid) (ETFE-g-PSSA). Also, the chemical stability of silane-crosslinked fuel cell membranes was more improved than that of non-crosslinked fuel cell membrane.

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.

Preparation of decellularized vascular matrix by co-crosslinking of procyanidins and glutaraldehyde.

PubMed

Wang, Xiaotong; Ma, Bing; Chang, Jiang

2015-01-01

Vascular extracellular matrices (vECMs) have shown potential for small-diameter blood vessel tissue engineering applications. However, problems such as chemical instability and easy calcification are still remained. Chemical crosslinking using crosslinkers such as glutaraldehyde (GA) can improve mechanical properties and proteolysis resistance of vECMs, but leads to calcification and cytotoxicity. Procyanidins (PC) can crosslink ECMs with anti-calcification property and cytocompatibility, but the mechanical properties and chemical stability are unsatisfactory. A novel co-crosslinking technique using PC and GA was developed, which combines the advantages of both PC and GA for enhancing mechanical properties and stability of vECMs with reduced calcification and cytotoxicity. Fresh carotid were decellularized and then crosslinked by PC and subsequent GA for 6 h respectively. The mechanical properties, dynamic release of PC, enzymatic degradation, calcification and cytotoxicity of crosslinked samples were evaluated. The co-crosslinked vECMs showed enhanced tensile strength, chemical and biological stability, comparable anti-calcification property as compared to pure PC-crosslinked samples. Cytotoxicity assay showed that the co-crosslinked vECMs were cytocompatible for supporting the adhesion and proliferation of HUVECs. Co-crosslinking with PC and GA might be a useful method for preparation of vECM scaffolds with potential applications in small-diameter blood vessel tissue engineering.

Probabilistic cross-link analysis and experiment planning for high-throughput elucidation of protein structure.

PubMed

Ye, Xiaoduan; O'Neil, Patrick K; Foster, Adrienne N; Gajda, Michal J; Kosinski, Jan; Kurowski, Michal A; Bujnicki, Janusz M; Friedman, Alan M; Bailey-Kellogg, Chris

2004-12-01

Emerging high-throughput techniques for the characterization of protein and protein-complex structures yield noisy data with sparse information content, placing a significant burden on computation to properly interpret the experimental data. One such technique uses cross-linking (chemical or by cysteine oxidation) to confirm or select among proposed structural models (e.g., from fold recognition, ab initio prediction, or docking) by testing the consistency between cross-linking data and model geometry. This paper develops a probabilistic framework for analyzing the information content in cross-linking experiments, accounting for anticipated experimental error. This framework supports a mechanism for planning experiments to optimize the information gained. We evaluate potential experiment plans using explicit trade-offs among key properties of practical importance: discriminability, coverage, balance, ambiguity, and cost. We devise a greedy algorithm that considers those properties and, from a large number of combinatorial possibilities, rapidly selects sets of experiments expected to discriminate pairs of models efficiently. In an application to residue-specific chemical cross-linking, we demonstrate the ability of our approach to plan experiments effectively involving combinations of cross-linkers and introduced mutations. We also describe an experiment plan for the bacteriophage lambda Tfa chaperone protein in which we plan dicysteine mutants for discriminating threading models by disulfide formation. Preliminary results from a subset of the planned experiments are consistent and demonstrate the practicality of planning. Our methods provide the experimenter with a valuable tool (available from the authors) for understanding and optimizing cross-linking experiments.

Tracking of Nuclear Cable Insulation Polymer Structural Changes using the Gel Fraction and Uptake Factor Method

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

Correa, Miguel; Huang, Qian; Fifield, Leonard S.

Cross-linked polyethylene (XLPE) cable insulation samples were exposed to heat and gamma radiation at a series of temperatures, dose rates, and exposure times to evaluate the effects of these variables on material degradation. The samples were tested using the solvent incubation method to collect gel fraction and uptake factor data in order to assess the crosslinking and chain scission occurring in polymer samples with aging. Consistent with previous reports, gel fraction values were observed to increase and uptake factor values to decrease with radiation and thermal exposure. The trends seen were also more prominent as exposure time increased, suggesting thismore » to be a viable method of tracking structural changes in the XLPE-insulated cable material over extended periods. For the conditions explored, the cable insulation material evaluated did not indicate signs of anomalous aging such as inverse temperature effect in which radiation-induced aging is more severe at lower temperature. Ongoing aging under identical radiation conditions and at lower temperature will further inform conclusions regarding the importance of inverse temperature effects for this material under these conditions.« less

A Review of Collagen Cross-Linking in Cornea and Sclera

PubMed Central

Zhang, Xiao; Tao, Xiang-chen; Zhang, Jian; Li, Zhi-wei; Xu, Yan-yun; Wang, Yu-meng; Zhang, Chun-xiao; Mu, Guo-ying

2015-01-01

Riboflavin/UVA cross-linking is a technique introduced in the past decades for the treatment of keratoconus, keratectasia, and infectious keratitis. Its efficacy and safety have been investigated with clinical and laboratory studies since its first clinical application by Wollensak for the treatment of keratoconus. Although its complications are encountered during clinical practice, such as infection inducing risk, minimal invasion merits a further investigation on its future application in clinical practice. Recently, collagen cross-linking in sclera shows a promising prospect. In present study, we summarized the representative studies describing the clinical and laboratory application of collagen cross-linking published in past decades and provided our opinion on the positive and negative results of cross-linking in the treatment of ophthalmic disorders. PMID:25922758

Preparation and characterizations of EGDE crosslinked chitosan electrospun membranes.

PubMed

Aqil, A; Tchemtchoua, V T; Colige, A; Atanasova, G; Poumay, Y; Jérôme, C

2015-01-01

Composite Crosslinked nanofibrous membranes of chitosan, ethylene glycol diglycidyl ether (EGDE) and polyethylene oxide was successfully prepared with bead free morphology via electrospinning technique followed by heat mediated chemical crosslinking. Architectural stability of nanofiber mat in aqueous medium was achieved by chemical crosslinking of only 1% EGDE, and tensile strength tests revealed that increasing EGDE content has considerably enhance the elastic modulus of nanofibers. The structure, morphology and mechanical properties of nanofibers were characterized by Attenuated Total Reflection-Fourier Transform Infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM) and Instron machine, respectively. Skin fibroblasts and endothelial cells showed good attachment, proliferation and viability on crosslinked electrospun membranes. The results indicate a good biocompatibility and non-toxic nature of the resulted membrane.

A general method for targeted quantitative cross-linking mass spectrometry

USDA-ARS?s Scientific Manuscript database

Chemical cross-linking mass spectrometry (XL-MS) provides protein structural information by identifying covalently linked proximal amino acid residues on protein surfaces. The information gained by this technique is complementary to other structural biology methods such as x-ray crystallography, NM...

Optimization of Formaldehyde Cross-Linking for Protein Interaction Analysis of Non-Tagged Integrin β1

PubMed Central

Klockenbusch, Cordula; Kast, Juergen

2010-01-01

Formaldehyde cross-linking of protein complexes combined with immunoprecipitation and mass spectrometry analysis is a promising technique for analysing protein-protein interactions, including those of transient nature. Here we used integrin β1 as a model to describe the application of formaldehyde cross-linking in detail, particularly focusing on the optimal parameters for cross-linking, the detection of formaldehyde cross-linked complexes, the utility of antibodies, and the identification of binding partners. Integrin β1 was found in a high molecular weight complex after formaldehyde cross-linking. Eight different anti-integrin β1 antibodies were used for pull-down experiments and no loss in precipitation efficiency after cross-linking was observed. However, two of the antibodies could not precipitate the complex, probably due to hidden epitopes. Formaldehyde cross-linked complexes, precipitated from Jurkat cells or human platelets and analyzed by mass spectrometry, were found to be composed of integrin β1, α4 and α6 or β1, α6, α2, and α5, respectively. PMID:20634879

Characterization of the crosslinking reaction in high performance phenolic resins

NASA Astrophysics Data System (ADS)

Patel, Jigneshkumar; Zou, Guo Xiang; Hsu, Shaw Ling; university of massachusetts/Polymer science; Engineering Team

In this study, a combination of thermal analysis, infrared spectroscopy (near and mid) in conjunction with low field NMR, was used to characterize the crosslinking reaction involving phenol formaldehyde resin and a crosslinking agent, Hexamethylenetetramine (HMTA). The strong hydrogen bonds in the resin and the completely crystalline HMTA (Tm = 280 °C) severely hamper the crosslinking process. Yet the addition of a small amount of plasticizer can induce a highly efficient crosslinking reaction to achieve the desired mechanical properties needed in a number of high performance organic-inorganic composites. The infrared spectroscopy clarifies the dissolution process of the crystalline crosslinker and the specific interactions needed to achieve miscibility of the reactants. The thermal analysis enabled us to follow the changing mobility of the system as a function of temperature. The low field NMR with the T1 inverse recovery technique allowed us to monitor the crosslinking process directly. For the first time, it is now possible to identify the functionality of the plasticizer and correlate the crosslinked structure achieved to the macroscopic performance needed for high performance organic-inorganic composites.

Dose response characteristics of polymethacrylic acid gel (PMAAG) for a polymerization-based dosimeter using NMR.

PubMed

Iskandar, S M; Elias, S; Jumiah, H; Asri, M T M; Masrianis, A; Ab Rahman, M Z; Taiman, K; Abdul Rashid, M Y

2004-05-01

The radiation-response characteristics of polymetharylic acid gel dosimeter prepared with different concentrations of monomer and cross-linker is described in these studies. The dosimeters were prepared under the hypoxic condition in a glove box and were then irradiated with gamma-rays produced by Co-60 radionuclide that was generated at 1.25MeV energy. The irradiation took place at different doses ranged from 0Gy to 19Gy. Due to the radiation activities, chain-reaction polymerisation processes had taken place in the formation of polymethacrylic acid (PMAA) gel, which cause the dose response mechanism increased in the NMR relaxation rates of protons. It has been observed that for higher concentration of monomer and cross-linker, the polymerization rate was increased.

Effect of electron beam irradiation on the properties of crosslinked rubbers

NASA Astrophysics Data System (ADS)

Banik, Indranil; Bhowmick, Anil K.

2000-05-01

Influence of electron beam (EB) irradiation on the mechanical and dynamic mechanical properties of crosslinked fluorocarbon (FKM) rubber, natural rubber (NR), ethylene propylene diene monomer (EPDM) rubber and nitrile rubber (NBR) has been investigated. The modulus, gel fraction, glass transition temperature ( Tg) and storage modulus increased, while the elongation at the break and the loss tangent (tan δ) Tg decreased. FKM and NBR vulcanizates have been shown to have EB radiation resistance up to 1500 kGy.

Influence of ionizing radiation on the mechanical properties of BisGMA/TEGDMA based experimental resin

NASA Astrophysics Data System (ADS)

LMP, Campos; Boaro, LC; LKG, Santos; Parra, DF; Lugão, AB

2015-10-01

Dental restorative composites are activated by visible light and the polymerization process, known as direct technique, is initiated by absorbing light in a specific wavelength range (450-500 nm). However this technique presented some disadvantages. If light is not inserted correctly, layers uncured can cause countless damage to restoration, especially with regard to mechanical properties. A clinical alternative used to reduce the shortcomings of direct application is the use of composite resins for indirect application. These composites are adaptations of resins prepared for direct use, with differences mainly in the healing process. Besides the traditional photoactivation, indirect application composites may be submitted to particular curing conditions, such as a slow curing rate, heating, vacuum, and inert-gas pressure leading to an oxygen-free environment. However few studies have been conducted on the process of post-curing by ionizing radiation at low doses. On this sense the purpose of this study was to evaluate possible interactions of ionizing radiation in the post-curing process of the experimental composites based on BisGMA/TEGDMA filled with silica Aerosil OX-50 silanized. Characterization of the experimental composites was performed by thermogravimetry analysis, infrared spectroscopy, elastic modulus and flexural strength. Statistical analysis of results was calculated by one-way ANOVA/Tukey's test. Cross-linking of the polymeric matrix caused by ionizing radiation, influenced the thermal stability of irradiated specimens. FTIR analysis showed that the ionizing radiation induced a post-cure reaction in the specimens. The irradiation dose influenced directly the mechanical properties that showed a strong positive correlation between flexural strength and irradiation and between modulus strength and irradiation.

Towards producing novel fish gelatin films by combination treatments of ultraviolet radiation and sugars (ribose and lactose) as cross-linking agents.

PubMed

Bhat, Rajeev; Karim, A A

2014-07-01

Developing novel fish gelatin films with better mechanical properties than mammalian gelatin is a challenging but promising endeavor. Studies were undertaken to produce fish gelatin films by combining treatments with different sugars (ribose and lactose) followed 'by' 'and' ultraviolet (UV) radiation, as possible cross-linking agents. Increase in tensile strength and percent elongation at break was recorded, which was more significant in films without sugars that were exposed to UV radiation. Films with added ribose showed decreased solubility after UV treatment and exhibited higher swelling percentage than films with added lactose, which readily dissolved in water. FTIR spectra of all the films showed identical patterns, which indicated no major changes to have occurred in the functional groups as a result of interaction between gelatin, sugars and UV irradiation. The results of this study could be explored for commercial use, depending on industrial needs for either production of edible films or for food packaging purposes.

Dose-Rate Effects in Breaking DNA Strands by Short Pulses of Extreme Ultraviolet Radiation.

PubMed

Vyšín, Luděk; Burian, Tomáš; Ukraintsev, Egor; Davídková, Marie; Grisham, Michael E; Heinbuch, Scott; Rocca, Jorge J; Juha, Libor

2018-05-01

In this study, we examined dose-rate effects on strand break formation in plasmid DNA induced by pulsed extreme ultraviolet (XUV) radiation. Dose delivered to the target molecule was controlled by attenuating the incident photon flux using aluminum filters as well as by changing the DNA/buffer-salt ratio in the irradiated sample. Irradiated samples were examined using agarose gel electrophoresis. Yields of single- and double-strand breaks (SSBs and DSBs) were determined as a function of the incident photon fluence. In addition, electrophoresis also revealed DNA cross-linking. Damaged DNA was inspected by means of atomic force microscopy (AFM). Both SSB and DSB yields decreased with dose rate increase. Quantum yields of SSBs at the highest photon fluence were comparable to yields of DSBs found after synchrotron irradiation. The average SSB/DSB ratio decreased only slightly at elevated dose rates. In conclusion, complex and/or clustered damages other than cross-links do not appear to be induced under the radiation conditions applied in this study.

Synthesis and characterization of psyllium-NVP based drug delivery system through radiation crosslinking polymerization

NASA Astrophysics Data System (ADS)

Singh, Baljit; Kumar, S.

2008-08-01

In order to develop the hydrogels meant for the drug delivery, we have prepared psyllium- N-vinylpyrrolidone (NVP) based hydrogels by radiation induced crosslinking. Polymers were characterized with SEMs, FTIR and swelling studies. Swelling of the hydrogels was studied as a function of monomer concentration, total radiation dose, temperature, pH and [NaCl] of the swelling medium. The swelling kinetics of the hydrogels and release dynamics of anticancer model drug (5-fluorouracil) from the hydrogels have been carried out for the evaluation of swelling and drug release mechanism. It has been observed that diffusion exponent ' n' have 0.8, 0.9, 0.8 and gel characteristics constant ' k' have 9.22 × 10 -3, 2.06 × 10 -3, 11.72 × 10 -3 values for the release of drug from the drug loaded hydrogels in distilled water, pH 2.2 buffer and pH 7.4 buffer, respectively. The present study shows that the release of drug from the hydrogels occurred through Non-Fickian diffusion mechanism.

Three-dimensional bioprinting of complex cell laden alginate hydrogel structures.

PubMed

Tabriz, Atabak Ghanizadeh; Hermida, Miguel A; Leslie, Nicholas R; Shu, Wenmiao

2015-12-21

Different bioprinting techniques have been used to produce cell-laden alginate hydrogel structures, however these approaches have been limited to 2D or simple three-dimension (3D) structures. In this study, a new extrusion based bioprinting technique was developed to produce more complex alginate hydrogel structures. This was achieved by dividing the alginate hydrogel cross-linking process into three stages: primary calcium ion cross-linking for printability of the gel, secondary calcium cross-linking for rigidity of the alginate hydrogel immediately after printing and tertiary barium ion cross-linking for long-term stability of the alginate hydrogel in culture medium. Simple 3D structures including tubes were first printed to ensure the feasibility of the bioprinting technique and then complex 3D structures such as branched vascular structures were successfully printed. The static stiffness of the alginate hydrogel after printing was 20.18 ± 1.62 KPa which was rigid enough to sustain the integrity of the complex 3D alginate hydrogel structure during the printing. The addition of 60 mM barium chloride was found to significantly extend the stability of the cross-linked alginate hydrogel from 3 d to beyond 11 d without compromising the cellular viability. The results based on cell bioprinting suggested that viability of U87-MG cells was 93 ± 0.9% immediately after bioprinting and cell viability maintained above 88% ± 4.3% in the alginate hydrogel over the period of 11 d.

Studies on water treeing and chemiluminescence on irradiated polyethylene

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

Notingher, P.V.; Ciuprina, F.; Radu, I.

The effect of {gamma}-radiations on the growth kinetics of water trees is examined using the CNRS laboratory model in LDPE samples of different origins. The effect of radiations on the material is studied from crosslinking degree measurements, IRTF spectroscopy and chemiluminescence. Correlations between the non-uniformity of the degradation and the growth of water trees are observed.

Investigation on γ-irradiated PP/ethylene acrylic elastomer TPVs by rheological and thermal approaches

NASA Astrophysics Data System (ADS)

Dutta, Anindya; Ghosh, Anup K.

2018-03-01

Polypropylene (PP) was melt blended with varying concentration of ethylene acrylic elastomer (AEM) in a twin screw extruder and then γ-irradiated at several radiation doses to achieve a series of thermoplastic vulcanizates (TPV). The effect of AEM concentration and γ-irradiation on flow characteristics, crystallization and thermal degradation of blends were explained using melt dynamic rheology, differential scanning calorimetry and thermogravimetric analysis. Gel content values and dynamic rheological data of PP and AEM at different radiation doses confirmed the incessant scissioning of PP chains with radiation doses except for highest radiation dose, where crosslinking of PP chains took place and the incessant crosslinking of AEM chains irrespective of radiation doses. Oxidative degradation of PP was confirmed by FTIR spectroscopy, which also exhibited absence of any chemical interaction between two constituent polymers. Normalized crystallinity and melting point of compositions, obtained from DSC, decreased with the radiation doses. Furthermore, with the radiation doses clear shifts of maxima of the melting peak towards the lower temperature were observed for neat PP and blends. Thermal stability of PP and blends, as observed by TGA, reduced significantly with irradiation; whereas for AEM, no discernable change was observed. Enhanced chain scissioning of PP in presence of AEM reduced the thermal stability of blends, especially at lower irradiation. This reduction of thermal stability was established by "rule of mixture", applied to the activation energy of thermal degradation. Thus, optimization of radiation doses to prepare TPVs was established.

The effects of crosslinkers on physical, mechanical, and cytotoxic properties of gelatin sponge prepared via in-situ gas foaming method as a tissue engineering scaffold.

PubMed

Poursamar, S Ali; Lehner, Alexander N; Azami, Mahmoud; Ebrahimi-Barough, Somayeh; Samadikuchaksaraei, Ali; Antunes, A P M

2016-06-01

In this study porous gelatin scaffolds were prepared using in-situ gas foaming, and four crosslinking agents were used to determine a biocompatible and effective crosslinker that is suitable for such a method. Crosslinkers used in this study included: hexamethylene diisocyanate (HMDI), poly(ethylene glycol) diglycidyl ether (epoxy), glutaraldehyde (GTA), and genipin. The prepared porous structures were analyzed using Fourier Transform Infrared Spectroscopy (FT-IR), thermal and mechanical analysis as well as water absorption analysis. The microstructures of the prepared samples were analyzed using Scanning Electron Microscopy (SEM). The effects of the crosslinking agents were studied on the cytotoxicity of the porous structure indirectly using MTT analysis. The affinity of L929 mouse fibroblast cells for attachment on the scaffold surfaces was investigated by direct cell seeding and DAPI-staining technique. It was shown that while all of the studied crosslinking agents were capable of stabilizing prepared gelatin scaffolds, there are noticeable differences among physical and mechanical properties of samples based on the crosslinker type. Epoxy-crosslinked scaffolds showed a higher capacity for water absorption and more uniform microstructures than the rest of crosslinked samples, whereas genipin and GTA-crosslinked scaffolds demonstrated higher mechanical strength. Cytotoxicity analysis showed the superior biocompatibility of the naturally occurring genipin in comparison with other synthetic crosslinking agents, in particular relative to GTA-crosslinked samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Early biocompatibility of crosslinked and non-crosslinked biologic meshes in a porcine model of ventral hernia repair.

PubMed

Melman, L; Jenkins, E D; Hamilton, N A; Bender, L C; Brodt, M D; Deeken, C R; Greco, S C; Frisella, M M; Matthews, B D

2011-04-01

Biologic meshes have unique physical properties as a result of manufacturing techniques such as decellularization, crosslinking, and sterilization. The purpose of this study is to directly compare the biocompatibility profiles of five different biologic meshes, AlloDerm(®) (non-crosslinked human dermal matrix), PeriGuard(®) (crosslinked bovine pericardium), Permacol(®) (crosslinked porcine dermal matrix), Strattice(®) (non-crosslinked porcine dermal matrix), and Veritas(®) (non-crosslinked bovine pericardium), using a porcine model of ventral hernia repair. Full-thickness fascial defects were created in 20 Yucatan minipigs and repaired with the retromuscular placement of biologic mesh 3 weeks later. Animals were euthanized at 1 month and the repair sites were subjected to tensile testing and histologic analysis. Samples of unimplanted (de novo) meshes and native porcine abdominal wall were also analyzed for their mechanical properties. There were no significant differences in the biomechanical characteristics between any of the mesh-repaired sites at 1 month postimplantation or between the native porcine abdominal wall without implanted mesh and the mesh-repaired sites (P > 0.05 for all comparisons). Histologically, non-crosslinked materials exhibited greater cellular infiltration, extracellular matrix (ECM) deposition, and neovascularization compared to crosslinked meshes. While crosslinking differentiates biologic meshes with regard to cellular infiltration, ECM deposition, scaffold degradation, and neovascularization, the integrity and strength of the repair site at 1 month is not significantly impacted by crosslinking or by the de novo strength/stiffness of the mesh.

E-beam sterilizable thermoplastics elastomers for healthcare devices: Mechanical, morphology, and in vivo studies.

PubMed

Balaji, Ananad Bellam; Ratnam, Chantara Thevy; Khalid, Mohammad; Walvekar, Rashmi

2018-03-01

The effect of electron beam radiation on ethylene-propylene diene terpolymer/polypropylene blends is studied as an attempt to develop radiation sterilizable polypropylene/ethylene-propylene diene terpolymer blends suitable for medical devices. The polypropylene/ethylene-propylene diene terpolymer blends with mixing ratios of 80/20, 50/50, 20/80 were prepared in an internal mixer at 165°C and a rotor speed of 50 rpm/min followed by compression molding. The blends and the individual components were radiated using 3.0 MeV electron beam accelerator at doses ranging from 0 to 100 kGy in air and room temperature. All the samples were tested for tensile strength, elongation at break, hardness, impact strength, and morphological properties. After exposing to 25 and 100 kGy radiation doses, 50% PP blend was selected for in vivo studies. Results revealed that radiation-induced crosslinking is dominating in EPDM dominant blends, while radiation-induced degradation is prevailing in PP dominant blends. The 20% PP blend was found to be most compatible for 20-60 kGy radiation sterilization. The retention in impact strength with enhanced tensile strength of 20% PP blend at 20-60 kGy believed to be associated with increased compatibility between PP and EPDM along with the radiation-induced crosslinking. The scanning electron micrographs of the fracture surfaces of the PP/EPDM blends showed evidences consistent with the above contentation. The in vivo studies provide an instinct that the radiated blends are safe to be used for healthcare devices.

Degradation Mechanisms and Mechanical Property Variation of Epdm Rubbers for Automotive Radiator Hosess

NASA Astrophysics Data System (ADS)

Kwak, Eung-Bum; Choi, Nak-Sam

The degradation behaviors of EPDM (ethylene-propylene diene monomer) rubbers used for automotive radiator hoses subjected to thermo-oxidative and electrochemical stresses were studied. As a result of the thermo-oxidative aging tests, the IRHD (international rubber hardness degrees) hardness of the rubber specimens increased, while their elongation at break decreased much. A slight increase in crosslink density indicated that changes in the properties were caused by the concentration of carbonyl groups in the skin layer. For the electrochemical degradation (ECD), the weight of rubber specimens increased whereas their elongation and hardness much decreased because water solution penetrated into the skin part. There was little change in crosslink density. Formation of many chain scissions and thus microvoid networks in the skin layer induced the swelling behavior leading to a linear reduction of hardness versus the weight increase.

Ultraviolet-B radiation induced crosslinking improves physical properties of cold- and warm-water fish gelatin gels and films

USDA-ARS?s Scientific Manuscript database

Cold- and warm-water fish gelatin granules were exposed to ultraviolet-B radiation for doses up to 29.7 J/cm2. Solutions and films were prepared from the granules. Gel electrophoresis and refractive index were used to examine changes in molecular weight of the samples. Also, the gel strength and rhe...

Mechanical and thermomechanical properties of radiation modified poly(ethylene-octene)/Ni-Zn ferrite nanocomposites

NASA Astrophysics Data System (ADS)

Reinholds, I.; Kalkis, V.; Zicans, J.; Merijs Meri, R.; Bockovs, I.; Grigalovica, A.; Muizzemnieks, G.

2013-12-01

Poly(ethylene-1-octene) copolymer (POE) composites filled with nickel-zinc ferrite nanoparticles have been modified by exposure to an electron beam at doses up to 500 kGy. The influence of radiation dose and ferrite content on mechanical properties has been investigated. Thermomechanical properties - thermorelaxation stresses formed in thermal heating and thermo residual stresses resulting in the process of full setting and cooling of materials have been investigated for radiation cross-linked oriented (extended up to 100%) composite samples. Increase of concentration of ferrite particles and increase of radiation dose affects a notable increase of elastic modulus and reduces the deformability in comparison to entire elastomer. Improvement of thermomechanical properties especially at low irradiation doses (100-150 kGy) have been detected for composites with increase of ferrite filler content up to 5 wt. %. It was found that gel content of POE increased up to 85% for pristine POE material with increase of irradiation dose up to 500 kGy due to the formation of cross-linked structure, increase of filler concentration up to 5 wt. % affect reduction in gel fraction due to uniform dispersion in amorphous (ethylene and substituted with hexyl branches) POE phases.

Protein Structural Analysis via Mass Spectrometry-Based Proteomics

PubMed Central

Artigues, Antonio; Nadeau, Owen W.; Rimmer, Mary Ashley; Villar, Maria T.; Du, Xiuxia; Fenton, Aron W.; Carlson, Gerald M.

2017-01-01

Modern mass spectrometry (MS) technologies have provided a versatile platform that can be combined with a large number of techniques to analyze protein structure and dynamics. These techniques include the three detailed in this chapter: 1) hydrogen/deuterium exchange (HDX), 2) limited proteolysis, and 3) chemical crosslinking (CX). HDX relies on the change in mass of a protein upon its dilution into deuterated buffer, which results in varied deuterium content within its backbone amides. Structural information on surface exposed, flexible or disordered linker regions of proteins can be achieved through limited proteolysis, using a variety of proteases and only small extents of digestion. CX refers to the covalent coupling of distinct chemical species and has been used to analyze the structure, function and interactions of proteins by identifying crosslinking sites that are formed by small multi-functional reagents, termed crosslinkers. Each of these MS applications is capable of revealing structural information for proteins when used either with or without other typical high resolution techniques, including NMR and X-ray crystallography. PMID:27975228

Fast Fourier Transform IR Characterization of Epoxy GY Systems Crosslinked with Aliphatic and Cycloaliphatic EH Polyamine Adducts

PubMed Central

Nikolic, Goran; Zlatkovic, Sasa; Cakic, Milorad; Cakic, Suzana; Lacnjevac, Caslav; Rajic, Zoran

2010-01-01

The use of fast FT-IR spectroscopy as a sensitive method to estimate a change of the crosslinking kinetics of epoxy resin with polyamine adducts is described in this study. A new epoxy formulation based on the use of polyamine adducts as the hardeners was analyzed. Crosslinking reactions of the different stoichiometric mixtures of the unmodified GY250 epoxy resin with the aliphatic EH606 and the cycloaliphatic EH637 polyamine adducts were studied using mid FT-IR spectroscopic techniques. As the crosslinking proceeded, the primary amine groups in polyamine adduct are converted to secondary and the tertiary amines. The decrease in the IR band intensity of epoxy groups at about 915 cm−1, as well as at about 3,056 cm−1, was observed due to process. Mid IR spectral analysis was used to calculate the content of the epoxy groups as a function of crosslinking time and the crosslinking degree of resin. The amount of all the epoxy species was estimated from IR spectra to changes during the crosslinking kinetics of epichlorhydrin. PMID:22315562

Crosslinkable coatings from phosphorylcholine-based polymers.

PubMed

Lewis, A L; Cumming, Z L; Goreish, H H; Kirkwood, L C; Tolhurst, L A; Stratford, P W

2001-01-01

2-Methacryloyloxyethyl phosphorylcholine (MPC) was synthesised and then used in the preparation of crosslinked polymer membranes with lauryl methacrylate, hydroxypropyl methacrylate and trimethoxysilylpropyl methacrylate (crosslinker) comonomers. Some physical aspects of the membrane properties were evaluated in order to establish the basis for the synthesis of a series of post-crosslinkable polymers. These materials were made by copolymerisation of the constituent monomers via a free radical method, and characterised using NMR, FT-IR, viscometry and elemental analysis. The optimum crosslink density and conditions required for curing coatings of these polymers were investigated using atomic force microscopy (AFM) and showed the inclusion of 5 mol% silyl crosslinking agent to be ideal. A nanoindentation technique was employed to determine if the coating developed elasticity upon crosslinking. The biological properties of the coatings were evaluated using a variety of protein adsorption assays and blood contacting experiments, and an enzyme immunoassay was developed to detect E. coli in order to assess the level of bacterial adhesion to these biomaterials. Polymers of this type were shown to be very useful as coating materials for improving the biocompatibility of, or reducing the levels of adherent bacteria to medical devices.

Monte Carlo Simulation of Endlinking Oligomers

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Young, Jennifer A.

1998-01-01

This report describes initial efforts to model the endlinking reaction of phenylethynyl-terminated oligomers. Several different molecular weights were simulated using the Bond Fluctuation Monte Carlo technique on a 20 x 20 x 20 unit lattice with periodic boundary conditions. After a monodisperse "melt" was equilibrated, chain ends were linked whenever they came within the allowed bond distance. Ends remained reactive throughout, so that multiple links were permitted. Even under these very liberal crosslinking assumptions, geometrical factors limited the degree of crosslinking. Average crosslink functionalities were 2.3 to 2.6; surprisingly, they did not depend strongly on the chain length. These results agreed well with the degrees of crosslinking inferred from experiment in a cured phenylethynyl-terminated polyimide oligomer.

Salinity Gradient Energy from Expansion and Contraction of Poly(allylamine hydrochloride) Hydrogels.

PubMed

Bui, Tri Quang; Cao, Vinh Duy; Do, Nu Bich Duyen; Christoffersen, Trine Eker; Wang, Wei; Kjøniksen, Anna-Lena

2018-06-22

Salinity gradients exhibit a great potential for production of renewable energy. Several techniques such as pressure-retarded osmosis and reverse electrodialysis have been employed to extract this energy. Unfortunately, these techniques are restricted by the high costs of membranes and problems with membrane fouling. However, the expansion and contraction of hydrogels can be a new and cheaper way to harvest energy from salinity gradients since the hydrogels swell in freshwater and shrink in saltwater. We have examined the effect of cross-linker concentration and different external loads on the energy recovered for this type of energy-producing systems. Poly(allylamine hydrochloride) hydrogels were cross-linked with glutaraldehyde to produce hydrogels with excellent expansion and contraction properties. Increasing the cross-linker concentration markedly improved the energy that could be recovered from the hydrogels, especially at high external loads. A swollen hydrogel of 60 g could recover more than 1800 mJ when utilizing a high cross-linker concentration, and the maximum amount of energy produced per gram of polymer was 3.4 J/g. Although more energy is recovered at high cross-linking densities, the maximum amount of energy produced per gram of polymer is highest at an intermediate cross-linking concentration. Energy recovery was reduced when the salt concentration was increased for the low-concentration saline solution. The results illustrate that hydrogels are promising for salinity gradient energy recovery, and that optimizing the systems significantly increases the amount of energy that can be recovered.

Free-Standing and Self-Crosslinkable Hybrid Films by Core-Shell Particle Design and Processing.

PubMed

Vowinkel, Steffen; Paul, Stephen; Gutmann, Torsten; Gallei, Markus

2017-11-15

The utilization and preparation of functional hybrid films for optical sensing applications and membranes is of utmost importance. In this work, we report the convenient and scalable preparation of self-crosslinking particle-based films derived by directed self-assembly of alkoxysilane-based cross-linkers as part of a core-shell particle architecture. The synthesis of well-designed monodisperse core-shell particles by emulsion polymerization is the basic prerequisite for subsequent particle processing via the melt-shear organization technique. In more detail, the core particles consist of polystyrene (PS) or poly(methyl methacrylate) (PMMA), while the comparably soft particle shell consists of poly(ethyl acrylate) (PEA) and different alkoxysilane-based poly(methacrylate)s. For hybrid film formation and convenient self-cross-linking, different alkyl groups at the siloxane moieties were investigated in detail by solid-state Magic-Angle Spinning Nuclear Magnetic Resonance (MAS, NMR) spectroscopy revealing different crosslinking capabilities, which strongly influence the properties of the core or shell particle films with respect to transparency and iridescent reflection colors. Furthermore, solid-state NMR spectroscopy and investigation of the thermal properties by differential scanning calorimetry (DSC) measurements allow for insights into the cross-linking capabilities prior to and after synthesis, as well as after the thermally and pressure-induced processing steps. Subsequently, free-standing and self-crosslinked particle-based films featuring excellent particle order are obtained by application of the melt-shear organization technique, as shown by microscopy (TEM, SEM).

Fatigue crack propagation resistance of virgin and highly crosslinked, thermally treated ultra-high molecular weight polyethylene.

PubMed

Gencur, Sara J; Rimnac, Clare M; Kurtz, Steven M

2006-03-01

To prolong the life of total joint replacements, highly crosslinked ultra-high molecular weight polyethylenes (UHMWPEs) have been introduced to improve the wear resistance of the articulating surfaces. However, there are concerns regarding the loss of ductility and potential loss in fatigue crack propagation (FCP) resistance. The objective of this study was to evaluate the effects of gamma radiation-induced crosslinking with two different post-irradiation thermal treatments on the FCP resistance of UHMWPE. Two highly crosslinked and one virgin UHMWPE treatment groups (ram-extruded, orthopedic grade, GUR 1050) were examined. For the two highly crosslinked treatment groups, UHMWPE rods were exposed to 100 kGy and then underwent post-irradiation thermal processing either above the melt temperature or below the melt temperature (2 h-150 degrees C, 110 degrees C). Compact tension specimens were cyclically loaded to failure and the fatigue crack growth rate, da/dN, vs. cyclic stress intensity factor, DeltaK, behavior was determined and compared between groups. Scanning electron microscopy was used to examine fracture surface characteristics. Crosslinking was found to decrease the ability of UHMWPE to resist crack inception and propagation under cyclic loading. The findings also suggested that annealing as a post-irradiation treatment may be somewhat less detrimental to FCP resistance of UHMWPE than remelting. Scanning electron microscopy examination of the fracture surfaces demonstrated that the virgin treatment group failed in a more ductile manner than the two highly crosslinked treatment groups.

Method of cross-linking polyvinyl alcohol and other water soluble resins

NASA Technical Reports Server (NTRS)

Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)

1980-01-01

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

A new fractionation assay, based on the size of formaldehyde-crosslinked, mildly sheared chromatin, delineates the chromatin structure at promoter regions

PubMed Central

Ishihara, Satoru; Varma, Rajat; Schwartz, Ronald H.

2010-01-01

To explore the higher order structure of transcribable chromatin in vivo, its local configuration was assessed through the accessibility of the chromatin to crosslinking with formaldehyde. The application of crosslinked and mildly sheared chromatin to sedimentation velocity centrifugation followed by size-fractionation of the DNA enabled us to biochemically distinguish between chromatin with heavily versus sparsely crosslinkable structures. The separated fractions showed a good correlation with gene expression profiles. Genes with poor crosslinking around the promoter region were actively transcribed, while transcripts were hardly detected from genes with extensive crosslinking in their promoter regions. For the inducible gene, Il2, the distribution of the promoter shifted in the gradient following T-cell receptor stimulation, consistent with a change in structure at this locus during activation. The kinetics of this switch preceded the chromatin change observed in a DNase I accessibility assay. Thus, this new chromatin fractionation technique has revealed a change in chromatin structure that has not been previously characterized. PMID:20371521

Application of radiation processing in asia and the pacific region: Focus on malaysia

NASA Astrophysics Data System (ADS)

Mohd Dahlan, Khairul Zaman HJ.

1995-09-01

Applications of radiation processing in Malaysia and other developing countries in Asia and the Pacific region is increasing as the countries move toward industrialisation. At present, there are more than 85 gamma facilities and 334 electron accelerators in Asia and the Pacific region which are mainly in Japan, Rep. of Korea and China. The main applications which are in the interest of the region are radiation sterilisation of medical products; radiation crosslinking of wire and cable, heat shrinkable film and tube, and foam; radiation curing of surface coatings, printing inks and adhesive; radiation vulcanisation of natural rubber latex; radiation processing of agro-industrial waste; radiation treatment of sewage sludge and municipal waste; food irradiation; tissue grafts and radiation synthesis of bioactive materials.

Graphene Oxide-A Tool for the Preparation of Chemically Crosslinking Free Alginate-Chitosan-Collagen Scaffolds for Bone Tissue Engineering.

PubMed

Kolanthai, Elayaraja; Sindu, Pugazhendhi Abinaya; Khajuria, Deepak Kumar; Veerla, Sarath Chandra; Kuppuswamy, Dhandapani; Catalani, Luiz Henrique; Mahapatra, D Roy

2018-04-18

Developing a biodegradable scaffold remains a major challenge in bone tissue engineering. This study was aimed at developing novel alginate-chitosan-collagen (SA-CS-Col)-based composite scaffolds consisting of graphene oxide (GO) to enrich porous structures, elicited by the freeze-drying technique. To characterize porosity, water absorption, and compressive modulus, GO scaffolds (SA-CS-Col-GO) were prepared with and without Ca 2+ -mediated crosslinking (chemical crosslinking) and analyzed using Raman, Fourier transform infrared (FTIR), X-ray diffraction (XRD), and scanning electron microscopy techniques. The incorporation of GO into the SA-CS-Col matrix increased both crosslinking density as indicated by the reduction of crystalline peaks in the XRD patterns and polyelectrolyte ion complex as confirmed by FTIR. GO scaffolds showed increased mechanical properties which were further increased for chemically crosslinked scaffolds. All scaffolds exhibited interconnected pores of 10-250 μm range. By increasing the crosslinking density with Ca 2+ , a decrease in the porosity/swelling ratio was observed. Moreover, the SA-CS-Col-GO scaffold with or without chemical crosslinking was more stable as compared to SA-CS or SA-CS-Col scaffolds when placed in aqueous solution. To perform in vitro biochemical studies, mouse osteoblast cells were grown on various scaffolds and evaluated for cell proliferation by using MTT assay and mineralization and differentiation by alizarin red S staining. These measurements showed a significant increase for cells attached to the SA-CS-Col-GO scaffold compared to SA-CS or SA-CS-Col composites. However, chemical crosslinking of SA-CS-Col-GO showed no effect on the osteogenic ability of osteoblasts. These studies indicate the potential use of GO to prepare free SA-CS-Col scaffolds with preserved porous structure with elongated Col fibrils and that these composites, which are biocompatible and stable in a biological medium, could be used for application in engineering bone tissues.

Chemical cross-linking and native mass spectrometry: A fruitful combination for structural biology

PubMed Central

Sinz, Andrea; Arlt, Christian; Chorev, Dror; Sharon, Michal

2015-01-01

Mass spectrometry (MS) is becoming increasingly popular in the field of structural biology for analyzing protein three-dimensional-structures and for mapping protein–protein interactions. In this review, the specific contributions of chemical crosslinking and native MS are outlined to reveal the structural features of proteins and protein assemblies. Both strategies are illustrated based on the examples of the tetrameric tumor suppressor protein p53 and multisubunit vinculin-Arp2/3 hybrid complexes. We describe the distinct advantages and limitations of each technique and highlight synergistic effects when both techniques are combined. Integrating both methods is especially useful for characterizing large protein assemblies and for capturing transient interactions. We also point out the future directions we foresee for a combination of in vivo crosslinking and native MS for structural investigation of intact protein assemblies. PMID:25970732

Hemostatic granules and dressing prepared from formulations of carboxymethyl cellulose, kappa-carrageenan and polyethylene oxide crosslinked by gamma radiation

NASA Astrophysics Data System (ADS)

Barba, Bin Jeremiah D.; Aranilla, Charito T.; Relleve, Lorna S.; Cruz, Veriza Rita C.; Vista, Jeanina Richelle; Abad, Lucille V.

2018-03-01

Uncontrolled hemorrhage remains a persistent problem especially in anatomical areas where compression and tourniquet cannot be applied. Hemostatic agents are materials which can achieve control of bleeding in acute, life-threatening traumatic coagulopathy. In this study, we prepared biocompatible hydrogel-based hemostat crosslinked by ionizing radiation. Granules made from carboxymethyl cellulose and dressing from kappa carrageenan and polyethylene oxide were characterized by FT-IR, SEM, and gel analysis. Gamma radiation with a dose of 25 kGy was used for sterilization process. Stability studies indicate that the products remain effective with a shelf life of up to 18 months based on accelerated aging. Both hemostatic agents were demonstrated to be effective in vitro blood clotting assays showing a low blood clotting index, high platelet adhesion capacity and accelerated clotting time. Hemostat granules and dressing were also used in a femoral artery rat bleeding model where hemorrhage control was achieved in 90 s without compression and resulted in 100% survival rate after a 7 and 14-day observation.

Analysis of simultaneous thermal/gamma radiation aging of cross-linked polyethylene (XLPE) insulation—interim status report

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

Fifield, Leonard S.; Correa, Miguel

Cross-linked polyethylene (XLPE) is the most common cable insulation found in nuclear containment, and is therefore a priority material for investigation of long term aging effect from elevated temperature combined with gamma radiation exposure. Prior work has identified the possibility of anomalous aging behavior in XLPE such as the inverse temperature effect in which radiation exposure is more damaging at lower temperatures than at higher temperatures. We explored simultaneous aging of XLPE insulation from modern Firewall® III nuclear cables at 60, 90, and 115 °C, at gamma dose rates from 116 to 540 Gy/h, for exposure periods up to 25more » d. XLPE samples exposed in this way were characterized using the percent gel and uptake factor method. For the conditions and material examine, degradation behavior was seen to track proportionally with increasing temperature, rather than to exhibit greater degradation at lower temperatures. Ongoing work including similar aging at 25 °C and characterization of the XLPE samples using other methods will further elucidate these initial results« less

Properties of crosslinked ultra-high-molecular-weight polyethylene.

PubMed

Lewis, G

2001-02-01

Substantially reducing the rate of generation of wear particles at the surfaces of ultra-high-molecular-weight polyethylene (UHMWPE) orthopedic implant bearing components, in vivo, is widely regarded as one of the most formidable challenges in modern arthroplasty. In the light of this, much research attention has been paid to the myriad of endogenous and exogenous factors that have been postulated to affect this wear rate, one such factor being the polymer itself. In recent years, there has been a resurgence of interest in crosslinking the polymer as a way of improving its properties that are considered relevant to its use for fabricating bearing components. Such properties include wear resistance, fatigue life, and fatigue crack propagation rate. Although a large volume of literature exists on the topic on the impact of crosslinking on the properties of UHMWPE, no critical appraisal of this literature has been published. This is one of the goals of the present article, which emphasizes three aspects. The first is the trade-off between improvement in wear resistance and depreciation in other mechanical and physical properties. The second aspect is the presentation of a method of estimating the optimal value of a crosslinking process variable (such as dose in radiation-induced crosslinking) that takes into account this trade-off. The third aspect is the description of a collection of under- and unexplored research areas in the field of crosslinked UHMWPE, such as the role of starting resin on the properties of the crosslinked polymer, and the in vitro evaluation of the wear rate of crosslinked tibial inserts and other bearing components that, in vivo, are subjected to nearly unidirectional motion.

A PI 4. 6 peroxidase that specifically crosslinks extensin precursors

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

Upham, B.L; Alizadeh, H.; Ryan, K.J.

1991-05-01

The primary cell wall is a microcomposite of cellulose, pectin, hemicellulose and protein. The warp-weft model of the primary cell wall hypothesize that extensin monomers are intermolecularly crosslinked orthogonal to the cellulose microfibril thus mechanically coupling the major load-bearing polymer: cellulose. Media of tomato cell cultures contains heat labile, peroxide dependent crosslinking activity, as determined by the rate of decrease in monomer concentration analyzed via Superose-6. Isoelectric focusing of tomato cell culture media indicated crosslinking was predominantly in the acidic peroxidase fraction (pI4.6). This peroxidase was partially purified by ultracentrifugation, DEAE-Trisacryl and HPLC-DEAE chromatography techniques resulting in a 90 foldmore » purification and 45% yield. A second acidic peroxidase eluted from the HPLC-DEAE column had 25% of the crosslinking activity of the pI 4.6 peroxidase. Purified basic peroxidase had only 0.7% of the activity of the pI 4.6 peroxidase. The specific activity of the pI 4.6 peroxidase was 5,473 mg extensin crosslinked/min/mg peroxidase. The pI 4.6 peroxidase crosslinked the following extensins: tomato I and II, carrot, Ginkgo II and did not crosslink Ginkgo I, Douglas Fir, Maize, Asparagus I and II, and sugarbeet extensins as well as bovine serum albumin. Comparison of motifs common to extensins that are crosslinked by the pI 4.6 peroxidase may help identify the crosslink domain(s) of extension.« less

Ab initio simulations of bond breaking in sulfur crosslinked isoprene oligomer units

NASA Astrophysics Data System (ADS)

Gehrke, Sascha; Alznauer, Hans Tobias; Karimi-Varzaneh, Hossein Ali; Becker, Jörg August

2017-12-01

Sulfur crosslinked polyisoprene (rubber) is used in important material components for a number of technical tasks (e.g., in tires and sealings). If mechanical stress, like tension or shear, is applied on these material components, the sulfur crosslinks suffer from homolytic bond breaking. In this work, we have simulated the bond breaking mechanism of sulfur crosslinks between polyisoprene chains using Car-Parrinello molecular dynamic simulations and investigated the maximum forces which can be resisted by the crosslinks. Small model systems with crosslinks formed by chains of N = 1 to N = 6 sulfur atoms have been simulated with the slow growth-technique, known from the literature. The maximum force can be thereby determined from the calculated energies as a function of strain (elongation). The stability of the crosslink under strain is quantified in terms of the maximum force that can be resisted by the system before the crosslink breaks. As shown by our simulations, this maximum force decreases with the sulfur crosslink length N in a step like manner. Our findings indicate that in bridges with N = 1, 2, and 3 sulfur atoms predominantly, carbon-sulfur bonds break, while in crosslinks with N > 3, the breaking of a sulfur-sulfur bond is the dominant failure mechanism. The results are explained within a simple chemical bond model, which describes how the delocalization of the electrons in the generated radicals can lower their electronic energy and decrease the activation barriers. It is described which of the double bonds in the isoprene units are involved in the mechanochemistry of crosslinked rubber.

Identification of mammalian proteins cross-linked to DNA by ionizing radiation.

PubMed

Barker, Sharon; Weinfeld, Michael; Zheng, Jing; Li, Liang; Murray, David

2005-10-07

Ionizing radiation (IR) is an important environmental risk factor for various cancers and also a major therapeutic agent for cancer treatment. Exposure of mammalian cells to IR induces several types of damage to DNA, including double- and single-strand breaks, base and sugar damage, as well as DNA-DNA and DNA-protein cross-links (DPCs). Little is known regarding the biological consequences of DPCs. Identifying the proteins that become cross-linked to DNA by IR would be an important first step in this regard. We have therefore undertaken a proteomics study to isolate and identify proteins involved in IR-induced DPCs. DPCs were induced in AA8 Chinese hamster ovary or GM00637 human fibroblast cells using 0-4 gray of gamma-rays under either aerated or hypoxic conditions. DPCs were isolated using a recently developed method, and proteins were identified by mass spectrometry. We identified 29 proteins as being cross-linked to DNA by IR under aerated and/or hypoxic conditions. The identified proteins include structural proteins, actin-associated proteins, transcription regulators, RNA-splicing components, stress-response proteins, cell cycle regulatory proteins, and GDP/GTP-binding proteins. The involvement of several proteins (actin, histone H2B, and others) in DPCs was confirmed by using Western blot analysis. The dose responsiveness of DPC induction was examined by staining one-dimensional SDS-polyacrylamide gels with SYPRO Tangerine followed by analysis using fluorescence imaging. Quantitation of the fluorescence signal indicated no significant difference in total yields of IR-induced DPCs generated under aerated or hypoxic conditions, although differences were observed for several individual protein bands.

Hybrid Core-Shell (HyCoS) Nanoparticles produced by Complex Coacervation for Multimodal Applications

NASA Astrophysics Data System (ADS)

Vecchione, D.; Grimaldi, A. M.; Forte, E.; Bevilacqua, Paolo; Netti, P. A.; Torino, E.

2017-03-01

Multimodal imaging probes can provide diagnostic information combining different imaging modalities. Nanoparticles (NPs) can contain two or more imaging tracers that allow several diagnostic techniques to be used simultaneously. In this work, a complex coacervation process to produce core-shell completely biocompatible polymeric nanoparticles (HyCoS) for multimodal imaging applications is described. Innovations on the traditional coacervation process are found in the control of the reaction temperature, allowing a speeding up of the reaction itself, and the production of a double-crosslinked system to improve the stability of the nanostructures in the presence of a clinically relevant contrast agent for MRI (Gd-DTPA). Through the control of the crosslinking behavior, an increase up to 6 times of the relaxometric properties of the Gd-DTPA is achieved. Furthermore, HyCoS can be loaded with a high amount of dye such as ATTO 633 or conjugated with a model dye such as FITC for in vivo optical imaging. The results show stable core-shell polymeric nanoparticles that can be used both for MRI and for optical applications allowing detection free from harmful radiation. Additionally, preliminary results about the possibility to trigger the release of a drug through a pH effect are reported.

Microfabrication of biocompatible hydrogels by proton beam writing

NASA Astrophysics Data System (ADS)

Nagasawa, Naotsugu; Kimura, Atsushi; Idesaki, Akira; Yamada, Naoto; Koka, Masashi; Satoh, Takahiro; Ishii, Yasuyuki; Taguchi, Mitsumasa

2017-10-01

Functionalization of biocompatible materials is expected to be widely applied in biomedical engineering and regenerative medicine fields. Hydrogel has been expected as a biocompatible scaffold which support to keep an organ shape during cell multiplying in regenerative medicine. Therefore, it is important to understanding a surface microstructure (minute shape, depth of flute) and a chemical characteristic of the hydrogel affecting the cell culture. Here, we investigate the microfabrication of biocompatible polymeric materials, such as the water-soluble polysaccharide derivatives hydroxypropyl cellulose and carboxymethyl cellulose, by use of proton beam writing (PBW). These polymeric materials were dissolved thoroughly in pure water using a planetary centrifugal mixer, and a sample sheet (1 mm thick) was formed on polyethylene terephthalate (PET) film. Crosslinking to form hydrogels was induced using a 3.0 MeV focused proton beam from the single-ended accelerator at Takasaki Ion Accelerators for Advanced Radiation Application. The aqueous samples were horizontally irradiated with the proton beam through the PET cover film, and then rinsed with deionized water. Microstructured hydrogels were obtained on the PET film using the PBW technique without toxic crosslinking reagents. Cell adhesion and proliferation on the microfabricated biocompatible hydrogels were investigated. Microfabrication of HPC and CMC by the use of PBW is expected to produce new biocompatible materials that can be applied in biological and medical applications.

Radiation Resistant Electrical Insulation Materials for Nuclear Reactors: Final Report

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

Duckworth, Robert C.; Aytug, Tolga; Paranthaman, M. Parans

The instrument and control cables in future nuclear reactors will be exposed to temperatures, dose rates, and accumulated doses exceeding those originally anticipated for the 40-year operational life of the nuclear power plant fleet. The use of nanocomposite dielectrics as insulating material for such cables has been considered a route to performance improvement. In this project, nanoparticles were developed and successfully included in three separate material systems [cross-linked polyvinyl alcohol (PVA/XLPVA), cross-linked polyethylene (PE/XLPE), and polyimide (PI)], and the chemical, electrical, and mechanical performance of each was analyzed as a function of environmental exposure and composition. Improvements were found inmore » each material system; however, refinement of each processing pathway is needed, and the consequences of these refinements in the context of thermal, radiation, and moisture exposures should be evaluated before transferring knowledge to industry.« less

The Importance of Non-accessible Crosslinks and Solvent Accessible Surface Distance in Modeling Proteins with Restraints From Crosslinking Mass Spectrometry*

PubMed Central

Bullock, Joshua Matthew Allen; Schwab, Jannik; Thalassinos, Konstantinos; Topf, Maya

2016-01-01

Crosslinking mass spectrometry (XL-MS) is becoming an increasingly popular technique for modeling protein monomers and complexes. The distance restraints garnered from these experiments can be used alone or as part of an integrative modeling approach, incorporating data from many sources. However, modeling practices are varied and the difference in their usefulness is not clear. Here, we develop a new scoring procedure for models based on crosslink data—Matched and Nonaccessible Crosslink score (MNXL). We compare its performance with that of other commonly-used scoring functions (Number of Violations and Sum of Violation Distances) on a benchmark of 14 protein domains, each with 300 corresponding models (at various levels of quality) and associated, previously published, experimental crosslinks (XLdb). The distances between crosslinked lysines are calculated either as Euclidean distances or Solvent Accessible Surface Distances (SASD) using a newly-developed method (Jwalk). MNXL takes into account whether a crosslink is nonaccessible, i.e. an experimentally observed crosslink has no corresponding SASD in a model due to buried lysines. This metric alone is shown to have a significant impact on modeling performance and is a concept that is not considered at present if only Euclidean distances are used. Additionally, a comparison between modeling with SASD or Euclidean distance shows that SASD is superior, even when factoring out the effect of the nonaccessible crosslinks. Our benchmarking also shows that MNXL outperforms the other tested scoring functions in terms of precision and correlation to Cα-RMSD from the crystal structure. We finally test the MNXL at different levels of crosslink recovery (i.e. the percentage of crosslinks experimentally observed out of all theoretical ones) and set a target recovery of ∼20% after which the performance plateaus. PMID:27150526

Application of Polymers for the Long-Term Storage and Disposal of Low- and Intermediate-Level Radioactive Waste

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

Bonin, Hugues W.; Walker, Michael W.; Bui, Van Tam

2004-01-15

Research carried out at the Royal Military College of Canada on the effects of mixed fields of radiation on high polymer adhesives and composite materials has shown that some polymers are quite resistant to radiation and could well serve in the fabrication of radioactive-waste disposal containers. A research program was launched to investigate the possibilities of using advanced polymers and polymer-based composites for high-level radioactive waste management on one hand and for intermediate- and low-level radioactive waste disposal on the other hand. Research was thus conducted in parallel on both fronts, and the findings for the later phase are presented.more » Thermoplastic polymers were studied for this application because they are superior materials, having the advantage over metals of not corroding and of displaying high resistance to chemical aggression. The experimental methods used in this research focused on determining the effects of radiation on the properties of the materials considered: polypropylene, nylon 66, polycarbonate, and polyurethane, with and without glass fiber reinforcement. The method involved submitting injection-molded tensile test bars to the mixed radiation field generated by the SLOWPOKE-2 nuclear reactor at the Royal Military College of Canada to accumulate doses ranging from 0.5 to 3.0 MGy. The physical, mechanical, and chemical effects of the various radiation doses on the materials were measured from density, tensile, differential scanning calorimetry, and scanning electron microscopy tests.For each polymer, the test results evidenced predominant cross-linking of the polymeric chains severed by radiation. This was evident from observed changes in the mechanical and chemical properties of the polymers, typical of cross-linking. The mechanical changes observed included an overall increase in density, an increase in Young's modulus, a decrease in strain at break, and only minor changes in strength. The chemical changes included differences in chemical transition temperatures characteristic of radiation damage. All the changes in these properties are characteristic of the cross-linking phenomenon. For the glass-fiber-reinforced polymers, the results of the tests evidenced minor radiation degradation at the fiber/matrix interfaces. Based on these results, any of the investigated polymers could potentially be used for disposal containers due to their abilities to adequately resist radiation. This allowed proceeding one step further into determining a potential design framework for containers for the long-term storage and disposal of low- and intermediate-level radioactive waste.« less

Novel Spray Dried Glycerol 2-Phosphate Cross-Linked Chitosan Microparticulate Vaginal Delivery System—Development, Characterization and Cytotoxicity Studies

PubMed Central

Szymańska, Emilia; Szekalska, Marta; Czarnomysy, Robert; Lavrič, Zoran; Srčič, Stane; Miltyk, Wojciech; Winnicka, Katarzyna

2016-01-01

Chitosan microparticulate delivery systems containing clotrimazole were prepared by a spray drying technique using glycerol 2-phosphate as an ion cross-linker. The impact of a cross-linking ratio on microparticle characteristics was evaluated. Drug-free and drug-loaded unmodified or ion cross-linked chitosan microparticles were examined for the in vitro cytotoxicity in VK2/E6E7 human vaginal epithelial cells. The presence of glycerol 2-phosphate influenced drug loading and encapsulation efficacy in chitosan microparticles. By increasing the cross-linking ratio, the microparticles with lower diameter, moisture content and smoother surface were observed. Mucoadhesive studies displayed that all formulations possessed mucoadhesive properties. The in vitro release profile of clotrimazole was found to alter considerably by changing the glycerol 2-phosphate/chitosan ratio. Results from cytotoxicity studies showed occurrence of apoptotic cells in the presence of chitosan and ion cross-linked chitosan microparticles, followed by a loss of membrane potential suggesting that cell death might go through the mitochondrial apoptotic pathway. PMID:27690062

Hydrogels of polyvinylpyrrolidone (PVP) and poly(acrylic acid) (PAA) synthesized by radiation-induced crosslinking of homopolymers

NASA Astrophysics Data System (ADS)

Kadłubowski, Sławomir; Henke, Artur; Ulański, Piotr; Rosiak, Janusz M.

2010-03-01

pH-sensitive PVP-PAA hydrogels have been prepared by electron-beam-induced irradiation at pH close to pKa of carboxylic groups. Protonation of these groups promoted the formation of hydrogen bonds between the PAA and PVP segments within the crosslinked structure and caused interpolymer complex formation. To demonstrate possible future application of such gels, we tested them as simple chemical detectors. When loaded with glucose oxidase, the PAA-PVP gel's turbidity and shrinkage was triggered by the presence of glucose due to a drop in pH caused by the enzymatic reaction.

Adaptive Power Control for Space Communications

NASA Technical Reports Server (NTRS)

Thompson, Willie L., II; Israel, David J.

2008-01-01

This paper investigates the implementation of power control techniques for crosslinks communications during a rendezvous scenario of the Crew Exploration Vehicle (CEV) and the Lunar Surface Access Module (LSAM). During the rendezvous, NASA requires that the CEV supports two communication links: space-to-ground and crosslink simultaneously. The crosslink will generate excess interference to the space-to-ground link as the distances between the two vehicles decreases, if the output power is fixed and optimized for the worst-case link analysis at the maximum distance range. As a result, power control is required to maintain the optimal power level for the crosslink without interfering with the space-to-ground link. A proof-of-concept will be described and implemented with Goddard Space Flight Center (GSFC) Communications, Standard, and Technology Lab (CSTL).

Identification of MS-Cleavable and Non-Cleavable Chemically Crosslinked Peptides with MetaMorpheus.

PubMed

Lu, Lei; Millikin, Robert J; Solntsev, Stefan K; Rolfs, Zach; Scalf, Mark; Shortreed, Michael R; Smith, Lloyd M

2018-05-25

Protein chemical crosslinking combined with mass spectrometry has become an important technique for the analysis of protein structure and protein-protein interactions. A variety of crosslinkers are well developed, but reliable, rapid, and user-friendly tools for large-scale analysis of crosslinked proteins are still in need. Here we report MetaMorpheusXL, a new search module within the MetaMorpheus software suite that identifies both MS-cleavable and non-cleavable crosslinked peptides in MS data. MetaMorpheusXL identifies MS-cleavable crosslinked peptides with an ion-indexing algorithm, which enables an efficient large database search. The identification does not require the presence of signature fragment ions, an advantage compared to similar programs such as XlinkX. One complication associated with the need for signature ions from cleavable crosslinkers such as DSSO (disuccinimidyl sulfoxide) is the requirement for multiple fragmentation types and energy combinations, which is not necessary for MetaMorpheusXL. The ability to perform proteome-wide analysis is another advantage of MetaMorpheusXl compared to such programs as MeroX and DXMSMS. MetaMorpheusXL is also faster than other currently available MS-cleavable crosslink search software programs. It is imbedded in MetaMorpheus, an open-source and freely available software suite that provides a reliable, fast, user-friendly graphical user interface that is readily accessible to researchers.

Effect of concentration of polyfunctional monomers on physical properties of acrylonitrile butadiene rubber under electron-beam irradiation

NASA Astrophysics Data System (ADS)

Yasin, Tariq; Ahmed, Shamshad; Ahmed, Munir; Yoshii, Fumio

2005-06-01

An investigation has been undertaken to find out the effect of concentration of different polyfunctional monomers (PFMs) on the physical properties of the acrylonitrile-butadiene rubber (NBR) crosslinked by electron beam (EB). The PFMs used were diethylene glycol dimethacrylate, trimethylol propane trimethacrylate and trimethylol propane triacrylate. The physical properties of EB-irradiated NBR sheets were evaluated by measuring the tensile strength, elongation percent at break, hardness and gel fraction. The results showed a remarkable increase in tensile strength, hardness and gel fraction as the concentration of PFMs was increased from 1 part per hundred (phr) to 5 phr in the NBR samples whereas elongation percent decreased in a steady manner. The improvement in physical properties of radiation crosslinked NBR in the presence of PFMs may be attributed to its increased crosslinking density as observed by the corresponding increase in gel content.

Insulating epoxy/barite and polyester/barite composites for radiation attenuation.

PubMed

El-Sarraf, M A; El-Sayed Abdo, A

2013-09-01

A trial has been made to create insulating Epoxy/Barite (EP/Brt) (ρ=2.85 g cm(-3)) and Crosslinked Unsaturated Polyester/Barite (CUP/Brt) (ρ=3.25 g cm(-3)) composites with radiation attenuation and shielding capabilities. Experimental work regarding mechanical and physical properties was performed to study the composites integrity for practical applications. The properties were found to be reasonable. Radiation attenuation properties have been carried out using emitted collimated beam from a fission (252)Cf (100 µg) neutron source, and the neutron-gamma spectrometer with stilbene scintillator. The pulse shape discriminating (P.S.D) technique based on the zero cross-over method was used to discriminate between neutron and gamma-ray pulses. Thermal neutron fluxes, measured using the BF3 detector and thermal neutron detection system, were used to plot the attenuation relations. The fast neutron macroscopic effective removal cross-section ΣR, gamma ray total attenuation coefficient µ and thermal neutron macroscopic cross-section Σ have been evaluated. Theoretical calculations have been achieved using MCNP-4C2 code to calculate ΣR, µ and Σ. Also, MERCSF-N program was used to calculate macroscopic effective removal cross-section ΣR. Measured and calculated results have been compared and were found to be in reasonable agreement. Copyright © 2013 Elsevier Ltd. All rights reserved.

Post-deformation shape-recovery behavior of vitamin E-diffused, radiation crosslinked polyethylene acetabular components.

PubMed

Takahashi, Yasuhito; Tateiwa, Toshiyuki; Shishido, Takaaki; Masaoka, Toshinori; Kubo, Kosuke; Yamamoto, Kengo

2016-10-01

The in-vivo progression of creep and wear in ultra-high molecular weight polyethylene (UHMWPE) acetabular liners has been clinically evaluated by measuring radiographic penetration of femoral heads. In such clinical assessments, however, viscoelastic strain relaxation has been rarely considered after a removal of hip joint loading, potentially leading to an underestimation of the penetrated thickness. The objective of this study was to investigate shape-recovery behavior of pre-compressed, radiation crosslinked and antioxidant vitamin E-diffused UHMWPE acetabular liners, and also to characterize the effects of varying their internal diameter (ID) and wall thickness (WT). We applied uniaxial compression to the UHMWPE specimens of various ID (28, 32, 36mm) and WT (4.8, 6.8, 8.9mm) for 4320min under the constant load of 3000N, and subsequently monitored the strain-relaxation behavior as a function of time after unloading. It was observed that there was a considerable shape recovery of the components after removal of the external static load. Reducing ID and WT significantly accelerated the rate of creep strain recovery, and varying WT was more sensitive to the recovery behavior than ID. Creep deformation of the tested liners recovered mostly within the first 300min after unloading. Note that approximately half of the total recovery amount proceeded just within 5min after unloading. These results suggest a remarkably high capability of shape recovery of vitamin E-diffused highly crosslinked UHMWPE. In conclusion, the time-dependent shape recovering and the diameter-thickness effect on its behavior should be carefully considered when the postoperative penetration is quantified in highly crosslinked UHMWPE acetabular liners (especially on the non-weight bearing radiographs). Copyright © 2016 Elsevier Ltd. All rights reserved.

Preparation and characterization of electrospun in-situ cross-linked gelatin-graphite oxide nanofibers.

PubMed

Zhan, Jianchao; Morsi, Yosry; Ei-Hamshary, Hany; Al-Deyab, Salem S; Mo, Xiumei

2016-01-01

Electrospun gelatin(Gel) nanofibers scaffold has such defects as poor mechanical property and quick degradation due to high solubility. In this study, the in situ cross-linked electrospinning technique was used for the production of gelatin nanofibers. Deionized water was chosen as the spinning solvent and graphite oxide (GO) was chosen as the enhancer. The morphological structure, porosity, thermal property, moisture absorption, and moisture retention performance, hydrolysis resistance, mechanical property, and biocompatibility of the produced nanofibers were investigated. Compared with in situ cross-linked gelatin nanofibers scaffold, in situ cross-linked Gel-GO nanofibers scaffold has the following features: (1) the hydrophilicity, moisture absorption, and moisture retention performance slightly reduce, while the hydrolysis resistance is improved; (2) the breaking strength, breaking elongation, and Young's modulus are significantly improved; (3) the porosity slightly reduces while the biocompatibility considerably increases. The in situ cross-linked Gel-GO nanofibers scaffold is likely to be applied in such fields as drug delivery and scaffold for skin tissue engineering.

Elasticity, biodegradability and cell adhesive properties of chitosan/hyaluronan multilayer films

NASA Astrophysics Data System (ADS)

Schneider, Aurore; Richert, Ludovic; Francius, Gregory; Voegel, Jean-Claude; Picart, Catherine

2007-03-01

In the bioengineering field, a recent and promising approach to modifying biomaterial surfaces is the layer-by-layer (LbL) technique used to build thin polyelectrolyte multilayer films. In this work, we focused on polyelectrolyte multilayer films made of two polysaccharides, chitosan (CHI) and hyaluronan (HA), and on the control of their physico-chemical and cell adhesive properties by chemical cross-linking. CHI/HA films were cross-linked using a water soluble carbodiimide and observed by confocal laser scanning microscopy (CLSM) with a fluorescently labeled CHI. Film thicknesses were similar for native and cross-linked films. The film nanometer roughness was measured by atomic force microscopy and was found to be higher for cross-linked films. Cross-linking the films also leads to a drastic change in film stiffness. The elastic modulus of the films (Young's modulus) as measured by AFM nano-indentation was about tenfold increased for cross-linked films as compared to native ones. From a biological point of view, cross-liked films are more resistant to enzymatic degradation by hyaluronidase. Furthermore, the increase in film stiffness has a favorable effect on the adhesion and spreading of chondrosarcoma cells. Thus, the CHI/HA cross-linked films could be used for various applications due to their adhesive properties and to their mechanical properties (including stability in enzymatic media).

Hekate: Software Suite for the Mass Spectrometric Analysis and Three-Dimensional Visualization of Cross-Linked Protein Samples

PubMed Central

2013-01-01

Chemical cross-linking of proteins combined with mass spectrometry provides an attractive and novel method for the analysis of native protein structures and protein complexes. Analysis of the data however is complex. Only a small number of cross-linked peptides are produced during sample preparation and must be identified against a background of more abundant native peptides. To facilitate the search and identification of cross-linked peptides, we have developed a novel software suite, named Hekate. Hekate is a suite of tools that address the challenges involved in analyzing protein cross-linking experiments when combined with mass spectrometry. The software is an integrated pipeline for the automation of the data analysis workflow and provides a novel scoring system based on principles of linear peptide analysis. In addition, it provides a tool for the visualization of identified cross-links using three-dimensional models, which is particularly useful when combining chemical cross-linking with other structural techniques. Hekate was validated by the comparative analysis of cytochrome c (bovine heart) against previously reported data.1 Further validation was carried out on known structural elements of DNA polymerase III, the catalytic α-subunit of the Escherichia coli DNA replisome along with new insight into the previously uncharacterized C-terminal domain of the protein. PMID:24010795

Radiation processing and market economy

NASA Astrophysics Data System (ADS)

Zagórski, Z. P.

1998-06-01

In the system of totalitarian economy, regulated by bureaucracy, the real value of equipment, materials and services is almost completely unknown, what makes impossible the comparison of different technologies, eliminates competition, disturbs research and development. With introduction of market economy in Central and Eastern Europe, the radiation processing has lost doubtful support, becoming an independent business, subject to laws of free market economy. Only the most valuable objects of processing have survived that test. At the top of the list are: radiation sterilization of medical equipment and radiation induced crosslinking of polymers, polyethylene in particular. New elements of competition has entered the scene, as well as questions of international regulations and standards have appeared.

The evolution of and challenges for industrial radiation processing—2012

NASA Astrophysics Data System (ADS)

Berejka, A. J.; Cleland, M. R.; Walo, M.

2014-01-01

The evolution of industrial radiation processing is traced from Roentgen's discovery of X-radiation in 1895 by following the development of high current, electron beam accelerators (EB) throughout the twentieth century. Although Becquerel soon followed Roentgen with his discovery of what became to be known as radioactivity, electrical sources for ionizing radiation dominate industrial processing with there being more than ten times as many industrial installations using high current EB equipment than the facilities relying upon large concentrations of radioactive isotopes. In the 1950s, the discovery that ionizing radiation would enhance the value of what has become the world's largest volume commodity plastic, polyethylene (PE), opened the way for full scale commercial use of high current EB equipment. While the crosslinking of the PE insulation on wire became one of the first major industrial applications, other uses of EB processing soon followed. In the 1970s, low-energy, self-shielded EB equipment made the surface curing of inks, coatings and adhesives more industrially viable. In the early part of the twenty-first century, new market applications involving the low-energy EB surface decontamination of packaging materials emerged. This new area poses challenges for the metrology needed to control industrial processes, in that there is limited EB penetration into what have been used as dosimeters by industry. Major industrial use of radiation process is now over 50 years old. Because of the diversity of end-uses and the fact that the use of ionizing radiation in industry is a process technique, it is hard to quantify the value-added to numerous commercial products that benefit from this energy efficient process. It may be in excess of a trillion Euros in value-added to articles of commerce. In this milieu, there are some broad-based opportunities for research which are noted.

The Application of an Emerging Technique for Protein–Protein Interaction Interface Mapping: The Combination of Photo-Initiated Cross-Linking Protein Nanoprobes with Mass Spectrometry

PubMed Central

Ptáčková, Renata; Ječmen, Tomáš; Novák, Petr; Hudeček, Jiří; Stiborová, Marie; Šulc, Miroslav

2014-01-01

Protein–protein interaction was investigated using a protein nanoprobe capable of photo-initiated cross-linking in combination with high-resolution and tandem mass spectrometry. This emerging experimental approach introduces photo-analogs of amino acids within a protein sequence during its recombinant expression, preserves native protein structure and is suitable for mapping the contact between two proteins. The contact surface regions involved in the well-characterized interaction between two molecules of human 14-3-3ζ regulatory protein were used as a model. The employed photo-initiated cross-linking techniques extend the number of residues shown to be within interaction distance in the contact surface of the 14-3-3ζ dimer (Gln8–Met78). The results of this study are in agreement with our previously published data from molecular dynamic calculations based on high-resolution chemical cross-linking data and Hydrogen/Deuterium exchange mass spectrometry. The observed contact is also in accord with the 14-3-3ζ X-ray crystal structure (PDB 3dhr). The results of the present work are relevant to the structural biology of transient interaction in the 14-3-3ζ protein, and demonstrate the ability of the chosen methodology (the combination of photo-initiated cross-linking protein nanoprobes and mass spectrometry analysis) to map the protein-protein interface or regions with a flexible structure. PMID:24865487

Methacrylate based cross-linkers for improved thermomechanical properties and retention of radiation detection response in plastic scintillators

NASA Astrophysics Data System (ADS)

Mahl, Adam; Lim, Allison; Latta, Joseph; Yemam, Henok A.; Greife, Uwe; Sellinger, Alan

2018-03-01

Pulse shape discrimination (PSD) is an important method that can efficiently sort and separate neutron and gamma radiation signals. PSD is currently achieved in plastic scintillators by over-doping poly(vinyl toluene) (PVT) matrices with fluorescent molecules. Meaningful separation of the signals requires addition of >20 wt% 2,5-diphenyloxazole (PPO) fluor in PVT. At these concentrations PPO acts as a plasticizer, negatively affecting the physical properties of the final plastic such as hardness, machinability, and thermomechanical stability. This work addresses these issues by implementing a cost-effective solution using cross-linking chemistry via commercially available bisphenol A dimethacrylate (BPA-DM), and a synthesized fluorinated analogue. Both improve the physical properties of over-doped PPO based plastic scintillators without degrading the measured light yield or PSD and Figure of Merit (FoM). In addition, the fluorinated analogue appears to enhance the hydrophobicity of the surface of the plastic scintillators, which may improve the scintillators' resistance to water diffusion and subsequent radiation response degradation. The new formulations improve the feasibility of widely deploying long lifetime PSD capable plastic scintillators in large area coverage assemblies.

Radiation-induced aging of PDMS Elastomer TR-55: a summary of constitutive, mesoscale, and population-based models

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

Maiti, A; Weisgraber, T. H.; Dinh, L. N.

Filled and cross-linked elastomeric rubbers are versatile network materials with a multitude of applications ranging from artificial organs and biomedical devices to cushions, coatings, adhesives, interconnects, and seismic-isolation-, thermal-, and electrical barriers. External factors like mechanical stress, temperature fluctuations, or radiation are known to create chemical changes in such materials that can directly affect the molecular weight distribution (MWD) of the polymer between cross-links and alter the structural and mechanical properties. From a Materials Science point of view it is highly desirable to understand, effect, and manipulate such property changes in a controlled manner. In this report we summarize ourmore » modeling efforts on a polysiloxane elastomer TR-55, which is an important component in several of our systems, and representative of a wide class of filled rubber materials. The primary aging driver in this work has been γ-radiation, and a variety of modeling approaches have been employed, including constitutive, mesoscale, and population-based models. The work utilizes diverse experimental data, including mechanical stress-strain and compression set measurements, as well as MWD measurements using multiquantum NMR.« less

Applications of FT-IR spectroscopy to the studies of esterification and crosslinking of cellulose by polycarboxylic acids: Part II. The performance of the crosslinked cotton fabrics

NASA Astrophysics Data System (ADS)

Wei, Weishu; Yang, Charles Q.

1998-06-01

Durable press finishing processes are commonly used in the textile industry to produce wrinkle-free cotton fabrics and garments. A durable press finishing agent forms covalent bands with cellulosic hydroxyl groups, thus crosslinking the cellulose molecules. The crosslinking of cellulose increases wrinkle resistance of the treated cotton fabric and reduces fabric mechanical strength. Wrinkle recovery angle (WRA) and tensile strength are the two most important parameters used to evaluate the performance of the crosslinked cotton fabrics and garments. In this study, we investigated the correlation between WRA and tensile strength on one hand, and the amount of crosslinkages formed by the crosslinking agents including dimethyloldihydroxylethyleneurea (DMDHEU) and 1,2,3,4-butanetetracarboxylic acid (BTCA) determined by FT-IR spectroscopy on the other hand. Linear regression curves between the carbonyl band absorbance, and WRA and tensile strength of the treated cotton fabric were developed. The data indicated that FT-IR spectroscopy is a reliable technique for predicting the performance of durable press finished cotton fabrics, therefore can be used as a convenient instrumental method for quality control in the textile and garment industry.

A study on the swelling behavior of poly(acrylic acid) hydrogels obtained by electron beam crosslinking

NASA Astrophysics Data System (ADS)

Sheikh, N.; Jalili, L.; Anvari, F.

2010-06-01

Poly(acrylic acid) (PAA) hydrogels were prepared by using electron beam (EB) crosslinking of PAA homopolymer from its aqueous solutions. The swelling behavior of the hydrogels was studied as a function of the concentration of PAA solution, radiation dose, pH of the swelling medium and swelling time. Also the environmental pH effect on the water diffusion mode into hydrogels was investigated. These hydrogels clearly showed pH-sensitive swelling behavior with Fickian type of diffusion in the stomach-like pH medium (pH 1.3) and non-Fickian type in the intestine-like pH medium (pH 6.8).

Size measuring techniques as tool to monitor pea proteins intramolecular crosslinking by transglutaminase treatment.

PubMed

Djoullah, Attaf; Krechiche, Ghali; Husson, Florence; Saurel, Rémi

2016-01-01

In this work, techniques for monitoring the intramolecular transglutaminase cross-links of pea proteins, based on protein size determination, were developed. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis profiles of transglutaminase-treated low concentration (0.01% w/w) pea albumin samples, compared to the untreated one (control), showed a higher electrophoretic migration of the major albumin fraction band (26 kDa), reflecting a decrease in protein size. This protein size decrease was confirmed, after DEAE column purification, by dynamic light scattering (DLS) where the hydrodynamic radius of treated samples appears to be reduced compared to the control one. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of intermediate-energy electrons on mechanical and molecular properties of a polyetherimide

NASA Technical Reports Server (NTRS)

Long, S. A. T.; Long, E. R., Jr.

1984-01-01

An experiment, using 100-keV electrons and 10 to the 9th -rad doses, was conducted on Ultem polyetherimide film. Mechanical, electron paramagnetic resonance, and infrared spectroscopic data suggested that the radiation produced crosslinking and embrittlement of the material.

3D Printing All-Aromatic Polyimides using Mask-Projection Stereolithography: Processing the Nonprocessable.

PubMed

Hegde, Maruti; Meenakshisundaram, Viswanath; Chartrain, Nicholas; Sekhar, Susheel; Tafti, Danesh; Williams, Christopher B; Long, Timothy E

2017-08-01

High-performance, all-aromatic, insoluble, engineering thermoplastic polyimides, such as pyromellitic dianhydride and 4,4'-oxydianiline (PMDA-ODA) (Kapton), exhibit exceptional thermal stability (up to ≈600 °C) and mechanical properties (Young's modulus exceeding 2 GPa). However, their thermal resistance, which is a consequence of the all-aromatic molecular structure, prohibits processing using conventional techniques. Previous reports describe an energy-intensive sintering technique as an alternative technique for processing polyimides with limited resolution and part fidelity. This study demonstrates the unprecedented 3D printing of PMDA-ODA using mask-projection stereolithography, and the preparation of high-resolution 3D structures without sacrificing bulk material properties. Synthesis of a soluble precursor polymer containing photo-crosslinkable acrylate groups enables light-induced, chemical crosslinking for spatial control in the gel state. Postprinting thermal treatment transforms the crosslinked precursor polymer to PMDA-ODA. The dimensional shrinkage is isotropic, and postprocessing preserves geometric integrity. Furthermore, large-area mask-projection scanning stereolithography demonstrates the scalability of 3D structures. These unique high-performance 3D structures offer potential in fields ranging from water filtration and gas separation to automotive and aerospace technologies. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a freeze-tolerant solar water heater using crosslinked polyethylene as a material of construction. Final report, June 18, 1976--October 1, 1977

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

Bradley, J.M.

The feasibility of building a freeze-tolerant absorber for a solar water heater out of carbon-black-reinforced crosslinked polyethylene has been explored. Ten-foot tube specimens made from various crosslinked polyethylene formulations were filled with water at various pressures, and then placed into a deep freeze, then thawed and frozen again for 100 freeze-thaw cycles, or until the tube specimen failed. Tube diameters were measured before and after each freezing to determine how much distention the freezing caused, and how much permanent distention was caused by the strains of repeated freezings. Five tube specimens containing water at as high as 80 psi survivedmore » 100 freeze-thaw cycles. Also, a flat plate collector was fabricated using as absorber surface a single 400 ft tube of carbon-black-reinforced crosslinked polyethylene in the form of a flat spiral coil and this collector was tested for performance at the Los Alamos Scientific Laboratory. The performance test indicates that the absorbancy of such a flat spiral coil to solar radiation is similar to typical black surfaces used on solar absorbers. Thus, it does seem very feasible that domestic water can be directly heated in a solar collector having an absorber made from crosslinked polyethylene, and that this collector can safely withstand at least 100 freeze-thaw cycles.« less

Solid-state NMR characterization of cross-linking in EPDM/PP blends from 1H-13C polarization transfer dynamics.

PubMed

Aluas, Mihaela; Filip, Claudiu

2005-05-01

A novel approach for solid-state NMR characterization of cross-linking in polymer blends from the analysis of (1)H-(13)C polarization transfer dynamics is introduced. It extends the model of residual dipolar couplings under permanent cross-linking, typically used to describe (1)H transverse relaxation techniques, by considering a more realistic distribution of the order parameter along a polymer chain in rubbers. Based on a systematic numerical analysis, the extended model was shown to accurately reproduce all the characteristic features of the cross-polarization curves measured on such materials. This is particularly important for investigating blends of great technological potential, like thermoplastic elastomers, where (13)C high-resolution techniques, such as CP-MAS, are indispensable to selectively investigate structural and dynamical properties of the desired component. The validity of the new approach was demonstrated using the example of the CP build-up curves measured on a well resolved EPDM resonance line in a series of EPDM/PP blends.

The IBA Easy-E-Beam™ Integrated Processing System

NASA Astrophysics Data System (ADS)

Cleland, Marshall R.; Galloway, Richard A.; Lisanti, Thomas F.

2011-06-01

IBA Industrial Inc., (formerly known as Radiation Dynamics, Inc.) has been making high-energy and medium-energy, direct-current proton and electron accelerators for research and industrial applications for many years. Some industrial applications of high-power electron accelerators are the crosslinking of polymeric materials and products, such as the insulation on electrical wires, multi-conductor cable jackets, heat-shrinkable plastic tubing and film, plastic pipe, foam and pellets, the partial curing of rubber sheet for automobile tire components, and the sterilization of disposable medical devices. The curing (polymerization and crosslinking) of carbon and glass fiber-reinforced composite plastic parts, the preservation of foods and the treatment of waste materials are attractive possibilities for future applications. With electron energies above 1.0 MeV, the radiation protection for operating personnel is usually provided by surrounding the accelerator facility with thick concrete walls. With lower energies, steel and lead panels can be used, which are substantially thinner and more compact than the equivalent concrete walls. IBA has developed a series of electron processing systems called Easy-e-Beam™ for the medium energy range from 300 keV to 1000 keV. These systems include the shielding as an integral part of a complete radiation processing facility. The basic concepts of the electron accelerator, the product processing equipment, the programmable control system, the configuration of the radiation shielding and some performance characteristics are described in this paper.

Wear Behaviours and Oxidation Effects on Different UHMWPE Acetabular Cups Using a Hip Joint Simulator

PubMed Central

Jaber, Sami Abdel; Merola, Massimiliano

2018-01-01

Given the long-term problem of polyethylene wear, medical interest in the new improved cross-linked polyethylene (XLPE), with or without the adding of vitamin E, has risen. The main aim of this study is to gain further insights into the mutual effects of radiation cross-linking and addition of vitamin E on the wear performance of ultra-high-molecular-weight polyethylene (UHMWPE). We tested four different batches of polyethylene (namely, a standard one, a vitamin E-stabilized, and two cross-linked) in a hip joint simulator for five million cycles where bovine calf serum was used as lubricant. The acetabular cups were then analyzed using a confocal profilometer to characterize the surface topography. Moreover; the cups were analyzed by using Fourier Transformed Infrared Spectroscopy and Differential Scanning Calorimetry in order to assess the chemical characteristics of the pristine materials. Comparing the different cups’ configuration, mass loss was found to be higher for standard polyethylene than for the other combinations. Mass loss negatively correlated to the cross-link density of the polyethylenes. None of the tested formulations showed evidence of oxidative degradation. We found no correlation between roughness parameters and wear. Furthermore, we found significantly differences in the wear behavior of all the acetabular cups. XLPEs exhibited lower weight loss, which has potential for reduced wear and decreased osteolysis. However, surface topography revealed smoother surfaces of the standard and vitamin E stabilized polyethylene than on the cross-linked samples. This observation suggests incipient crack generations on the rough and scratched surfaces of the cross-linked polyethylene liners. PMID:29547536

Radiation cured polyester compositions containing metal-properties

NASA Astrophysics Data System (ADS)

Szalińska, H.; Pietrzak, M.; Gonerski, A.

The subject of the studies was unsaturated polyester resin, Polimal-109 and its compositions containing acrylates of: sodium, potassium, calcium, magnesium, barium, manganese, iron, cobalt, copper and acrylic acid. Polyester resin modified with acrylic acid salts was cured with 60Co gamma radiation. Measurements of Vicat softening temperature, water absorption, creep current resistance, volume and surface resistivity, the tangent of dielectric loss angle and permittivity of radiation cured compositions were carried out. The results of the studies presented testify to the fact that the properties of cross-linked polymers alter after ionogenic compounds have been introduced into them.

E-Beam Processing of Polymer Matrix Composites for Multifunctional Radiation Shielding

NASA Technical Reports Server (NTRS)

Hou, Tan-Hung; Wilson, John W.; Jensen, Brian J.; Thibeault, Sheila A.; Chang, Chie K.; Kiefer, Richard L.

2005-01-01

Aliphatic polymers were identified as optimum radiation shielding polymeric materials for building multifunctional structural elements for in-space habitats. Conceptual damage tolerant configurations of polyolefins have been proposed, but many manufacturing issues relied on methods and materials which have sub-optimal radiation shielding characteristics (for example, epoxy matrix and adhesives). In the present approach, we shall investigate e-beam processing technologies for inclusion of high-strength aliphatic polymer reinforcement structures into a highly cross-linked polyolefin matrix. This paper reports the baseline thermo-mechanical properties of low density polyethylene and highly crystallized polyethylene.

Role of solvent-mediated carbodiimide cross-linking in fabrication of electrospun gelatin nanofibrous membranes as ophthalmic biomaterials.

PubMed

Chou, Shih-Feng; Luo, Li-Jyuan; Lai, Jui-Yang; Ma, David Hui-Kang

2017-02-01

Due to their ability to mimic the structure of extracellular matrix, electrospun gelatin nanofibers are promising cell scaffolding materials for tissue engineering applications. However, the hydrophilic gelatin molecules usually need stabilization before use in aqueous physiological environment. Considering that biomaterials cross-linked via film immersion technique may have a more homogeneous cross-linked structure than vapor phase cross-linking, this work aims to investigate the chemical modification of electrospun gelatin nanofibrous membranes by liquid phase carbodiimide in the presence of ethanol/water co-solvents with varying ethanol concentrations ranging from 80 to 99.5vol%. The results of characterization showed that increasing water content in the binary reaction solvent system increases the extent of cross-linking of gelatin nanofibers, but simultaneously promotes the effect of biopolymer swelling and distortion in fiber mat structure. As compared to non-cross-linked counterparts, carbodiimide treated gelatin nanofibrous mats exhibited better thermal and biological stability where the shrinkage temperature and resistance to enzymatic degradation varied in response to ethanol/water solvent composition-mediated generation of cross-links. Irrespective of their cross-linking density, all studied membrane samples did not induce any responses in ocular epithelial cell cultures derived from cornea, lens, and retina. Unlike many other cross-linking agents and/or methods (e.g., excessive vapor phase cross-linking) that may pose a risk of toxicity, our study demonstrated that these nanofibrous materials are well tolerated by anterior segment tissues. These findings also indicate the safety of using ethanol/water co-solvents for chemical cross-linking of gelatin to engineer nanofibrous materials with negligible biological effects. In summary, the present results suggest the importance of solvent-mediated carbodiimide cross-linking in modulating structure-property relationship without compromising in vitro and in vivo biocompatibility of electrospun gelatin nanofibers for future ophthalmic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters

NASA Astrophysics Data System (ADS)

Babic, Steven; Schreiner, L. John

2006-09-01

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters.

PubMed

Babic, Steven; Schreiner, L John

2006-09-07

In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

Photo-crosslinkable cyanoacrylate bioadhesive: shrinkage kinetics, dynamic mechanical properties, and biocompatibility of adhesives containing TMPTMA and POSS nanostructures as crosslinking agents.

PubMed

Ghasaban, S; Atai, M; Imani, M; Zandi, M; Shokrgozar, M-A

2011-11-01

The study investigates the photo-polymerization shrinkage behavior, dynamic mechanical properties, and biocompatibility of cyanoacrylate bioadhesives containing POSS nanostructures and TMPTMA as crosslinking agents. Adhesives containing 2-octyl cyanoacrylate (2-OCA) and different percentages of POSS nanostructures and TMPTMA as crosslinking agents were prepared. The 1-phenyl-1, 2-propanedione (PPD) was incorporated as photo-initiator into the adhesive in 1.5, 3, and 4 wt %. The shrinkage strain of the specimens was measured using bonded-disk technique. Shrinkage strain, shrinkage strain rate, maximum and time at maximum shrinkage strain rate were measured and compared. Mechanical properties of the adhesives were also studied using dynamic mechanical thermal analysis (DMTA). Biocompatibility of the adhesives was examined by MTT method. The results showed that shrinkage strain increased with increasing the initiator concentration up to 3 wt % in POSS-containing and 1.5 wt % in TMPTMA-containing specimens and plateaued out at higher concentrations. By increasing the crosslinking agent, shrinkage strain, and shrinkage strain rate increased and the time at maximum shrinkage strain rate decreased. The study indicates that the incorporation of crosslinking agents into the cyanoacrylate adhesives resulted in improved mechanical properties. Preliminary MTT studies also revealed better biocompatibility profile for the adhesives containing crosslinking agents comparing to the neat specimens. Copyright © 2011 Wiley Periodicals, Inc.

Stimuli-responsive cross-linked micelles for on-demand drug delivery against cancers

PubMed Central

Li, Yuanpei; Xiao, Kai; Zhu, Wei; Deng, Wenbin; Lam, Kit S.

2013-01-01

Stimuli-responsive cross-linked micelles (SCMs) represent an ideal nanocarrier system for drug delivery against cancers. SCMs exhibit superior structural stability compared to their non-crosslinked counterpart. Therefore, these nanocarriers are able to minimize the premature drug release during blood circulation. The introduction of environmentally sensitive crosslinkers or assembly units makes SCMs responsive to single or multiple stimuli present in tumor local microenvironment or exogenously applied stimuli. In these instances, the payload drug is released almost exclusively in cancerous tissue or cancer cells upon accumulation via enhanced permeability and retention effect or receptor mediated endocytosis. In this review, we highlight recent advances in the development of SCMs for cancer therapy. We also introduce the latest biophysical techniques, such as electron paramagnetic resonance (EPR) spectroscopy and fluorescence resonance energy transfer (FRET), for the characterization of the interactions between SCMs and blood proteins. PMID:24060922

Effect of Formulation and Process Parameters on Chitosan Microparticles Prepared by an Emulsion Crosslinking Technique.

PubMed

Rodriguez, Lidia B; Avalos, Abraham; Chiaia, Nicholas; Nadarajah, Arunan

2017-05-01

There are many studies about the synthesis of chitosan microparticles; however, most of them have very low production rate, have wide size distribution, are difficult to reproduce, and use harsh crosslinking agents. Uniform microparticles are necessary to obtain repeatable drug release behavior. The main focus of this investigation was to study the effect of the process and formulation parameters during the preparation of chitosan microparticles in order to produce particles with narrow size distribution. The technique evaluated during this study was emulsion crosslinking technique. Chitosan is a biocompatible and biodegradable material but lacks good mechanical properties; for that reason, chitosan was ionically crosslinked with sodium tripolyphosphate (TPP) at three different ratios (32, 64, and 100%). The model drug used was acetylsalicylic acid (ASA). During the preparation of the microparticles, chitosan was first mixed with ASA and then dispersed in oil containing an emulsifier. The evaporation of the solvents hardened the hydrophilic droplets forming microparticles with spherical shape. The process and formulation parameters were varied, and the microparticles were characterized by their morphology, particle size, drug loading efficiency, and drug release behavior. The higher drug loading efficiency was achieved by using 32% mass ratio of TPP to chitosan. The average microparticle size was 18.7 μm. The optimum formulation conditions to prepare uniform spherical microparticles were determined and represented by a region in a triangular phase diagram. The drug release analyses were evaluated in phosphate buffer solution at pH 7.4 and were mainly completed at 24 h.

Fabrication and characterization of hydrothermal cross-linked chitosan porous scaffolds for cartilage tissue engineering applications.

PubMed

Shamekhi, Mohammad Amin; Rabiee, Ahmad; Mirzadeh, Hamid; Mahdavi, Hamid; Mohebbi-Kalhori, Davod; Baghaban Eslaminejad, Mohamadreza

2017-11-01

The use of various chemical cross-linking agents for the improvement of scaffolds physical and mechanical properties is a common practical method, which is limited by cytotoxicity effects. Due to exerting contract type forces, chondrocytes are known to implement shrinkage on the tissue engineered constructs, which can be avoided by the scaffold cross-linking. In the this research, chitosan scaffolds are cross-linked with hydrothermal treatment with autoclave sterilization time of 0, 10, 20 and 30min, to avoid the application of the traditional chemical toxic materials. The optimization studies with gel content and crosslink density measurements indicate that for 20min sterilization time, the gel content approaches to ~80%. The scaffolds are fully characterized by the conventional techniques such as SEM, porosity and permeability, XRD, compression, thermal analysis and dynamic mechanical thermal analysis (DMTA). FT-IR studies shows that autoclave inter-chain cross-linking reduces the amine group absorption at 1560cm -1 and increase the absorption of N-acetylated groups at 1629cm -1 . It is anticipated, that this observation evidenced by chitosan scaffold browning upon autoclave cross-linking is an indication of the familiar maillard reaction between amine moieties and carbonyl groups. The biodegradation rate analysis shows that chitosan scaffolds with lower concentrations, possess suitable degradation rate for cartilage tissue engineering applications. In addition, cytotoxicity analysis shows that fabricated scaffolds are biocompatible. The human articular chondrocytes seeding into 3D cross-linked scaffolds shows a higher viability and proliferation in comparison with the uncross-linked samples and 2D controls. Investigation of cell morphology on the scaffolds by SEM, shows a more spherical morphology of chondrocytes on the cross-linked scaffolds for 21days of in vitro culture. Copyright © 2017. Published by Elsevier B.V.

A photochemical crosslinking technology for tissue engineering: enhancement of the physico-chemical properties of collagen-based scaffolds

NASA Astrophysics Data System (ADS)

Chan, Barbara P.

2005-04-01

Collagen gel is a natural biomaterial commonly used in tissue engineering because of its close resemblance to nature, negligible immunogenecity and excellent biocompatibility. However, unprocessed collagen gel is mechanically weak, highly water binding and vulnerable to chemical and enzymatic attacks that limits its use in tissue engineering in particular tissues for weight-bearing purposes. The current project aimed to strengthen and stabilize collagen scaffolds using a photochemical crosslinking technique. Photochemical crosslinking is rapid, efficient, non-thermal and does not involve toxic chemicals, comparing with other crosslinking methods such as glutaraldehyde and gamma irradiation. Collagen scaffolds were fabricated using rat-tail tendon collagen. An argon laser was used to process the collagen gel after equilibrating with a photosensitizing reagent. Scanning electronic microscope was used to characterize the surface and cross-sectional morphology of the membranes. Physico-chemical properties of the collagen scaffolds such as water-binding capacity, mechanical properties and thermostability were studied. Photochemical crosslinking significantly reduced the water-binding capacity, a parameter inversely proportional to the extent of crosslinking, of collagen scaffolds. Photochemical crosslinking also significantly increased the ultimate stress and tangent modulus at 90% of the rupture strain of the collagen scaffolds. Differential scanning calorimetry analysis showed a significantly higher shrinkage temperature and absence of the denaturation peak during the thermoscan comparing with the controls. This means greater thermostability in the photochemically crosslinked collagen scaffolds. This study demonstrates that the photochemical crosslinking technology is able to enhance the physicochemical propterties of collagen scaffolds by strengthening, stabilizing and controlling the swelling ratio of the collagen scaffolds so as to enable their use for tissue engineering.

Photomodulation of the nucleating activity of a photocleavable crosslinked actin dimer.

PubMed

Marriott, G; Miyata, H; Kinosita, K

1992-04-01

The ability to generate substrate concentration jumps through photo-deprotection of amine, carboxyl and phosphate groups has been an important development for investigations of protein activity in complex systems. To broaden the versatility and applications of photo-deprotection techniques for the photomodulation of protein activity we describe the synthesis and characterisation of a reagent for generating free thiol from thioether groups and a related photocleavable, heterobifunctional crosslinking reagent. Chemical and spectroscopic studies of a model thiol protected derivative were used to show some features of thiol group photodeprotection. To demonstrate how the photocleavable crosslinking reagent may be used to modulate the activity of proteins we investigated the effect of light on the nucleating activity of crosslinked actin dimer; thus following near-ultraviolet irradiation of the actin dimer the crosslink was cleaved, presumeably at the thioether bond, resulting in the concomitant dissociation of dimer, loss of nucleating activity and creation of a concentration jump of polymerisable G-actin monomer. On the basis of this initial study we discuss applications and limitations of these reagents for the photomodulation of protein activity in vitro and in vivo.

Synthesis and characterization of photo-crosslinkable 4-styryl-pyridine modified alginate.

PubMed

Elsayed, Nadia H; Monier, M; Alatawi, Raedah A S

2016-07-10

In this article photo-crosslinkablestyryl-pyridine modified alginate (ASP-Alg) was prepared and entirely investigated utilizing different instrumental techniques such as Elemental analysis, Fourier transform infrared (FTIR),(13)C and (1)H nuclear magnetic resonance (NMR), ultraviolet-visible light (UV-vis), X-ray diffraction (XRD) spectra and scanning electron microscope (SEM). Upon irradiation in the UV region, the casted ASP-Alg membranes were cross-linked through the [2π+2π] cycloaddition reaction of the inserted photo-active styryl pyridine moieties. Both cross-linking density and kinetics were monitored by examining the UV-vis light spectra of the irradiated membrane at predetermined time intervals and the obtained results were found to fit with the second order mathematical kinetic model, revealing the performance of the cross-linking via bimolecular [2π+2π] cycloaddition reaction. Also, the swelling behaviors along with biodegradability were also studied, and the results indicated the decrease of the swelling ratio and degradation rate by increasing the cross-linking density. Moreover, the mechanical properties were also examined under both wet and dry conditions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Calcium Channels: Structure and Function (Annals of the New York Academy of Sciences. Volume 560)

DTIC Science & Technology

1989-06-26

many protease inhibitors were used , we believe that proteolysis was a problem. We therefore modified our purification protocol and have obtained a...recover activity by selective combination of fractions were unsuccessful. Chemical Cross-Linking of [ 25 Jo-CgTX Cross-linking of w-CgTX derivatives using ... using the planar bilayer recording technique and by comparing ligand-dependent gating, ionic selectivity , and pharmacology of purified ryanodine

E-beam-Cure Fabrication of Polymer Fiber/Matrix Composites for Multifunctional Radiation Shielding

NASA Technical Reports Server (NTRS)

Wilson, John W.; Jensen, Brian J.; Thibeault, Sheila A.; Hou, Tan-Hung; Saether, Erik; Glaessgen, Edward H.; Humes, Donald H.; Chang, Chie K.; Badavi, Francis F.; Kiefer, Rrichard L.;

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications

NASA Astrophysics Data System (ADS)

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-12-01

We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications

PubMed Central

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-01-01

Abstract We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required. PMID:28804527

Synthesis and characterisation of cross-linked chitosan composites functionalised with silver and gold nanoparticles for antimicrobial applications.

PubMed

Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria

2017-01-01

We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.

Temperature effect on radiation induced reactions in ethylene and tetrafluoroethylene copolymer (ETFE)

NASA Astrophysics Data System (ADS)

Oshima, Akihiro; Ikeda, Shigetoshi; Seguchi, Tadao; Tabata, Yoneho

1997-11-01

Ethylene and tetrafluoroethylene copolymer (ETFE) was irradiated by γ-rays or electron beam (EB) under oxygen-free atmosphere at various temperatures ranging from 77 to 573 K. Mechanical and thermal properties, and absorption spectra of the irradiated ETFEs were measured. The mechanical properties of the film have been observed to change by irradiation. The modulus and yield strength increase with increasing dose, and these phenomena are clearly distinguished above the melting temperature of ETFE (533 K). Heat of crystallization changes drastically as a function of irradiation dose around the melting temperature, compared with other temperatures. The absorption band around 250 nm of irradiated ETFE shifts to a longer wavelength region with increase of irradiation temperature. Therefore, it was concluded from those experimental results mentioned above that crosslinking takes place and conjugated double bonds formation proceeds in a wide range of irradiation temperatures. Those reactions are enhanced by increasing temperature. The homogeneous crosslinking takes place in the molten state, while the heterogeneous crosslinking does in the crystalline solid state.

Minimizing material damage using low temperature irradiation

NASA Astrophysics Data System (ADS)

Craven, E.; Hasanain, F.; Winters, M.

2012-08-01

Scientific advancements in healthcare driven both by technological breakthroughs and an aging and increasingly obese population have lead to a changing medical device market. Complex products and devices are being developed to meet the demands of leading edge medical procedures. Specialized materials in these medical devices, including pharmaceuticals and biologics as well as exotic polymers present a challenge for radiation sterilization as many of these components cannot withstand conventional irradiation methods. The irradiation of materials at dry ice temperatures has emerged as a technique that can be used to decrease the radiation sensitivity of materials. The purpose of this study is to examine the effect of low temperature irradiation on a variety of polymer materials, and over a range of temperatures from 0 °C down to -80 °C. The effectiveness of microbial kill is also investigated under each of these conditions. The results of the study show that the effect of low temperature irradiation is material dependent and can alter the balance between crosslinking and chain scission of the polymer. Low temperatures also increase the dose required to achieve an equivalent microbiological kill, therefore dose setting exercises must be performed under the environmental conditions of use.

Winner of the society for biomaterials student award in the Ph.D. category for the annual meeting of the society for biomaterials, april 11-14, 2018, Atlanta, GA: Development of a bimodal, in situ crosslinking method to achieve multifactor release from electrospun gelatin.

PubMed

Kishan, Alysha; Walker, Taneidra; Sears, Nick; Wilems, Thomas; Cosgriff-Hernandez, Elizabeth

2018-05-01

To better mimic native tissue microenvironments, current efforts have moved beyond single growth factor delivery to more complex multiple growth factor delivery with distinct release profiles. Electrospun gelatin, a widely investigated drug delivery vehicle, requires postprocessing crosslinking techniques that generate a mesh with uniform crosslinking density, limiting the ability to deliver multiple factors at different rates. Herein, we describe a method to independently control release of multiple factors from a single electrospun gelatin mesh. Two in situ crosslinking modalities, photocrosslinking of methacyrlated gelatin and reactive crosslinking of gelatin with a diisocyanate, are coelectrospun to generate distinct fiber populations with different crosslinking chemistry and density in a single mesh. The photocrosslinked gelatin-methacrylate resulted in a relatively rapid release of a model protein (48 ± 12% at day 1, 96 ± 3% at day 10) due to diffusion of embedded protein from the crosslinked fibers. The reactive crosslinking system displayed a more sustained release (7 ± 5% at day 1, 33 ± 2% at day 10) that was attributed to the conjugation of protein to gelatin with the diisocyanate, requiring degradation of gelatin prior to diffusion out of the fibers. Both modalities displayed tunable release profiles. Subsequent release studies of a cospun mesh with two different crosslinked fiber populations confirmed that the cospun mesh displayed multifactor release with independent release profiles. Overall, this bimodal, in situ crosslinking approach enables the delivery of multiple factors with distinct release kinetics from a single mesh and is expected to have broad utility in tissue engineering. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 1155-1164, 2018. © 2018 Wiley Periodicals, Inc.

High temperature homogenization improves impact toughness of vitamin E-diffused, irradiated UHMWPE.

PubMed

Oral, Ebru; O'Brien, Caitlin; Doshi, Brinda; Muratoglu, Orhun K

2017-06-01

Diffusion of vitamin E into radiation cross-linked ultrahigh molecular weight polyethylene (UHMWPE) is used to increase stability against oxidation of total joint implant components. The dispersion of vitamin E throughout implant preforms has been optimized by a two-step process of doping and homogenization. Both of these steps are performed below the peak melting point of the cross-linked polymer (<140°C) to avoid loss of crystallinity and strength. Recently, it was discovered that the exposure of UHMWPE to elevated temperatures, around 300°C, for a limited amount of time in nitrogen, could improve the toughness without sacrificing wear resistance. We hypothesized that high temperature homogenization of antioxidant-doped, radiation cross-linked UHMWPE could improve its toughness. We found that homogenization at 300°C for 8 h resulted in an increase in the impact toughness (74 kJ/m 2 compared to 67 kJ/m 2 ), the ultimate tensile strength (50 MPa compared to 43 MPa) and elongation at break (271% compared to 236%). The high temperature treatment did not compromise the wear resistance or the oxidative stability as measured by oxidation induction time. In addition, the desired homogeneity was achieved at a much shorter duration (8 h compared to >240 h) by using high temperature homogenization. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 35:1343-1347, 2017. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

Electromagnetic and nuclear radiation detector using micromechanical sensors

DOEpatents

Thundat, Thomas G.; Warmack, Robert J.; Wachter, Eric A.

2000-01-01

Electromagnetic and nuclear radiation is detected by micromechanical sensors that can be coated with various interactive materials. As the micromechanical sensors absorb radiation, the sensors bend and/or undergo a shift in resonance characteristics. The bending and resonance changes are detected with high sensitivity by any of several detection methods including optical, capacitive, and piezoresistive methods. Wide bands of the electromagnetic spectrum can be imaged with picoJoule sensitivity, and specific absorptive coatings can be used for selective sensitivity in specific wavelength bands. Microcantilevers coated with optical cross-linking polymers are useful as integrating optical radiation dosimeters. Nuclear radiation dosimetry is possible by fabricating cantilevers from materials that are sensitive to various nuclear particles or radiation. Upon exposure to radiation, the cantilever bends due to stress and its resonance frequency shifts due to changes in elastic properties, based on cantilever shape and properties of the coating.

Flame-retardant EPDM compounds containing phenanthrene to enhance radiation resistance

NASA Astrophysics Data System (ADS)

Chen, Jian; Huang, Wei; Jiang, Shu-Bin; Li, Xiao-Yan; An, You; Li, Chuang; Gao, Xiao-Ling; Chen, Hong-Bing

2017-01-01

Ethylene propylene diene monomer (EPDM) compounds with good flame-retardant and γ-ray radiation resistant properties were prepared by adding complex flame retardants and phenathrene. The resultant EPDM formulations have a long time to ignition (TTI >46 s), a low peak heat release rate (PHRR 341 kW/m2) and a high limited oxygen index (LOI >30). Effects of γ-ray radiation on the resultant flame-retardant EPDM was investigated. The formulated EPDM is a crosslinking dominated polymer under γ-ray radiation. The γ-ray radiation resistant property of EPDM was enhanced by adding phenanthrene. Elongation at break of EPDM formulated with phenanthrene could retain 91% after being irradiated to 0.3 MGy and still retains 40% elongation even after being irradiated to 0.9 MGy, which is much better the control. It is expected that the formulated flame-retardant and radiation resistant EPDM materials could meet the requirements for use in radiation environments.

Photodegradable, Photoadaptable Hydrogels via Radical-Mediated Disulfide Fragmentation Reaction.

PubMed

Fairbanks, Benjamin D; Singh, Samir P; Bowman, Christopher N; Anseth, Kristi S

2011-04-26

Various techniques have been adopted to impart a biological responsiveness to synthetic hydrogels for the delivery of therapeutic agents as well as the study and manipulation of biological processes and tissue development. Such techniques and materials include polyelectrolyte gels that swell and deswell with changes in pH, thermosensitive gels that contract at physiological temperatures, and peptide cross-linked hydrogels that degrade upon peptidolysis by cell-secreted enzymes. Herein we report a unique approach to photochemically deform and degrade disulfide cross-linked hydrogels, mitigating the challenges of light attenuation and low quantum yield, permitting the degradation of hydrogels up to 2 mm thick within 120 s at low light intensities (10 mW/cm(2) at 365 nm). Hydrogels were formed by the oxidation of thiol-functionalized 4-armed poly(ethylene glycol) macromolecules. These disulfide cross-linked hydrogels were then swollen in a lithium acylphosphinate photoinitiator solution. Upon exposure to light, photogenerated radicals initiate multiple fragmentation and disulfide exchange reactions, permitting and promoting photodeformation, photowelding, and photodegradation. This novel, but simple, approach to generate photoadaptable hydrogels portends the study of cellular response to mechanically and topographically dynamic substrates as well as novel encapsulations by the welding of solid substrates. The principles and techniques described herein hold implications for more than hydrogel materials but also for photoadaptable polymers more generally.

On correction of model of stabilization of distribution of concentration of radiation defects in a multilayer structure with account experiment data

NASA Astrophysics Data System (ADS)

Pankratov, E. L.

2018-05-01

We introduce a model of redistribution of point radiation defects, their interaction between themselves and redistribution of their simplest complexes (divacancies and diinterstitials) in a multilayer structure. The model gives a possibility to describe qualitatively nonmonotonicity of distributions of concentrations of radiation defects on interfaces between layers of the multilayer structure. The nonmonotonicity was recently found experimentally. To take into account the nonmonotonicity we modify recently used in literature model for analysis of distribution of concentration of radiation defects. To analyze the model we used an approach of solution of boundary problems, which could be used without crosslinking of solutions on interfaces between layers of the considered multilayer structures.

3D freeform printing of silk fibroin.

PubMed

Rodriguez, Maria J; Dixon, Thomas A; Cohen, Eliad; Huang, Wenwen; Omenetto, Fiorenzo G; Kaplan, David L

2018-04-15

Freeform fabrication has emerged as a key direction in printing biologically-relevant materials and structures. With this emerging technology, complex structures with microscale resolution can be created in arbitrary geometries and without the limitations found in traditional bottom-up or top-down additive manufacturing methods. Recent advances in freeform printing have used the physical properties of microparticle-based granular gels as a medium for the submerged extrusion of bioinks. However, most of these techniques require post-processing or crosslinking for the removal of the printed structures (Miller et al., 2015; Jin et al., 2016) [1,2]. In this communication, we introduce a novel method for the one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite) and polyethylene glycol (PEG). Silk fibroin has been used as a biopolymer for bioprinting in several contexts, but chemical or enzymatic additives or bulking agents are needed to stabilize 3D structures. Our method requires no post-processing of printed structures and allows for in situ physical crosslinking of pure aqueous silk fibroin into arbitrary geometries produced through freeform 3D printing. 3D bioprinting has emerged as a technology that can produce biologically relevant structures in defined geometries with microscale resolution. Techniques for fabrication of free-standing structures by printing into granular gel media has been demonstrated previously, however, these methods require crosslinking agents and post-processing steps on printed structures. Our method utilizes one-step gelation of silk fibroin within a suspension of synthetic nanoclay (Laponite), with no need for additional crosslinking compounds or post processing of the material. This new method allows for in situ physical crosslinking of pure aqueous silk fibroin into defined geometries produced through freeform 3D printing. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Photosensitized UVA-Induced Cross-Linking between Human DNA Repair and Replication Proteins and DNA Revealed by Proteomic Analysis

PubMed Central

2016-01-01

Long wavelength ultraviolet radiation (UVA, 320–400 nm) interacts with chromophores present in human cells to induce reactive oxygen species (ROS) that damage both DNA and proteins. ROS levels are amplified, and the damaging effects of UVA are exacerbated if the cells are irradiated in the presence of UVA photosensitizers such as 6-thioguanine (6-TG), a strong UVA chromophore that is extensively incorporated into the DNA of dividing cells, or the fluoroquinolone antibiotic ciprofloxacin. Both DNA-embedded 6-TG and ciprofloxacin combine synergistically with UVA to generate high levels of ROS. Importantly, the extensive protein damage induced by these photosensitizer+UVA combinations inhibits DNA repair. DNA is maintained in intimate contact with the proteins that effect its replication, transcription, and repair, and DNA–protein cross-links (DPCs) are a recognized reaction product of ROS. Cross-linking of DNA metabolizing proteins would compromise these processes by introducing physical blocks and by depleting active proteins. We describe a sensitive and statistically rigorous method to analyze DPCs in cultured human cells. Application of this proteomics-based analysis to cells treated with 6-TG+UVA and ciprofloxacin+UVA identified proteins involved in DNA repair, replication, and gene expression among those most vulnerable to cross-linking under oxidative conditions. PMID:27654267

In vivo oxidation in remelted highly cross-linked retrievals.

PubMed

Currier, B H; Van Citters, D W; Currier, J H; Collier, J P

2010-10-20

Elimination of free radicals to prevent oxidation has played a major role in the development and product differentiation of the latest generation of highly cross-linked ultra-high molecular weight polyethylene bearing materials. In the current study, we (1) examined oxidation in a series of retrieved remelted highly cross-linked ultra-high molecular weight polyethylene bearings from a number of device manufacturers and (2) compared the retrieval results with findings for shelf-stored control specimens. The hypothesis was that radiation-cross-linked remelted ultra-high molecular weight polyethylene would maintain oxidative stability in vivo comparable with the stability during shelf storage and in published laboratory aging tests. Fifty remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners and nineteen remelted highly cross-linked ultra-high molecular weight polyethylene tibial inserts were received after retrieval from twenty-one surgeons from across the U.S. Thirty-two of the retrievals had been in vivo for two years or more. Each was measured for oxidation with use of Fourier transform infrared spectroscopy. A control series of remelted highly cross-linked ultra-high molecular weight polyethylene acetabular liners from three manufacturers was analyzed with electron paramagnetic resonance spectroscopy to measure free radical content and with Fourier transform infrared spectroscopy to measure oxidation initially and after eight to nine years of shelf storage in air. The never-implanted, shelf-aged controls had no measurable free-radical content initially or after eight to nine years of shelf storage. The never-implanted controls showed no increase in oxidation during shelf storage. Oxidation measurements showed measurable oxidation in 22% of the retrieved remelted highly cross-linked liners and inserts after an average of two years in vivo. Because never-implanted remelted highly cross-linked ultra-high molecular weight polyethylene materials had no measurable free-radical concentration and no increase in oxidation during shelf storage, these materials were expected to be oxidation-resistant in vivo. However, some remelted highly cross-linked ultra-high molecular weight polyethylene retrievals showed measurable oxidation after an average of more than two years in vivo. This apparent departure from widely expected behavior requires continued study of the process of in vivo oxidation of ultra-high molecular weight polyethylene materials.

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1980-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Polyvinyl pyridine microspheres

NASA Technical Reports Server (NTRS)

Rembaum, Alan (Inventor); Gupta, Amitava (Inventor); Volksen, Willi (Inventor)

1979-01-01

Microspheres are produced by cobalt gamma radiation initiated polymerization of a dilute aqueous vinyl pyridine solution. Addition of cross-linking agent provides higher surface area beads. Addition of monomers such as hydroxyethylmethacrylate acrylamide or methacrylamide increases hydrophilic properties and surface area of the beads. High surface area catalytic supports are formed in the presence of controlled pore glass substrate.

Radiation stability of resveratrol in immobilization on poly vinyl pyrrolidone hydrogel dressing for dermatological use

NASA Astrophysics Data System (ADS)

Momesso, Roberta G. R. A. P.; Moreno, Carolina S.; Rogero, Sizue O.; Rogero, José R.; Spencer, Patrick J.; Lugão, Ademar B.

2010-03-01

The polyphenol trans-resveratrol is a natural phytoalexin, which is found in red wine and in a wide variety of plant species. Resveratrol displays a wide array of biological activities, such as modulation of lipid metabolism, anti-inflammatory and antioxidant activities. This active compound immobilized in polyvinylpyrrolidone (PVP) hydrogel could be very interesting for topical administration, as a dressing form for dermatological use. However, PVP hydrogel obtained by radiation-induced crosslinking can cause undesirable hydrolysis reactions in the active compound. The aim of this work was to verify the resveratrol stability after irradiation at 0.5 and 1 kGy in the presence of ethanol, methanol or tert-butyl alcohol. The integrity of these samples was compared to unirradiated resveratrol by HPLC. The PVP hydrogel matrix was characterized by gel fraction, swelling and in vitro biocompatibility test. The results of gel fraction and swelling degree were approximately 90% and 1600%, respectively. The cytotoxicity assay showed absence of toxicity for this formulation after crosslinking and sterilization, indicating that the PVP hydrogel formulation was appropriate for resveratrol immobilization to produce a dressing for dermatological use.

Preparation and characterization of a magneto-polymeric nanocomposite: Fe 3O 4 nanoparticles in a grafted, cross-linked and plasticized poly(vinyl chloride) matrix

NASA Astrophysics Data System (ADS)

Rodríguez-Fernández, Oliverio S.; Rodríguez-Calzadíaz, C. A.; Yáñez-Flores, Isaura G.; Montemayor, Sagrario M.

In this work two kind of materials: (1) grafted, cross-linked and plasticized poly(vinyl chloride) (PVC) "plastic films" and (2) magnetic plastic films "magneto-polymeric nanocomposites" were prepared. Precursor solutions or "plastisols" used to obtain the plastic films were obtained by mixing PVC (emulsion grade) as polymeric matrix, di(2-ethylhexyl)phthalate (DOP) as plasticizer, a thermal stabilizer based in Ca/Zn salts, and a cross-linking agent, 3-mercaptopropyltrimethoxysilane (MTMS) or 3-aminopropyltriethoxysilane (ATES), at several concentrations. Flexible films were obtained from the plastisols using static casting. The stress-strain behavior and the gel content (determined by Soxhlet extraction with boiling THF) of the flexible films were measured in order to evaluate the effect of the cross-linking agent and their content on the degree of cross-linking. The magneto-polymeric nanocomposites were obtained by mixing the optimum composition of the plastisols (analyzed previously) with magnetite (Fe 3O 4)-based ferrofluid and DOP. Later, flexible films were obtained by static casting of the plastisol/ferrofluid systems. The magnetic films were characterized by the above-mentioned techniques and X-ray diffraction, vibrating sample magnetometry and thermogravimetrical analysis.

Investigation of molybdenum-crosslinker interfaces for affinity based electrochemical biosensing applications

NASA Astrophysics Data System (ADS)

Kamakoti, Vikramshankar; Shanmugam, Nandhinee Radha; Tanak, Ambalika Sanjeev; Jagannath, Badrinath; Prasad, Shalini

2018-04-01

Molybdenum (Mo) has been investigated for implementation as an electrode material for affinity based biosensing towards devloping flexibe electronic biosensors. Treatment of the native oxide of molybdenum was investigated through two surface treatment strategies namely thiol and carbodiimide crosslinking methods. The binding interaction between cross-linker molecules and Mo electrode surface has been characterized using Fourier Transform Infrared Spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and optical microscopy. The efficacy of treatment of Mo with its native oxide using carbodiimide cross linking methodology was established. The carbodiimide cross-linking chemistry was found to possess better surface coverage and binding affinity with Molybdenum electrode surface when compared to thiol cross-linking chemistry.Electrochemical characterization of Mo electrode using Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltametry (CV) techniques was performed to evaluate the effect of ionic properties of solution buffer on the Mo electrode's performance. Affinity based biosensing of C-Reactive Protein (CRP) has been demonstrated on a flexible nanoporous polymeric substrate with detection threshold of 100 pg/ml in synthetic urine buffer medium. The biosensor has been evaluated to be developed as a dipstick based point of care device for detection of biomarkers in urine.

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

Wilbur, Jeffrey D.; Gomez, Enrique D.; Ellsworth, Mark W.

A procedure for creating samples that can be repeatedly cycled between weakly aligned and strongly aligned states is described. Poly(styrene-b-isoprene) block copolymer samples were first shear-aligned and then cross-linked using a high energy electron beam. Samples with more than 1.0 cross-links per chain on average showed almost complete recovery of their initial alignment state even after 20 cycles of heating above the order–disorder transition temperature of the un-cross-linked block copolymer. Samples with 1.1 cross-links per chain, which showed over 90% loss of alignment on heating and almost 100% recovery of alignment on cooling, provided the best example of a reversiblemore » aligned-to-unaligned transition. Samples with lower cross-linking densities exhibited irreversible loss of alignment upon heating, while those with higher cross-linking densities exhibited less than 90% loss of alignment upon heating. Alignment was quantified by a technique that we call two color depolarized light scattering (TCDLS), an extension of the traditional depolarized light scattering experiment used to determine the state of order in block copolymers. Qualitative confirmation of our interpretation of TCDLS data was obtained by small-angle X-ray scattering and transmission electron microscopy.« less

Multifunctional structural lithium ion batteries for electrical energy storage applications

NASA Astrophysics Data System (ADS)

Javaid, Atif; Zeshan Ali, Muhammad

2018-05-01

Multifunctional structural batteries based on carbon fiber-reinforced polymer composites are fabricated that can bear mechanical loads and act as electrochemical energy storage devices simultaneously. Structural batteries, containing woven carbon fabric anode; lithium cobalt oxide/graphene nanoplatelets coated aluminum cathode; filter paper separator and cross-linked polymer electrolyte, were fabricated through resin infusion under flexible tooling (RIFT) technique. Compression tests, dynamic mechanical thermal analysis, thermogravimetric analysis and impedance spectroscopy were done on the cross-linked polymer electrolytes while cyclic voltammetry, impedance spectroscopy, dynamic mechanical thermal analysis and in-plane shear tests were conducted on the fabricated structural batteries. A range of solid polymer electrolytes with increasing concentrations of lithium perchlorate salt in crosslinked polymer epoxies were formulated. Increased concentrations of electrolyte salt in cross-linked epoxy increased the ionic conductivity, although the compressive properties were compromised. A structural battery, exhibiting simultaneously a capacity of 0.16 mAh L‑1, an energy density of 0.32 Wh L‑1 and a shear modulus of 0.75 GPa have been reported.

Adsorptive removal of Congo red from aqueous solutions using crosslinked chitosan and crosslinked chitosan immobilized bentonite.

PubMed

Huang, Ruihua; Zhang, Lujie; Hu, Pan; Wang, Jing

2016-05-01

Batch experiments were executed to investigate the removal of Congo red (CR) from aqueous solutions using the crosslinked chitosan (CCS) and crosslinked chitosan immobilized bentonite (CCS/BT composite). The CCS and CCS/BT composite were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The removal of CR was examined as a function of pH value of CR solution, contact time, and inorganic sodium salt and ionic strength. The equilibrium data of CCS and CCS/BT composite agreed well with the Langmuir model. The adsorption capacities of CCS and CCS/BT composite at 298K and natural pH value were 405 and 500 mg/g, respectively. The kinetic data correlated well with the pseudo-second-order model. The adsorption of CR onto the CCS was mainly controlled by chemisorption while the adsorption of CR onto the CCS/BT composite was controlled by chemisorption and the electrostatic attraction. Copyright © 2016 Elsevier B.V. All rights reserved.

A colloidal assembly approach to synthesize magnetic porous composite nanoclusters for efficient protein adsorption

NASA Astrophysics Data System (ADS)

Yang, Qi; Lan, Fang; Yi, Qiangying; Wu, Yao; Gu, Zhongwei

2015-10-01

A combination strategy of the inverse emulsion crosslinking approach and the colloidal assembly technique is first proposed to synthesize Fe3O4/histidine composite nanoclusters as new-type magnetic porous nanomaterials. The nanoclusters possess uniform morphology, high magnetic content and excellent protein adsorption capacity, exhibiting their great potential for bio-separation.A combination strategy of the inverse emulsion crosslinking approach and the colloidal assembly technique is first proposed to synthesize Fe3O4/histidine composite nanoclusters as new-type magnetic porous nanomaterials. The nanoclusters possess uniform morphology, high magnetic content and excellent protein adsorption capacity, exhibiting their great potential for bio-separation. Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c5nr05800g

Radiation processing of natural polymers: The IAEA contribution

NASA Astrophysics Data System (ADS)

Haji-Saeid, Mohammad; Safrany, Agnes; Sampa, Maria Helena de O.; Ramamoorthy, Natesan

2010-03-01

Radiation processing offers a clean and additive-free method for preparation of value-added novel materials based on renewable, non-toxic, and biodegradable natural polymers. Crosslinked natural polymers can be used as hydrogel wound dressings, face cleaning cosmetic masks, adsorbents of toxins, and non-bedsore mats; while low molecular weight products show antibiotic, antioxidant, and plant-growth promoting properties. Recognizing the potential benefits that radiation technology can offer for processing of natural polymers into useful products, the IAEA implemented a coordinated research project (CRP) on "Development of Radiation-processed products of Natural Polymers for application in Agriculture, Healthcare, Industry and Environment". This CRP was launched at the end of 2007 with participation of 16 MS to help connecting radiation technology and end-users to derive enhanced benefits from these new value-added products of radiation-processed natural materials. In this paper the results of activities in participating MS related to this work will be presented.

Effect of electron beam radiation processing on mechanical and thermal properties of fully biodegradable crops straw/poly (vinyl alcohol) biocomposites

NASA Astrophysics Data System (ADS)

Guo, Dan

2017-01-01

Fully biodegradable biocomposites based on crops straw and poly(vinyl alcohol) was prepared through thermal processing, and the effect of electron beam radiation processing with N,N-methylene double acrylamide as radiation sensitizer on mechanical and thermal properties of the biocomposites were investigated. The results showed that, when the radiation dose were in the range of 0-50 kGy, the mechanical and thermal properties of the biocomposites could be improved significantly through the electron beam radiation processing, and the interface compatibility was also improved because of the formation of stable cross-linked network structure, when the radiation dose were above the optimal value (50 kGy), the comprehensive properties of the biocomposites were gradually destroyed. EB radiation processing could be used as an effective technology to improve the comprehensive performance of the biocomposites, and as a green and efficient processing technology, radiation processing takes place at room temperature, and no contamination and by-product are possible.

Space environmental effects on polymeric materials

NASA Technical Reports Server (NTRS)

Kiefer, Richard L.; Orwoll, Robert A.

1988-01-01

Two of the major environmental hazards in the Geosynchronous Earth Orbit (GEO) are energetic charged particles and ultraviolet radiation. The charged particles, electrons and protons, range in energy from 0.1 to 4 MeV and each have a flux of 10 to the 8th sq cm/sec. Over a 30 year lifetime, materials in the GEO will have an absorbed dose from this radiation of 10 to the 10th rads. The ultraviolet radiation comes uninhibited from the sun with an irradiance of 1.4 kw/sq m. Radiation is known to initiate chain sission and crosslinking in polymeric materials, both of which affect their structural properties. The 30-year dose level from the combined radiation in the GEO exceeds the threshold for measurable damage in most polymer systems studied. Of further concern is possible synergistic effects from the simultaneous irradiation with charged particles and ultraviolet radiation. Most studies on radiation effects on polymeric materials use either electrons or ultraviolet radiation alone, or in a sequential combination.

Genome-Wide Profiling of RNA–Protein Interactions Using CLIP-Seq

PubMed Central

Stork, Cheryl; Zheng, Sika

2017-01-01

UV crosslinking immunoprecipitation (CLIP) is an increasingly popular technique to study protein–RNA interactions in tissues and cells. Whole cells or tissues are ultraviolet irradiated to generate a covalent bond between RNA and proteins that are in close contact. After partial RNase digestion, antibodies specific to an RNA binding protein (RBP) or a protein–epitope tag is then used to immunoprecipitate the protein–RNA complexes. After stringent washing and gel separation the RBP–RNA complex is excised. The RBP is protease digested to allow purification of the bound RNA. Reverse transcription of the RNA followed by high-throughput sequencing of the cDNA library is now often used to identify protein bound RNA on a genome-wide scale. UV irradiation can result in cDNA truncations and/or mutations at the crosslink sites, which complicates the alignment of the sequencing library to the reference genome and the identification of the crosslinking sites. Meanwhile, one or more amino acids of a crosslinked RBP can remain attached to its bound RNA due to incomplete digestion of the protein. As a result, reverse transcriptase may not read through the crosslink sites, and produce cDNA ending at the crosslinked nucleotide. This is harnessed by one variant of CLIP methods to identify crosslinking sites at a nucleotide resolution. This method, individual nucleotide resolution CLIP (iCLIP) circularizes cDNA to capture the truncated cDNA and also increases the efficiency of ligating sequencing adapters to the library. Here, we describe the detailed procedure of iCLIP. PMID:26965263

Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography [A post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon polymerization

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

Oakdale, James S.; Ye, Jianchao; Smith, William L.

Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.

Post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon lithography [A post-print UV curing method for improving the mechanical properties of prototypes derived from two-photon polymerization

DOE PAGES

Oakdale, James S.; Ye, Jianchao; Smith, William L.; ...

2016-11-28

Here, two photon polymerization (TPP) is a precise, reliable, and increasingly popular technique for rapid prototyping of micro-scale parts with sub-micron resolution. The materials of choice underlying this process are predominately acrylic resins cross-linked via free-radical polymerization. Due to the nature of the printing process, the derived parts are only partially cured and the corresponding mechanical properties, i.e. modulus and ultimate strength, are lower than if the material were cross-linked to the maximum extent. Herein, post-print curing via UV-driven radical generation, is demonstrated to increase the overall degree of cross-linking of low density, TPP-derived structures.

Utilizing stretch-tunable thermochromic elastomeric opal films as novel reversible switchable photonic materials.

PubMed

Schäfer, Christian G; Lederle, Christina; Zentel, Kristina; Stühn, Bernd; Gallei, Markus

2014-11-01

In this work, the preparation of highly thermoresponsive and fully reversible stretch-tunable elastomeric opal films featuring switchable structural colors is reported. Novel particle architectures based on poly(diethylene glycol methylether methacrylate-co-ethyl acrylate) (PDEGMEMA-co-PEA) as shell polymer are synthesized via seeded and stepwise emulsion polymerization protocols. The use of DEGMEMA as comonomer and herein established synthetic strategies leads to monodisperse soft shell particles, which can be directly processed to opal films by using the feasible melt-shear organization technique. Subsequent UV crosslinking strategies open access to mechanically stable and homogeneous elastomeric opal films. The structural colors of the opal films feature mechano- and thermoresponsiveness, which is found to be fully reversible. Optical characterization shows that the combination of both stimuli provokes a photonic bandgap shift of more than 50 nm from 560 nm in the stretched state to 611 nm in the fully swollen state. In addition, versatile colorful patterns onto the colloidal crystal structure are produced by spatial UV-induced crosslinking by using a photomask. This facile approach enables the generation of spatially cross-linked switchable opal films with fascinating optical properties. Herein described strategies for the preparation of PDEGMEMA-containing colloidal architectures, application of the melt-shear ordering technique, and patterned crosslinking of the final opal films open access to novel stimuli-responsive colloidal crystal films, which are expected to be promising materials in the field of security and sensing applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In Vivo Ultrasonic Detection of Polyurea Crosslinked Silica Aerogel Implants

PubMed Central

Sabri, Firouzeh; Sebelik, Merry E.; Meacham, Ryan; Boughter, John D.; Challis, Mitchell J.; Leventis, Nicholas

2013-01-01

Background Polyurea crosslinked silica aerogels are highly porous, lightweight, and mechanically strong materials with great potential for in vivo applications. Recent in vivo and in vitro studies have demonstrated the biocompatibility of this type of aerogel. The highly porous nature of aerogels allows for exceptional thermal, electric, and acoustic insulating capabilities that can be taken advantage of for non-invasive external imaging techniques. Sound-based detection of implants is a low cost, non-invasive, portable, and rapid technique that is routinely used and readily available in major clinics and hospitals. Methodology In this study the first in vivo ultrasound response of polyurea crosslinked silica aerogel implants was investigated by means of a GE Medical Systems LogiQe diagnostic ultrasound machine with a linear array probe. Aerogel samples were inserted subcutaneously and sub-muscularly in a) fresh animal model and b) cadaveric human model for analysis. For comparison, samples of polydimethylsiloxane (PDMS) were also imaged under similar conditions as the aerogel samples. Conclusion/significance Polyurea crosslinked silica aerogel (X-Si aerogel) implants were easily identified when inserted in either of the regions in both fresh animal model and cadaveric model. The implant dimensions inferred from the images matched the actual size of the implants and no apparent damage was sustained by the X-Si aerogel implants as a result of the ultrasonic imaging process. The aerogel implants demonstrated hyperechoic behavior and significant posterior shadowing. Results obtained were compared with images acquired from the PDMS implants inserted at the same location. PMID:23799093

In vivo ultrasonic detection of polyurea crosslinked silica aerogel implants.

PubMed

Sabri, Firouzeh; Sebelik, Merry E; Meacham, Ryan; Boughter, John D; Challis, Mitchell J; Leventis, Nicholas

2013-01-01

Polyurea crosslinked silica aerogels are highly porous, lightweight, and mechanically strong materials with great potential for in vivo applications. Recent in vivo and in vitro studies have demonstrated the biocompatibility of this type of aerogel. The highly porous nature of aerogels allows for exceptional thermal, electric, and acoustic insulating capabilities that can be taken advantage of for non-invasive external imaging techniques. Sound-based detection of implants is a low cost, non-invasive, portable, and rapid technique that is routinely used and readily available in major clinics and hospitals. In this study the first in vivo ultrasound response of polyurea crosslinked silica aerogel implants was investigated by means of a GE Medical Systems LogiQe diagnostic ultrasound machine with a linear array probe. Aerogel samples were inserted subcutaneously and sub-muscularly in a) fresh animal model and b) cadaveric human model for analysis. For comparison, samples of polydimethylsiloxane (PDMS) were also imaged under similar conditions as the aerogel samples. Polyurea crosslinked silica aerogel (X-Si aerogel) implants were easily identified when inserted in either of the regions in both fresh animal model and cadaveric model. The implant dimensions inferred from the images matched the actual size of the implants and no apparent damage was sustained by the X-Si aerogel implants as a result of the ultrasonic imaging process. The aerogel implants demonstrated hyperechoic behavior and significant posterior shadowing. Results obtained were compared with images acquired from the PDMS implants inserted at the same location.

Radiation processing of thermoplastic starch by blending aromatic additives: Effect of blend composition and radiation parameters

NASA Astrophysics Data System (ADS)

Khandal, Dhriti; Mikus, Pierre-Yves; Dole, Patrice; Coqueret, Xavier

2013-03-01

This paper reports on the effects of electron beam (EB) irradiation on poly α-1,4-glucose oligomers (maltodextrins) in the presence of water and of various aromatic additives, as model blends for gaining a better understanding at a molecular level the modifications occurring in amorphous starch-lignin blends submitted to ionizing irradiation for improving the properties of this type of bio-based thermoplastic material. A series of aromatic compounds, namely p-methoxy benzyl alcohol, benzene dimethanol, cinnamyl alcohol and some related carboxylic acids namely cinnamic acid, coumaric acid, and ferulic acid, was thus studied for assessing the ability of each additive to counteract chain scission of the polysaccharide and induce interchain covalent linkages. Gel formation in EB-irradiated blends comprising of maltodextrin was shown to be dependent on three main factors: the type of aromatic additive, presence of glycerol, and irradiation dose. The chain scission versus grafting phenomenon as a function of blend composition and dose were studied using Size Exclusion Chromatography by determining the changes in molecular weight distribution (MWD) from Refractive Index (RI) chromatograms and the presence of aromatic grafts onto the maltodextrin chains from UV chromatograms. The occurrence of crosslinking was quantified by gel fraction measurements allowing for ranking the cross-linking efficiency of the additives. When applying the method to destructurized starch blends, gel formation was also shown to be strongly affected by the moisture content of the sample submitted to irradiation. The results demonstrate the possibility to tune the reactivity of tailored blend for minimizing chain degradation and control the degree of cross-linking.

High-Performance Synthetic Fibers for Composites

DTIC Science & Technology

1992-04-01

under evaluation today include polyether ether ketone , polyamide, 23 polyamideimide, polyimide, polysulfone, and polyphenylene sulfide. Epoxy resins...shrinkage under intense neutron radiation . This attribute, together with other properties of high-temperature strength, toughness, and low nuclear...and (2) liquid or solid resins cross-linked with other esters in chopped-fiber and mineral-filled molding compounds. Polyether ether ketone (PEEK) A

Nano-channels in the spider fang for the transport of Zn ions to cross-link His-rich proteins pre-deposited in the cuticle matrix.

PubMed

Politi, Yael; Pippel, Eckhard; Licuco-Massouh, Ana C J; Bertinetti, Luca; Blumtritt, Horst; Barth, Friedrich G; Fratzl, Peter

2017-01-01

We identify the presence of multiple vascular channels within the spider fang. These channels seem to serve the transport of zinc to the tip of the fang to cross-link the protein matrix by binding to histidine residues. According to amino acid and elemental analysis of fangs extracted shortly after ecdysis, His-rich proteins are deposited before Zn is incorporated into the cuticle. Microscopic and spectroscopic investigations in the electron microscope and synchrotron radiation experiments suggest that Zn ions are transported through these channels in a liable (yet unidentified) form, and then form stable complexes upon His binding. The resulting cross-linking through the Zn-His complexes is conferring hardness to the fang. Our observations of nano-channels serving the Zn-transport within the His-rich protein matrix of the fibre reinforced spider fang may also support recent bio-inspired attempts to design artificial polymeric vascular materials for self-healing and in-situ curing. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

[Experimental realization of minimally invasive techniques of scleral collagen cross-linking].

PubMed

Iomdina, Е N; Tarutta, Е P; Semchishen, V А; Korigodskiy, А R; Zakharov, I D; Khoroshilova-Maslova, I P; Ignat'eva, N Yu; Kiseleva, Т N; Sianosyan, А А; Milash, S V

To realize two minimally invasive techniques of scleral collagen cross-linking (SXL) at the equator and posterior pole of the eye: 1) targeted irradiation of the region with ultraviolet A (UVA) and 2) sub-Tenon injection of Sklerateks. To perform UVA-SXL, a tool was developed that includes a UV-LED light source (370 nm, 3 mW/cm2) and a polymer-coated silica multimode optical fiber located in one of the two channels of a detachable metal tip. The other channel is used to deliver riboflavin to the scleral surface. The study included 8 Chinchillas' eyes. Intact fellow eyes served as the controls. Scleral echodensity was measured in vivo with Voluson 730 Pro (Kretz) prior to the procedure and then 2 days and 1 month after. After enucleation, the elastic modulus and the degree of scleral cross-linking were established at the same time-points. A placebo-controlled study on the safety and effectiveness of sub-Tenon Sklerateks injections (solution of amino acid salts in the form of succinates) was conducted on 47 Chinchilla rabbits (94 eyes). Sklerateks or placebo (0.1 ml) was injected below the Tenon's capsule of either eye once a week for 1 month (4 injections; 1st series) or 3 months (12 injections; 2nd series). After the end of the course, 22 eyes were studied morphologically. In 72 eyes, scleral samples were obtained in order to evaluate the elastic modulus (Autograph AGS-H tester, SHIMADZU, Japan) and the rate of cross-linking (judging from the denaturation temperature) by differential scanning calorimetry (Phoenix DSC 204 calorimeter, Netzsch, Germany). After UVA irradiation, the scleral echodensity increased from 86.7±5.1 to 98±4.9 dB. The elastic modulus appeared 1.5 times higher than that of the control samples. The denaturation temperature also increased indicating the rate of scleral cross-linking as high as 15-18%. Weekly Sklerateks for 1-3 months has been shown to induce neither clinical, nor morphological signs of local irritative, damaging, or toxic effect. The findings also include: a 1.8 times higher rate of scleral cross-linking, activation of cellular elements, neoformation of connective tissue on the scleral surface, and vascular growth, which together indicate a pronounced metabolic and strengthening effect of Sklerateks on the sclera. Experimental results on minimally invasive techniques of SXL allow to recommend them for further clinical investigation as a promising treatment of progressive myopia.

Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

NASA Astrophysics Data System (ADS)

Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A.; Monteiro, Paulo J. M.

2017-03-01

The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.

Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate.

PubMed

Geng, Guoqing; Myers, Rupert J; Li, Jiaqi; Maboudian, Roya; Carraro, Carlo; Shapiro, David A; Monteiro, Paulo J M

2017-03-10

The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is more deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca 2+ of the interlayer. Dreierketten chain cross-links act as 'columns' to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a 'bottom-up' approach.

Solving the problem of building models of crosslinked polymers: an example focussing on validation of the properties of crosslinked epoxy resins.

PubMed

Hall, Stephen A; Howlin, Brendan J; Hamerton, Ian; Baidak, Alex; Billaud, Claude; Ward, Steven

2012-01-01

The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE) and triglycidyl-p-amino phenol (TGAP) with the curing agent diamino diphenyl sulphone (DDS). The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (T(g)). Typical models comprise some 4200-4600 atoms (ca. 120-130 monomers). In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA) to measure T(g). Results for the three epoxy systems yield good agreement with experimental T(g) ranges of 200-220°C, 270-285°C and 285-290°C with corresponding simulated ranges of 210-230°C, 250-300°C, and 250-300°C respectively.

Solving the Problem of Building Models of Crosslinked Polymers: An Example Focussing on Validation of the Properties of Crosslinked Epoxy Resins

PubMed Central

Hall, Stephen A.; Howlin, Brendan J; Hamerton, Ian; Baidak, Alex; Billaud, Claude; Ward, Steven

2012-01-01

The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE) and triglycidyl-p-amino phenol (TGAP) with the curing agent diamino diphenyl sulphone (DDS). The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (Tg). Typical models comprise some 4200–4600 atoms (ca. 120–130 monomers). In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA) to measure Tg. Results for the three epoxy systems yield good agreement with experimental Tg ranges of 200–220°C, 270–285°C and 285–290°C with corresponding simulated ranges of 210–230°C, 250–300°C, and 250–300°C respectively. PMID:22916182

Preparation of Nanocellulose Reinforced Chitosan Films, Cross-Linked by Adipic Acid

PubMed Central

Falamarzpour, Pouria; Behzad, Tayebeh; Zamani, Akram

2017-01-01

Adipic acid, an abundant and nontoxic compound, was used to dissolve and cross-link chitosan. After the preparation of chitosan films through casting technique, the in situ amidation reaction was performed at 80–100 °C as verified by Fourier transform infrared (FT-IR). The reaction was accompanied by the release of water which was employed to investigate the reaction kinetics. Accordingly, the reaction rate followed the first-order model and Arrhenius equation, and the activation energy was calculated to be 18 kJ/mol. Furthermore, the mechanical properties of the chitosan films were comprehensively studied. First, optimal curing conditions (84 °C, 93 min) were introduced through a central composite design. In order to evaluate the effects of adipic acid, the mechanical properties of physically cross-linked (uncured), chemically cross-linked (cured), and uncross-linked (prepared by acetic acid) films were compared. The use of adipic acid improved the tensile strength of uncured and chemically cross-linked films more than 60% and 113%, respectively. Finally, the effect of cellulose nanofibrils (CNFs) on the mechanical performance of cured films, in the presence of glycerol as a plasticizer, was investigated. The plasticized chitosan films reinforced by 5 wt % CNFs showed superior properties as a promising material for the development of chitosan-based biomaterials. PMID:28208822

Preparation of Nanocellulose Reinforced Chitosan Films, Cross-Linked by Adipic Acid.

PubMed

Falamarzpour, Pouria; Behzad, Tayebeh; Zamani, Akram

2017-02-13

Adipic acid, an abundant and nontoxic compound, was used to dissolve and cross-link chitosan. After the preparation of chitosan films through casting technique, the in situ amidation reaction was performed at 80-100 °C as verified by Fourier transform infrared (FT-IR). The reaction was accompanied by the release of water which was employed to investigate the reaction kinetics. Accordingly, the reaction rate followed the first-order model and Arrhenius equation, and the activation energy was calculated to be 18 kJ/mol. Furthermore, the mechanical properties of the chitosan films were comprehensively studied. First, optimal curing conditions (84 °C, 93 min) were introduced through a central composite design. In order to evaluate the effects of adipic acid, the mechanical properties of physically cross-linked (uncured), chemically cross-linked (cured), and uncross-linked (prepared by acetic acid) films were compared. The use of adipic acid improved the tensile strength of uncured and chemically cross-linked films more than 60% and 113%, respectively. Finally, the effect of cellulose nanofibrils (CNFs) on the mechanical performance of cured films, in the presence of glycerol as a plasticizer, was investigated. The plasticized chitosan films reinforced by 5 wt % CNFs showed superior properties as a promising material for the development of chitosan-based biomaterials.

The effect of increasing honey concentration on the properties of the honey/polyvinyl alcohol/chitosan nanofibers.

PubMed

Sarhan, Wessam A; Azzazy, Hassan M E; El-Sherbiny, Ibrahim M

2016-10-01

The effect of increasing honey concentrations from 10% to 30% within the Honey (H)/polyvinyl alcohol (P)/chitosan (CS) nanofibers was investigated. Changes in the electrospun nanofiber diameters, crystallinity, thermal behavior, porosity and antibacterial activity have been assessed using SEM, XRD, DSC, TGA, mercury porosimeter and viable cell count technique. The HPCS nanofibers were cross-linked and tested for their swelling abilities and degradation behavior. The mean diameter of HPCS nanofibers increased from 284±97nm to 464±185nm upon increasing the honey concentration from 10% to 30%. Irrespective the honey concentrations, the nanofibers have demonstrated enhanced porosity. Increasing the honey concentration resulted in a reduction in the swelling of the 1h cross-linked HPCS nanofibers containing 10% and 30% H from 520% to 100%; respectively. Degradation after 30days was reduced in the 3h cross-linked HPCS nanofibers compared to the non-crosslinked HPCS nanofibers. Enhanced antibacterial activity was achieved against both Staphylococcus aureus and Escherichia coli upon increasing the honey concentration. Changing the honey concentration and the extent of nanofiber crosslinking can be used to adjust different parameters of the HPCS nanofibers to suit their applications in wound healing and tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

Crosslinked polymer nanoparticles containing single conjugated polymer chains

NASA Astrophysics Data System (ADS)

Ponzio, Rodrigo A.; Marcato, Yésica L.; Gómez, María L.; Waiman, Carolina V.; Chesta, Carlos A.; Palacios, Rodrigo E.

2017-06-01

Conjugated polymer nanoparticles are widely used in fluorescent labeling and sensing, as they have mean radii between 5 and 100 nm, narrow size dispersion, high brightness, and are photochemically stable, allowing single particle detection with high spatial and temporal resolution. Highly crosslinked polymers formed by linking individual chains through covalent bonds yield high-strength rigid materials capable of withstanding dissolution by organic solvents. Hence, the combination of crosslinked polymers and conjugated polymers in a nanoparticulated material presents the possibility of interesting applications that require the combined properties of constituent polymers and nanosized dimension. In the present work, F8BT@pEGDMA nanoparticles composed of poly(ethylene glycol dimethacrylate) (pEGDMA; a crosslinked polymer) and containing the commercial conjugated polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) were synthesized and characterized. Microemulsion polymerization was applied to produce F8BT@pEDGMA particles with nanosized dimensions in a ∼25% yield. Photophysical and size distribution properties of F8BT@pEDGMA nanoparticles were evaluated by various methods, in particular single particle fluorescence microscopy techniques. The results demonstrate that the crosslinking/polymerization process imparts structural rigidity to the F8BT@pEDGMA particles by providing resistance against dissolution/disintegration in organic solvents. The synthesized fluorescent crosslinked nanoparticles contain (for the most part) single F8BT chains and can be detected at the single particle level, using fluorescence microscopy, which bodes well for their potential application as molecularly imprinted polymer fluorescent nanosensors with high spatial and temporal resolution.

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.

Hydrogel membranes of PVAl/ clay by gamma radiation

NASA Astrophysics Data System (ADS)

de Oliveira, M. J. A.; Parra, D. F.; Amato, V. S.; Lugão, A. B.

2013-03-01

In the last decades several studies concerning the new methods for drug delivery system have been investigated. A new field known as "smart therapy" involves devices and drug delivery systems to detect, identify and treat the site affected by the disease, not interfering with the biological system. Cutaneous Leishmaniasis is an endemic disease that is characterized by the development of single or multiple localized lesions on exposed areas of skin and one coetaneous treatment could be a potential solution. The aim of this study was to obtain polymeric hydrogel matrices of poly(vinylalcohol)(PVAl) and chitosan with inorganic nanoparticles, which can release a drug according to the need of the treatment of injury caused by leishmania on the skin. The hydrogels matrices were obtained with PVAl/ chitosan and PVAl/ chitosan 0.5; 1.0 and 1.5% laponite RD clay, crosslinked by ionizing gamma radiation with dose of 25 kGy. The techniques used for characterization were swelling, gel fraction, Fourier transform infrared spectroscopy (FTIR) and thermogravimetry (TGA). After synthesis, the samples were immersed in distilled water and weighed in periods of time until 60 h for the swelling determination. The obtained results have indicated that the swelling of the membranes increases with clay concentration, in consequence of ionic groups present in the clay.

Electron-beam generated porous dextran gels: experimental and quantum chemical studies.

PubMed

Naumov, Sergej; Knolle, Wolfgang; Becher, Jana; Schnabelrauch, Matthias; Reichelt, Senta

2014-06-01

The aim of this work was to investigate the reaction mechanism of electron-beam generated macroporous dextran cryogels by quantum chemical calculation and electron paramagnetic resonance measurements. Electron-beam radiation was used to initiate the cross-linking reaction of methacrylated dextran in semifrozen aqueous solutions. The pore morphology of the resulting cryogels was visualized by scanning electron microscopy. Quantum chemical calculations and electron paramagnetic resonance studies provided information on the most probable reaction pathway and the chain growth radicals. The most probable reaction pathway was a ring opening reaction and the addition of a C-atom to the double-bond of the methacrylated dextran molecule. First detailed quantum chemical calculation on the reaction mechanism of electron-beam initiated cross-linking reaction of methacrylated dextran are presented.

Silk Electrogel Rheology

NASA Astrophysics Data System (ADS)

Tabatabai, A. P.; Urbach, J. S.; Blair, D. L.; Kaplan, D. L.

2014-03-01

We present experimental results on the rheology on electrogels derived from aqueous solutions of reconstituted Bombyx Mori silk fibroin protein. Through electrochemistry, the silk protein solution develops local pH changes resulting in the assembly of protein into a weak gel. We determine the physical properties of the electrogels by performing rheology and observe that they exhibit the characteristics of a crosslinked biopolymer network. Interestingly, we find that these silk gels exhibit linear elasticity over a range of up to two orders of magnitude larger than most crosslinked biopolymer networks. Moreover, the nonlinear rheology exhibits a strain-stiffening behavior that is fundamentally different than the strain-stiffening observed in crosslinked biopolymers. Through rheological techniques we aim to understand this distinctive material that cannot be explained by current polymeric models. This work is supported by a grant from the AFOSR FA9550-07-1-0130.

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.

Spatially controlled, in situ synthesis of polymers

DOEpatents

Caneba, Gerard T.; Tirumala, Vijaya Raghavan; Mancini, Derrick C.; Wang, Hsien-Hau

2005-03-22

An in situ polymer microstructure formation method. The monomer mixture is polymerized in a solvent/precipitant through exposure to ionizing radiation in the absence any chemical mediators. If an exposure mask is employed to block out certain regions of the radiation cross section, then a patterned microstructure is formed. The polymerization mechanism is based on the so-called free-radical retrograde-precipitation polymerization process, in which polymerization occurs while the system is phase separating above the lower critical solution temperature. This method was extended to produce a crosslinked line grid-pattern of poly (N-isopropylacrylamide), which has been known to have thermoreversible properties.

A comparison of the efficacy of various antioxidants on the oxidative stability of irradiated polyethylene.

PubMed

Hope, Natalie; Bellare, Anuj

2015-03-01

Ultrahigh-molecular-weight polyethylene (UHMWPE) is subjected to radiation crosslinking to form highly crosslinked polyethylene (HXLPE), which has improved wear resistance. First-generation HXLPE was subjected to thermal treatment to reduce or quench free radicals that can induce long-term oxidative degeneration. Most recently, antioxidants have been added to HXLPE to induce oxidative resistance rather than by thermal treatment. However, antioxidants can interfere with the efficiency of radiation crosslinking. We sought to identify (1) which antioxidant from among those tested (vitamin E, β-carotene, butylated hydroxytoluene, or pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]) causes the least reduction of crosslinking; (2) which promotes the greatest oxidative stability; and (3) which had the lowest ratio of oxidation index to crosslink density. Medical-grade polyethylene (PE) resin was blended with 0.1 weight % of the following stabilizers: alpha tocopherol (vitamin E), β-carotene, butylated hydroxytoluene (BHT), and pentaerythritol tetrakis [methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (a hindered phenol antioxidant [HPAO]). These blends were compression-molded into sheets and subjected to electron beam irradiation to a dose of 100 kGy. Equilibrium swelling experiments were conducted to calculate crosslink density. Each PE was subjected to accelerated aging for a period of 2 weeks and Fourier transform infrared spectroscopy was used to measure the maximum oxidation. Statistical analysis was conducted using analysis of variance with Fisher's protected least significant difference in which a p value of < 0.05 was used to define a significant difference. The least reduction of crosslinking in antioxidant-containing HXLPE was observed with HPAO, which had a crosslink density (n = 6) of 0.167 (effect size [ES] = 0.87; 95% confidence interval [CI], 0.162-0.173) mol/dm(3) compared with 0.139 (ES = 1.57; 95% CI, 0.132-0.146) mol/dm(3) (p = 0.020) for BHT, 0.131 (ES = 1.77; 95% CI, 0.123-0.139) mol/dm(3) (p = 0.004) for β-carotene, and 0.130 (ES = 1.79; 95% CI, 0.124-0.136) mol/dm(3) (p = 0.003) for vitamin E, whereas pure HXLPE had a crosslink density of 0.203 (95% CI, 0.170-0.235) mol/dm(3) (p = 0.005). BHT-PE had an oxidation index of 0.21 (ES = 13.14; 95% CI, 0.19-0.22) followed by HPAO-PE, vitamin E-PE and β-carotene-PE, which had oxidation indices of 0.28 (ES = 9.68; 95% CI, 0.28-0.29), 0.29 (ES = 9.59; 95% CI, 0.27-0.30), and 0.35 (ES = 6.68; 95% CI, 0.34-0.37), respectively (p < 0.001 for all groups). BHT-PE had the lowest ratio of oxidation index to crosslink density of the materials tested (1.49, ES = 1.94; 95% CI, 1.32-1.66) followed by HPAO-PE (1.70, ES = 1.52; 95% CI, 1.61-1.80), vitamin E-PE (2.21, ES = 0.52; 95% CI, 2.05-2.38), and β-carotene-PE (2.69, ES = -0.43; 95% CI, 2.46-2.93) compared with control PE (2.47, 95% CI, 2.07-2.88) with β-carotene (p = 0.208) and vitamin E (p = 0.129) not being different from the control. BHT-modified HXLPE was found in this study to have the lowest oxidation index as well as the lowest ratio of oxidation index to crosslink density compared with vitamin E, HPAO, and β-carotene-modified HXLPEs. More comprehensive studies are required such as wear testing using joint simulators as well as biocompatibility studies before BHT-modified HXLPE can be considered for clinical use. BHT is a synthetic antioxidant commonly used in the polymer industry to prevent long-term oxidative degradation and has been approved by the FDA for use in cosmetics and foodstuffs. It may be an attractive potential stabilizer for HXLPE in total joint replacements.

Study of the effect of gamma irradiation on a commercial polycyclooctene I. Thermal and mechanical properties

NASA Astrophysics Data System (ADS)

García-Huete, N.; Laza, J. M.; Cuevas, J. M.; Vilas, J. L.; Bilbao, E.; León, L. M.

2014-09-01

A gamma radiation process for modification of commercial polymers is a widely applied technique to promote new physical, chemical and mechanical properties. Gamma irradiation originates free radicals able to induce chain scission or recombination of radicals, which induces annihilation, branching or crosslinking processes. The aim of this work is to research the structural, thermal and mechanical changes induced on a commercial polycyclooctene (PCO) when it is irradiated with a gamma source of 60Co at different doses (25-200 kGy). After gamma irradiation, gel content was determined by Soxhlet extraction in cyclohexane. Furthermore, thermal properties were evaluated before and after Soxhlet extraction by means of Thermogravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC), as well as mechanical properties were measured by Dynamic Mechanical Thermal Analysis (DMTA). The results showed the variations of the properties depending on the irradiation dose. Finally, a first approach to evaluate qualitatively the shape memory behaviour of all irradiated PCO samples was performed by a visually monitoring shape recovery process.

Raman imaging spectroscopic characterization of modified poly(dimethylsiloxane) for micro total analysis systems applications.

PubMed

de Campos, Richard Piffer Soares; Yoshida, Inez Valeria Pagotto; Breitkreitz, Márcia Cristina; Poppi, Ronei Jesus; Fracassi da Silva, José Alberto

2013-01-01

Methacryloxypropyl-modified poly(dimethylsiloxane) rubbers were obtained from poly(dimethylsiloxane), PDMS, and methacryloxypropyltrimethoxysilane, MPTMS, by polycondensation reactions. The modified rubbers, prepared with 20 and 30% (v/v) of MPTMS, were used as substrates for microchannel fabrication by the CO(2) laser ablation technique. Raman imaging spectroscopy was used for the surface characterization, showing the homogeneity of the rubbery material, with uniform distribution of the crosslinking centers. Under the experimental conditions used, damage to the rubber from the CO(2) laser radiation used for the channel engraving was not observed. Correlation maps of the surface were obtained in order to spatially evaluate the modification inside and outside the channels. The correlations between the methacryloxypropyl-modified poly(dimethylsiloxane) rubbers and MPTMS (spectral range of 1800-1550 cm(-1)) and PDMS (spectral range of 820-670 cm(-1)) precursors were higher than 0.95 and 0.99, respectively. In addition, Raman imaging spectroscopy allows monitoring the topography of the fabricated microchannel. Copyright © 2012 Elsevier B.V. All rights reserved.

Chitosan/CNTs green nanocomposite membrane: synthesis, swelling and polyaromatic hydrocarbons removal.

PubMed

Bibi, Saira; Yasin, Tariq; Hassan, Safia; Riaz, Muhammad; Nawaz, Mohsan

2015-01-01

Carbon nanotubes (CNTs) were irradiated in air at 100 kGy under gamma radiations. The Raman spectroscopy of γ-treated CNTs showed distinctive changes in the absorption bands. The CNTs were mixed with blend of chitosan (Cs)/poly (vinyl alcohol) (PVA) and crosslinked with silane. The chemical reactions between the components affected the position and intensities of the infrared bands. Scanning electron micrograph of Cs/CNTs nanocomposite membrane showed the homogeneous dispersion of CNTs in the polymer matrix. The addition of CNTs lowered its swelling in water. Naphthalene (NAPH) was selected as a model compound and its removal was studied using HPLC technique. This membrane showed fast uptake of NAPH and 87% was removed from water within 30 min. The NAPH loaded membrane showed strong chemical interactions and cannot be desorbed. The fast uptake of PAHs and the green nature of this membrane made them suitable candidates for clean-up purposes. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquid-Crystal Thermosets, a New Generation of High-Performance Liquid-Crystal Polymers

NASA Technical Reports Server (NTRS)

Dingemans, Theo; Weiser, Erik; Hou, Tan; Jensen, Brian; St. Clair, Terry

2004-01-01

One of the major challenges for NASA's next-generation reusable-launch-vehicle (RLV) program is the design of a cryogenic lightweight composite fuel tank. Potential matrix resin systems need to exhibit a low coefficient of thermal expansion (CTE), good mechanical strength, and excellent barrier properties at cryogenic temperatures under load. In addition, the resin system needs to be processable by a variety of non-autoclavable techniques, such as vacuum-bag curing, resin-transfer molding (RTM), vacuum-assisted resin-transfer molding (VaRTM), resin-film infusion (RFI), pultrusion, and advanced tow placement (ATP). To meet these requirements, the Advanced Materials and Processing Branch (AMPB) at NASA Langley Research Center developed a new family of wholly aromatic liquid-crystal oligomers that can be processed and thermally cross-linked while maintaining their liquid-crystal order. All the monomers were polymerized in the presence of a cross-linkable unit by use of an environmentally benign melt-condensation technique. This method does not require hazardous solvents, and the only side product is acetic acid. The final product can be obtained as a powder or granulate and has an infinite shelf life. The obtained oligomers melt into a nematic phase and do not exhibit isotropization temperatures greater than the temperatures of decomposition (Ti > T(sub dec)). Three aromatic formulations were designed and tested and included esters, ester-amides, and ester-imides. One of the major advantages of this invention, named LaRC-LCR or Langley Research Center-Liquid Crystal Resin, is the ability to control a variety of resin characteristics, such as melting temperature, viscosity, and the cross-link density of the final part. Depending on the formulation, oligomers can be prepared with melt viscosities in the range of 10-10,000 poise (100 rad/s), which can easily be melt-processed using a variety of composite-processing techniques. This capability provides NASA with custom-made matrix resins that meet the required processing conditions for the fabrication of textile composites. Once the resin is in place, the temperature is raised to 375 C and the oligomers are cross-linked into a high-glass-transition-temperature (Tg) nematic network without releasing volatiles. The mechanical properties of the fully crosslinked, composite articles are comparable to typical composites based on commercially available epoxy resins.

An investigation of the microstructure, mechanical properties, and tribological performance of ultra high molecular weight polyethylene for applications in total joint arthroplasty

NASA Astrophysics Data System (ADS)

van Citters, Douglas W.

Ultra high molecular weight polyethylene (UHMWPE) is the most common bearing material in joint arthroplasty due to its biocompatibility, its wear resistance, and its mechanical toughness. Despite the favorable properties of UHMWPE and its success as a biomaterial, billions of dollars are spent annually to revise tens of thousands of failed artificial joints. Over half of these revision procedures are related to mechanical failure of the polymer bearing or osteolysis resulting from polymer wear. Contemporary material processing steps involving thermal treatment and/or radiation treatment seek to improve outcomes through improving the tribological properties of UHMWPE. However, it is widely recognized that achieving wear resistance through radiation-induced crosslinking comes at the cost of reduced mechanical properties. Moreover, current wear theories for orthopaedic UHMWPE are incomplete in that they predict zero wear in the absence of crossing motion. Wear nonetheless occurs in linear reciprocation, necessitating an alternate theory. The present work explains the effects of thermal treatments and radiation treatments on the properties of GUR1050 UHMWPE. A test matrix allows comparisons of different treatments across different test platforms. Characterization techniques include DSC, FTIR spectroscopy, tensile testing, x-ray diffraction, and electron microscopy. A novel quantitative stereology technique is developed to quantify crystallite size in the semicrystalline material. Seven clinically relevant materials are subjected to rolling-sliding tribotesting to determine polyethylene wear behavior in linear reciprocation. The multi-station tribotester employed for this work enables high throughput testing, and the specimen geometry allows direct measurement of wear rates without a gravimetric soak control. The results of the material characterization tests can be used to accurately predict the rolling-sliding wear behavior of UHMWPE. Wear rate is directly related to crystallite size divided by the material yield strength. A modification of the delamination theory of wear is proposed to explain the wear mechanism. The results and conclusions of the present study can be used to specify future UHMWPE treatments that might eliminate a toughness-reducing radiation dose while improving the wear properties of the polymer. Such treatments would improve the in vivo performance of UHMWPE and hence would improve orthopaedic surgery outcomes.

Gamma radiation effects on random copolymers based on poly(butylene succinate) for packaging applications

NASA Astrophysics Data System (ADS)

Negrin, M.; Macerata, E.; Consolati, G.; Quasso, F.; Genovese, L.; Soccio, M.; Giola, M.; Lotti, N.; Munari, A.; Mariani, M.

2018-01-01

Within the context of new bioplastic materials, poly(butylene succinate) (PBS) and four novel poly(butylene/thiodiethylene succinate) random copolymers (PBS-PTDGS), in sheets as well as in films, were exposed to gamma radiation, in air and in water, and their behavior along with the effect on their biodegradability was investigated. The molecular weight data obtained from gel permeation chromatography indicate that the sensibility to radiation increases with the amount of sulfur-containing co-unit (TDGS). At 200 kGy the average molecular weight of PBS film halves, while for P(BS60TDGS40) the residual molecular weight is about 20%. The calculated intermolecular crosslink Gx and scissioning Gs yields confirmed that degradation is predominant over crosslink for all the aliphatic systems. As shown by thermal analyses, gamma radiation affects the thermal properties, leading to an increased crystallinity of the systems, remarkable for PBS, and lower decomposition temperatures. Variations of crystallinity with the increasing absorbed dose were confirmed also by PALS analyses. Water contact angle measurements revealed post-irradiation wettability alterations that could positively affect polymer biodegradability. In particular, when irradiated in water at 100 kGy PBS film exhibits a water contact angle decrease of about 17%, indicating an enhanced wettability. After degradation in compost, changes in the surface morphology were observed by means of SEM and sample weight losses were determined, at different extent, according to the irradiation environment. Interestingly, after 52 days in compost PBS films, both pristine and irradiated in air at 25 kGy, showed a residual weight of about 60%, while the ones irradiated in water at 25 kGy of about 44%. Experimental data confirmed that gamma irradiation could represent a viable treatment to enhance biodegradation in compost of PBS and PBS-based copolymers.

DNA-protein crosslinking by trans-platinum(II)diamminedichloride in mammalian cells, a new method of analysis.

PubMed

Kohn, K W; Ewig, R A

1979-03-28

DNA-protien crosslinks produced in mouse leukemia L1210 cells by trans-Pt(II)diamminedichloride were quantitated using the technique of DNA alkaline elution. DNA single-strand segments that were or were not linked to protein were separable into distinct components by alkaline elution after exposure of the cells to 2--15 kR of X-ray. Protein-linked DNA strands were separated on the basis of their retention of filters at pH 12 while free DNA strands of the size generated by 2--15 kR of X-ray passed rapidly through the filters. The retention of protein-linked DNA strands was attributable to adsorption of protein to the filter under the conditions of alkaline elution. The results obeyed a simple quantitative model according to which the frequency of DNA-protein crosslinks could be calculated.

Chromatin structure and methylation of rat rRNA genes studied by formaldehyde fixation and psoralen cross-linking.

PubMed Central

Stancheva, I; Lucchini, R; Koller, T; Sogo, J M

1997-01-01

By using formaldehyde cross-linking of histones to DNA and gel retardation assays we show that formaldehyde fixation, similar to previously established psoralen photocross-linking, discriminates between nucleosome- packed (inactive) and nucleosome-free (active) fractions of ribosomal RNA genes. By both cross-linking techniques we were able to purify fragments from agarose gels, corresponding to coding, enhancer and promoter sequences of rRNA genes, which were further investigated with respect to DNA methylation. This approach allows us to analyse independently and in detail methylation patterns of active and inactive rRNA gene copies by the combination of Hpa II and Msp I restriction enzymes. We found CpG methylation mainly present in enhancer and promoter regions of inactive rRNA gene copies. The methylation of one single Hpa II site, located in the promoter region, showed particularly strong correlation with the transcriptional activity. PMID:9108154

Covalent cross-linking of insulin-like growth factor-1 to a specific inhibitor from human serum

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

Ooi, G.T.; Herington, A.C.

1986-05-29

Previous studies have shown that a specific inhibitor of insulin-like growth factor (IGF) action in vitro can be isolated from normal human serum and subsequently partially purified on an IGF-affinity column. The ability of the inhibitor to bind the IGFs has now been confirmed directly using covalent cross-linking techniques. When /sup 125/I-IGF-1 was cross-linked to inhibitor using disuccinimidyl suberate, five specifically labelled bands were seen on SDS-PAGE and autoradiography. Two bands (MW 21.5 K and 25.5 K) were intensely labelled, while the remaining three (MW 37 K, 34 K and 18 K) appeared as minor bands only. Inhibitor bioactivity, followingmore » further analysis by hydrophobic interaction chromatography or Con A-Sepharose affinity chromatography, was always associated with the presence of the 21.5 K and/or 25.5 K bands.« less

Studies on gonadotropin receptor of rat ovary and testis

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

Zhang, Q.

1989-01-01

The subunit structure of the testicular LH/hCG receptor was studied by a chemical cross-linking technique. Leydig cells isolated from rat testis were incubated with {sup 125}I-hCG, following which the bound {sup 125}I-hCG was covalently cross-linked to the receptor on the cell surface with a cleavable or a non-cleavable cross-linking reagent. The hormone-receptor complex was extracted and then either subjected to gel permeation chromatography under nondenaturing conditions, or resolved by SDS-polyacrylamide gel electrophoresis, followed by autoradiographic analysis. The ovarian LH/hCG receptor was studied with luteal cells from pseudopregnant rats. Purification of the receptor was achieved by ligand affinity chromatography following detergentmore » solubilization of the plasma membrane. The purified hCG receptor displayed properties identical to the membrane bound receptor with regard to binding specificity and affinity, and exhibited a molecular weight of approximately 130,000 dalton.« less

Fluorophore-labeling of core-crosslinked polymeric micelles for multimodal in vivo and ex vivo optical imaging

PubMed Central

Shi, Yang; Kunjachan, Sijumon; Wu, Zhuojun; Gremse, Felix; Moeckel, Diana; van Zandvoort, Marc; Kiessling, Fabian; Storm, Gert; van Nostrum, Cornelus F.; Hennink, Wim E.; Lammers, Twan

2015-01-01

Aim To enable multimodal in vivo and ex vivo optical imaging of the biodistribution and tumor accumulation of core-crosslinked polymeric micelles (CCPM). Materials & Methods mPEG-b-p(HPMAm-Lac)-based polymeric micelles, core-crosslinked via cystamine and covalently labeled with two fluorophores (Dy-676/488) were synthesized. The CCPM were intravenously injected in CT26 tumor-bearing mice. Results Upon intravenous injection, the CCPM accumulated in CT26 tumors reasonably efficiently, with values reaching ~4 %ID at 24 hours. Ex vivo TPLSM confirmed efficient extravasation of the iCCPM out of tumor blood vessels and deep penetration into the tumor interstitium. Conclusions CCPM were labeled with multiple fluorophores, and they exemplify that combining different in vivo and ex vivo optical imaging techniques is highly useful for analyzing the biodistribution and tumor accumulation of nanomedicines. PMID:25929568

Synthesis of a specific monolithic column with artificial recognition sites for L-glutamic acid via cryo-crosslinking of imprinted nanoparticles.

PubMed

Göktürk, Ilgım; Üzek, Recep; Uzun, Lokman; Denizli, Adil

2016-06-01

In this study, a new molecular imprinting (MIP)-based monolithic cryogel column was prepared using chemically crosslinked molecularly imprinted nanoparticles, to achieve a simplified chromatographic separation (SPE) for a model compound, L-glutamic acid (L-Glu). Cryogelation through crosslinking of imprinted nanoparticles forms stable monolithic cryogel columns. This technique reduces the leakage of nanoparticles and increases the surface area, while protecting the structural features of the cryogel for stable and efficient recognition of the template molecule. A non-imprinted monolithic cryogel column (NIP) was also prepared, using non-imprinted nanoparticles produced without the addition of L-Glu during polymerization. The molecularly imprinted monolithic cryogel column (MIP) indicates apparent recognition selectivity and a good adsorption capacity compared to the NIP. Also, we have achieved a significant increase in the adsorption capacity, using the advantage of high surface area of the nanoparticles.

Molecular characterization of the plant biopolyester cutin by AFM and spectroscopic techniques.

PubMed

Benítez, José J; Matas, Antonio J; Heredia, Antonio

2004-08-01

Atomic force microscopy, FT-IR spectroscopy, and solid-state nuclear magnetic resonance have been used to improve our current knowledge on the molecular characteristics of the biopolyester cutin, the main component of the plant cuticle. After comparison of samples of cutin isolated from young and mature tomato fruit cuticles has been possible to establish different degrees of cross-linking in the biopolymer and that the polymer is mainly formed after esterification of secondary hydroxyl groups of the monomers that form this type of cutin. Atomic force microscopy gave useful structural information on the molecular topography of the outer surface of the isolated samples. The texture of these samples is a consequence of the cross-linking degree or chemical status of the polymer. Thus, the more dense and cross-linked cutin from ripe or mature tomato fruit is characterized by a flatter and more globular texture in addition to the development of elongated and orientated superstructures.

Inter-crosslinking network gels having both shape memory and high ductility

NASA Astrophysics Data System (ADS)

Amano, Yoshitaka; Hidema, Ruri; Furukawa, Hidemitsu

2012-04-01

Medical treatment for injuries should be easy and quick in many accidents. Plasters or bandages are frequently used to wrap and fix injured parts. If plasters or bandages have additional smart functions, such as cooling, removability and repeatability, they will be much more useful and effective. Here we propose innovative biocompatible materials, that is, nontoxic high-strength shape-memory gels as novel smart medical materials. These smart gels were prepared from two monomers (DMAAm and SA), a polymer (HPC), and an inter-crosslinking agent (Karenz-MOI). In the synthesis of the gels, 1) a shape-memory copolymer network is made from the DMAAm and the SA, and 2) the copolymer and the HPC are crosslinked by the Karenz-MOI. Thus the crosslinking points are connected only between the different polymers. This is our original technique of developing a new network structure of gels, named Inter-Crosslinking Network (ICN). The ICN gels achieve high ductility, going up to 700% strain in tensile tests, while the ICN gels contain about 44% water. Moreover the SA has temperature dependence due to its crystallization properties; thus the ICN gels obtain shape memory properties and are named ICN-SMG. While the Young's modulus of the ICN-SMG is large below their crystallization temperature and the gels behave like plastic materials, the modulus becomes smaller above the temperature and the gels turn back to their original shape.

Crosslink Density and Molecular Weight Effects on the Viscoelastic Response of a Glassy High-Performance Polyimide

NASA Technical Reports Server (NTRS)

Nicholson, Lee M.; Whitley, Karen S.; Gates, Thomas S.

2001-01-01

Durability and long-term performance are among the primary concerns for the use of advanced polymer matrix composites (PMCs) in modern aerospace structural applications. For a PMC subJected to long-term exposure at elevated temperatures. the viscoelastic nature of the polymer matrix will contribute to macroscopic changes in composite stiffness, strength and fatigue life. Over time. changes in the polymer due to physical aging will have profound effects on tile viscoelastic compliance of the material, hence affecting its long-term durability. Thus, the ability to predict material performance using intrinsic properties, such as crosslink density and molecular weight, would greatly enhance the efficiency of design and development of PMCs. The objective of this paper is to discuss and present the results of an experimental study that considers the effects of crosslink density, molecular weight and temperature on the viscoelastic behavior including physical aging of an advanced polymer. Five distinct variations in crosslink density were used to evaluate the differences in mechanical performance of an advanced polyimide. The physical aging behavior was isolated by conducting sequenced, short-term isothermal creep compliance tests in tension. These tests were performed over a range of sub-glass transition temperatures. The material constants, material master curves and physical aging-related parameters were evaluated as a function of temperature crosslink density and molecular weight using time-temperature and time-aging time superposition techniques.

Long-term durability of HT-PEM fuel cells based on thermally cross-linked polybenzimidazole

NASA Astrophysics Data System (ADS)

Søndergaard, Tonny; Cleemann, Lars Nilausen; Becker, Hans; Aili, David; Steenberg, Thomas; Hjuler, Hans Aage; Seerup, Larisa; Li, Qingfeng; Jensen, Jens Oluf

2017-02-01

Long-term durability of high temperature polymer electrolyte membrane fuel cells based on thermally cross-linked polybenzimidazole membranes was studied and compared with reference membranes based on linear polybenzimidazole. The test was conducted at 160 °C under constant load currents of 200 mA cm-2 for periods of 1000, 4400, and 13,000 h. Extensive beginning-of-life (BoL) and end-of-test (EoT) characterisation was carried out, and disturbance of the steady state operated cells was minimised by limiting in-line diagnostics to the low-invasive technique of electrochemical impedance spectroscopy (EIS). Up until the operating time of 9200 h, the cell equipped with the cross-linked membrane showed an average degradation rate of 0.5 μV h-1, compared to 2.6 μV h-1 for the reference membrane, though parallel tests for a shorter period of time showed deviations, likely due to malfunctioning contact between layers or cell components. For the full test period of 13,000 h, the average voltage decay rate was about 1.4 and 4.6 μV h-1 for cells equipped with cross-linked and linear polybenzimidazole membranes, respectively. EIS and post-test analysis revealed that the cross-linked membrane showed better stability in terms of area specific resistance due to improved acid retention characteristics.

Antibacterial electrospun chitosan-polyethylene oxide nanocomposite mats containing ZIF-8 nanoparticles.

PubMed

Kohsari, Iraj; Shariatinia, Zahra; Pourmortazavi, Seied Mahdi

2016-10-01

Antimicrobial chitosan-polyethylene oxide (CS-PEO) nanofiber mats loaded with 3, 5 and 10% (w/w) of zeolitic imidazolate framework-8 nanoparticles (ZIF-8 NPs, ∼60nm diameter) were developed by electrospinning technique. The CS-PEO-GA-3% ZIF-8 NPs crosslinked with glutaraldehyde (GA) vapor was also prepared. The electrospun mats were characterized by various analysis including FE-SEM, EDAX, elemental mapping, FT-IR, contact angle, TGA/DSC as well as tensile strength analysis. The nanofibers had average diameters within the range ∼70-120nm. Antimicrobial activities of the CS-PEO and CS-PEO-3% ZIF-8 mats were evaluated by the viable cell-counting method for determining their effectiveness in reducing or halting the growth of Staphylococcus aureus and Escherichia coli bacteria so that the CS-PEO mat containing 3% ZIF-8 revealed 100% bactericidal activity against both kinds of bacteria. The crosslinked CS-PEO-GA-3% ZIF-8 NPs sample was less thermally stable but more hydrophilic than its related non-crosslinked mat reflecting there was no need to crosslink the fibers using a chemical crosslinker having adverse effects. The highest hydrophobicity and appropriate thermal and tensile properties of CS-PEO-3% ZIF-8 NPs among those of the mats including 5 and 10% ZIF-8 NPs suggested that the mentioned mat is the most suitable sample for food coating applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Crosslinked plastic scintillators: a new detection system for radioactivity measurement in organic and aggressive media.

PubMed

Bagán, Héctor; Tarancón, Alex; Ye, Lei; García, José F

2014-12-10

The measurement of radioactive solutions containing organic or aggressive media may cause stability problems in liquid and plastic scintillation (PS) techniques. In the case of PS, this can be overcome by adding a crosslinker to the polymer structure. The objectives of this study are to synthesise a suitable crosslinked plastic scintillator (C-PS) for radioactivity determination in organic and aggressive media. The results indicated that an increase in the crosslinker content reduces the detection efficiency and a more flexible crosslinker yields higher detection efficiency. For the polymer composition studied, 2,5-diphenyloxazole (PPO) is the most adequate fluorescent solute and an increase in its concentration causes little change in the detection efficiency. The inclusion of a secondary fluorescent solute 1,4-bis-2-(5-phenyloxazolyl) benzene (POPOP) improves the C-PS radiometrical characteristics. For the final composition chosen, the synthesis of the C-PS exhibits good reproducibility with elevated yield. The obtained C-PS also displays high stability in different organic (toluene, hydrotreated vegetable oil (HVO) and methanol) and aggressive media (hydrochloric acid, nitric acid and hydrogen peroxide). Finally, the C-PS exhibits high detection efficiency both in water and in aggressive media and can also be applied in organic media showing similar or even higher detection efficiency values. Copyright © 2014 Elsevier B.V. All rights reserved.

Gellan gum microspheres crosslinked with trivalent ion: effect of polymer and crosslinker concentrations on drug release and mucoadhesive properties.

PubMed

Boni, Fernanda Isadora; Prezotti, Fabíola Garavello; Cury, Beatriz Stringhetti Ferreira

2016-08-01

Gellan gum microspheres were obtained by ionotropic gelation technique, using the trivalent ion Al(3+). The percentage of entrapment efficiency ranged from 48.76 to 87.52% and 2(2) randomized full factorial design demonstrated that both the increase of polymer concentration and the decrease of crosslinker concentration presented a positive effect in the amount of encapsulated drug. Microspheres size and circularity ranged from 700.17 to 938.32 μm and from 0.641 to 0.796 μm, respectively. The increase of polymer concentration (1-2%) and crosslinker concentration (3-5%) led to the enlargement of particle size and circularity. However, the association of increased crosslinker concentration and reduced polymer content made the particles more irregular. In vitro and ex vivo tests evidenced the high mucoadhesiveness of microspheres. The high liquid uptake ability of the microspheres was demonstrated and the pH variation did not affect this parameter. Drug release was pH dependent, with low release rates in acid pH (42.40% and 44.93%) and a burst effect in phosphate buffer pH (7.4). The Weibull model had the best correlation with the drug release data, demonstrating that the release process was driven by a complex mechanism involving the erosion and swelling of the matrix or by non-Fickian diffusion.

MSX-3D: a tool to validate 3D protein models using mass spectrometry.

PubMed

Heymann, Michaël; Paramelle, David; Subra, Gilles; Forest, Eric; Martinez, Jean; Geourjon, Christophe; Deléage, Gilbert

2008-12-01

The technique of chemical cross-linking followed by mass spectrometry has proven to bring valuable information about the protein structure and interactions between proteic subunits. It is an effective and efficient way to experimentally investigate some aspects of a protein structure when NMR and X-ray crystallography data are lacking. We introduce MSX-3D, a tool specifically geared to validate protein models using mass spectrometry. In addition to classical peptides identifications, it allows an interactive 3D visualization of the distance constraints derived from a cross-linking experiment. Freely available at http://proteomics-pbil.ibcp.fr

Persistence of bone collagen cross-links in skeletons of the Nuraghi population living in Sardinia 1500-1200 B.C

NASA Technical Reports Server (NTRS)

Wojtowicz, A.; Yamauchi, M.; Montella, A.; Bandiera, P.; Sotowski, R.; Ostrowski, K.

1999-01-01

Bone collagen has a specific molecular ultrastructure which can be proved by birefringence. This protein, forming the main organic component of bone tissue, is known to survive millennia in paleontological bones and teeth. Birefringence of bone collagen obtained from the skeletons of the Nuraghi population living in Sardinia c-ca 1500 years B.C. was found previously by the use of polarizing microscopy [1]. In this paper, using high pressure liquid chromatography (HPLC) techniques, we show the existence of bone collagen cross-links preserved in Nuraghi skeletons after more than 3000 years.

Fractography and oxidative analysis of gamma inert sterilized posterior-stabilized tibial insert post fractures: report of two cases.

PubMed

Ansari, Farzana; Chang, Jennifer; Huddleston, James; Van Citters, Douglas; Ries, Michael; Pruitt, Lisa

2013-12-01

Highly crosslinked ultra-high molecular weight polyethylene (UHMWPE) has shown success in reducing wear in hip arthroplasty but there remains skepticism about its use in Total Knee Replacement (TKR) inserts that are known to experience fatigue loading and higher local cyclic contact stresses. Two Legacy Posterior-Stabilized (LPS) Zimmer NexGen tibial implants sterilized by gamma irradiation in an inert environment with posts that fractured in vivo were analyzed. Failure mechanisms were determined using optical and scanning electron microscopy along with oxidative analysis via Fourier Transform Infra-Red (FTIR) spectroscopy. Micrographs of one retrieval revealed fatigue crack initiation on opposite sides of the post and quasi-brittle micromechanisms of crack propagation. FTIR of this retrieval revealed no oxidation. The fracture surface image of the second retrieval indicated a brittle fracture process and FTIR revealed oxidation in the explant. These two cases suggest that crosslinking of UHMWPE as a manufacturing process or sterilization method in conjunction with designs that incorporate high stress concentrations, such as the tibial post, may reduce material strength. Moreover, free radicals generated from ionizing radiation can render the polymer susceptible to oxidative embrittlement. Our findings suggest that tibial post fractures may be the results of in vivo oxidation and low level crosslinking. These and previous reports of fractured crosslinked UHMWPE devices implores caution when used with high stress concentrations, particularly when considering the potential for in vivo oxidation in TKR. Copyright © 2013 Elsevier B.V. All rights reserved.

Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

DOE PAGES

Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi; ...

2017-03-10

The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is moremore » deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca 2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.« less

Aluminum-induced dreierketten chain cross-links increase the mechanical properties of nanocrystalline calcium aluminosilicate hydrate

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

Geng, Guoqing; Myers, Rupert J.; Li, Jiaqi

The incorporation of Al and increased curing temperature promotes the crystallization and cross-linking of calcium (alumino)silicate hydrate (C-(A-)S-H), which is the primary binding phase in most contemporary concrete materials. However, the influence of Al-induced structural changes on the mechanical properties at atomistic scale is not well understood. Herein, synchrotron radiation-based high-pressure X-ray diffraction is used to quantify the influence of dreierketten chain cross-linking on the anisotropic mechanical behavior of C-(A-)S-H. We show that the ab-planar stiffness is independent of dreierketten chain defects, e.g. vacancies in bridging tetrahedra sites and Al for Si substitution. The c-axis of non-cross-linked C-(A-)S-H is moremore » deformable due to the softer interlayer opening but stiffens with decreased spacing and/or increased zeolitic water and Ca 2+ of the interlayer. Dreierketten chain cross-links act as ‘columns’ to resist compression, thus increasing the bulk modulus of C-(A-)S-H. We provide the first experimental evidence on the influence of the Al-induced atomistic configurational change on the mechanical properties of C-(A-)S-H. Our work advances the fundamental knowledge of C-(A-)S-H on the lowest level of its hierarchical structure, and thus can impact the way that innovative C-(A-)S-H-based cementitious materials are developed using a ‘bottom-up’ approach.« less

Remarkable effect of halogenation of aromatic compounds on efficiency of nanowire formation through polymerization/crosslinking by high-energy single particle irradiation

NASA Astrophysics Data System (ADS)

Horio, Akifumi; Sakurai, Tsuneaki; Kayama, Kazuto; Lakshmi, G. B. V. S.; Kumar Avasthi, Devesh; Sugimoto, Masaki; Yamaki, Tetsuya; Chiba, Atsuya; Saito, Yuichi; Seki, Shu

2018-01-01

Irradiation of high-energy ion particles on organic films induced solid-state polymerization and crosslinking reactions of the materials along the ion trajectories, resulting in the formation of insoluble uniform nanowires with a precise diameter. The nanowires were isolated by the development process i.e. the irradiated film was immersed in organic solvents, and their morphology was visualized by atomic force microscopy. The target organic materials are 4-vinyltriphenylamine, poly(4-vinyltriphenylamine), and polystyrene derivatives with/without the partial substitutions by halogen atoms. It was found that 4-vinyltriphenylamines, in spite of their small molecular sizes, afforded nanowires more clearly than poly(4-vinyltriphenylamine)s. Moreover, the efficiency of demonstrated polymerization/crosslinking reactions obviously depends on the substituted halogen atom species. The averaged diameters of nanowires from bromo- or iodo- substituted 4-vinyltriphenylamine (9.3 and 9.4 nm, respectively) were larger than that obtained from simple 4-vinyltriphenylamine (6.8 nm). The remarkable effect of halogenation of aromatic compounds on the efficiency of the radiation-induced reactions was also observed for polystyrene derivatives. This contrast was considered to originate from the sum of the efficiency of elementary reactions including dissociative electron attachment.

Nanogels from Metal-Chelating Crosslinkers as Versatile Platforms Applied to Copper-64 PET Imaging of Tumors and Metastases

DOE PAGES

Lux, Jacques; White, Alexander G.; Chan, Minnie; ...

2015-01-01

Metals are essential in medicine for both therapy and diagnosis. We recently created the first metal-chelating nanogel imaging agent, which employed versatile, reproducible chemistry that maximizes chelation stability. Here we demonstrate that our metal chelating crosslinked nanogel technology is a powerful platform by incorporating 64Cu to obtain PET radiotracers. Polyacrylamide-based nanogels were crosslinked with three different polydentate ligands (DTPA, DOTA, NOTA). NOTA-based nanogels stably retained 64Cu in mouse serum and accumulated in tumors in vivo as detected by PET/CT imaging. Measurement of radioactivity in major organs ex vivo confirmed this pattern, revealing a high accumulation (12.3% ID/g and 16.6% ID/g)more » in tumors at 24 and 48 h following administration, with lower accumulation in the liver (8.5% ID/g at 24 h) and spleen (5.5% ID/g). Nanogels accumulated even more efficiently in metastases (29.9% and 30.4% ID/g at 24 and 48 h). These metal-chelating nanogels hold great promise for future application as bimodal PET/MRI agents; chelation of β-emitting radionuclides could enable radiation therapy.« less

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.

Computational Design of Epoxy/ Boron Carbide Nanocomposites for Radiation Shielding Applications

NASA Astrophysics Data System (ADS)

Bejagam, Karteek; Galehdari, Nasim; Espinosa, Ingrid; Deshmukh, Sanket A.; Kelkar, Ajit D.

An individual working in industries that include nuclear power plants, healthcare industry, and aerospace are knowingly or unknowingly exposed to radiations of different energies. Exposure to high-energy radiations such as α/ β particle emissions or gamma ray electromagnetic radiations enhances the health risks that can lead to carcinogenesis, cardiac problems, cataracts, and other acute radiation syndromes. The best possible solution to protect one from the exposure to radiations is shielding. In the present study, we have developed a new algorithm to generate a range of different structures of Diglycidyl Ether of Bisphenol F (EPON 862) and curing agent Diethylene Toluene Diamine (DETDA) resins with varying degrees of crosslinking. 3, 5, and 10 weight percent boron carbide was employed as filling materials to study its influence on the thermal and mechanical properties of composite. We further conduct the reactive molecular dynamics (RMD) simulations to investigate the effect of radiation exposure on the structural, physical, and mechanical properties of these Epoxy/Boron Carbide nanocomposites. Where possible the simulation results were compared with the experimental data.

Effect of Ex Vivo Ionizing Radiation on Static and Fatigue Properties of Mouse Vertebral Bodies

NASA Technical Reports Server (NTRS)

Emerzian, Shannon R.; Pendleton, Megan M.; Li, Alfred; Liu, Jennifer W.; Alwood, Joshua S.; O’Connell, Grace D.; Keaveny, Tony M.

2018-01-01

For a variety of medical and scientific reasons, human bones can be exposed to a wide range of ionizing radiation levels. In vivo radiation therapy (0.05 kGy) is used in cancer treatment, and ex vivo irradiation (25-35 kGy) is used to sterilize bone allografts. Ionizing radiation in these applications has been shown to increase risk of fracture, decrease bone quality and degrade collagen integrity. Past studies have investigated the deleterious effects of radiation on cortical or trabecular bone specimens individually, but to date no studies have examined whole bones containing both cortical and trabecular tissue. Furthermore, a clear relationship between the dose and the mechanical and biochemical response of bone's extracellular matrix has yet to be established for doses ranging from cancer therapy to allograft sterilization (0.05-35 kGy). To gain insight into these issues, we conducted an ex vivo radiation study to investigate non-cellular (i.e. matrix) effects of ionizing radiation dose on vertebral whole bone mechanical properties, over a range of radiation doses (0.05-35 kGy), with a focus on any radiation-induced changes in collagen. With underlying mechanisms of action in mind, we hypothesized that any induced reductions in mechanical properties would be associated with changes in collagen integrity. METHODS: 20-week old female mice were euthanized and the lumbar spine was dissected using IACUC approved protocols. The lumbar vertebrae (L1- S1) were extracted from the spine via cuts through adjacent intervertebral discs, and the endplates, posterior processes, surrounding musculature, and soft tissues were removed (approx. 1.5mm diameter, approx. 2mm height). Specimens were randomly assigned to one of five groups for ex vivo radiation exposure: x-ray irradiation at 0.05, 1, 17, or 35 kGy, or a 0 kGy control. Following irradiation, the vertebrae were imaged using microcomputed tomography (micro-CT) and then subjected to either monotonic compressive loading to failure or uniform cyclic compressive loading. During cyclic testing, samples were loaded in force control to a force level that corresponded to a strain of 0.46%, as determined in advance by a linearly elastic micro-CT-based finite element analysis for each specimen. Tests were stopped at imminent fracture, defined as a rapid increase in strain. The main outcome for the monotonic test was the strength (maximum force); for cyclic testing it was the fatigue life (log of the number of cycles of loading at imminent failure). A fluorometric assay was used on the S1 vertebrae to measure the number of non-enzymatic collagen crosslinks[4]. A one-way ANOVA was performed on mechanical properties and collagen crosslinks; means were compared with controls using Dunnett's method, with a Tukey-Kramer post-hoc analysis when significance was found (p < or = 0.05). RESULTS: Compared to the unirradiated control group, the concentration of non-enzymatic collagen crosslinks was significantly increased for all irradiated groups (p < 0.0001), and being higher by at least 50% (Figure 1a). By contrast, the radiation effects on the collagen were only evident at the higher doses. For irradiation exposures of 17 kGy or more, strength decreased substantially as the radiation level was increased, but no effect was evident below 17 kGy (Figure 1b). There was no significant change in the stiffness or maximum displacement for any radiation dose (p>0.05). The finite element analysis prescribed force level for cyclic loading exceeded the measured (monotonic) strength of the 17 and 35 kGy irradiated groups (mean +/- SD, 20.6 +/- 5.6 N; 13.2 +/- 3.7 N, respectively) and therefore these groups were eliminated from the fatigue study. The fatigue life for the 0.05 and 1 kGy groups were similar to each other and were not statistically significantly different from the control group (Figure 1c).

Two-photon induced collagen cross-linking in bioartificial cardiac tissue

NASA Astrophysics Data System (ADS)

Kuetemeyer, Kai; Kensah, George; Heidrich, Marko; Meyer, Heiko; Martin, Ulrich; Gruh, Ina; Heisterkamp, Alexander

2011-08-01

Cardiac tissue engineering is a promising strategy for regenerative therapies to overcome the shortage of donor organs for transplantation. Besides contractile function, the stiffness of tissue engineered constructs is crucial to generate transplantable tissue surrogates with sufficient mechanical stability to withstand the high pressure present in the heart. Although several collagen cross-linking techniques have proven to be efficient in stabilizing biomaterials, they cannot be applied to cardiac tissue engineering, as cell death occurs in the treated area. Here, we present a novel method using femtosecond (fs) laser pulses to increase the stiffness of collagen-based tissue constructs without impairing cell viability. Raster scanning of the fs laser beam over riboflavin-treated tissue induced collagen cross-linking by two-photon photosensitized singlet oxygen production. One day post-irradiation, stress-strain measurements revealed increased tissue stiffness by around 40% being dependent on the fibroblast content in the tissue. At the same time, cells remained viable and fully functional as demonstrated by fluorescence imaging of cardiomyocyte mitochondrial activity and preservation of active contraction force. Our results indicate that two-photon induced collagen cross-linking has great potential for studying and improving artificially engineered tissue for regenerative therapies.

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Industrial uses of radiation processing in Belgium

NASA Astrophysics Data System (ADS)

Lacroix, J. P.

Since 1979, the Irradiation Department of IRE, in conjunction with universities and the industrial sector, has set up an extensive programme of research, development and promotion of the radiation process applied to cross-linking and polymerization of plastics, to waste treatment and to food preservation. Starting from scratch, it is thanks to our research in this last-mentioned field that we have been able to develop and to increase the application of the irradiation process within the food industry. At present, two irradiation facilities of a total design capacity of 2.5 10 6 Ci irradiate 24 hours per day mostly for the agro-industry.

Deformable microparticles with multiple functions for drug delivery and device testing

NASA Astrophysics Data System (ADS)

Thula, Taili T.

Since the HIV epidemic of the 1990s, researchers have attempted to develop a red blood cell analog. Even though some of these substitutes are now in Phase III of clinical trials, their use is limited by side effects and short half-life in the human body. As a result, there is still a need for an effective erythrocyte analog with minimum immunogenic and side effects, so that it can be used for multiple applications. Finding new approaches to develop more efficient blood substitutes will not only bring valuable advances in the clinical approach, but also in the area of in vitro testing of medical devices. We examined the feasibility of creating a deformable multi-functional, biodegradable, biocompatible particle for applications in drug delivery and device testing. As a preliminary evaluation, we synthesized different types of microcapsules using natural and synthetic polymers, various cross-linking agents, and diverse manufacturing techniques. After fully characterizing of each system, we determined the most promising red blood cell analog in terms of deformability, stability and toxicity. We also examined the encapsulation and release of bovine serum albumin (BSA) within these deformable particles. After removal of cross-linkers, zinc- and copper-alginate microparticles surrounded by multiple polyelectrolyte layers of chitosan oligosaccharide and alginate were deformable and remained stable under physiological pressures applied by the micropipette technique. In addition, multiple coatings decreased toxicity of heavy-metal crosslinked particles. BSA encapsulation and release from chitosan-alginate microspheres were contingent on the crosslinker and number of polyelectrolyte coatings, respectively. Further rheological studies are needed to determine how closely these particles simulate the behavior of erythrocytes. Also, studies on the encapsulation and release of different proteins, including hemoglobin, are needed to establish the desired controlled release of bioactive agents for the proposed delivery system.

Radiation and temperature effects on the time-dependent response of T300/934 graphite/epoxy

NASA Technical Reports Server (NTRS)

Yancey, Robert N.; Pindera, Marek-Jerzy

1988-01-01

A time-dependent characterization study was performed on T300/934 graphite/epoxy in a simulated space environment. Creep tests on irradiated and nonirradiated graphite/epoxy and bulk resin specimens were carried out at temperatures of 72 and 250 F. Irradiated specimens were exposed to dosages of penetrating electron radiation equal to 30 years exposure at GEO-synchronous orbit. Radiation was shown to have little effect on the creep response of both the composite and bulk resin specimens at 72 F while radiation had a significant effect at 250 F. A healing process was shown to be present in the irradiated specimens where broken bonds in the epoxy due to radiation recombined over time to form cross-links in the 934 resin structure. An analytical micromechanical model was also developed to predict the viscoelastic response of fiber reinforced composite materials. The model was shown to correlate well with experimental results for linearly viscoelastic materials with relatively small creep strains.

Anatomic Mesenchymal Stem Cell-Based Engineered Cartilage Constructs for Biologic Total Joint Replacement

PubMed Central

Saxena, Vishal; Kim, Minwook; Keah, Niobra M.; Neuwirth, Alexander L.; Stoeckl, Brendan D.; Bickard, Kevin; Restle, David J.; Salowe, Rebecca; Wang, Margaret Ye; Steinberg, David R.

2016-01-01

Cartilage has a poor healing response, and few viable options exist for repair of extensive damage. Hyaluronic acid (HA) hydrogels seeded with mesenchymal stem cells (MSCs) polymerized through UV crosslinking can generate functional tissue, but this crosslinking is not compatible with indirect rapid prototyping utilizing opaque anatomic molds. Methacrylate-modified polymers can also be chemically crosslinked in a cytocompatible manner using ammonium persulfate (APS) and N,N,N′,N′-tetramethylethylenediamine (TEMED). The objectives of this study were to (1) compare APS/TEMED crosslinking with UV crosslinking in terms of functional maturation of MSC-seeded HA hydrogels; (2) generate an anatomic mold of a complex joint surface through rapid prototyping; and (3) grow anatomic MSC-seeded HA hydrogel constructs using this alternative crosslinking method. Juvenile bovine MSCs were suspended in methacrylated HA (MeHA) and crosslinked either through UV polymerization or chemically with APS/TEMED to generate cylindrical constructs. Minipig porcine femoral heads were imaged using microCT, and anatomic negative molds were generated by three-dimensional printing using fused deposition modeling. Molded HA constructs were produced using the APS/TEMED method. All constructs were cultured for up to 12 weeks in a chemically defined medium supplemented with TGF-β3 and characterized by mechanical testing, biochemical assays, and histologic analysis. Both UV- and APS/TEMED-polymerized constructs showed increasing mechanical properties and robust proteoglycan and collagen deposition over time. At 12 weeks, APS/TEMED-polymerized constructs had higher equilibrium and dynamic moduli than UV-polymerized constructs, with no differences in proteoglycan or collagen content. Molded HA constructs retained their hemispherical shape in culture and demonstrated increasing mechanical properties and proteoglycan and collagen deposition, especially at the edges compared to the center of these larger constructs. Immunohistochemistry showed abundant collagen type II staining and little collagen type I staining. APS/TEMED crosslinking can be used to produce MSC-seeded HA-based neocartilage and can be used in combination with rapid prototyping techniques to generate anatomic MSC-seeded HA constructs for use in filling large and anatomically complex chondral defects or for biologic joint replacement. PMID:26871863

Wear Measurement of Highly Cross-linked UHMWPE using a 7Be Tracer Implantation Technique

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

Wimmer, Markus A.; Laurent, Michael P.; Dwivedi, Yasha

2013-01-01

The very low wear rates achieved with the current highly cross-linked ultrahigh molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are there- fore being explored. The purpose of this study was to perform a proof-of-concept experiment on the use of the radioactive tracer beryllium-7 (7Be) for the determination of in vitro wear in a highly cross-linked orthopedic UHMWPE. Three cross-linked and four conventional UHMWPE pins made from compression- molded GUR 1050, were activated with 109 to 1010 7Be nuclei using a new implantation setup that produced a homogenousmore » distribution of implanted nuclei up to 8.5 lm below the surface. The pins were tested for wear in a six-station pin-on-flat appara- tus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and esti- mated to be 17 6 3 lg per million cycles. The conventional-to- cross-linked ratio of the wear rates was 13.1 6 0.8, in the expected range for these materials. Oxidative degradation dam- age from implantation was negligible; however, a weak depend- ence of wear on implantation dose was observed limiting the number of radioactive tracer atoms that can be introduced. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.« less

Novel laser communications transceiver with internal gimbal-less pointing and tracking

NASA Astrophysics Data System (ADS)

Chalfant, Charles H., III; Orlando, Fred J., Jr.; Gregory, Jeff T.; Sulham, Clifford; O'Neal, Chad B.; Taylor, Geoffrey W.; Craig, Douglas M.; Foshee, James J.; Lovett, J. Timothy

2002-12-01

This paper describes a novel laser communications transceiver for use in multi-platform satellite networks or clusters that provides internal pointing and tracking technique allowing static mounting of the transceiver subsystems and minimal use of mechanical stabilization techniques. This eliminates the need for the large, power hungry, mechanical gimbals that are required for laser cross-link pointing, acquisition and tracking. The miniature transceiver is designed for pointing accuracies required for satellite cross-link distances of between 500 meters to 5000 meters. Specifically, the designs are targeting Air Force Research Lab's TechSat21 Program, although alternative transceiver configurations can provide for much greater link distances and other satellite systems. The receiver and transmitter are connected via fiber optic cabling from a separate electronics subsystem containing the optoelectronics PCBs, thereby eliminating active optoelectronic elements from the transceiver's mechanical housing. The internal acquisition and tracking capability is provided by an advanced micro-electro-mechanical system (MEMS) and an optical design that provides a specific field-of-view based on the satellite cluster's interface specifications. The acquisition & tracking control electronics will utilize conventional closed loop tracking techniques. The link optical power budget and optoelectronics designs allow use of transmitter sources with output powers of near 100 mW. The transceiver will provide data rates of up to 2.5 Gbps and operate at either 1310 nm or 1550 nm. In addition to space-based satellite to satellite cross-links, we are planning to develop a broad range of applications including air to air communications between highly mobile airborne platforms and terrestrial fixed point to point communications.

Using a surrogate contact pair to evaluate polyethylene wear in prosthetic knee joints.

PubMed

Sanders, Anthony P; Lockard, Carly A; Weisenburger, Joel N; Haider, Hani; Raeymaekers, Bart

2016-01-01

With recent improvements to the properties of ultra-high molecular weight polyethylene (UHMWPE) used in joint replacements, prosthetic knee and hip longevity may extend beyond two decades. However, it is difficult and costly to replicate such a long in vivo lifetime using clinically relevant in vitro wear testing approaches such as walking gait joint simulators. We advance a wear test intermediate in complexity between pin-on-disk and knee joint simulator tests. The test uses a surrogate contact pair, consisting of a surrogate femoral and tibial specimen that replicate the contact mechanics of any full-scale knee condyle contact pair. The method is implemented in a standard multi-directional pin-on-disk wear test machine, and we demonstrate its application via a two-million-cycle wear test of three different UHMWPE formulations. Further, we demonstrate the use of digital photography and image processing to accurately quantify fatigue damage based on the reduced transmission of light through a damage area in a UHMWPE specimen. The surrogate contact pairs replicate the knee condyle contact areas within -3% to +12%. The gravimetric wear test results reflect the dose of crosslinking radiation applied to the UHMWPE: 35 kGy yielded a wear rate of 7.4 mg/Mcycles, 55 kGy yielded 1.0 mg/Mcycles, and 75 kGy (applied to a 0.1% vitamin E stabilized UHMWPE) yielded 1.5 mg/Mcycles. A precursor to spalling fatigue is observed and precisely measured in the radiation-sterilized (35 kGy) and aged UHMWPE specimen. The presented techniques can be used to evaluate the high-cycle fatigue performance of arbitrary knee condyle contact pairs under design-specific contact stresses, using existing wear test machines. This makes the techniques more economical and well-suited to standardized comparative testing. © 2015 Wiley Periodicals, Inc.

Dimensional Stabilization of Wood In Use

Treesearch

R. M. Rowell; R. L. Youngs

1981-01-01

Many techniques have been devised to reduce the tendency of wood to change dimensions in contact with moisture. Treatments such as cross-lamination, water-resistant coatings, hygroscopicity reduction, crosslinking, and bulking are reviewed and recommendations for future research are given.

Potential apoptotic effect of ultraviolet-A irradiation during cross-linking: a study on ex vivo cultivated limbal epithelial cells.

PubMed

Matalia, Himanshu; Shetty, Rohit; Dhamodaran, Kamesh; Subramani, Murali; Arokiaraj, Vincent; Das, Debashish

2012-10-01

To study the effects of ultraviolet-A (UV-A) irradiation, in the presence or absence of riboflavin, on ex vivo cultured limbal epithelial cells (LECs). The study was carried out in a super specialty ophthalmic hospital. Ex vivo cultured LECs were grown on denuded amniotic membranes and exposed to similar levels of UV-A radiation used during corneal cross-linking (CXL), in the presence or absence of the photosensitiser, riboflavin. These cells were then used for extraction of RNA, cDNA conversion, and antibody staining. Quantitative PCR and immunofluorescence staining were performed to evaluate the apoptotic state of treated and non-treated LECs. Statistical analyses were evaluated using a Student's t test. We found that bcl-2, an antiapoptotic gene, was downregulated, whereas, bax, a proapoptotic gene, was upregulated. After LECs were exposed to UV-A radiation, a significant upregulation of both caspase 3 and caspase 9 was observed in treated cells when compared with untreated LECs. These results indicate that exposure of LECs to UV-A dosages similar to those used in the CXL procedure promotes the expression of genes known to promote apoptosis. In the presence of riboflavin, the damage caused by UV-A treatment was marginalised, but not totally blocked.

Sources of background light on space based laser communications links

NASA Astrophysics Data System (ADS)

Farrell, Thomas C.

2018-05-01

We discuss the sources and levels of background light that should be expected on space based laser communication (lasercom) crosslinks and uplinks, as well as on downlinks to ground stations. The analyses are valid for both Earth orbiting satellites and inter-planetary links. Fundamental equations are derived suitable for first order system engineering analyses of potential lasercom systems. These divide sources of background light into two general categories: extended sources which fill the field of view of a receiver's optics, and point sources which cannot be resolved by the optics. Specific sources of background light are discussed, and expected power levels are estimated. For uplinks, reflected sunlight and blackbody radiation from the Earth dominates. For crosslinks, depending on specific link geometry, sources of background light may include the Sun in the field of view (FOV), reflected sunlight and blackbody radiation from planets and other bodies in the solar system, individual bright stars in the FOV, the amalgam of dim stars in the FOV, zodiacal light, and reflected sunlight off of the transmitting spacecraft. For downlinks, all of these potentially come into play, and the effects of the atmosphere, including turbulence, scattering, and absorption contribute as well. Methods for accounting for each of these are presented. Specific examples are presented to illustrate the relative contributions of each source for various link geometries.

Exploring the influence of radiation crosslinking on high-performance hydrogenated acrylonitrile butadiene rubber and polyamide 12 based blends with special reference to heat and oil resistance

NASA Astrophysics Data System (ADS)

Mohammed Reffai, Syed Ismail Syed; Chatterjee, Tuhin; Naskar, Kinsuk

2018-07-01

This paper reports the heat and oil resistant hydrogenated acrylonitrile butadiene rubber (HNBR)/Polyamide 12 (PA12) blends prepared by electron beam irradiation. Electron beam irradiated blends are characterized by processing behaviour like thermoplastic at elevated temperature and performance properties of vulcanized rubber at ambient temperature. In the present work, a new class of blends based on Hydrogenated acrylonitrile butadiene rubber (HNBR) and polyamide (PA12) has been developed. The blends are cured with different radiation dosage at a fixed blend ratio (70:30) of (HNBR/PA12). The blend having the 75 kGy shows the highest level of mechanical properties as well as superior thermal stability. Dynamic mechanical analysis (DMA) also demonstrates the tanδ values of all the blends are lower and the storage modules are higher for HE-75 kGy blend system compared to other blend system. Heat aging, oil aging, oil swelling and cross-link density study have also been carried out in details to understand the performance behaviour of these blends at service condition (150 °C). These blends are considered to find potential application in automotive sector especially for automotive under-the-hood-applications.

Use of radiation in biomaterials science

NASA Astrophysics Data System (ADS)

Benson, Roberto S.

2002-05-01

Radiation is widely used in the biomaterials science for surface modification, sterilization and to improve bulk properties. Radiation is also used to design of biochips, and in situ photopolymerizable of bioadhesives. The energy sources most commonly used in the irradiation of biomaterials are high-energy electrons, gamma radiation, ultraviolet (UV) and visible light. Surface modification involves placement of selective chemical moieties on the surface of a material by chemical reactions to improve biointeraction for cell adhesion and proliferation, hemocompatibility and water absorption. The exposure of a polymer to radiation, especially ionizing radiation, can lead to chain scission or crosslinking with changes in bulk and surface properties. Sterilization by irradiation is designed to inactivate most pathogens from the surface of biomedical devices. An overview of the use of gamma and UV radiation to improve surface tissue compatibility, bulk properties and surface properties for wear resistance, formation of hydrogels and curing dental sealants and bone adhesives is presented. Gamma and vacuum ultraviolet (VUV) irradiated ultrahigh molecular weight polyethylene (UHMWPE) exhibit improvement in surface modulus and hardness. The surface modulus and hardness of UHMWPE showed a dependence on type of radiation, dosage and processing. VUV surface modified e-PTFE vascular grafts exhibit increases in hydrophilicity and improvement towards adhesion of fibrin glue.

Tuning chemical and physical cross-links in silk electrogels for morphological analysis and mechanical reinforcement.

PubMed

Lin, Yinan; Xia, Xiaoxia; Shang, Ke; Elia, Roberto; Huang, Wenwen; Cebe, Peggy; Leisk, Gary; Omenetto, Fiorenzo; Kaplan, David L

2013-08-12

Electrochemically controlled, reversible assembly of biopolymers into hydrogel structures is a promising technique for on-demand cell or drug encapsulation and release systems. An electrochemically sol-gel transition has been demonstrated in regenerated Bombyx mori silk fibroin, offering a controllable way to generate biocompatible and reversible adhesives and other biomedical materials. Despite the involvement of an electrochemically triggered electrophoretic migration of the silk molecules, the mechanism of the reversible electrogelation remains unclear. It is, however, known that the freshly prepared silk electrogels (e-gels) adopt a predominantly random coil conformation, indicating a lack of cross-linking as well as thermal, mechanical, and morphological stabilities. In the present work, the tuning of covalent and physical β-sheet cross-links in silk hydrogels was studied for programming the structural properties. Scanning electron microscopy (SEM) revealed delicate morphology, including locally aligned fibrillar structures, in silk e-gels, preserved by combining glutaraldehyde-cross-linking and ethanol dehydration. Fourier transform infrared (FTIR) spectroscopic analysis of either electrogelled, vortex-induced or spontaneously formed silk hydrogels showed that the secondary structure of silk e-gels was tunable between non-β-sheet-dominated and β-sheet-dominated states. Dynamic oscillatory rheology confirmed the mechanical reinforcement of silk e-gels provided by controlled chemical and physical cross-links. The selective incorporation of either chemical or physical or both cross-links into the electrochemically responsive, originally unstructured silk e-gel should help in the design for electrochemically responsive protein polymers.

Ribose mediated crosslinking of collagen-hydroxyapatite hybrid scaffolds for bone tissue regeneration using biomimetic strategies.

PubMed

Krishnakumar, Gopal Shankar; Gostynska, Natalia; Campodoni, Elisabetta; Dapporto, Massimiliano; Montesi, Monica; Panseri, Silvia; Tampieri, Anna; Kon, Elizaveta; Marcacci, Maurilio; Sprio, Simone; Sandri, Monica

2017-08-01

This study explores for the first time the application of ribose as a highly biocompatible agent for the crosslinking of hybrid mineralized constructs, obtained by bio-inspired mineralization of self-assembling Type I collagen matrix with magnesium-doped-hydroxyapatite nanophase, towards a biomimetic mineralized 3D scaffolds (MgHA/Coll) with excellent compositional and structural mimicry of bone tissue. To this aim, two different crosslinking mechanisms in terms of pre-ribose glycation (before freeze drying) and post-ribose glycation (after freeze drying) were investigated. The obtained results explicate that with controlled freeze-drying, highly anisotropic porous structures with opportune macro-micro porosity are obtained. The physical-chemical features of the scaffolds characterized by XRD, FTIR, ICP and TGA demonstrated structural mimicry analogous to the native bone. The influence of ribose greatly assisted in decreasing solubility and increased enzymatic resistivity of the scaffolds. In addition, enhanced mechanical behaviour in response to compressive forces was achieved. Preliminary cell culture experiments reported good cytocompatibility with extensive cell adhesion, proliferation and colonization. Overall, scaffolds developed by pre-ribose glycation process are preferred, as the related crosslinking technique is more facile and robust to obtain functional scaffolds. As a proof of concept, we have demonstrated that ribose crosslinking is cost-effective, safe and functionally effective. This study also offers new insights and opportunities in developing promising scaffolds for bone tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

Relating microstructure to rheology of a bundled and cross-linked F-actin network in vitro

NASA Astrophysics Data System (ADS)

Shin, J. H.; Gardel, M. L.; Mahadevan, L.; Matsudaira, P.; Weitz, D. A.

2004-06-01

The organization of individual actin filaments into higher-order structures is controlled by actin-binding proteins (ABPs). Although the biological significance of the ABPs is well documented, little is known about how bundling and cross-linking quantitatively affect the microstructure and mechanical properties of actin networks. Here we quantify the effect of the ABP scruin on actin networks by using imaging techniques, cosedimentation assays, multiparticle tracking, and bulk rheology. We show how the structure of the actin network is modified as the scruin concentration is varied, and we correlate these structural changes to variations in the resultant network elasticity.

Gamma radiation effects on polydimethylsiloxane rubber foams under different radiation conditions

NASA Astrophysics Data System (ADS)

Sui, H. L.; Liu, X. Y.; Zhong, F. C.; Li, X. Y.; Wang, L.; Ju, X.

2013-07-01

Polydimethylsiloxane rubber foams were irradiated by gamma ray under different radiation conditions designed by orthogonal design method. Compression set measurement, infrared attenuated total reflectance spectroscopy (ATR) and X-ray induced photoelectron spectroscopy (XPS) were used. Three aging factors' influence effects on the mechanical property and chemical structure were studied. It was found that among the three factors and the chosen levels, both properties were affected most by radiation dose, while radiation dose rate had no obvious influence on both properties. The stiffening of the rubber foams was caused by cross-linking reactions in the Si-CH3. At the same radiation dose, the rigidity of the foams irradiated in air was lower than that in nitrogen. When polydimethylsiloxane was irradiated at a high dose in sealed nitrogen atmosphere, carbon element distribution would be changed. Hydrocarbons produced by gamma ray in the sealed tube would make the carbon content in the skin-deep higher than that in the middle, which indicated that polydimethylsiloxane rubber foams storing in a sealed atmosphere filled with enough hydrocarbons should be helpful to extend the service life.

Photothermal triggering of self-healing processes applied to the reparation of bio-based polymer networks

NASA Astrophysics Data System (ADS)

Altuna, F. I.; Antonacci, J.; Arenas, G. F.; Pettarin, V.; Hoppe, C. E.; Williams, R. J. J.

2016-04-01

Green laser irradiation successfully activated self-healing processes in epoxy-acid networks modified with low amounts of gold nanoparticles (NPs). A bio-based polymer matrix, obtained by crosslinking epoxidized soybean oil (ESO) with an aqueous citric acid (CA) solution, was self-healed through molecular rearrangements produced by transesterification reactions of β-hydroxyester groups generated in the polymerization reaction. The temperature increase required for the triggering of these thermally activated reactions was attained by green light irradiation of the damaged area. Compression force needed to assure a good contact between crack faces was achieved by volume dilatation generated by the same temperature rise. Gold NPs dispersed in the polymer efficiently generated heat in the presence of electromagnetic radiation under plasmon resonance, acting as nanometric heating sources and allowing remote activation of the self-healing in the crosslinked polymer.

Effect of radiation, heat, and aging on in vitro wear resistance of polyethylene.

PubMed

Muratoglu, Orhun K; Merrill, Edward W; Bragdon, Charles R; O'Connor, Daniel; Hoeffel, Daniel; Burroughs, Brian; Jasty, Murali; Harris, William H

2003-12-01

Radiation cross-linking increases the wear resistance of polyethylene used in total hip replacement. Radiation also generates residual free radicals, which are detrimental to long-term properties of polyethylene. Two approaches are used to stabilize the residual free radicals and terminally sterilize the components. One is postirradiation annealing with gas sterilization and the other is postirradiation melting with gamma sterilization in nitrogen. The hypothesis of the current study is that postirradiation annealing followed by gamma sterilization in nitrogen will result in more free radicals in polyethylene than gamma sterilization either in air or in nitrogen alone. To test this hypothesis, concentration of residual free radicals was quantified in polyethylene that was annealed and gamma sterilized in nitrogen and control polyethylenes gamma sterilized in air versus in nitrogen. Three crosslinked polyethylenes that were melted and gas sterilized also were included in the study. The effects of residual free radicals were studied by accelerated aging. Oxidation levels and weight loss in bidirectional pin-on-disk tests were determined before and after aging. Polyethylene that was subjected to postirradiation annealing and gamma sterilization resulted in 58% more residual free radicals than control polyethylenes. Weight loss of the annealed polyethylene increased by 16-fold on accelerated aging and had three times higher oxidation levels than that measured in control polyethylenes after aging. In contrast, polyethylenes that were stabilized with postirradiation melting and terminally gas sterilized showed no detectable residual free radicals. Accelerated aging did not affect the weight loss and oxidation levels of melted polyethylenes.

Customized Corneal Cross-Linking-A Mathematical Model.

PubMed

Caruso, Ciro; Epstein, Robert L; Ostacolo, Carmine; Pacente, Luigi; Troisi, Salvatore; Barbaro, Gaetano

2017-05-01

To improve the safety, reproducibility, and depth of effect of corneal cross-linking with the ultraviolet A (UV-A) exposure time and fluence customized according to the corneal thickness. Twelve human corneas were used for the experimental protocol. They were soaked using a transepithelial (EPI-ON) technique using riboflavin with the permeation enhancer vitamin E-tocopheryl polyethylene glycol succinate. The corneas were then placed on microscope slides and irradiated at 3 mW/cm for 30 minutes. The UV-A output parameters were measured to build a new equation describing the time-dependent loss of endothelial protection induced by riboflavin during cross-linking, as well as a pachymetry-dependent and exposure time-dependent prescription for input UV-A fluence. The proposed equation was used to establish graphs prescribing the maximum UV-A fluence input versus exposure time that always maintains corneal endothelium exposure below toxicity limits. Analysis modifying the Lambert-Beer law for riboflavin oxidation leads to graphs of the maximum safe level of UV-A radiation fluence versus the time applied and thickness of the treated cornea. These graphs prescribe UV-A fluence levels below 1.8 mW/cm for corneas of thickness 540 μm down to 1.2 mW/cm for corneas of thickness 350 μm. Irradiation times are typically below 15 minutes. The experimental and mathematical analyses establish the basis for graphs that prescribe maximum safe fluence and UV-A exposure time for corneas of different thicknesses. Because this clinically tested protocol specifies a corneal surface clear of shielding riboflavin on the corneal surface during UV-A irradiation, it allows for shorter UV-A irradiation time and lower fluence than in the Dresden protocol.

Supermacroporous chemically cross-linked poly(aspartic acid) hydrogels.

PubMed

Gyarmati, Benjámin; Mészár, E Zsuzsanna; Kiss, Lóránd; Deli, Mária A; László, Krisztina; Szilágyi, András

2015-08-01

Chemically cross-linked poly(aspartic acid) (PASP) gels were prepared by a solid-liquid phase separation technique, cryogelation, to achieve a supermacroporous interconnected pore structure. The precursor polymer of PASP, polysuccinimide (PSI) was cross-linked below the freezing point of the solvent and the forming crystals acted as templates for the pores. Dimethyl sulfoxide was chosen as solvent instead of the more commonly used water. Thus larger temperatures could be utilized for the preparation and the drawback of increase in specific volume of water upon freezing could be eliminated. The morphology of the hydrogels was characterized by scanning electron microscopy and interconnectivity of the pores was proven by the small flow resistance of the gels. Compression tests also confirmed the interconnected porous structure and the complete re-swelling and shape recovery of the supermacroporous PASP hydrogels. The prepared hydrogels are of interest for several biomedical applications as scaffolding materials because of their cytocompatibility, controllable morphology and pH-responsive character. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Covalent trapping of human DNA polymerase beta by the oxidative DNA lesion 2-deoxyribonolactone.

PubMed

DeMott, Michael S; Beyret, Ergin; Wong, Donny; Bales, Brian C; Hwang, Jae-Taeg; Greenberg, Marc M; Demple, Bruce

2002-03-08

Oxidized abasic residues in DNA constitute a major class of radiation and oxidative damage. Free radical attack on the nucleotidyl C-1' carbon yields 2-deoxyribonolactone (dL) as a significant lesion. Although dL residues are efficiently incised by the main human abasic endonuclease enzyme Ape1, we show here that subsequent excision by human DNA polymerase beta is impaired at dL compared with unmodified abasic sites. This inhibition is accompanied by accumulation of a protein-DNA cross-link not observed in reactions of polymerase beta with unmodified abasic sites, although a similar form can be trapped by reduction with sodium borohydride. The formation of the stably cross-linked species with dL depends on the polymerase lysine 72 residue, which forms a Schiff base with the C-1 aldehyde during excision of an unmodified abasic site. In the case of a dL residue, attack on the lactone C-1 by lysine 72 proceeds more slowly and evidently produces an amide linkage, which resists further processing. Consequently dL residues may not be readily repaired by "short-patch" base excision repair but instead function as suicide substrates in the formation of protein-DNA cross-links that may require alternative modes of repair.

High-Temperature Shape Memory Polymers

NASA Technical Reports Server (NTRS)

Yoonessi, Mitra; Weiss, Robert A.

2012-01-01

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing radiation ( radiation, neutrons), or by chemical crosslinking to form a covalent permanent network. With respect to other shape memory polymers, this invention is novel in that it describes the use of a thermoplastic composition that can be thermally molded or solution-cast into complex "permanent" shapes, and then reheated or redissolved and recast from solution to prepare another shape. It is also unique in that the shape memory behavior is provided by a non-polymer additive.

Interfacial friction and adhesion of cross-linked polymer thin films swollen with linear chains.

PubMed

Zhang, Qing; Archer, Lynden A

2007-07-03

The preparation and interfacial properties of a new type of tethered, thin-film lubricant coating are presented. These coatings are composed of three components: a dense self-assembled monolayer (SAM) underlayer that presents reactive vinyl groups at its surface; a cross-linked polydimethylsiloxane (PDMS) overlayer that is covalently tethered to the SAM; and free, mobile linear PDMS chains dispersed in the network. We investigate the influence of the molecular weight (Ms) and concentration of the free PDMS chains on the structure and equilibrium swelling properties of the cross-linked films. Using a bead-probe lateral force microscopy measurement technique, we also quantify the interfacial friction and adhesion characteristics of surfaces functionalized with these coatings. We find that both the volume fraction and the molecular weight of free PDMS molecules in the coatings influence their interfacial friction and adhesion properties. For example, the addition of short PDMS chains in dry, cross-linked PDMS thin films yields tethered surface coatings with ultralow friction coefficients (mu = 5.2 x 10(-3)). An analysis based on classical lubrication theory suggests that the reduction in friction force produced by free polymer is a consequence of the gradual separation of asperities on opposing surfaces and the consequent substitution of solid-solid friction by viscous drag of the free polymer chains in the network.

Chitosan-starch beads prepared by ionotropic gelation as potential matrices for controlled release of fertilizers.

PubMed

Perez, Jonas J; Francois, Nora J

2016-09-05

The present study examines the agrochemical application of macrospheres prepared with chitosan and chitosan-starch blends by an easy dripping technique, using a sodium tripolyphosphate aqueous solution as the crosslinking agent. These biopolymers form hydrogels that could be a viable alternative method to obtain controlled-release fertilizers (CRFs). Three different concentrations (ranging from 20 to 100wt/wt% of chitosan) and two crosslinking times (2 or 4h) were used. The resulting polymeric matrices were examined by scanning electron microscopy coupled with energy dispersive X-ray, X-ray diffraction, Fourier transform infrared spectroscopy, solid-state nuclear magnetic resonance, thermogravimetric analysis and differential scanning calorimetry. Ionotropic gelation and neutralization induced the formation of the macrospheres. The crosslinking time and the composition of the polymeric hydrogel controlled the crosslinking degree, the swelling behavior and the fertilizer loading capability. Potassium nitrate-loaded beads were shown to be useful as a controlled-release fertilizer. After 14days of continuous release into distilled water, the cumulative concentration in the release medium reached between 70 and 93% of the initially loaded salt, depending on the matrix used. The prepared beads showed properties that make them suitable for use in the agrochemical industry as CRFs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Versatile peroxidase as a valuable tool for generating new biomolecules by homogeneous and heterogeneous cross-linking.

PubMed

Salvachúa, Davinia; Prieto, Alicia; Mattinen, Maija-Liisa; Tamminen, Tarja; Liitiä, Tiina; Lille, Martina; Willför, Stefan; Martínez, Angel T; Martínez, María Jesús; Faulds, Craig B

2013-05-10

The modification and generation of new biomolecules intended to give higher molecular-mass species for biotechnological purposes, can be achieved by enzymatic cross-linking. The versatile peroxidase (VP) from Pleurotus eryngii is a high redox-potential enzyme with oxidative activity on a wide variety of substrates. In this study, VP was successfully used to catalyze the polymerization of low molecular mass compounds, such as lignans and peptides, as well as larger macromolecules, such as protein and complex polysaccharides. Different analytical, spectroscopic, and rheological techniques were used to determine structural changes and/or variations of the physicochemical properties of the reaction products. The lignans secoisolariciresinol and hydroxymatairesinol were condensed by VP forming up to 8 unit polymers in the presence of organic co-solvents and Mn(2+). Moreover, 11 unit of the peptides YIGSR and VYV were homogeneously cross-linked. The heterogeneous cross-linking of one unit of the peptide YIGSR and several lignan units was also achieved. VP could also induce gelation of feruloylated arabinoxylan and the polymerization of β-casein. These results demonstrate the efficacy of VP to catalyze homo- and hetero-condensation reactions, and reveal its potential exploitation for polymerizing different types of compounds. Copyright © 2013 Elsevier Inc. All rights reserved.

Effects of electron beam irradiation on polyamide 12 with fiberglass reinforcement

NASA Astrophysics Data System (ADS)

Jeun, Joon-Pyo; Shin, Bum-Sik; Kim, Hyun-Bin; Nho, Young-Chang; Kang, Phil-Hyun

2010-06-01

In the present study, the effects of electron beam irradiation of polyamide 12 (PA12) with fiberglass reinforcement on the thermal and wear properties were investigated. Electron beam irradiation of PA 12 was carried out over a range of irradiation doses (100-600 kGy) in air. The gel formation in the presence of a curing agent was dependent on the radiation doses. The thermal properties of irradiated PA 12 were studied in the temperature region 50-250° C to observe the changes in the melting point with radiation dose. The dimensional stability was significantly increased by electron beam irradiation and the related crosslinking of the PA 12.

Accelerated aging and stabilization of radiation-vulcanized EPDM rubber

NASA Astrophysics Data System (ADS)

Basfar, A. A.; Abdel-Aziz, M. M.; Mofti, S.

2000-03-01

The effect of different antioxidants and their mixtures on the thermal aging and accelerated weathering of γ-radiation vulcanized EPDM rubber in presence of crosslinking coagent, was investigated. The compounds used were either a synergistic blend of phenolic and phosphite antioxidants, i.e. 1:4 Irganox 1076: Irgafos 168 or a blend of arylamine and quinoline type antioxidants, i.e. 1:1 IPPD: TMQ, at fixed concentration. Tinuvin 622 LD hindered amine light stabilized (HALS) was also used. The response was evaluated by the tensile strength and elongation at break for irradiated samples after thermal aging at 100°C for 28 days and accelerated weathering (Xenon test) up to 200 h.

Mechanical and thermal properties and morphological studies of 10 MeV electron beam irradiated LDPE/hydroxyapatite nano-composite

NASA Astrophysics Data System (ADS)

Soltani, Z.; Ziaie, F.; Ghaffari, M.; Afarideh, H.; Ehsani, M.

2013-02-01

In this work the nano-composite samples were prepared using the LDPE filled with different weight percentages of hydroxyapatite powder which was synthesized via hydrolysis method. The samples were subjected to irradiation under 10 MeV electron beam in 75-250 kGy doses. Mechanical and thermal properties as well as the morphology of the nano-composite samples were investigated and compared. The hot-set and swelling tests confirmed the radiation crosslinking induced in the polymer matrix especially between the matrix and reinforcement phase. The result indicates that the mechanical and thermal parameters are strongly dependent on the hydroxyapatite content in comparison to radiation.

Effects of electron beam irradiation on polyamide 12 with fiberglass reinforcement

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

Jeun, Joon-Pyo; Shin, Bum-Sik; Kim, Hyun-Bin

2010-06-02

In the present study, the effects of electron beam irradiation of polyamide 12 (PA12) with fiberglass reinforcement on the thermal and wear properties were investigated. Electron beam irradiation of PA 12 was carried out over a range of irradiation doses (100-600 kGy) in air. The gel formation in the presence of a curing agent was dependent on the radiation doses. The thermal properties of irradiated PA 12 were studied in the temperature region 50-250 deg. C to observe the changes in the melting point with radiation dose. The dimensional stability was significantly increased by electron beam irradiation and the relatedmore » crosslinking of the PA 12.« less

The Evolving Contribution of Mass Spectrometry to Integrative Structural Biology

NASA Astrophysics Data System (ADS)

Faini, Marco; Stengel, Florian; Aebersold, Ruedi

2016-06-01

Protein complexes are key catalysts and regulators for the majority of cellular processes. Unveiling their assembly and structure is essential to understanding their function and mechanism of action. Although conventional structural techniques such as X-ray crystallography and NMR have solved the structure of important protein complexes, they cannot consistently deal with dynamic and heterogeneous assemblies, limiting their applications to small scale experiments. A novel methodological paradigm, integrative structural biology, aims at overcoming such limitations by combining complementary data sources into a comprehensive structural model. Recent applications have shown that a range of mass spectrometry (MS) techniques are able to generate interaction and spatial restraints (cross-linking MS) information on native complexes or to study the stoichiometry and connectivity of entire assemblies (native MS) rapidly, reliably, and from small amounts of substrate. Although these techniques by themselves do not solve structures, they do provide invaluable structural information and are thus ideally suited to contribute to integrative modeling efforts. The group of Brian Chait has made seminal contributions in the use of mass spectrometric techniques to study protein complexes. In this perspective, we honor the contributions of the Chait group and discuss concepts and milestones of integrative structural biology. We also review recent examples of integration of structural MS techniques with an emphasis on cross-linking MS. We then speculate on future MS applications that would unravel the dynamic nature of protein complexes upon diverse cellular states.

Single chain technology: Toward the controlled synthesis of polymer nanostructures

NASA Astrophysics Data System (ADS)

Lyon, Christopher

A technique for fabricating advanced polymer nanostructures enjoying recent popularity is the collapse or folding of single polymer chains in highly dilute solution mediated by intramolecular cross-linking. We term the resultant structures single-chain nanoparticles (SCNP). This technique has proven particularly valuable in the synthesis of nanomaterials on the order of 5 -- 20 nm. Many different types of covalent and non-covalent chemistries have been used to this end. This dissertation investigates the use of so-called single-chain technology to synthesize nanoparticles using modular techniques that allow for easy incorporation of functionality or special structural or characteristic features. Specifically, the synthesis of linear polymers functionalized with pendant monomer units and the subsequent intramolecular polymerization of these monomer units is discussed. In chapter 2, the synthesis of SCNP using alternating radical polymerization is described. Polymers functionalized with pendant styrene and stilbene groups are synthesized via a modular post-polymerization Wittig reaction. These polymers were exposed to radical initiators in the presence (and absence) of maleic anhydride and other electron deficient monomers in order to form intramolecular cross-links. Chapter 3 discusses templated acyclic diene metathesis (ADMET) polymerization using single-chain technology, starting with the controlled ring-opening polymerization of a glycidyl ether functionalized with an ADMET monomer. This polymer was then exposed to Grubbs' catalyst to polymerize the ADMET monomer units. The ADMET polymer was hydrolytically cleaved from the template and separated. Upon characterization, it was found that the daughter ADMET polymer had a similar degree of polymerization, but did not retain the low dispersity of the template. Chapter 4 details the synthesis of aldehyde- and diol-functionalized polymers toward the synthesis of SCNP containing dynamic, acid-degradable acetal cross-links. SCNP fabrication with these materials is beyond the scope of this dissertation.

Morphology of Thermally Degraded PU and Irradiated PE

NASA Astrophysics Data System (ADS)

Harris, Douglas; Gillen, Kenneth; Celina, Mathias; Assink, Roger

2001-03-01

Several 1H and 13C NMR techniques have been applied to study the morphology and chemical structure of thermally degraded polyurethane rubber and irradiated polyethylene cable insulation. The combination of heat and presence of air results in oxidation of the hydroxyl-terminated polybutadiene/isophorone diisocyanate polyurethane and the gel content increases. The oxidation is inhomogeneous: pristine regions remain with a length scale of approximately 20 nm. The morphology and oxidation products were characterized by 1H spin diffusion with 13C detection. In addition, dynamics were probed with 1H and 2D WISE experiments. Radiation of cross-linked polyethylene cable insulation obeys anomalous aging behavior where lower temperature can result in a greater loss in ultimate tensile elongation. Annealing of the irradiated polyethylene allows significant recovery of mechanical properties. Analysis of 13C NMR data was used to study this "Lazarus effect" and the inverse temperature relationship. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under Contract DE-AC04-94AL8500.

Radiation synthesis of superabsorbent CMC based hydrogels for agriculture applications

NASA Astrophysics Data System (ADS)

Raafat, Amany I.; Eid, Mona; El-Arnaouty, Magda B.

2012-07-01

A series of superabsorbent hydrogel based on carboxymethylcellulose (CMC) and polyvinylpyrrolidone (PVP) crosslinked with gamma irradiation have been proposed for agriculture application. The effect of preparation conditions such as feed solution composition and absorbed irradiation dose on the gelation and swelling degree was evaluated. The structure and the morphology of the superabsorbent CMC/PVP hydrogel were characterized using Fourier transform infrared spectroscopy technique (FTIR), and scanning electron microscope (SEM). Effect of ionic strength and cationic and anionic kinds on the swelling behavior of the obtained hydrogel was investigated. Urea as an agrochemical model was loaded onto the obtained hydrogel to provide nitrogen (N) nutrients. The water retention capability and the urea release behavior of the CMC/PVP hydrogels were investigated. It was found that, the obtained CMC/PVP hydrogels have good swelling degree that greatly affected by its composition and absorbed dose. The swelling was also extremely sensitive to the ionic strength and cationic kind. Owing to its considerable slow urea release, good water retention capacity, being economical, and environment-friendly, it might be useful for its application in agriculture field.

An investigation of the curing process for moisture-crosslinkable polyethylene used in cable coating extrusion

NASA Astrophysics Data System (ADS)

Cantor, Kirk Martin

1998-12-01

Moisture-crosslinkable polyethylene used in the extrusion coating of electrical cable has many advantages over other polymer systems used for crosslinked cable coating. However, one of its major drawbacks is the long cure times required. The purpose of this study was to describe how curing takes place in cable systems using moisture-crosslinkable polyethylene, with an ultimate goal of gaining insight into how cure times might be reduced. Crosslinking was investigated with an emphasis on how the curing reaction proceeds through the coating, using analyses to characterize processing conditions and resulting mechanical and structural properties. In the design of the study, material compounds were varied as were curing conditions. Cable coatings were sectioned by position through the coating thickness and characterized using several techniques. Mechanical, thermal, and structural properties of the polymer coating were measured. A significant finding from the study was that the degree of cure was highest at positions in the coating closest to the conductor. Because this was opposite to what was expected, an investigation into the cause of this finding was pursued. It was found that during cure at elevated temperature, the inside surface of the coating remains at a generally higher temperature than the outside surface. This provides a more favorable cure condition for positions in the coating closest to the conductor. Based on the results of this study, a list of suggested follow-up studies is provided at the end of the dissertation. One proposal for investigating reduced cure times involves providing heat to the interior of the cable during cure.

Wear Measurement of Highly Cross-Linked UHMWPE Using a 7Be Tracer Implantation Technique

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

Wimmer, Markus; Laurent, Michael P.; Dwivedi, Yash

2013-01-29

The very low wear rates achieved with the current highly cross-linked ultra-high molecular weight polyethylenes (UHMWPE) used in joint prostheses have proven to be difficult to measure accurately by gravimetry. Tracer methods are therefore being explored. The purpose of this study was to effect a proof-of-concept on the use of the radioactive tracer beryllium-7 (7Be) for the determination of wear in a highly cross-linked orthopedic UHMWPE. Three crosslinked and four conventional UHMWPE pins made from compression-molded GUR 1050, were activated with 109 to 1010 7Be nuclei using a new implantation setup that produced a homogenous distribution of implanted nuclei upmore » to 8.5 μm below the surface. The pins were tested for wear in a six-station pin-on-flat apparatus for up to 7.1 million cycles (178 km). A Germanium gamma detector was employed to determine activity loss of the UHMWPE pins at preset intervals during the wear test. The wear of the cross-linked UHMWPE pins was readily detected and estimated to be 17 ± 3 μg/Mc. The conventional-to-cross-linked ratio of the wear rates was 13.1 ± 0.8, in the expected range for these materials. It was estimated that implantation reduced the average wear rate by approximately 20%, and the oxidative degradation damage from implantation was negligible. Future applications of this tracer technology may include the analysis of location-specific wear, such as loss of material in the post or backside of a tibial insert.« less

Status and future trends of radiation processing in Brazil

NASA Astrophysics Data System (ADS)

Lugão, A. B.; Andrade, E.; Silva, L. G.

1998-06-01

Electron-beam and gamma irradiation of polymers are widely applied in Brazil today. The main applications are: - radio-induced crosslinking of wire and cable for automobile and appliance industry; - heat shrinkable tubes for appliance, automobile and electronic; - heat shrinkable packing for food processing industry; - sterilization of medical supplies and so on. Nevertheless, there are only a few industrial facilities about 20 years old in full operation at present and there are some new low energy machines for food packing. The reason for such absence of investment in this area was studied and the relation between automobile and appliance production with radiation processing was fully demonstrated for Brazil case. In conclusion, it was shown that the industry of radiation processing of polymers is likely to experience a strong growth based on the continuous increase in the production of automobiles and appliances. The R&D activities of IPEN are an important support for developing the necessary technology and developing the necessary confidence in the radiation as tool for economical and social growth.

Biodegradation pattern and tissue integration of native and cross-linked porcine collagen soft tissue augmentation matrices – an experimental study in the rat

PubMed Central

2014-01-01

Introduction Within the last decades, collagen types I and III have been established as a sufficient biomaterial for GBR and GTR procedures. They might also be an adequate matrix for soft tissue augmentations. However, collagen materials differ significantly regarding resorption time, biodegradation pattern and the invasion of inflammatory cells. The aim of the present study was to compare the biodegradation and tissue integration of native, differently processed and cross-linked collagen scaffolds in rats. Methods Four experimental porcine collagen matrices of 1.0 mm thickness, developed for soft tissue augmentation procedures, were tested. Based on the same native dermal Type I and III collagen, native (ND, Mucoderm® prototype), specifically defatted (DD), ethylene dioxide cross-linked (ECL) and dehydrothermally cross-linked (DCL) dermis collagen (AAP/Botiss Biomaterials, Berlin, Germany) were evaluated. Two specimens of 1 × 1 cm were fixed around a non-absorbable spacer using non-absorbable sutures. After rehydration, specimens (N = 8) were randomly allocated in unconnected subcutaneous pouches on the back of 40 Wistar rats. Rats were divided into five groups (1, 2, 4, 8 and 12 weeks), including eight animals each. After each period, eight rats were sacrificed and explanted specimens were prepared for histological analysis. The following parameters were evaluated: membrane thickness as a sign of biodegradation and volume stability, cell ingrowth, vascularization, tissue integration and foreign body reaction. Results Biodegradation pattern of the non cross-linked collagen scaffolds differed only slightly in terms of presence of inflammatory cells and cell invasion into the matrix. In terms of biodegradation, ECL displayed a considerable slower resorption than ND, DCL and DD. Chemical cross-linking using ethylene dioxide showed a significant higher invasion of inflammatory cells. Conclusion Within the limits of the present study it was concluded that the processing techniques influenced the collagen properties in a different intensity. Dehydrothermal cross-linking and special defatting did not notably change the biodegradation pattern, whereas cross-linking using ethylene dioxide led to significant higher volume stability of the matrix. However, ECL showed an increased inflammatory response and compromised tissue integration. Therefore, ethylene dioxide seems to be not suitable for stabilization of collagen matrices for soft tissue augmentation procedures. PMID:24670219

Sub-30 nm patterning of molecular resists based on crosslinking through tip based oxidation

NASA Astrophysics Data System (ADS)

Lorenzoni, Matteo; Wagner, Daniel; Neuber, Christian; Schmidt, Hans-Werner; Perez-Murano, Francesc

2018-06-01

Oxidation Scanning Probe Lithography (o-SPL) is an established method employed for device patterning at the nanometer scale. It represents a feasible and inexpensive alternative to standard lithographic techniques such as electron beam lithography (EBL) and nanoimprint lithography (NIL). In this work we applied non-contact o-SPL to an engineered class of molecular resists in order to obtain crosslinking by electrochemical driven oxidation. By patterning and developing various resist formulas we were able to obtain a reliable negative tone resist behavior based on local oxidation. Under optimal conditions, directly written patterns can routinely reach sub-30 nm lateral resolution, while the final developed features result wider, approaching 50 nm width.

Ultrahigh Molecular Weight Aromatic Siloxane Polymers

NASA Technical Reports Server (NTRS)

Ludwick, L. M.

1983-01-01

Silphenylene-siloxane polymers can be prepared by a condensation reaction of a diol 1,4-bis(hydroxydimethylsilyl)benzene and a silane bis(dimethylamino)dimethylsilane. Using a stepwise condensation technique, a polymer (R=CH3) with a molecular weight in excess of 1.0 x 1 million has been produced. The polymer exhibits increased thermal stability, compared to a methyl siloxane polymer without the aromatic phenyl ring in the backbone. The use of bis(dimethylamino)methylvinylsilane should allow for ready crosslinking at the vinyl sites (R=-CH=CH2) introduced into the backbone. However, under the conditions of the reaction system a high molecular weight polymer was not obtained or the polymer underwent a crosslinking process during the synthesis.

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

Koeller, E.; Dobmann, G.; Kuhn, W.

Initial results are presented on the application of NMR techniques to prepregs in order to characterize the crosslink state under exposure to room and elevated (50 C) temperature. The experiments were conducted with a MSL-400 Bruker NMR spectrometer and microimaging system which works at 400 MHz. Aside from the sensitive measurement of the cross-link density there is also the potential to separate the influence of moisture content as a further parameter contributing to the aging process. It is shown that these experimental results correlate with results of destructive tests and document the potential of NMR as a NDT tool. Anmore » NMR-image of the moisture distribution in a glassfiber reinforced expoxy resin sample is shown. 17 refs.« less

Solvent and solute ingress into hydrogels resolved by a combination of imaging techniques

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

Wagner, D.; Burbach, J.; Egelhaaf, S. U.

2016-05-28

Using simultaneous neutron, fluorescence, and optical brightfield transmission imaging, the diffusion of solvent, fluorescent dyes, and macromolecules into a crosslinked polyacrylamide hydrogel was investigated. This novel combination of different imaging techniques enables us to distinguish the movements of the solvent and fluorescent molecules. Additionally, the swelling or deswelling of the hydrogels can be monitored. From the sequence of images, dye and solvent concentrations were extracted spatially and temporally resolved. Diffusion equations and different boundary conditions, represented by different models, were used to quantitatively analyze the temporal evolution of these concentration profiles and to determine the diffusion coefficients of solvent andmore » solutes. Solute size and network properties were varied and their effect was investigated. Increasing the crosslinking ratio or partially drying the hydrogel was found to hinder solute diffusion due to the reduced pore size. By contrast, solvent diffusion seemed to be slightly faster if the hydrogel was only partially swollen and hence solvent uptake enhanced.« less

Manipulation of in vitro collagen matrix architecture for scaffolds of improved physiological relevance

NASA Astrophysics Data System (ADS)

Hapach, Lauren A.; VanderBurgh, Jacob A.; Miller, Joseph P.; Reinhart-King, Cynthia A.

2015-12-01

Type I collagen is a versatile biomaterial that is widely used in medical applications due to its weak antigenicity, robust biocompatibility, and its ability to be modified for a wide array of applications. As such, collagen has become a major component of many tissue engineering scaffolds, drug delivery platforms, and substrates for in vitro cell culture. In these applications, collagen constructs are fabricated to recapitulate a diverse set of conditions. Collagen fibrils can be aligned during or post-fabrication, cross-linked via numerous techniques, polymerized to create various fibril sizes and densities, and copolymerized into a wide array of composite scaffolds. Here, we review approaches that have been used to tune collagen to better recapitulate physiological environments for use in tissue engineering applications and studies of basic cell behavior. We discuss techniques to control fibril alignment, methods for cross-linking collagen constructs to modulate stiffness, and composite collagen constructs to better mimic physiological extracellular matrix.

Implantation of a Multifocal Toric Intraocular Lens after Radial Keratotomy and Cross-Linking with Hyperopia and Astigmatism Residues: A Case Report.

PubMed

Nuzzi, Raffaele; Monteu, Francesca; Tridico, Federico

2017-01-01

Radial keratotomy is a refractive surgical technique, widely used in the 80s and early 90s to correct myopia and astigmatism, but now overcome by more recent laser techniques. Important consequences, often in patients with more than 45 years of age, are progressive hyperopic shift and/or an increase in corneal astigmatism, whose main cause seems to be an increase in the curvature radius of the central portion of the cornea. This seems to be due to radial keratotomy incisions - with the consequent need for cross-linking - intraocular pressure, and corneal biomechanical parameters. The authors propose phacoemulsification with a customized multifocal toric intraocular lens implantation to correct the induced shift and hyperopic astigmatism. A decent postoperative visual acuity was observed with good patient satisfaction. A specific protocol must be applied to optimize the correct diagnosis, presurgical evaluation and postsurgical outcomes that are to be maintained over time, without regressions.

Genipin-modified gelatin nanocarriers as swelling controlled drug delivery system for in vitro release of cytarabine.

PubMed

Khan, Huda; Shukla, R N; Bajpai, A K

2016-04-01

The aim of the present investigation was to design biocompatible gelatin nanoparticles, capable of releasing the cytarabine drug in a controllable way by regulating the extent of swelling of nanoparticles. In order to achieve the proposed objectives, gelatin (Type A, derived from acid cured tissue) was modified by crosslinking with genipin and nanoparticles of crosslinked gelatin were prepared using single water in oil (W/O) emulsion technique. The nanoparticles were characterized by techniques like FTIR, SEM, TEM, particles size analysis, and surface potential measurements. The nanoparticle chemical architecture was found to influence drug-releasing capacity. The influence of experimental conditions such as pH and simulated physiological fluids as the release medium was also investigated on the release profiles of cytarabine. It is possible to fabricate high-performance materials, by designing of controlled size gelatin nanoparticles with good biocompatible properties along with desired drug release profiles. Copyright © 2015 Elsevier B.V. All rights reserved.

Radiation-induced changes affecting polyester based polyurethane binder

NASA Astrophysics Data System (ADS)

Pierpoint, Sujita Basi

The application of thermoplastic polyurethane elastomers as binders in the high energy explosives particularly when used in weapons presents a significantly complex and challenging problem due to the impact of the aging of this polymer on the useful service life of the explosive. In this work, the effects of radiation on the aging of the polyester based polyurethane were investigated using both electron beam and gamma irradiation at various dose rates in the presence and absence of oxygen. It was found by means of GPC that, in the presence and absence of oxygen, the poly (ester urethane) primarily undergoes cross-linking, by means of a carbon-centered secondary alkyl radical. It was also concluded that the polymer partially undergoes scission of the backbone of the main chain at C-O, N-C, and C-C bonds. Substantial changes in the conditions of irradiation and in dose levels did not affect the cross-linking and scission yields. Experiments were also performed with EPR spectroscopy for the purpose of identifying the initial carbon-centered free radicals and for studying the decay mechanisms of these radicals. It was found that the carbon-centered radical which is produced via C-C scission (primary alkyl radical) is rapidly converted to a long-lived allylic species at higher temperatures; more than 80% radicals are converted to allyl species in 2.5 hours. In the presence of oxygen, the allyl radical undergoes a fast reaction to produce a peroxyl radical; this radical decays with a 1.7 hour half-life by pseudo first-order kinetics to negligible levels in 13 hours. FTIR measurements were conducted to identify the radiation-induced changes to the functional groups in the polyester polyurethane. These measurements show an increase in carbonyl, amine and carboxylic groups as a result of reaction of H atoms with R-C-O·, ·NH-R and R-COO·. The FTIR results also demonstrate the production of the unsaturation resulting from hydrogen atom transfer during intrachain conversion of the primary alkyl radical to the allyl species, prompt trans-vinylene production in tetramethylene units, and hydrogen atom abstraction by alkyl radicals on neighboring chains. The production of unsaturation is substantiated by the EPR studies. Finally, a free radical mechanism is proposed for the production of cross-linking in polyester polyurethane.

Rapid and high throughput fabrication of high temperature stable structures through PDMS transfer printing

NASA Astrophysics Data System (ADS)

Hohenberger, Erik; Freitag, Nathan; Korampally, Venumadhav

2017-07-01

We report on a facile and low cost fabrication approach for structures—gratings and enclosed nanochannels, through simple solution processed chemistries in conjunction with nanotransfer printing techniques. The ink formulation primarily consisting of an organosilicate polymeric network with a small percentage of added 3-aminopropyl triethoxysilane crosslinker allows one to obtain robust structures that are not only stable towards high temperature processing steps as high as 550 °C but also exhibit exceptional stability against a host of organic solvent washes. No discernable structure distortion was observed compared to the as-printed structures (room temperature processed) when printed structures were subjected to temperatures as high as 550 °C. We further demonstrate the applicability of this technique towards the fabrication of more complex nanostructures such as enclosed channels through a double transfer method, leveraging the exceptional room temperature cross-linking ability of the printed structures and their subsequent resistance to dissolution in organic solvent washes. The exceptional temperature and physico-chemical stability of the nanotransfer printed structures makes this a useful fabrication tool that may be applied as is, or integrated with conventional lithographic techniques for the large area fabrication of functional nanostructures and devices.

Evidence for cross-linking in tomato cutin using HR-MAS NMR spectroscopy.

PubMed

Deshmukh, Ashish P; Simpson, André J; Hatcher, Patrick G

2003-11-01

Cutin is a polyester biopolymer component of plant leaf and fruit cuticles, most often associated with waxes and cuticular polysaccharides, and sometimes with another aliphatic biopolymer called cutan. Insolubility of these cuticular biopolymers has made it difficult to apply traditional analytical techniques for structure determination, because most techniques providing molecular level details require solubility. By using the relatively new technique of one and two-dimensional high-resolution magic angle spinning (HR-MAS) NMR spectroscopy, with added information from solid-state 13C NMR spectroscopy, detailed through-bond connectivities and assignments are made for cutin from Lycopersicon esculentum (tomato) fruit. Based on the data obtained, tomato cutin is found to be predominantly an aliphatic polyester with some olefinic and aromatic moieties, consistent with previous studies that employed various degradative approaches. Aside from esters, there are free primary and secondary alcohol groups, as well as free fatty acids. A significant finding is the presence of alpha-branched fatty acids/esters. Mid-chain hydroxyls appear to be generally unesterified, but esters of mid-chain hydroxyls have been identified. The alpha-branched fatty acids/esters and esters of mid-chain hydroxyls could point towards cross-linking.

Degradation of poly(2-hydroxyethyl methacrylate) by gamma irradiation

NASA Astrophysics Data System (ADS)

Hill, David J. T.; O'Donnell, James H.; Pomery, Peter J.; Saadat, Giti

1996-11-01

Electron Spin Resinance (ESR) spectroscopy has been utilised to examine the effect of high energy radiation on poly(2-hydroxyethyl methacrylate) PHEMA. Radiation chemical yields ( G-values) for radicals were 1.7 and 1.2 for γ-irradiation at 77 K and ambient temperature, respectively. The ESR spectra at 77 and 300 K were simulated. The ESR spectrum at 77 K is a combination of six types of radicals ·CH 3, ·CH 2CH 2OH, COOCHCH 2OH, ·COO-, -CH- and ·CHO. However, after room temperature irradiation, the spectrum is a combination of methacrylate main chain scission radical and -CH-. The high stability of this radical at room temperature indicates the system is very rigid as a result of hydrogen bonding from the inherent side chain structure and radiation induced crosslinking due to labile hydrogen atoms in the side chain.

Stability of silk and collagen protein materials in space.

PubMed

Hu, Xiao; Raja, Waseem K; An, Bo; Tokareva, Olena; Cebe, Peggy; Kaplan, David L

2013-12-05

Collagen and silk materials, in neat forms and as silica composites, were flown for 18 months on the International Space Station [Materials International Space Station Experiment (MISSE)-6] to assess the impact of space radiation on structure and function. As natural biomaterials, the impact of the space environment on films of these proteins was investigated to understand fundamental changes in structure and function related to the future utility in materials and medicine in space environments. About 15% of the film surfaces were etched by heavy ionizing particles such as atomic oxygen, the major component of the low-Earth orbit space environment. Unexpectedly, more than 80% of the silk and collagen materials were chemically crosslinked by space radiation. These findings are critical for designing next-generation biocompatible materials for contact with living systems in space environments, where the effects of heavy ionizing particles and other cosmic radiation need to be considered.

Stability of Silk and Collagen Protein Materials in Space

PubMed Central

Hu, Xiao; Raja, Waseem K.; An, Bo; Tokareva, Olena; Cebe, Peggy; Kaplan, David L.

2013-01-01

Collagen and silk materials, in neat forms and as silica composites, were flown for 18 months on the International Space Station [Materials International Space Station Experiment (MISSE)-6] to assess the impact of space radiation on structure and function. As natural biomaterials, the impact of the space environment on films of these proteins was investigated to understand fundamental changes in structure and function related to the future utility in materials and medicine in space environments. About 15% of the film surfaces were etched by heavy ionizing particles such as atomic oxygen, the major component of the low-Earth orbit space environment. Unexpectedly, more than 80% of the silk and collagen materials were chemically crosslinked by space radiation. These findings are critical for designing next-generation biocompatible materials for contact with living systems in space environments, where the effects of heavy ionizing particles and other cosmic radiation need to be considered. PMID:24305951

The IBA Rhodotron: an industrial high-voltage high-powered electron beam accelerator for polymers radiation processing

NASA Astrophysics Data System (ADS)

Van Lancker, Marc; Herer, Arnold; Cleland, Marshall R.; Jongen, Yves; Abs, Michel

1999-05-01

The Rhodotron is a high-voltage, high-power electron beam accelerator based on a design concept first proposed in 1989 by J. Pottier of the French Atomic Agency, Commissariat à l'Energie Atomique (CEA). In December 1991, the Belgian particle accelerator manufacturer, Ion Beam Applications s.a. (IBA) entered into an exclusive agreement with the CEA to develop and industrialize the Rhodotron. Electron beams have long been used as the preferential method to cross-link a variety of polymers, either in their bulk state or in their final form. Used extensively in the wire and cable industry to toughen insulating jackets, electron beam-treated plastics can demonstrate improved tensile and impact strength, greater abrasion resistance, increased temperature resistance and dramatically improved fire retardation. Electron beams are used to selectively cross-link or degrade a wide range of polymers in resin pellets form. Electron beams are also used for rapid curing of advanced composites, for cross-linking of floor-heating and sanitary pipes and for cross-linking of formed plastic parts. Other applications include: in-house and contract medical device sterilization, food irradiation in both electron and X-ray modes, pulp processing, electron beam doping of semi-conductors, gemstone coloration and general irradiation research. IBA currently markets three models of the Rhodotron, all capable of 10 MeV and alternate beam energies from 3 MeV upwards. The Rhodotron models TT100, TT200 and TT300 are typically specified with guaranteed beam powers of 35, 80 and 150 kW, respectively. Founded in 1986, IBA, a spin-off of the Cyclotron Research Center at the University of Louvain (UCL) in Belgium, is a pioneer in accelerator design for industrial-scale production.

Covalent adaptable networks: smart, reconfigurable and responsive network systems.

PubMed

Kloxin, Christopher J; Bowman, Christopher N

2013-09-07

Covalently crosslinked materials, classically referred to as thermosets, represent a broad class of elastic materials that readily retain their shape and molecular architecture through covalent bonds that are ubiquitous throughout the network structure. These materials, in particular in their swollen gel state, have been widely used as stimuli responsive materials with their ability to change volume in response to changes in temperature, pH, or other solvent conditions and have also been used in shape memory applications. However, the existence of a permanent, unalterable shape and structure dictated by the covalently crosslinked structure has dramatically limited their abilities in this and many other areas. These materials are not generally reconfigurable, recyclable, reprocessable, and have limited ability to alter permanently their stress state, topography, topology, or structure. Recently, a new paradigm has been explored in crosslinked polymers - that of covalent adaptable networks (CANs) in which covalently crosslinked networks are formed such that triggerable, reversible chemical structures persist throughout the network. These reversible covalent bonds can be triggered through molecular triggers, light or other incident radiation, or temperature changes. Upon application of this stimulus, rather than causing a temporary shape change, the CAN structure responds by permanently adjusting its structure through either reversible addition/condensation or through reversible bond exchange mechanisms, either of which allow the material to essentially reequilibrate to its new state and condition. Here, we provide a tutorial review on these materials and their responsiveness to applied stimuli. In particular, we review the broad classification of these materials, the nature of the chemical bonds that enable the adaptable structure, how the properties of these materials depend on the reversible structure, and how the application of a stimulus causes these materials to alter their shape, topography, and properties.

Biocompatibility of NGF-grafted GTG membranes for peripheral nerve repair using cultured Schwann cells.

PubMed

Chen, Pei-Ru; Chen, Ming-Hong; Sun, Jui-Sheng; Chen, Mei-Hsiu; Tsai, Chien-Chen; Lin, Feng-Huei

2004-11-01

We previously developed a biodegradable composite with potentially good biocompatibility composed by tricalcium phosphate and gluataraldehyde cross-linking gelatin (GTG) with good mechanical property feasible for surgical manipulation. The purpose of this study was to evaluate the feasibility of immobilizing nerve growth factor (NGF) onto the composite (GTG) with carbodiimide (GEN composite). Cultured Schwann cells were seeded onto the GTG and GEN composites. For comparison, GTG membrane soaked in NGF solution without carbodiimide (GN composite) as cross-linking agent was also used to culture Schwann cells. Cell morphology was observed by a scanning electron microscope. Cell survival, cytotoxicity and cellular metabolism on the NGF-grafted GTG membrane were assessed quantitatively in terms of cell protein content, leakage of cytosolic lactate dehydrogenase (LDH) activity and by the well-established MTT assay, respectively. The result of LDH study did not show significant difference among GTG, NGF-modified GTG and control group. This indicated that GTG composite, whether cross-linking with NGF or not, has little cytotoxic effect. Comparing the protein content and MTT assay among GEN, GN composite and control group, the data confirmed more attachment of Schwann cells on GEN composite. Although GTG cross-linking with NGF did not promote Schwann cell proliferation, the techniques we used in this study provided a method to fabricate a novel biomaterial incorporation of Schwann cells and covalently immobilized NGF.

Single-molecule analysis of DNA cross-links using nanopore technology

NASA Astrophysics Data System (ADS)

Wolna, Anna H.

The alpha-hemolysin (alpha-HL) protein ion channel is a potential next-generation sequencing platform that has been extensively used to study nucleic acids at a single-molecule level. After applying a potential across a lipid bilayer, the imbedded alpha-HL allows monitoring of the duration and current levels of DNA translocation and immobilization. Because this method does not require DNA amplification prior to sequencing, all the DNA damage present in the cell at any given time will be present during the sequencing experiment. The goal of this research is to determine if these damage sites give distinguishable current levels beyond those observed for the canonical nucleobases. Because DNA cross-links are one of the most prevalent types of DNA damage occurring in vivo, the blockage current levels were determined for thymine-dimers, guanine(C8)-thymine(N3) cross-links and platinum adducts. All of these cross-links give a different blockage current level compared to the undamaged strands when immobilized in the ion channel, and they all can easily translocate across the alpha-HL channel. Additionally, the alpha-HL nanopore technique presents a unique opportunity to study the effects of DNA cross-links, such as thymine-dimers, on the secondary structure of DNA G-quadruplexes folded from the human telomere sequence. Using this single-molecule nanopore technique we can detect subtle structural differences that cannot be easily addressed using conventional methods. The human telomere plays crucial roles in maintaining genome stability. In the presence of suitable cations, the repetitive 5'-TTAGGG human telomere sequence can fold into G-quadruplexes that adopt the hybrid fold in vivo. The telomere sequence is hypersensitive to UV-induced thymine-dimer (T=T) formation, and yet the presence of thymine dimers does not cause telomere shortening. The potential structural disruption and thermodynamic stability of the T=T-containing natural telomere sequences were studied to understand how this damage is tolerated in telomeric DNA. The alpha-HL experiments determined that T=Ts disrupt double-chain reversal loop formation but are well tolerated in edgewise and diagonal loops of the hybrid G-quadruplexes. These studies demonstrated the power of the alpha-HL ion channel to analyze DNA modifications and secondary structures at a single-molecule level.

Ionizing Radiation-Induced DNA Damage and Its Repair in Human Cells

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

Dizdaroglu, Miral

DNA damage in mammalian chromatin in vitro and in cultured mammalian cells including human cells was studied. In the first phase of these studies, a cell culture laboratory was established. Necessary equipment including an incubator, a sterile laminar flow hood and several centrifuges was purchased. We have successfully grown several cell lines such as murine hybridoma cells, V79 cells and human K562 leukemia cells. This was followed by the establishment of a methodology for the isolation of chromatin from cells. This was a very important step, because a routine and successful isolation of chromatin was a prerequisite for the successmore » of the further studies in this project, the aim of which was the measurement of DNA darnage in mammalian chromatin in vitro and in cultured cells. Chromatin isolation was accomplished using a slightly modified procedure of the one described by Mee & Adelstein (1981). For identification and quantitation of DNA damage in cells, analysis of chromatin was preferred over the analysis of "naked DNA" for the following reasons: i. DNA may not be extracted efficiently from nucleoprotein in exposed cells, due to formation of DNA-protein cross-links, ii. the extractability of DNA is well known to decrease with increasing doses of radiation, iii. portions of DNA may not be extracted due to fragmentation, iv. unextracted DNA may contain a significant portion of damaged DNA bases and DNA-protein cross-links. The technique of gas chromatography/mass spectrometry (GC/MS), which was used in the present project, permits the identification and quantitation of modified DNA bases in chromatin in the presence of proteins without the necessity of first isolating DNA from chromatin. This has been demonstrated previously by the results from our laboratory and by the results obtained during the course of the present project. The quality of isolated chromatin was tested by measurement of its content of DNA, proteins, and RNA, by analysis of its protein components using gel electrophoresis, and by absorption spectral analysis. GeneraUy, the RNA content was <5% of the amount of DNA, and the ratio of the amount of protein to that of DNA was =1. 8-2 (w/w). Having developed a suitable methodology for routine isolation of chromatin from mammalian cells, studies of DNA damage in chromatin in vitro and in cultured human cells were pursued.« less

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

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.

Seed-mediated synthesis of cross-linked Pt-NiO nanochains for methanol oxidation

NASA Astrophysics Data System (ADS)

Gu, Zhulan; Bin, Duan; Feng, Yue; Zhang, Ke; Wang, Jin; Yan, Bo; Li, Shumin; Xiong, Zhiping; Wang, Caiqin; Shiraishi, Yukihide; Du, Yukou

2017-07-01

A simple method was reported for employing NiO nanoparticles act as seeds and then different amounts of Pt2+ were reduced on the NiO nanoparticles, forming a cross-linked Pt-NiO nanocatalysts. These as-prepared catalysts were characterized using different physical-chemical techniques, including X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results indicate that the morphology of the cross-linked Pt-NiO nanochain was successfully produced regardless of the molar ratio of Pt2+ to NiO precursors. The electrochemical characteristics of Pt-NiO nanochain catalysts were evaluated for the oxidation of methanol as a model reaction, which verify that the Pt-NiO catalysts show enhanced activity and high stability in comparison with the commercial Pt/C catalyst. The optimized ratio of Pt to NiO is 1:1, then tuned by simple adjusting the feed ratio of the precursors as well. The synthesized nanocatalysts will be found the great potential applications as electrocatalysts for fuel cells owe to their enhanced catalytic performance and long-term stability.

Characterization and comparison of Fumonisin B(1)-protein conjugates by six methods.

PubMed

Wang, Ying; He, Cheng-Hua; Zheng, Hao; Zhang, Hai-Bin

2012-01-01

In order to generate an antibody against a small hapten molecule, the hapten is cross-linked with carrier protein to make it immunogenic. In this study, the hapten (Fumonisin B(1), FB(1)) was coupled to ovalbumin (OVA) and bovine serum albumin (BSA), respectively by a short cross-linker reagent (glutaraldehyde, GA). To develop a technique for detecting the conjugation, the hapten-protein conjugates (FB(1)-OVA and FB(1)-BSA) were characterized thoroughly by ultraviolet (UV) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, gel electrophoresis and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), respectively. The molecular weights of FB(1)-BSA and FB(1)-OVA were 74,355.301 Da and 48,009.212 Da, respectively determined by the method of MALDI-TOF-MS. The molecular coupling ratios were 11 and 5 in FB(1)-BSA and FB(1)-OVA, respectively. In this experiment, MALDI-TOF-MS was selected as the most efficient method to evaluate the cross-linking effect and calculate the molecular coupling ratio.

Preparation of crosslinked amphiphilic silver nanogel as thin film corrosion protective layer for steel.

PubMed

Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; Ezzat, Abdelrahman O

2014-07-17

Monodisperse silver nanoparticles were synthesized by a new developed method via reaction of AgNO3 and oleic acid with the addition of a trace amount of Fe3+ ions. Emulsion polymerization at room temperature was employed to prepare a core-shell silver nanoparticle with controllable particle size. N,N'-methylenebisacrylamide (MBA) and potassium peroxydisulfate (KPS) were used as a crosslinker, and as redox initiator system, respectively for crosslinking polymerization. The structure and morphology of the silver nanogels were characterized by Fourier transform infrared spectroscopy (FTIR), transmission and scanning electron microscopy (TEM and SEM). The effectiveness of the synthesized compounds as corrosion inhibitors for steel in 1 M HCl was investigated by various electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Monolayers of silver nanoparticle were self-assembled on the fresh active surface of the steel electrode and have been tested as a corrosion inhibitor for steel in 1 M HCl solution. The results of polarization measurements showed that nanogel particles act as a mixed type inhibitor.

Preparation of protein- and cell-resistant surfaces by hyperthermal hydrogen induced cross-linking of poly(ethylene oxide).

PubMed

Bonduelle, Colin V; Lau, Woon M; Gillies, Elizabeth R

2011-05-01

The functionalization of surfaces with poly(ethylene oxide) (PEO) is an effective means of imparting resistance to the adsorption of proteins and the attachment and growth of cells, properties that are critical for many biomedical applications. In this work, a new hyperthermal hydrogen induced cross-linking (HHIC) method was explored as a simple one-step approach for attaching PEO to surfaces through the selective cleavage of C-H bonds and subsequent cross-linking of the resulting carbon radicals. In order to study the effects of the process on the polymer, PEO-coated silicon wafers were prepared and the effects of different treatment times were investigated. Subsequently, using an optimized treatment time and a modified butyl polymer with increased affinity for PEO, the technique was applied to butyl rubber surfaces. All of the treated surfaces exhibited significantly reduced protein adsorption and cell growth relative to control surfaces and compared favorably with surfaces that were functionalized with PEO using conventional chemical methods. Thus HHIC is a simple and effective means of attaching PEO to non-functional polymer surfaces.

Electron irradiation effects on partially fluorinated polymer films: Structure-property relationships

NASA Astrophysics Data System (ADS)

Nasef, Mohamed Mahmoud; Dahlan, Khairul Zaman M.

2003-04-01

The effects of electron beam irradiation on two partially fluorinated polymer films i.e. poly(vinylidene fluoride) (PVDF) and poly(ethylene-tetrafluoroethylene) copolymer (ETFE) are studied at doses ranging from 100 to 1200 kGy in air at room temperature. Chemical structure, thermal and mechanical properties of irradiated films are investigated. FTIR show that both PVDF and ETFE films undergo similar changes in their chemical structures including the formation of carbonyl groups and double bonding. The changes in melting and crystallisation temperatures ( Tm and Tc) in both irradiated films are functions of irradiation dose and reflect the disorder in the chemical structure caused by the competition between crosslinking and chain scission. The heat of melting (Δ Hm) and the degree of crystallinity ( Xc) of PVDF films show no significant changes with the dose increase, whereas those of ETFE films are reduced rapidly after the first 100 kGy. The tensile strength of PVDF films is improved by irradiation compared to its rapid deterioration in ETFE films, which stemmed from the degradation prompted by the presence of radiation sensitive tetrafluoroethylene (TFE) comonomer units. The elongation at break of both films drops gradually with the dose increase indicating the formation of predominant crosslinked structures at high doses. However, the response of each polymer to crosslinking and main chain scission at various irradiation doses varies from PVDF to ETFE films.

Resistance of hypoxic cells to ionizing radiation is influenced by homologous recombination status

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

Sprong, Debbie; Janssen, Hilde L.; Vens, Conchita

2006-02-01

Purpose: To determine the role of DNA repair in hypoxic radioresistance. Methods and Materials: Chinese hamster cell lines with mutations in homologous recombination (XRCC2, XRCC3, BRAC2, RAD51C) or nonhomologous end-joining (DNA-PKcs) genes were irradiated under normoxic (20% oxygen) and hypoxic (<0.1% oxygen) conditions, and the oxygen enhancement ratio (OER) was calculated. In addition, Fanconi anemia fibroblasts (complementation groups C and G) were compared with fibroblasts from nonsyndrome patients. RAD51 foci were studied using immunofluorescence. Results: All hamster cell lines deficient in homologous recombination showed a decrease in OER (1.5-2.0 vs. 2.6-3.0 for wild-types). In contrast, the OER for the DNA-PKcs-deficientmore » line was comparable to wild-type controls. The two Fanconi anemia cell strains also showed a significant reduction in OER. The OER for RAD51 foci formation at late times after irradiation was considerably lower than that for survival in wild-type cells. Conclusion: Homologous recombination plays an important role in determining hypoxic cell radiosensitivity. Lower OERs have also been reported in cells deficient in XPF and ERCC1, which, similar to homologous recombination genes, are known to play a role in cross-link repair. Because Fanconi anemia cells are also sensitive to cross-linking agents, this strengthens the notion that the capacity to repair cross-links determines hypoxic radiosensitivity.« less

Reactive oxygen-mediated damage to a human DNA replication and repair protein.

PubMed

Montaner, Beatriz; O'Donovan, Peter; Reelfs, Olivier; Perrett, Conal M; Zhang, Xiaohong; Xu, Yao-Zhong; Ren, Xiaolin; Macpherson, Peter; Frith, David; Karran, Peter

2007-11-01

Ultraviolet A (UVA) makes up more than 90% of incident terrestrial ultraviolet radiation. Unlike shorter wavelength UVB, which damages DNA directly, UVA is absorbed poorly by DNA and is therefore considered to be less hazardous. Organ transplant patients treated with the immunosuppressant azathioprine frequently develop skin cancer. Their DNA contains 6-thioguanine-a base analogue that generates DNA-damaging singlet oxygen ((1)O(2)) when exposed to UVA. Here, we show that this (1)O(2) damages proliferating cell nuclear antigen (PCNA), the homotrimeric DNA polymerase sliding clamp. It causes covalent oxidative crosslinking between the PCNA subunits through a histidine residue in the intersubunit domain. Crosslinking also occurs after treatment with higher-although still moderate-doses of UVA alone or with chemical oxidants. Chronic accumulation of oxidized proteins is linked to neurodegenerative disorders and ageing. Our findings identify oxidative damage to an important DNA replication and repair protein as a previously unrecognized hazard of acute oxidative stress.

Bio-inspired metal-coordinate hydrogels with programmable viscoelastic material functions controlled by longwave UV light.

PubMed

Grindy, Scott C; Holten-Andersen, Niels

2017-06-07

Control over the viscoelastic mechanical properties of hydrogels intended for use as biomedical materials has long been a goal of soft matter scientists. Recent research has shown that materials made from polymers with reversibly associating transient crosslinks are a promising strategy for controlling viscoelasticity in hydrogels, for example leading to systems with precisely tunable mechanical energy-dissipation. We and others have shown that bio-inspired histidine:transition metal ion complexes allow highly precise and tunable control over the viscoelastic properties of transient network hydrogels. In this paper, we extend the design of these hydrogels such that their viscoelastic properties respond to longwave UV radiation. We show that careful selection of the histidine:transition metal ion crosslink mixtures allows unique control over pre- and post-UV viscoelastic properties. We anticipate that our strategy for controlling stimuli-responsive viscoelastic properties will aid biomedical materials scientists in the development of soft materials with specific stress-relaxing or energy-dissipating properties.

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

Driscoll, Mark S.; Smith, Jennifer L.; Woods, Sean

One of the main problems associated with the use of natural fibers as reinforcing agents in composites is their uptake of moisture. Many natural fibers are lignocellulosic, which causes them to swell and shrink as the amount of available moisture changes. Swelling and shrinking can cause composites to prematurely fail. This paper presents the results of a preliminary study that considers the use of two different low molecular weight monomers, hydroxyethyl methacrylate (HEMA) and hydroxyethyl acrylate (HEA), polymerized by electron beam ionizing radiation, to dimensionally stabilize natural fibers. Eight different treatments consisting of varying amounts of monomer, encapsulating agent, andmore » cross-linkers, were evaluated for their ability to dimensionally stabilize sisal fiber. Results indicate that both polymerized HEA and HEMA can reduce the swelling of sisal fiber. The effectiveness of HEA and HEMA can be further enhanced with the use of a cross-linker (SR 454). The use of hydroxylated monomers to dimensionally stabilize natural fibers may play an important role in reducing delamination and improving fiber-resin adhesion in composites.« less

Experimental design for the formulation and optimization of novel cross-linked oilispheres developed for in vitro site-specific release of Mentha piperita oil.

PubMed

Sibanda, Wilbert; Pillay, Viness; Danckwerts, Michael P; Viljoen, Alvaro M; van Vuuren, Sandy; Khan, Riaz A

2004-03-12

A Plackett-Burman design was employed to develop and optimize a novel crosslinked calcium-aluminum-alginate-pectinate oilisphere complex as a potential system for the in vitro site-specific release of Mentha piperita, an essential oil used for the treatment of irritable bowel syndrome. The physicochemical and textural properties (dependent variables) of this complex were found to be highly sensitive to changes in the concentration of the polymers (0%-1.5% wt/vol), crosslinkers (0%-4% wt/vol), and crosslinking reaction times (0.5-6 hours) (independent variables). Particle size analysis indicated both unimodal and bimodal populations with the highest frequency of 2 mm oilispheres. Oil encapsulation ranged from 6 to 35 mg/100 mg oilispheres. Gravimetric changes of the crosslinked matrix indicated significant ion sequestration and loss in an exponential manner, while matrix erosion followed Higuchi's cube root law. Among the various measured responses, the total fracture energy was the most suitable optimization objective (R2 = 0.88, Durbin-Watson Index = 1.21%, Coefficient of Variation (CV) = 33.21%). The Lagrangian technique produced no significant differences (P > .05) between the experimental and predicted total fracture energy values (0.0150 vs 0.0107 J). Artificial Neural Networks, as an alternative predictive tool of the total fracture energy, was highly accurate (final mean square error of optimal network epoch approximately 0.02). Fused-coated optimized oilispheres produced a 4-hour lag phase followed by zero-order kinetics (n > 0.99), whereby analysis of release data indicated that diffusion (Fickian constant k1 = 0.74 vs relaxation constant k2 = 0.02) was the predominant release mechanism.

High-energy radiation and polymers: A review of commercial processes and emerging applications

NASA Astrophysics Data System (ADS)

Clough, R. L.

2001-12-01

Ionizing radiation has been found to be widely applicable in modifying the structure and properties of polymers, and can be used to tailor the performance of either bulk materials or surfaces. Fifty years of research in polymer radiation chemistry has led to numerous applications of commercial and economic importance, and work remains active in the application of radiation to practical uses involving polymeric materials. This paper provides a survey of radiation-processing methods of industrial interest, ranging from technologies already commercially well established, through innovations in the active R&D stage which show exceptional promise for future commercial use. Radiation-processing technologies are discussed under the following categories: cross-linking of plastics and rubbers, curing of coatings and inks, heat-shrink products, fiber-matrix composites, chain-scission for processing control, surface modification, grafting, hydrogels, sterilization, natural product enhancement, plastics recycling, ceramic precursors, electronic property materials, ion-track membranes and lithography for microdevice production. In addition to new technological innovations utilizing conventional gamma and e-beam sources, a number of promising new applications make use of novel radiation types which include ion beams (heavy ions, light ions, highly focused microscopic beams and high-intensity pulses), soft X-rays which are focused, coherent X-rays (from a synchrotron) and e-beams which undergo scattering to generate patterns.

Impact of Pb content on the physical parameters of Se-Te-Pb system

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

Anjali,; Sharma, Raman; Thakur, Nagesh

2015-05-15

In the present study, we have investigated the impact of Pb content on the physical parameters in Se-Te-Pb system via average coordination number, constraints, the fraction of floppy modes, cross-linking density, lone pairs electrons, heat of atomization, mean bond energy, cohesive energy and electronegativity. The bulk samples have been prepared by using melt quenching technique. X-ray diffraction pattern of various samples indicates the amorphous nature of investigated glassy alloys. It is observed that average coordination number, average number of constraints and cross-linking density increase with Pb content. However, lone-pair electrons, floppy modes, average heat of atomization, cohesive energy and meanmore » bond energy are found to decrease with Pb atomic percentage.« less

Cyclopentadiene evolution during pyrolysis-gas chromatography of PMR polyimides

NASA Technical Reports Server (NTRS)

Alston, William B.; Gluyas, Richard E.; Snyder, William J.

1992-01-01

The effect of formulated molecular weight (FMW), extent of cure, and cumulative aging on the amount of cyclopentadiene (CPD) evolved from Polymerization of Monomeric Reactants (PMR) polyimides were investigated by pyrolysis-gas chromotography (PY-GC). The PMR polyimides are additional crosslinked resins formed from an aromatic diamine, a diester of an aromatic tetracarboxylic acid and a monoester of 5-norbornene-2, 3-dicarboxylic acid. The PY-GC results were related to the degree of crosslinking and to the thermo-oxidative stability (weight loss) of PMR polyimides. Thus, PY-GC has shown to be a valid technique for the characterization of PMR polyimide resins and composites via correlation of the CPD evolved versus the thermal history of the PMR sample.

Readily functionalized AAA-DDD triply hydrogen-bonded motifs.

PubMed

Tong, Feng; Linares-Mendez, Iamnica J; Han, Yi-Fei; Wisner, James A; Wang, Hong-Bo

2018-04-25

Herein we present a new, readily functionalized AAA-DDD hydrogen bond array. A novel AAA monomeric unit (3a-b) was obtained from a two-step synthetic procedure starting with 2-aminonicotinaldehyde via microwave radiation (overall yield of 52-66%). 1H NMR and fluorescence spectroscopy confirmed the complexation event with a calculated association constant of 1.57 × 107 M-1. Likewise, the usefulness of this triple hydrogen bond motif in supramolecular polymerization was demonstrated through viscosity measurements in a crosslinked supramolecular alternating copolymer.

Polymer biomaterial constructs for regenerative medicine and functional biological systems

NASA Astrophysics Data System (ADS)

Meng, Linghui

The use of collagen as a biomaterial is currently undergoing a renaissance in the tissue engineering field. The excellent biocompatibility and safety due to its biological characteristics, such as biodegradability and weak antigenicity, make collagen a primary material resource in medical applications. Described herein is work towards the development of novel collagen-based matrices, with additional multi-functionality imparted through a novel in-situ crosslinking approach. The process of electrospinning has become a widely used technique for the creation of fibrous scaffolds for tissue engineering applications due to its ability to rapidly create structures composed of nano-scale polymer fibers closely resembling the architecture of the extracellular matrix (ECM). Collagen-PCL sheath-core bicomponent fibrous scaffolds were fabricated using a novel variation on traditional electrospinning, known as co-axial electrospinning. The results showed that the addition of a synthetic polymer core into collagen nanofibers remarkably increased the mechanical strength of collagen matrices spun from the benign solvent system. A novel single-step, in-situ collagen crosslink approach was developed in order to solve the problems dominating traditional collagen crosslinking methods, such as dimensional shrinking and loss of porous morphology, and to simplify the crosslinking procedure for electrospun collagen scaffolds. The excess amount of NHS present in the crosslinking mixture was found to delay the EDC/collagen coupling reaction in a controlled fashion. Fundamental investigations into the development and characterization of in-situ crosslinked collagen matrices such as fibrous scaffolds, gels and sponges, as well as their biomedical applications including cell culture substrates, wound dressings, drug delivery matrices and bone regeneration substitutes, were performed. The preliminary mice studies indicated that the in-situ crosslinked collagen matrices could be good candidates for wound healing and skin regeneration. Polyelectrolyte fibrous tubes of highly-crosslinked poly (acrylic acid) were fabricated by means of electrospinning as polymer models for functional biological systems, with special attention to the axon cortical layer and its cation-exchange properties. The processing parameters of fiber formation and the reversible phase transitions of PAA tubes according to monovalent-divalent ion exchange in solution were systematically investigated. The results showed that the neutralized PAA tubes were responsive to calcium ions, exhibiting significant shrinkage that could be reversed with a chelator such as citrate. Study of such phase transitions may help to better understand the electrophysiological processes known as nerve excitation and conduction in the nervous system, and the resulting PAA tubes might be used as polymer models of artificial axons for potential tissue engineering and nerve repair applications.

Preparation and characterization of cellulose acetate organic/inorganic hybrid films

Treesearch

Saeed S. Shojaie; Timothy G. Rials; Stephen S. Kelley

1995-01-01

A series of organic/inorganic hybrid (OIH) films were prepared using cellulose acetate (CA) as the organic component and tetraethyl orthosilicate (TEOS) as the inorganic component. The chemical, morphological, and mechanical properties of these films were evaluated with a variety of analytical techniques. The results of these evaluations showed that crosslinked CA OIH...

Polyether/Polyester Graft Copolymers

NASA Technical Reports Server (NTRS)

Bell, Vernon L., Jr.; Wakelyn, N.; Stoakley, D. M.; Proctor, K. M.

1986-01-01

Higher solvent resistance achieved along with lower melting temperature. New technique provides method of preparing copolymers with polypivalolactone segments grafted onto poly (2,6-dimethyl-phenylene oxide) backbone. Process makes strong materials with improved solvent resistance and crystalline, thermally-reversible crosslinks. Resulting graft copolymers easier to fabricate into useful articles, including thin films, sheets, fibers, foams, laminates, and moldings.

Degradation mechanisms of cable insulation materials during radiation-thermal ageing in radiation environment

NASA Astrophysics Data System (ADS)

Seguchi, Tadao; Tamura, Kiyotoshi; Ohshima, Takeshi; Shimada, Akihiko; Kudoh, Hisaaki

2011-02-01

Radiation and thermal degradation of ethylene-propylene rubber (EPR) and crosslinked polyethylene (XLPE) as cable insulation materials were investigated by evaluating tensile properties, gel-fraction, and swelling ratio, as well as by the infrared (FTIR) analysis. The activation energy of thermal oxidative degradation changed over the range 100-120 °C for both EPR and XLPE. This may be attributed to the fact that the content of an antioxidant used as the stabilizer for polymers decreases by evaporation during thermal ageing at high temperatures. The analysis of antioxidant content and oxidative products in XLPE as a model sample showed that a small amount of antioxidant significantly reduced the extent of thermal oxidation, but was not effective for radiation induced oxidation. The changes in mechanical properties were well reflected by the degree of oxidation. A new model of polymer degradation mechanisms was proposed where the degradation does not take place by chain reaction via peroxy radical and hydro-peroxide. The role of the antioxidant in the polymer is the reduction of free radical formation in the initiation step in thermal oxidation, and it could not stop radical reactions for either radiation or thermal oxidation.

IS GUTTACORE MORE EASILY REMOVED FROM THE ROOT CANAL THAN THERMAFIL? AN EX-VIVO STUDY.

PubMed

Nevares, Giselle; de Albuquerque, Diana Santana; Bueno, Carlos Eduardo da Silveira; Cunha, Rodrigo Sanches

2015-01-01

GuttaCore is a new cross-linked gutta-percha carrier. Its handling time and ease of removal were compared with those of a plastic carrier (Thermafil) and the continuous wave of condensation technique (control). Forty-five maxillary central incisors were randomly divided 3 groups according to filling technique and retreatment was carried out in all samples with NiTi rotary files, hand files and ultrasonic inserts. Time required for filling removal was recorded. Roots were then split longitudinally and photographed under 5x magnification, and residual filling material was quantified. Removal time was significantly longer for Thermafil (7.10 minutes) than GuttaCore (2.91 minutes) and the control group (1.93 minutes) (p < 0.001). The amount of residual filling material did not differ among the groups: Thermafil 8.31%, GuttaCore 6.27 and control 8.68% (p > 0.05). In conclusion, replacing plastic core with cross-linked gutta-percha allows easier removal of carrier from the root canal. The remnants of filling material in all samples illustrate that retreatment remains a challenge in endodontics.

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.

Investigation of Polymer Liquid Crystals

NASA Technical Reports Server (NTRS)

Han, Kwang S.

1996-01-01

The positron annihilation lifetime spectroscopy (PALS) using a low energy flux generator may provide a reasonably accurate technique for measuring molecular weights of linear polymers and characterization of thin polyimide films in terms of their dielectric constants and hydrophobity etc. Among the tested samples are glassy poly arylene Ether Ketone films, epoxy and other polyimide films. One of the proposed techniques relates the free volume cell size (V(sub f)) with sample molecular weight (M) in a manner remarkably similar to that obtained by Mark Houwink (M-H) between the inherent viscosity (eta) and molecular wieght of polymer solution. The PALS has also demonstrated that free-volume cell size in thermoset is a versatile, useful parameter that relates directly to the polymer segmental molecular weight, the cross-link density, and the coefficient of thermal expansion. Thus, a determination of free volume cell size provides a viable basis for complete microstructural characterization of thermoset polyimides and also gives direct information about the cross-link density and coefficient of expansion of the test samples. Seven areas of the research conducted are reported here.

Injection initiated fracture in soft solids

NASA Astrophysics Data System (ADS)

Hutchens, Shelby; Yang, Steven

Damage accumulation in soft materials under hydrostatic loading conditions is a primary injury mechanism in blast and blunt force trauma. A recently explored technique known as cavitation rheology (CR) provides a promising avenue for quickly and inexpensively approximating hydrostatic conditions via the reverse loading scenario, void pressurization. Past CR measurements of synthetic, polymeric materials at length scales from mm's to μm's have been found to correlate with both elastic modulus and fracture energy. The technique is performed via pressurization of fluid within a needle that is embedded within a material. This experimental setup allows crack evolution to be monitored, similar to traditional pre-notched failure samples. We observe a systematic evolution of crack morphology as a function of cross-link density in a soft elastomer. Crack shape is quantified using micro-computed tomography and shown to transition from being roughly penny-shaped to multi-lobed (predominately three) to spherical with decreasing crosslinking. Moduli are on the order of kPa. We describe this morphology evolution using a balance between the energetic costs of the strain energy in deforming the surrounding material and the intrinsic fracture energy necessary to form a new surface.

In-Situ Strain Analysis of Potential Habitat Composites Exposed to a Simulated Long-Term Lunar Radiation Exposure

NASA Technical Reports Server (NTRS)

Rojdev, Kristina; O'Rourke, Mary Jane; Hill, Charles; Nutt, Steven; Atwell, William

2010-01-01

NASA is studying the effects of long-term space radiation on potential multifunctional composite materials for habitats to better determine their characteristics in the harsh space environment. Two composite materials were selected for the study and were placed in a test stand that simulated the stresses of a pressure vessel wall on the material. The samples in the test stand were exposed to radiation at either a fast dose rate or a slow dose rate, and their strain and temperature was recorded during the exposure. It was found that during a fast dose rate exposure the materials saw a decreased strain with time, or a shrinking of the materials. Given previous radiation studies of polymers, this is believed to be a result of crosslinking occurring in the matrix material. However, with a slow dose rate, the materials saw an increase in strain with time, or a stretching of the materials. This result is consistent with scission or degradation of the matrix occurring, possibly due to oxidative degradation.

Radiation-induced preparation of core/shell gold/albumin nanoparticles

NASA Astrophysics Data System (ADS)

Flores, Constanza Y.; Achilli, Estefania; Grasselli, Mariano

2018-01-01

Nanoparticles (NPs) are one of the most promising nanomaterials to be used in the biomedical field. Gold NPs (Au-NPs) have been covered with monolayers of many different molecules and macromolecules to prepare different kinds of biosensors. However, these coatings based on physisorption methods are not stable enough to prepare functional nanomaterials to be used in complex mixtures or in vivo applications. The aim of this work was to prepare a protein coating of Au-NPs based on a protein multilayer covering, stabilized by a novel radiation-induced crosslinking process. Albumins from human and bovine source were added to Au-NPs suspension and followed by ethanol addition to induce protein aggregation. Samples were irradiated with a gamma source at 10 kGy to induce a protein crosslinking according to recent findings. Samples containing 30%v/v ethanol showed a plasmon peak at about 532 nm, demonstrating the presence of non-aggregated Au-NPs. Using higher ethanol concentrations, the absorbance of plasmon peak showed NP aggregation. By Dynamic Light Scattering measurements, a new particle population with an average diameter of about 60 nm was found. Moreover, TEM images showed that the NPs had spherical shape and the presence of a low-density halo around the metal core confirmed the presence of the protein shell. An irradiation dose of one kGy was enough to show changes in the plasmon peak characteristics. The increase in the chemical stability of protein shell was demonstrated by the reduction in the NP dissolution kinetics in presence of cyanate.

Radiation polymerisable compositions containing 3-sorboyloxy-2-hydroxypropyl groups

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

Green, G.E.

1976-02-03

Compounds having at least three 3-sorboyloxy-2-hydroxypropyl groups directly attached to ether oxygen atoms are polymerised by exposure to actinic radiation, preferably in the presence of a sensitizer such as Michler's ketone or benzoin. The compounds may be obtained by the reaction either of sorbic acid with a substance having at least three glycidyl ether groups or of glycidyl sorbate with a substance having at least three phenolic or alcoholic hydroxyl groups: if desired, not all of the glycidyl groups may be consumed, so that, after actinically induced polymerisation, the epoxide-containing polymer may be cross-linked by reaction with a curing agentmore » for epoxide resins. The compounds are useful in making printed circuits or printing plates for offset printing.« less

Irradiation of organic matter by uranium decay in the Alum Shale, Sweden

NASA Astrophysics Data System (ADS)

Lewan, M. D.; Buchardt, B.

1989-06-01

The Alum Shale of Sweden contains black shales with anomalously high uranium concentrations in excess of 100 ppm. Syngenetic or early diagenetic origin of this uranium indicates that organic matter within these shales has been irradiated by decaying uranium for approximately 500 Ma. Radiation-induced polymerization of alkanes through a free-radical cross-linking mechanism appears to be responsible for major alterations within the irradiated organic matter. Specific radiation-induced alterations include generation of condensate-like oils at reduced yields from hydrous pyrolysis experiments, decrease in atomic H/C ratios of kerogens, decrease in bitumen/organic-carbon ratios, and a relative increase in low-molecular weight triaromatic steroid hydrocarbons. Conversely, stable carbon isotopes of kerogens, reflectance of vitrinite-like macerais, oil-generation kinetics, and isomerization of 20R to 20S αα C 29-steranes were not affected by radiation. The radiation dosage needed to cause the alterations observed in the Alum Shale has been estimated to be in excess of 10 5 Mrads with respect to organic carbon. This value is used to estimate the potential for radiation damage to thermally immature organic matter in black shales through the geological rock record. High potential for radiation damage is not likely in Cenozoic and Mesozoic black shales but becomes more likely in lower Paleozoic and Precambrian black shales.

Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.

PubMed

Futera, Zdeněk; Burda, Jaroslav V

2014-07-15

Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (η(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA. Copyright © 2014 Wiley Periodicals, Inc.

Transepithelial photorefractive keratectomy with crosslinking for keratoconus.

PubMed

Mukherjee, Achyut N; Selimis, Vasilis; Aslanides, Ioannis

2013-01-01

To analyse visual, refractive and topographic outcomes of combining transepithelial photorefractive keratectomy (tPRK) with simultaneous corneal crosslinking for the visual rehabilitation of contact lens intolerant keratoconus patients. Patients with topographically significant keratoconus, limited corrected vision and intolerant of contact lenses were prospectively recruited, subject to ethical approval and consent. All patients underwent single step aspheric tPRK and sequential crosslinking. Preoperative vision, refraction, corneal topography and wavefront were assessed, with postoperative assessment at 1, 3, 6, and 12 months. 22 eyes of 14 patients were included in the pilot study. Mean age was 32 years (SD 6.8, range 24 to 43). Mean preoperative unaided vision was 1.39 LogMAR (SD 0.5) best corrected 0.31 LogMAR (SD 0.2). Mean preoperative spherical equivalent was -2.74 Diopters (D) (SD 4.1 range -12.25 to +7.75), and mean cylinder -2.9 D (SD 1.2, range 0 to -5.5). Mean central corneal thickness was 461um (SD 29, range 411 to 516). Vision improved postoperatively; unaided 0.32 LogMAR (SD 0.4), best corrected 0.11 (SD 0.13) (P=<0.005). Mean postoperative cylinder was -1.4D (SD1.2), significantly reduced (p<0.005). Maximum keratometry (Kmax) was stable throughout postoperative follow up. (p<0.05). Non topographic transepithelial PRK with simultaneous crosslinking improves vision, and may offer an alternative to keratoplasty in contact lens intolerant keratoconus. Further comparative studies to topographic PRK techniques are indicated.

Transepithelial Photorefractive Keratectomy with Crosslinking for Keratoconus

PubMed Central

Mukherjee, Achyut N; Selimis, Vasilis; Aslanides, Ioannis

2013-01-01

Purpose: To analyse visual, refractive and topographic outcomes of combining transepithelial photorefractive keratectomy (tPRK) with simultaneous corneal crosslinking for the visual rehabilitation of contact lens intolerant keratoconus patients. Methods: Patients with topographically significant keratoconus, limited corrected vision and intolerant of contact lenses were prospectively recruited, subject to ethical approval and consent. All patients underwent single step aspheric tPRK and sequential crosslinking. Preoperative vision, refraction, corneal topography and wavefront were assessed, with postoperative assessment at 1, 3, 6, and 12 months. Results: 22 eyes of 14 patients were included in the pilot study. Mean age was 32 years (SD 6.8, range 24 to 43). Mean preoperative unaided vision was 1.39 LogMAR (SD 0.5) best corrected 0.31 LogMAR (SD 0.2). Mean preoperative spherical equivalent was -2.74 Diopters (D) (SD 4.1 range -12.25 to +7.75), and mean cylinder -2.9 D (SD 1.2, range 0 to -5.5). Mean central corneal thickness was 461um (SD 29, range 411 to 516). Vision improved postoperatively; unaided 0.32 LogMAR (SD 0.4), best corrected 0.11 (SD 0.13) (P=<0.005). Mean postoperative cylinder was -1.4D (SD1.2), significantly reduced (p<0.005). Maximum keratometry (Kmax) was stable throughout postoperative follow up. (p<0.05). Conclusions: Non topographic transepithelial PRK with simultaneous crosslinking improves vision, and may offer an alternative to keratoplasty in contact lens intolerant keratoconus. Further comparative studies to topographic PRK techniques are indicated. PMID:24222809

Chitosan-bound pyridinedicarboxylate Ni(II) and Fe(III) complex biopolymer films as waste water decyanidation agents.

PubMed

Adewuyi, Sheriff; Jacob, Julianah Modupe; Olaleye, Oluwatoyin Omolola; Abdulraheem, Taofiq Olanrewaju; Tayo, Jubril Ayopo; Oladoyinbo, Fatai Oladipupo

2016-10-20

Chitosan is a biopolymer with immense structural advantage for chemical and mechanical modifications to generate novel properties, functions and applications. This work depicts new pyridinedicarboxylicacid (PDC) crosslinked chitosan-metal ion films as veritable material for cyanide ion removal from aqueous solution. The PDC-crosslinked chitosan-metal films (PDC-Chit-Ni(II) and PDC-Chit-Fe(III)) were formed by complexing PDC-crosslinked chitosan film with anhydrous nickel(II) and iron(III) chloride salts respectively. The PDC-Chit and its metal films were characterized employing various analytical and spectroscopic techniques. The FT-IR, UV-vis and the XRD results confirm the presence of the metal ions in the metal coordinated PDC-crosslinked chitosan film. The surface morphological difference of PDC-Chit-Ni(II) film before and after decyanidation was explored with scanning electron microscopy. Furthermore, the quantitative amount of nickel(II) and iron(III) present in the complex were determined using Atomic Absorption Spectrophotometer as 32.3 and 37.2μg/g respectively which portends the biopolymer film as a good complexing agent. Removal of cyanide from aqueous solution with PDC-Chit, PDC-Chit-Ni(II) and PDC-Chit-Fe(III) films was studied with batch equilibrium experiments. At equilibrium, decyanidation capacity (DC) followed the order PDC-Chit-Ni (II)≈PDC-Chit-Fe(III)>PDC-Chit. PDC-Chit-Ni(II) film gave 100% CN(-) removal within 40min decyanidation owing to favorable coordination geometry. Copyright © 2016 Elsevier Ltd. All rights reserved.

A facile approach toward multifunctional polyethersulfone membranes via in situ cross-linked copolymerization.

PubMed

Sun, Chuangchao; Ji, Haifeng; Qin, Hui; Nie, Shengqiang; Zhao, Weifeng; Zhao, Changsheng

2015-01-01

In this study, multifunctional polyethersulfone (PES) membranes are prepared via in situ cross-linked copolymerization coupled with a liquid-liquid phase separation technique. Acrylic acid (AA) and N-vinylpyrrolidone (VP) are copolymerized in PES solution, and the solution is then directly used to prepare PES membranes. The infrared and X-ray photoelectron spectroscopy testing, scanning electron microscopy, and water contact angle measurements confirm the successful modification of pristine PES membrane. Protein adsorption, platelet adhesion, plasma recalcification time, and activated partial thromboplastin time assays convince that the modified PES membranes have a better biocompatibility than pristine PES membrane. In addition, the modified membranes showed good protein antifouling property and significant adsorption property of cationic dye. The loading of Ag nanoparticles into the modified membranes endows the composite membranes with antibacterial activity.

Covalent immobilization of lipase onto chitosan-mesoporous silica hybrid nanomaterials by carboxyl functionalized ionic liquids as the coupling agent.

PubMed

Xiang, Xinran; Suo, Hongbo; Xu, Chao; Hu, Yi

2018-05-01

Chitosan-mesoporous silica SBA-15 hybrid nanomaterials (CTS-SBA-15) were synthesized by means of carboxyl functionalized ionic liquids as the coupling agent. The as-prepared CTS-SBA-15 support was characterized by TEM, FTIR, TG and nitrogen adsorption-desorption techniques. Porcine pancreas lipase (PPL) was then bound to the hybrid nanomaterials by using the cross-linking reagent glutaraldehyde (GA). Further, the parameters like cross-linking concentration, time and ratio of supports to enzyme were optimized. The property of immobilized lipase were tested in detail by enzyme activity assays. The results indicated that the hybrid nanomaterials could form three-dimensional (3D) structure with homogeneous mesoporous structures and immobilized PPL revealed excellent enzymatic performance. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of gamma irradiation on the thermal, mechanical and structural properties of chlorinated polyvinyl chloride

NASA Astrophysics Data System (ADS)

Nouh, S. A.

Non isothermal studies were carried out using thermogravimetry (TG) and differential thermogravimetry (DTG) to obtain the activation energy of decomposition for chlorinated polyvinyl chloride (CPVC) before and after exposure to gamma doses at levels between 5.0 and 50.0 KGy. Thermal gravitational analysis (TGA) indicated that the CPVC polymer decomposes in one main breakdown stage and a decrease in activation energies was observed followed by an increase on increasing the gamma dose. The variation of melting temperatures with the gamma dose has been determined using differential thermal analysis (DTA). Also, mechanical and structural property studies were performed on all irradiated and non-irradiated CPVC samples using stress-strain relations and X-ray diffraction. The results indicated that the exposure to gamma doses at levels between 27.5 and 50 KGy leads to further enhancement of the thermal stability, tensile strength and isotropic character of the polymer samples due to the crosslinking phenomenon. This suggests that gamma radiation could be a suitable technique for producing a plastic material with enhanced properties that can be suitable for high temperature applications and might be a suitable candidate for dosimetric applications.

A Study into the Collision-induced Dissociation (CID) Behavior of Cross-Linked Peptides*

PubMed Central

Giese, Sven H.; Fischer, Lutz; Rappsilber, Juri

2016-01-01

Cross-linking/mass spectrometry resolves protein–protein interactions or protein folds by help of distance constraints. Cross-linkers with specific properties such as isotope-labeled or collision-induced dissociation (CID)-cleavable cross-linkers are in frequent use to simplify the identification of cross-linked peptides. Here, we analyzed the mass spectrometric behavior of 910 unique cross-linked peptides in high-resolution MS1 and MS2 from published data and validate the observation by a ninefold larger set from currently unpublished data to explore if detailed understanding of their fragmentation behavior would allow computational delivery of information that otherwise would be obtained via isotope labels or CID cleavage of cross-linkers. Isotope-labeled cross-linkers reveal cross-linked and linear fragments in fragmentation spectra. We show that fragment mass and charge alone provide this information, alleviating the need for isotope-labeling for this purpose. Isotope-labeled cross-linkers also indicate cross-linker-containing, albeit not specifically cross-linked, peptides in MS1. We observed that acquisition can be guided to better than twofold enrich cross-linked peptides with minimal losses based on peptide mass and charge alone. By help of CID-cleavable cross-linkers, individual spectra with only linear fragments can be recorded for each peptide in a cross-link. We show that cross-linked fragments of ordinary cross-linked peptides can be linearized computationally and that a simplified subspectrum can be extracted that is enriched in information on one of the two linked peptides. This allows identifying candidates for this peptide in a simplified database search as we propose in a search strategy here. We conclude that the specific behavior of cross-linked peptides in mass spectrometers can be exploited to relax the requirements on cross-linkers. PMID:26719564

Thermal stability of electron-irradiated poly(tetrafluoroethylene) - X-ray photoelectron and mass spectroscopic study

NASA Technical Reports Server (NTRS)

Wheeler, Donald R.; Pepper, Stephen V.

1990-01-01

Polytetrafluoroethylene (PTFE) was subjected to 3 keV electron bombardment and then heated in vacuum to 300 C. The behavior of the material as a function of radiation dose and temperature was studied by X-ray photoelectron spectroscopy (XPS) of the surface and mass spectroscopy of the species evolved. Lightly damaged material heated to 300 C evolved saturated fluorocarbon species, whereas unsaturated fluorocarbon species were evolved from heavily damaged material. After heating the heavily damaged material, those features in the XPS spectrum that were associated with damage diminished, giving the appearance that the radiation damage had annealed. The observations were interpreted by incorporating mass transport of severed chain fragments and thermal decomposition of severely damaged material into the branched and cross-linked network model of irradiated PTFE. The apparent annealing of the radiation damage was due to covering of the network by saturated fragments that easily diffused through the decomposed material to the surface region upon heating.

Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

PubMed

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2013-12-30

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

Enrichment of Cross-Linked Peptides Using Charge-Based Fractional Diagonal Chromatography (ChaFRADIC).

PubMed

Tinnefeld, Verena; Venne, A Saskia; Sickmann, Albert; Zahedi, René P

2017-02-03

Chemical cross-linking of proteins is an emerging field with huge potential for the structural investigation of proteins and protein complexes. Owing to the often relatively low yield of cross-linking products, their identification in complex samples benefits from enrichment procedures prior to mass spectrometry analysis. So far, this is mainly accomplished by using biotin moieties in specific cross-linkers or by applying strong cation exchange chromatography (SCX) for a relatively crude enrichment. We present a novel workflow to enrich cross-linked peptides by utilizing charge-based fractional diagonal chromatography (ChaFRADIC). On the basis of two-dimensional diagonal SCX separation, we could increase the number of identified cross-linked peptides for samples of different complexity: pure cross-linked BSA, cross-linked BSA spiked into a simple protein mixture, and cross-linked BSA spiked into a HeLa lysate. We also compared XL-ChaFRADIC with size exclusion chromatography-based enrichment of cross-linked peptides. The XL-ChaFRADIC approach is straightforward, reproducible, and independent of the cross-linking chemistry and cross-linker properties.

Effects of (monomer - crosslinker – initiator) composition during non imprinted polymers synthesis for catechin retention

NASA Astrophysics Data System (ADS)

Triadhi, U.; Zulfikar, M. A.; Setiyanto, H.; Amran, M. B.

2018-05-01

MISPE (molecularly imprinted Solid Phase Extraction) is a separation technique using a solid adsorbent as a principle of MI (molecularly imprinted). Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, benzoyl peroxide (BPO) as an initiator and acetonitrile (ACN) as a porogen. Catechin will be used as the template. Thermal and microwave methods were employed in the synthesis method. When analyzed using FTIR spectra, it was found that there were no significant differences between NIP (non-imprinted polymer) resulting from thermal method and that resulting from microwave method. Preparation of polymers by microwave method required 4 mins at 60-65 °C, significantly less than thermal method, that took 60 minutes at the same temperature. The variations of mole ratios of the monomer, the crosslinker, and the initiator were also performed. Based on the FTIR spectra, intensity of some peaks were changed due to the decreases of concentration. The optimum composition for NIP synthesis was MAA: EGDMA: BPO ratio of 5:30:0.5 (in mmole). The TGA curve showed that the NIP sythesized using microwave method experienced mass loss of around 98.50% at 604.8 °C.

Nondestructive assessment of collagen hydrogel cross-linking using time-resolved autofluorescence imaging

NASA Astrophysics Data System (ADS)

Sherlock, Benjamin E.; Harvestine, Jenna N.; Mitra, Debika; Haudenschild, Anne; Hu, Jerry; Athanasiou, Kyriacos A.; Leach, J. Kent; Marcu, Laura

2018-03-01

We investigate the use of a fiber-based, multispectral fluorescence lifetime imaging (FLIm) system to nondestructively monitor changes in mechanical properties of collagen hydrogels caused by controlled application of widely used cross-linking agents, glutaraldehyde (GTA) and ribose. Postcross-linking, fluorescence lifetime images are acquired prior to the hydrogels being processed by rheological or tensile testing to directly probe gel mechanical properties. To preserve the sterility of the ribose-treated gels, FLIm is performed inside a biosafety cabinet (BSC). A pairwise correlation analysis is used to quantify the relationship between mean hydrogel fluorescence lifetimes and the storage or Young's moduli of the gels. In the GTA study, we observe strong and specific correlations between fluorescence lifetime and the storage and Young's moduli. Similar correlations are not observed in the ribose study and we postulate a reason for this. Finally, we demonstrate the ability of FLIm to longitudinally monitor dynamic cross-link formation. The strength of the GTA correlations and deployment of our fiber-based FLIm system inside the aseptic environment of a BSC suggests that this technique may be a valuable tool for the tissue engineering community where longitudinal assessment of tissue construct maturation in vitro is highly desirable.

Micro X-Ray Computed Tomography Mass Loss Assessment of Different UHMWPE: A Hip Joint Simulator Study on Standard vs. Cross-Linked Polyethylene

PubMed Central

Zanini, Filippo; Carmignato, Simone

2017-01-01

More than 60.000 hip arthroplasty are performed every year in Italy. Although Ultra-High-Molecular-Weight-Polyethylene remains the most used material as acetabular cup, wear of this material induces over time in vivo a foreign-body response and consequently osteolysis, pain, and the need of implant revision. Furthermore, oxidative wear of the polyethylene provoke several and severe failures. To solve these problems, highly cross-linked polyethylene and Vitamin-E-stabilized polyethylene were introduced in the last years. In in vitro experiments, various efforts have been made to compare the wear behavior of standard PE and vitamin-E infused liners. In this study we compared the in vitro wear behavior of two different configurations of cross-linked polyethylene (with and without the add of Vitamin E) vs. the standard polyethylene acetabular cups. The aim of the present study was to validate a micro X-ray computed tomography technique to assess the wear of different commercially available, polyethylene’s acetabular cups after wear simulation; in particular, the gravimetric method was used to provide reference wear values. The agreement between the two methods is documented in this paper. PMID:28107468

Preparation and characterization of cross-linked poly (vinyl alcohol)-graphene oxide nanocomposites as an interlayer for Schottky barrier diodes

NASA Astrophysics Data System (ADS)

Badrinezhad, Lida; Bilkan, Çigdem; Azizian-Kalandaragh, Yashar; Nematollahzadeh, Ali; Orak, Ikram; Altindal, Şemsettin

2018-01-01

Cross-linked polyvinyl alcohol (PVA) graphene oxide (GO) nanocomposites were prepared by simple solution-mixing route and characterized by Raman, UV-visible and fourier transform infrared (FT-IR) spectroscopy analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The XRD pattern and SEM analysis showed significant changes in the nanocomposite structures, and the FT-IR spectroscopy results confirmed the chemical interaction between the GO filler and the PVA matrix. After these morphological characterizations, PVA-GO-based diodes were fabricated and their electrical properties were characterized using current-voltage (I-V) and impedance-voltage-frequency (Z-V-f) measurements at room temperature. Semilogarithmic I-V characteristics of diode showed a good rectifier behavior. The values of C and G/ω increased with decreasing frequency due to the surface/interface states (Nss) which depend on the relaxation time and the frequency of the signal. The voltage, dependent profiles of Nss and series resistance (Rs) were obtained from the methods of high-low frequency capacitance and Nicollian and Brews, respectively. The obtained values of Nss and Rs were attributed to the use of cross-linked PVA-GO interlayer at the Au/n-Si interface.

pH-Mediated Fluorescent Polymer Particles and Gel from Hyperbranched Polyethylenimine and the Mechanism of Intrinsic Fluorescence.

PubMed

Liu, Shi Gang; Li, Na; Ling, Yu; Kang, Bei Hua; Geng, Shuo; Li, Nian Bing; Luo, Hong Qun

2016-02-23

We report that fluorescence properties and morphology of hyperbranched polyethylenimine (hPEI) cross-linked with formaldehyde are highly dependent on the pH values of the cross-linking reaction. Under acidic and neutral conditions, water-soluble fluorescent copolymer particles (CPs) were produced. However, under basic conditions, white gels with weak fluorescence emission would be obtained. The water-soluble hPEI-formaldehyde (hPEI-F) CPs show strong intrinsic fluorescence without the conjugation to any classical fluorescent agents. By the combination of spectroscopy and microscopy techniques, the mechanism of fluorescence emission was discussed. We propose that the intrinsic fluorescence originates from the formation of a Schiff base in the cross-linking process between hPEI and formaldehyde. Schiff base bonds are the fluorescence-emitting moieties, and the compact structure of hPEI-F CPs plays an important role in their strong fluorescence emission. The exploration on fluorescence mechanism may provide a new strategy to prepare fluorescent polymer particles. In addition, the investigation shows that the hPEI-F CPs hold potential as a fluorescent probe for the detection of copper ions in aqueous media.

Novel Magnetic Cross-Linked Cellulase Aggregates with a Potential Application in Lignocellulosic Biomass Bioconversion.

PubMed

Jia, Junqi; Zhang, Weiwei; Yang, Zengjie; Yang, Xianling; Wang, Na; Yu, Xiaoqi

2017-02-10

The utilization of renewable biomass resources to produce high-value chemicals by enzymatic processes is beneficial for alternative energy production, due to the accelerating depletion of fossil fuels. As immobilization techniques can improve enzyme stability and reusability, a novel magnetic cross-linked cellulase aggregate has been developed and applied for biomass bioconversion. The crosslinked aggregates could purify and immobilize enzymes in a single operation, and could then be combined with magnetic nanoparticles (MNPs), which provides easy separation of the materials. The immobilized cellulase showed a better activity at a wider temperature range and pH values than that of the free cellulase. After six cycles of consecutive reuse, the immobilized cellulase performed successful magnetic separation and retained 74% of its initial activity when carboxylmethyl cellulose (CMC) was used as the model substrate. Furthermore, the structure and morphology of the immobilized cellulase were studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Moreover, the immobilized cellulase was shown to hydrolyze bamboo biomass with a yield of 21%, and was re-used in biomass conversion up to four cycles with 38% activity retention, which indicated that the immobilized enzyme has good potential for biomass applications.

Crosslinking of agarose bioplastic using citric acid.

PubMed

Awadhiya, Ankur; Kumar, David; Verma, Vivek

2016-10-20

We report chemical crosslinking of agarose bioplastic using citric acid. Crosslinking was confirmed using Fourier transform infrared (FTIR) spectroscopy. The effects of crosslinking on the tensile strength, swelling, thermal stability, and degradability of the bioplastic were studied in detail. The tensile strength of the bioplastic films increased from 25.1MPa for control films up to a maximum of 52.7MPa for citric acid crosslinked films. At 37°C, the amount of water absorbed by crosslinked agarose bioplastic was only 11.5% of the amount absorbed by non-crosslinked controls. Thermogravimetric results showed that the crosslinked samples retain greater mass at high temperature (>450°C) than control samples. Moreover, while the crosslinked films were completely degradable, the rate of degradation was lower compared to non-crosslinked controls. Copyright © 2016 Elsevier Ltd. All rights reserved.

Characterization of UVC-induced DNA damage in bloodstains: forensic implications.

PubMed

Hall, Ashley; Ballantyne, Jack

2004-09-01

The ability to detect DNA polymorphisms using molecular genetic techniques has revolutionized the forensic analysis of biological evidence. DNA typing now plays a critical role within the criminal justice system, but one of the limiting factors with the technology is that DNA isolated from biological stains recovered from the crime scene is sometimes so damaged as to be intractable to analysis. Potential remedies for damaged DNA are likely to be dependent upon the precise nature of the DNA damage present in any particular sample but, unfortunately, current knowledge of the biochemical nature, and the extent, of such DNA damage in dried biological stains is rudimentary. As a model for DNA damage assessment in biological stains recovered from crime scenes, we have subjected human bloodstains and naked DNA in the hydrated and dehydrated states to varying doses of UVC radiation. It was possible to damage the DNA sufficiently in a bloodstain to cause a standard autosomal short tandem repeat (STR) profile to be lost. However, a detailed analysis of the process, based upon assays developed to detect bipyrimidine photoproducts (BPPPs), single- and double-strand breaks, and DNA-DNA crosslinks, produced some unexpected findings. Contrary to the situation with living tissues or cells in culture, the predominant UVC-induced damage to DNA in bloodstains appears not to be pyrimidine dimers. Although some evidence for the presence of BPPPs and DNA crosslinks was obtained, the major form of UVC damage causing genetic profile loss appeared to be single-strand breaks. It was not possible, however, to preclude the possibility that a combination of damage types was responsible for the profile loss observed. We demonstrate here that a significant measure of protection against UVC-mediated genetic profile loss in dried biological stain material is afforded by the dehydrated state of the DNA and, to a lesser extent, the DNA cellular milieu.

Pulse radiolysis in model studies toward radiation processing

NASA Astrophysics Data System (ADS)

Von Sonntag, C.; Bothe, E.; Ulanski, P.; Deeble, D. J.

1995-02-01

Using the pulse radiolysis technique, the OH-radical-induced reactions of poly(vinyl alcohol) PVAL, poly(acrylic acid) PAA, poly(methacrylic acid) PMA, and hyaluronic acid have been investigated in dilute aqueous solution. The reactions of the free-radical intermediates were followed by UV-spectroscopy and low-angle laser light-scattering; the scission of the charged polymers was also monitored by conductometry. For more detailed product studies, model systems such as 2,4-dihydroxypentane (for PVAL) and 2,4-dimethyl glutaric acid (for PAA) was also investigated. With PVA, OH-radicals react predominantly by abstraction of an H-atom in α-position to the hydroxyl group (70%). The observed bimolecular decay rate constant of the PVAL-radicals decreases with time. This has been interpreted as being due to an initially fast decay of proximate radicals and a decrease of the probability of such encounters with time. Intramolecular crosslinking (loop formation) predominates at high doses per pulse. In the presence of O 2, peroxyl radicals are formed which in the case of the α-hydroxyperoxyl radicals can eliminate HO 2-radicals in competition with bimolecular decay processes which lead to a fragmentation of the polymer. In PAA, radicals both in α-position (characterized by an absorption near 300 nm) and in β-position to the carboxylate groups are formed in an approximately 1:2 ratio. The lifetime of the radicals increases with increasing electrolytic dissociation of the polymer. The β-radicals undergo a slow (intra- as well as intermolecular) H-abstraction yielding α-radicals, in competition to crosslinking and scission reactions. In PMA only β-radicals are formed. Their fragmentation has been followed by conductometry. In hyaluronic acid, considerable fragmeentation is observed even in the absence of oxygen which, in fact, has some protective effect against this process. Thus free-radical attack on this important biopolymer makes it especially vulnerable with respect to a reduction of its viscosity, and in rheumatic diseases this effect may be the reason for their painfulnes.

Methotrexate loaded alginate microparticles and effect of Ca2+ post-crosslinking: An in vitro physicochemical and biological evaluation.

PubMed

Dhanka, Mukesh; Shetty, Chaitra; Srivastava, Rohit

2018-04-15

Methotrexate (MTX) loaded alginate microparticles were produced by simple water-in-oil (W/O) emulsion solvent diffusion method with homogenization and then subsequently cross-linked by Ca 2+ . The mean sizes of developed microparticles (bare non-crosslinked, crosslinked, drug-loaded non-crosslinked, and drug-loaded cross-linked) were found to be <11μm. The morphology of bare non-crosslinked and crosslinked microparticles were observed to be spherical with smooth surface morphology. However, MTX loaded non-crosslinked and crosslinked microparticles were found to have an irregular shape with rough surface morphology. The encapsulation efficiency (% EE) and loading capacity (% LC) of MTX loaded non-crosslinked microparticles were estimated to be 92.19±1.85 and 9.35±0.22, respectively. However, in case of cross-linked microparticles, the % EE and % LC values slightly decreased, i.e., 83.26±1.69% and 8.44±0.21%, respectively. Crosslinked microparticles were found to release MTX at a slower rate as compared to non-crosslinked microparticles. The physicochemical characterizations of microparticles by Fourier Transform Infrared Spectroscopy and High-Resolution X-Ray Diffraction have shown that drug encapsulated in the microparticles without chemical interactions has lost its crystalline nature. The biocompatibility and hemocompatibility studies of the microparticles have demonstrated that microparticles are biocompatible and were non-hemolytic at low concentrations. Copyright © 2017 Elsevier B.V. All rights reserved.

Structure-based non-canonical amino acid design to covalently crosslink an antibody–antigen complex

PubMed Central

Xu, Jianqing; Tack, Drew; Hughes, Randall A.; Ellington, Andrew D.; Gray, Jeffrey J.

2014-01-01

Engineering antibodies to utilize non-canonical amino acids (NCAA) should greatly expand the utility of an already important biological reagent. In particular, introducing crosslinking reagents into antibody complementarity determining regions (CDRs) should provide a means to covalently crosslink residues at the antibody–antigen interface. Unfortunately, finding the optimum position for crosslinking two proteins is often a matter of iterative guessing, even when the interface is known in atomic detail. Computer-aided antibody design can potentially greatly restrict the number of variants that must be explored in order to identify successful crosslinking sites. We have therefore used Rosetta to guide the introduction of an oxidizable crosslinking NCAA, l-3,4-dihydroxyphenylalanine (l-DOPA), into the CDRs of the anti-protective antigen scFv antibody M18, and have measured crosslinking to its cognate antigen, domain 4 of the anthrax protective antigen. Computed crosslinking distance, solvent accessibility, and interface energetics were three factors considered that could impact the efficiency of l-DOPA-mediated crosslinking. In the end, 10 variants were synthesized, and crosslinking efficiencies were generally 10% or higher, with the best variant crosslinking to 52% of the available antigen. The results suggest that computational analysis can be used in a pipeline for engineering crosslinking antibodies. The rules learned from l-DOPA crosslinking of antibodies may also be generalizable to the formation of other crosslinked interfaces and complexes. PMID:23680795

Untying a nanoscale knotted polymer structure to linear chains for efficient gene delivery in vitro and to the brain

NASA Astrophysics Data System (ADS)

Newland, B.; Aied, A.; Pinoncely, A. V.; Zheng, Y.; Zhao, T.; Zhang, H.; Niemeier, R.; Dowd, E.; Pandit, A.; Wang, W.

2014-06-01

The purpose of this study was to develop a platform transfection technology, for applications in the brain, which could transfect astrocytes without requiring cell specific functionalization and without the common cause of toxicity through high charge density. Here we show that a simple and scalable preparation technique can be used to produce a ``knot'' structured cationic polymer, where single growing chains can crosslink together via disulphide intramolecular crosslinks (internal cyclizations). This well-defined knot structure can thus ``untie'' under reducing conditions, showing a more favorable transfection profile for astrocytes compared to 25 kDa-PEI (48-fold), SuperFect® (39-fold) and Lipofectamine®2000 (18-fold) whilst maintaining neural cell viability at over 80% after four days of culture. The high transfection/lack of toxicity of this knot structured polymer in vitro, combined with its ability to mediate luciferase transgene expression in the adult rat brain, demonstrates its use as a platform transfection technology which should be investigated further for neurodegenerative disease therapies.The purpose of this study was to develop a platform transfection technology, for applications in the brain, which could transfect astrocytes without requiring cell specific functionalization and without the common cause of toxicity through high charge density. Here we show that a simple and scalable preparation technique can be used to produce a ``knot'' structured cationic polymer, where single growing chains can crosslink together via disulphide intramolecular crosslinks (internal cyclizations). This well-defined knot structure can thus ``untie'' under reducing conditions, showing a more favorable transfection profile for astrocytes compared to 25 kDa-PEI (48-fold), SuperFect® (39-fold) and Lipofectamine®2000 (18-fold) whilst maintaining neural cell viability at over 80% after four days of culture. The high transfection/lack of toxicity of this knot structured polymer in vitro, combined with its ability to mediate luciferase transgene expression in the adult rat brain, demonstrates its use as a platform transfection technology which should be investigated further for neurodegenerative disease therapies. Electronic supplementary information (ESI) available: 1H NMR spectroscopy data and gel permeation chromatography data. See DOI: 10.1039/c3nr06737h

Relationship between apposition pressure during welding and tensile strength of the acute weld

NASA Astrophysics Data System (ADS)

Wu, Paul J.; Walsh, Joseph T., Jr.

2001-05-01

Dye-assisted photothermal welding is a technique used to close wounds by thermally cross-linking collagen across apposed tissue edges. For a successful weld, not only do laser parameters have to be optimized, but also apposition of the incision has to be consistent and controlled. The objective of this study was to quantify the relationship between the applied apposition pressure (i.e., the compressive force holding the wound closed during the welding procedure divided by the area of the skin-to-skin interface) and the tensile strength of the wound following the welding procedure. By using a clamping device made of two complementary pieces, each 3 cm wide with a row of 10 equally spaced blunt wire mesh tips, the apposition pressure along a 2-cm-long incision in each albino guinea pig was quantified using a 127-micrometers -thick load cell and varied from 0-1.8 kgf/cm2. A continuous wave, Nd:YAG laser emitting 10.0 W of 1.06-micrometers radiation from a 600-micrometers -diameter fiber irradiating a 5-mm-diameter spot size was scanned across the incision in order to deliver 300 J of total energy. As the apposition pressure of the incisions was increased, the resulting tensile strength of welded skin increased in a sigmoidal manner. For this welding technique, an apposition pressure of at least 1.2 kgf/cm2 is necessary to obtain maximum weld strength of the skin (2.56+/- 0.36 kg/cm2).

Investigation of Test Methods, Material Properties, and Processes for Solar Cell Encapsulants

NASA Technical Reports Server (NTRS)

Willis, P. B.; Baum, B.

1979-01-01

The reformulation of a commercial grade of ethylene/vinyl acetate copolymer for use as a pottant in solar cell module manufacture was investigated. Potentially successful formulations were prepared by compounding the raw polymer with antioxidants, ultraviolet absorbers and crosslinking agents to yield stabilized and curable compositions. The resulting elastomer was found to offer low cost (approximately $0.80/lb.), low temperature processability, high transparency (91% transmission), and low modulus. Cured specimens of the final formulation endured 4000 hours of fluorescent sunlamp radiation without change which indicates excellent stability.

A study of the dynamic flammability of radiation cross-linked flame-retardant HDPE/EPDM/silicon-elastomer compound

NASA Astrophysics Data System (ADS)

Jia, Shaojin; Zhang, Zhicheng; Du, Zhiwen; Teng, Renrui; Wang, Zhengzhou

2003-04-01

A dynamic flammability study of flame-retardant compound consisting of HDPE, EPDM and silicon elastomer blended with additives, as wire and cable insulation was made before and after irradiation. The data of RHR, EHC, SEC and the concentration of CO and CO 2 from cone colorimeter shown in the burning process were accessed. By blending silicon elastomer, CO release rate was reduced and the thermal endurance was improved. Oxygen index, mechanical property, morphology of the char formed in dynamical flame and thermal stability were also investigated.

Friedel–Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery

PubMed Central

Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan

2014-01-01

Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel–Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion. PMID:24957118

The Formation Mechanism of Hydrogels.

PubMed

Lu, Liyan; Yuan, Shiliang; Wang, Jing; Shen, Yun; Deng, Shuwen; Xie, Luyang; Yang, Qixiang

2017-06-12

Hydrogels are degradable polymeric networks, in which cross-links play a vital role in structure formation and degradation. Cross-linking is a stabilization process in polymer chemistry that leads to the multi-dimensional extension of polymeric chains, resulting in network structures. By cross-linking, hydrogels are formed into stable structures that differ from their raw materials. Generally, hydrogels can be prepared from either synthetic or natural polymers. Based on the types of cross-link junctions, hydrogels can be categorized into two groups: the chemically cross-linked and the physically cross-linked. Chemically cross-linked gels have permanent junctions, in which covalent bonds are present between different polymer chains, thus leading to excellent mechanical strength. Although chemical cross-linking is a highly resourceful method for the formation of hydrogels, the cross-linkers used in hydrogel preparation should be extracted from the hydrogels before use, due to their reported toxicity, while, in physically cross-linked gels, dissolution is prevented by physical interactions, such as ionic interactions, hydrogen bonds or hydrophobic interactions. Physically cross-linked methods for the preparation of hydrogels are the alternate solution for cross-linker toxicity. Both methods will be discussed in this essay. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Novel magnetic cross-linked lipase aggregates for improving the resolution of (R, S)-2-octanol.

PubMed

Liu, Ying; Guo, Chen; Liu, Chun-Zhao

2015-03-01

Novel magnetic cross-linked lipase aggregates were fabricated by immobilizing the cross-linked lipase aggregates onto magnetic particles with a high number of -NH2 terminal groups using p-benzoquinone as the cross-linking agent. At the optimal fabrication conditions, 100% of immobilization efficiency and 139% of activity recovery of the magnetic cross-linked lipase aggregates were achieved. The magnetic cross-linked lipase aggregates were able to efficiently resolve (R, S)-2-octanol, and retained 100% activity and 100% enantioselectivity after 10 cycles of reuse, whereas the cross-linked lipase aggregates only retained about 50% activity and 70% enantioselectivity due to insufficient cross-linking. These results provide a great potential for industrial applications of the magnetic cross-linked lipase aggregates. © 2014 Wiley Periodicals, Inc.

Electrochemical detection of Hg (II) ions using EDTA-PANI/SWNTs nanocomposite modified SS electrode

NASA Astrophysics Data System (ADS)

Deshmukh, M. A.; Patil, H. K.; Shirsat, M. D.; Ramanavicius, A.

2017-05-01

Detection of Hg (II) ions using EDTA modified polyaniline (PANI) and single walled carbon nanotubes (SWNTs) nanocomposite (PANI/SWNTs) was performed electrochemically via cyclic voltammetry (CV) technique. Dodecyl benzene sulphonic next step, PANI/SWNTs nanocomposite was modified acid sodium salt (DBSA) was used as a surfactant during this synthesis to get uniform suspension SWNTs. In the by EDTA solution containing crosslinking agent 1-ethyl-3(3-(dimethylamino) propyl) - carbodiimide (EDC) utilizing dip coating technique. The sensitivity of EDTA modified PANI/SWNTs nanocomposite towards Hg (II) ions was investigated. Differential pulse voltammetry (DPV) technique was applied for the electrochemical detection of Hg (II) ions.

Mechanical Properties and Morphologies of Carboxyl-Terminated Butadiene Acrylonitrile Liquid Rubber/Epoxy Blends Compatibilized by Pre-Crosslinking.

PubMed

Xu, Shiai; Song, Xiaoxue; Cai, Yangben

2016-07-29

In order to enhance the compatibilization and interfacial adhesion between epoxy and liquid carboxyl-terminated butadiene acrylonitrile (CTBN) rubber, an initiator was introduced into the mixture and heated to initiate the cross-linking reaction of CTBN. After the addition of curing agents, the CTBN/epoxy blends with a localized interpenetrating network structure were prepared. The mechanical properties and morphologies of pre-crosslinked and non-crosslinked CTBN/epoxy blends were investigated. The results show that the tensile strength, elongation at break and impact strength of pre-crosslinked CTBN/epoxy blends are significantly higher than those of non-crosslinked CTBN/epoxy blends, which is primarily due to the enhanced interfacial strength caused by the chemical bond between the two phases and the localized interpenetrating network structure. Both pre-crosslinked and non-crosslinked CTBN/epoxy blends show a bimodal distribution of micron- and nano-sized rubber particles. However, pre-crosslinked CTBN/epoxy blends have smaller micron-sized rubber particles and larger nano-sized rubber particles than non-crosslinked CTBN/epoxy blends. The dynamic mechanical analysis shows that the storage modulus of pre-crosslinked CTBN/epoxy blends is higher than that of non-crosslinked CTBN/epoxy blends. The glass transition temperature of the CTBN phase in pre-crosslinked CTBN/epoxy blends increases slightly compared with the CTBN/epoxy system. The pre-crosslinking of rubber is a promising method for compatibilization and controlling the morphology of rubber-modified epoxy materials.

Mechanical Properties and Morphologies of Carboxyl-Terminated Butadiene Acrylonitrile Liquid Rubber/Epoxy Blends Compatibilized by Pre-Crosslinking

PubMed Central

Xu, Shiai; Song, Xiaoxue; Cai, Yangben

2016-01-01

In order to enhance the compatibilization and interfacial adhesion between epoxy and liquid carboxyl-terminated butadiene acrylonitrile (CTBN) rubber, an initiator was introduced into the mixture and heated to initiate the cross-linking reaction of CTBN. After the addition of curing agents, the CTBN/epoxy blends with a localized interpenetrating network structure were prepared. The mechanical properties and morphologies of pre-crosslinked and non-crosslinked CTBN/epoxy blends were investigated. The results show that the tensile strength, elongation at break and impact strength of pre-crosslinked CTBN/epoxy blends are significantly higher than those of non-crosslinked CTBN/epoxy blends, which is primarily due to the enhanced interfacial strength caused by the chemical bond between the two phases and the localized interpenetrating network structure. Both pre-crosslinked and non-crosslinked CTBN/epoxy blends show a bimodal distribution of micron- and nano-sized rubber particles. However, pre-crosslinked CTBN/epoxy blends have smaller micron-sized rubber particles and larger nano-sized rubber particles than non-crosslinked CTBN/epoxy blends. The dynamic mechanical analysis shows that the storage modulus of pre-crosslinked CTBN/epoxy blends is higher than that of non-crosslinked CTBN/epoxy blends. The glass transition temperature of the CTBN phase in pre-crosslinked CTBN/epoxy blends increases slightly compared with the CTBN/epoxy system. The pre-crosslinking of rubber is a promising method for compatibilization and controlling the morphology of rubber-modified epoxy materials. PMID:28773762

The effect of riboflavin/UVA collagen cross-linking therapy on the structure and hydrodynamic behaviour of the ungulate and rabbit corneal stroma.

PubMed

Hayes, Sally; Kamma-Lorger, Christina S; Boote, Craig; Young, Robert D; Quantock, Andrew J; Rost, Anika; Khatib, Yasmeen; Harris, Jonathan; Yagi, Naoto; Terrill, Nicholas; Meek, Keith M

2013-01-01

To examine the effect of riboflavin/UVA corneal crosslinking on stromal ultrastructure and hydrodynamic behaviour. One hundred and seventeen enucleated ungulate eyes (112 pig and 5 sheep) and 3 pairs of rabbit eyes, with corneal epithelium removed, were divided into four treatment groups: Group 1 (28 pig, 2 sheep and 3 rabbits) were untreated; Group 2 (24 pig) were exposed to UVA light (3.04 mW/cm(2)) for 30 minutes and Group 3 (29 pig) and Group 4 (31 pig, 3 sheep and 3 rabbits) had riboflavin eye drops applied to the corneal surface every 5 minutes for 35 minutes. Five minutes after the initial riboflavin instillation, the corneas in Group 4 experienced a 30 minute exposure to UVA light (3.04 mW/cm(2)). X-ray scattering was used to obtain measurements of collagen interfibrillar spacing, spatial order, fibril diameter, D-periodicity and intermolecular spacing throughout the whole tissue thickness and as a function of tissue depth in the treated and untreated corneas. The effect of each treatment on the hydrodynamic behaviour of the cornea (its ability to swell in saline solution) and its resistance to enzymatic digestion were assessed using in vitro laboratory techniques. Corneal thickness decreased significantly following riboflavin application (p<0.01) and also to a lesser extent after UVA exposure (p<0.05). With the exception of the spatial order factor, which was higher in Group 4 than Group 1 (p<0.01), all other measured collagen parameters were unaltered by cross-linking, even within the most anterior 300 microns of the cornea. The cross-linking treatment had no effect on the hydrodynamic behaviour of the cornea but did cause a significant increase in its resistance to enzymatic digestion. It seems likely that cross-links formed during riboflavin/UVA therapy occur predominantly at the collagen fibril surface and in the protein network surrounding the collagen.

The Effect of Riboflavin/UVA Collagen Cross-linking Therapy on the Structure and Hydrodynamic Behaviour of the Ungulate and Rabbit Corneal Stroma

PubMed Central

Hayes, Sally; Kamma-Lorger, Christina S.; Boote, Craig; Young, Robert D.; Quantock, Andrew J.; Rost, Anika; Khatib, Yasmeen; Harris, Jonathan; Yagi, Naoto; Terrill, Nicholas; Meek, Keith M.

2013-01-01

Purpose To examine the effect of riboflavin/UVA corneal crosslinking on stromal ultrastructure and hydrodynamic behaviour. Methods One hundred and seventeen enucleated ungulate eyes (112 pig and 5 sheep) and 3 pairs of rabbit eyes, with corneal epithelium removed, were divided into four treatment groups: Group 1 (28 pig, 2 sheep and 3 rabbits) were untreated; Group 2 (24 pig) were exposed to UVA light (3.04 mW/cm2) for 30 minutes and Group 3 (29 pig) and Group 4 (31 pig, 3 sheep and 3 rabbits) had riboflavin eye drops applied to the corneal surface every 5 minutes for 35 minutes. Five minutes after the initial riboflavin instillation, the corneas in Group 4 experienced a 30 minute exposure to UVA light (3.04 mW/cm2). X-ray scattering was used to obtain measurements of collagen interfibrillar spacing, spatial order, fibril diameter, D-periodicity and intermolecular spacing throughout the whole tissue thickness and as a function of tissue depth in the treated and untreated corneas. The effect of each treatment on the hydrodynamic behaviour of the cornea (its ability to swell in saline solution) and its resistance to enzymatic digestion were assessed using in vitro laboratory techniques. Results Corneal thickness decreased significantly following riboflavin application (p<0.01) and also to a lesser extent after UVA exposure (p<0.05). With the exception of the spatial order factor, which was higher in Group 4 than Group 1 (p<0.01), all other measured collagen parameters were unaltered by cross-linking, even within the most anterior 300 microns of the cornea. The cross-linking treatment had no effect on the hydrodynamic behaviour of the cornea but did cause a significant increase in its resistance to enzymatic digestion. Conclusions It seems likely that cross-links formed during riboflavin/UVA therapy occur predominantly at the collagen fibril surface and in the protein network surrounding the collagen. PMID:23349690

The role of living/controlled radical polymerization in the formation of improved imprinted polymers.

PubMed

Salian, Vishal D; Vaughan, Asa D; Byrne, Mark E

2012-06-01

In this work, living/controlled radical polymerization (LRP) is compared with conventional free radical polymerization in the creation of highly and weakly cross-linked imprinted poly(methacrylic acid-co-ethylene glycol dimethacrylate) networks. It elucidates, for the first time, the effect of LRP on the chain level and begins to explain why the efficiency of the imprinting process is improved using LRP. Imprinted polymers produced via LRP exhibited significantly higher template affinity and capacity compared with polymers prepared using conventional methods. The use of LRP in the creation of highly cross-linked imprinted polymers resulted in a fourfold increase in binding capacity without a decrease in affinity; whereas weakly cross-linked gels demonstrated a nearly threefold increase in binding capacity at equivalent affinity when LRP was used. In addition, by adjusting the double bond conversion, we can choose to increase either the capacity or the affinity in highly cross-linked imprinted polymers, thus allowing the creation of imprinted polymers with tailorable binding parameters. Using free radical polymerization in the creation of polymer chains, as the template-monomer ratio increased, the average molecular weight of the polymer chains decreased despite a slight increase in the double bond conversion. Thus, the polymer chains formed were shorter but greater in number. Using LRP neutralized the effect of the template. The addition of chain transfer agent resulted in slow, uniform, simultaneous chain growth, resulting in the formation of longer more monodisperse chains. Reaction analysis revealed that propagation time was extended threefold in the formation of highly cross-linked polymers when LRP techniques were used. This delayed the transition to the diffusion-controlled stage of the reaction, which in turn led to the observed enhanced binding properties, decreased polydispersity in the chains, and a more homogeneous macromolecular architecture. Copyright © 2012 John Wiley & Sons, Ltd.

Effect of X-ray flux on polytetrafluoroethylene in X-ray photoelectron spectroscopy

NASA Technical Reports Server (NTRS)

Wheeler, D. R.; Pepper, S. V.

1982-01-01

The effect of the X-ray flux in X-ray photoelectron spectroscopy (STAT) on the constitution of the polytetrafluoroethylene (PTFE) surface has been examined. The radiation dose rate for our specimen was about 10 to the 7th rad/s. The structure, magnitude and binding energy of the C(1s) and F(1s) features of the XPS spectrum and the mass spectrum of gaseous species evolved during irradiation are observed. The strong time dependence of these signals over a period of several hours indicated that the surface constitution of PTFE is greatly affected by this level of radiation dose. The results are consistent with the development of a heavily cross-linked or branched structure in the PTFE surface region and the evolution of short chain fragments into the gas phase.

Radiation-induced polymerization for the immobilization of penicillin acylase

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

Boccu, E.; Carenza, M.; Lora, S.

The immobilization of Escherichia coli penicillin acylase was investigated by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperature. A leak-proof composite that does not swell in water was obtained by adding the cross-linking agent trimethylolpropane trimethacrylate to the monomer-aqueous enzyme mixture. Penicillin acylase, which was immobilized with greater than 70% yield, possessed a higher Km value toward the substrate 6-nitro-3-phenylacetamidobenzoic acid than the free enzyme form (Km = 1.7 X 10(-5) and 1 X 10(-5) M, respectively). The structural stability of immobilized penicillin acylase, as assessed by heat, guanidinium chloride, and pH denaturation profiles, was very similar to that ofmore » the free-enzyme form, thus suggesting that penicillin acylase was entrapped in its native state into aqueous free spaces of the polymer matrix.« less

Modeling Protein Excited-state Structures from "Over-length" Chemical Cross-links.

PubMed

Ding, Yue-He; Gong, Zhou; Dong, Xu; Liu, Kan; Liu, Zhu; Liu, Chao; He, Si-Min; Dong, Meng-Qiu; Tang, Chun

2017-01-27

Chemical cross-linking coupled with mass spectroscopy (CXMS) provides proximity information for the cross-linked residues and is used increasingly for modeling protein structures. However, experimentally identified cross-links are sometimes incompatible with the known structure of a protein, as the distance calculated between the cross-linked residues far exceeds the maximum length of the cross-linker. The discrepancies may persist even after eliminating potentially false cross-links and excluding intermolecular ones. Thus the "over-length" cross-links may arise from alternative excited-state conformation of the protein. Here we present a method and associated software DynaXL for visualizing the ensemble structures of multidomain proteins based on intramolecular cross-links identified by mass spectrometry with high confidence. Representing the cross-linkers and cross-linking reactions explicitly, we show that the protein excited-state structure can be modeled with as few as two over-length cross-links. We demonstrate the generality of our method with three systems: calmodulin, enzyme I, and glutamine-binding protein, and we show that these proteins alternate between different conformations for interacting with other proteins and ligands. Taken together, the over-length chemical cross-links contain valuable information about protein dynamics, and our findings here illustrate the relationship between dynamic domain movement and protein function. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Polymer electrolyte based on crosslinked poly(glycidyl methacrylate) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

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

Fei, Beatrice Wong Chui; Hanifah, Sharina Abu; Ahmad, Azizan

2015-09-25

Polymer electrolytes based on crosslinked poly(glycidyl methacrylate) as polymer host and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BmimTFSI) as incorporated salt were prepared by in-situ photopolymerization technique. The complexes with different mass ratio of glycidyl methacrylate (GMA) monomer to BmimTFSI were investigated. The ionic conductivity of the polymer electrolyte was increased and reach the highest value of 7.50 × 10{sup −4} S cm{sup −1} at the ratio of 3:7 (GMA: BmimTFSI). The interaction between the polymer host and ionic liquid was proved by Attenuated Total Reflectance-Fourier Transformation Infra-Red Spectroscopy (ATR-FTIR). Meanwhile, the X-ray diffraction analysis shows the amorphousity of the polymer electrolyte film increasemore » with the ionic liquid ratio.« less

Photoresist Design for Elastomeric Light Tunable Photonic Devices

PubMed Central

Nocentini, Sara; Martella, Daniele; Parmeggiani, Camilla; Wiersma, Diederik S.

2016-01-01

An increasing interest in tunable photonic structures is growing within the photonic community. The usage of Liquid Crystalline Elastomer (LCE) structures in the micro-scale has been motivated by the potential to remotely control their properties. In order to design elastic photonic structures with a three-dimensional lithographic technique, an analysis of the different mixtures used in the micro-printing process is required. Previously reported LCE microstructures suffer damage and strong swelling as a limiting factor of resolution. In this article, we reported a detailed study on the writing process with four liquid crystalline photoresists, in which the percentage of crosslinker is gradually increased. The experiments reveal that exploiting the crosslinking degree is a possible means in which to obtain suspended lines with good resolution, quite good rigidity, and good elasticity, thereby preserving the possibility of deformation by light irradiation. PMID:28773646

Photoresist Design for Elastomeric Light Tunable Photonic Devices.

PubMed

Nocentini, Sara; Martella, Daniele; Parmeggiani, Camilla; Wiersma, Diederik S

2016-06-29

An increasing interest in tunable photonic structures is growing within the photonic community. The usage of Liquid Crystalline Elastomer (LCE) structures in the micro-scale has been motivated by the potential to remotely control their properties. In order to design elastic photonic structures with a three-dimensional lithographic technique, an analysis of the different mixtures used in the micro-printing process is required. Previously reported LCE microstructures suffer damage and strong swelling as a limiting factor of resolution. In this article, we reported a detailed study on the writing process with four liquid crystalline photoresists, in which the percentage of crosslinker is gradually increased. The experiments reveal that exploiting the crosslinking degree is a possible means in which to obtain suspended lines with good resolution, quite good rigidity, and good elasticity, thereby preserving the possibility of deformation by light irradiation.

The advancement of chemical cross-linking and mass spectrometry for structural proteomics: from single proteins to protein interaction networks.

PubMed

Sinz, Andrea

2014-12-01

During the last 15 years, chemical cross-linking combined with mass spectrometry (MS) and computational modeling has advanced from investigating 3D-structures of isolated proteins to deciphering protein interaction networks. In this article, the author discusses the advent, the development and the current status of the chemical cross-linking/MS strategy in the context of recent technological developments. A direct way to probe in vivo protein-protein interactions is by site-specific incorporation of genetically encoded photo-reactive amino acids or by non-directed incorporation of photo-reactive amino acids. As the chemical cross-linking/MS approach allows the capture of transient and weak interactions, it has the potential to become a routine technique for unraveling protein interaction networks in their natural cellular environment.

Levels of mature cross-links and advanced glycation end product cross-links in human vitreous.

PubMed

Matsumoto, Yukihiro; Takahashi, Masaaki; Chikuda, Makoto; Arai, Kiyomi

2002-01-01

To determine the levels of pyridinoline and deoxypyridinoline, two mature enzymatic cross-links, and pentosidine, an advanced glycation end product (AGE) cross-link, in the human vitreous, and to investigate the correlations among the cross-links and the effects of aging and diabetes mellitus (DM) on the levels of cross-links. Forty-five vitreous samples were collected from 32 patients (32 eyes) undergoing vitrectomy for diabetic retinopathy (DM group) and from 13 patients (13 eyes) (control group) who were age- and sex-matched patients with idiopathic macular hole or epiretinal membrane with no systemic conditions. The levels of the cross-links were determined using high-performance liquid chromatography after acid hydrolysis and pretreatment with SP-Sephadex. The levels of pentosidine, pyridinoline, and deoxypyridinoline were 27.3 +/- 23.1 (mean +/- SD) pmol/mL (detectable in 45 of 45 specimens), 79.0 +/- 40.2 ng/mL (43 of 45 specimens), and 54.0 +/- 9.5 (32 of 45 specimens) ng/mL, respectively. When the vitreous samples from the DM and the control groups were compared, a significant difference (P <.05) was found in the pentosidine level but not in the levels of pyridinoline or deoxypyridinoline. No significant correlations were found between age and the cross-links. Significant correlations (P <.01) were found among the cross-links. The results indicate that mature cross-link substances exist in the human vitreous. The results also suggest that glycation may occur in the vitreous after mature cross-links form and result in the formation of AGE cross-links. In human vitreous from patients with DM, increased levels of AGE cross-links may stabilize the formation of mature cross-links, but they did not increase the mature cross-links.

To Cross-Link or Not to Cross-Link? Cross-Linking Associated Foreign Body Response of Collagen-Based Devices

PubMed Central

Delgado, Luis M.; Bayon, Yves; Pandit, Abhay

2015-01-01

Collagen-based devices, in various physical conformations, are extensively used for tissue engineering and regenerative medicine applications. Given that the natural cross-linking pathway of collagen does not occur in vitro, chemical, physical, and biological cross-linking methods have been assessed over the years to control mechanical stability, degradation rate, and immunogenicity of the device upon implantation. Although in vitro data demonstrate that mechanical properties and degradation rate can be accurately controlled as a function of the cross-linking method utilized, preclinical and clinical data indicate that cross-linking methods employed may have adverse effects on host response, especially when potent cross-linking methods are employed. Experimental data suggest that more suitable cross-linking methods should be developed to achieve a balance between stability and functional remodeling. PMID:25517923

Laccase immobilization and insolubilization: from fundamentals to applications for the elimination of emerging contaminants in wastewater treatment.

PubMed

Ba, Sidy; Arsenault, Alexandre; Hassani, Thanina; Jones, J Peter; Cabana, Hubert

2013-12-01

Over the last few decades many attempts have been made to use biocatalysts for the biotransformation of emerging contaminants in environmental matrices. Laccase, a multicopper oxidoreductase enzyme, has shown great potential in oxidizing a large number of phenolic and non-phenolic emerging contaminants. However, laccases and more broadly enzymes in their free form are biocatalysts whose applications in solution have many drawbacks rendering them currently unsuitable for large scale use. To circumvent these limitations, the enzyme can be immobilized onto carriers or entrapped within capsules; these two immobilization techniques have the disadvantage of generating a large mass of non-catalytic product. Insolubilization of the free enzymes as cross-linked enzymes (CLEAs) is found to yield a greater volume ratio of biocatalyst while improving the characteristics of the biocatalyst. Ultimately, novel techniques of enzymes insolubilization and stabilization are feasible with the combination of cross-linked enzyme aggregates (combi-CLEAs) and enzyme polymer engineered structures (EPESs) for the elimination of emerging micropollutants in wastewater. In this review, fundamental features of laccases are provided in order to elucidate their catalytic mechanism, followed by different chemical aspects of the immobilization and insolubilization techniques applicable to laccases. Finally, kinetic and reactor design effects for enzymes in relation with the potential applications of laccases as combi-CLEAs and EPESs for the biotransformation of micropollutants in wastewater treatment are discussed.

Magnetic response of gelatin ferrogels across the sol-gel transition: the influence of high energy crosslinking on thermal stability.

PubMed

Wisotzki, Emilia I; Eberbeck, Dietmar; Kratz, Harald; Mayr, Stefan G

2016-05-07

As emerging responsive materials, ferrogels have demonstrated significant potential for applications in areas of engineering to regenerative medicine. Promising techniques to study the behavior of magnetic nanoparticles (MNPs) in such matrices include magnetic particle spectroscopy (MPS) and magnetorelaxometry (MRX). This work investigated the magnetic response of gelatin-based ferrogels with increasing temperatures, before and after high energy crosslinking. The particle response was characterized by the nonlinear magnetization using MPS and quasistatic magnetization measurements as well as MRX to discriminate between Néel and Brownian relaxation mechanisms. The effective magnetic response of MNPs in gelatin was suppressed, indicating that the magnetization of the ferrogels was strongly influenced by competing dipole-dipole interactions. Significant changes in the magnetic behavior were observed across the gelatin sol-gel transition, as influenced by the matrix viscosity. These relaxation processes were modeled by Fourier transformation of the Langevin function, combined with a Debye term for the nonlinear magnetic response, for single core MNPs embedded in matrices of changing viscosities. Using high energy electron irradiation as a crosslinking method, modified ferrogels exhibited thermal stability on a range of timescales. However, MRX relaxation times revealed a slight softening around the gelatin sol-gel transition felt by the smallest particles, demonstrating a high sensitivity to observe local changes in the viscoelasticity. Overall, MPS and MRX functioned as non-contact methods to observe changes in the nanorheology around the native sol-gel transition and in crosslinked ferrogels, as well as provided an understanding of how MNPs were integrated into and influenced by the surrounding matrix.

Surface Wave Elastometry of the Cornea in Porcine and Human Donor Eyes

PubMed Central

Dupps, William J.; Netto, Marcelo V.; Herekar, Satish; Krueger, Ronald R.

2007-01-01

PURPOSE To introduce a nondestructive technique for characterization of corneal stiffness, determine measurement precision, and investigate comparative stiffness values along central, radial, and circumferential vectors in porcine corneas. The effects of epithelial debridement, relaxing incisions, and crosslink-mediated stiffening on surface wave velocity are also studied. METHODS A handheld prototype system was used to measure ultrasound surface wave propagation time between two fixed-distance transducers along a ten-position map. Repeatability was assessed with replicate measurements in 6 porcine corneas. In 12 porcine globes with controlled intraocular pressure (IOP), serial measurements were performed before and after epithelial removal, then after 250- and 750-μm-deep relaxing incisions. In human globes with constant intravitreal pressure, central wave velocity and transcorneal IOP measurements were compared before and after collagen cross-linking. RESULTS Measurement repeatability across all regions was between 2.2% and 8.1%. Epithelial removal resulted in increases in measured stiffness in 67% of eyes, but statistical power was insufficient to detect a systematic change. Wave velocity across a central incision decreased significantly after 250-μm keratotomy (P<.001), but did not undergo a significant further decrease with deeper keratotomy. Meridional stiffness changes consistent with coupling effects were detected after keratotomy. Surface wave velocity and transcorneal IOP measurements increased markedly after collagen cross-linking despite maintenance of a constant IOP. CONCLUSIONS Handheld corneal elastometry provides a repeatable measure of regional stiffness changes after relaxing incisions and collagen cross-linking in in vitro experiments. Surface wave elastometry allows focal assessment of corneal biomechanical properties that are relevant in refractive surgery, ectatic disease, and glaucoma. PMID:17269246

Polymerase cross-linking spiral reaction (PCLSR) for detection of African swine fever virus (ASFV) in pigs and wild boars

PubMed Central

Woźniakowski, Grzegorz; Frączyk, Magdalena; Kowalczyk, Andrzej; Pomorska-Mól, Małgorzata; Niemczuk, Krzysztof; Pejsak, Zygmunt

2017-01-01

The study reports the development of a polymerase cross-linking spiral reaction (PCLSR) for the detection of African swine fever virus (ASFV) DNA in blood collected from infected pigs and wild boars. The method uses 3 specifically designed primers. Two outer-spiral primers comprising of 3′ sequences complementary to ASFV p72 gene sequence and 5′end sequences complementary to exogenous gene of black widow alpha-latrotoxin as well as additional ASFV specific cross-linking primer. The method is specific exclusively to ASFV DNA without cross-reactions with cDNA of classical swine fever virus (CSFV), porcine reproductive respiratory syndrome (PRRSV) or porcine epidemic diarrhea virus (PEDV). The sensitivity of this technique reached 7.2 × 102 copies per μl−1 of plasmid containing p72 gene. The PCLSR was conducted at 65 °C creating cross-linked complex structures. The results of PCLSR were visualized using SYBR Green I dye, gel electrophoresis while the reaction progress was traced using real-time PCR system that resulted in registration of fluorescent curves and melting peaks at 85.3 °C. The developed PCLSR was examined using blood or tissue samples collected from selected 17 ASF cases from infected wild boars and 3 outbreaks in pigs. Further tests have been also conducted using 55 tissue samples from 23 outbreaks and 22 cases. These results showed that PCLSR might be further used for preliminary and cost-effective detection and surveillance of ASFV. PMID:28198455

Polymerase cross-linking spiral reaction (PCLSR) for detection of African swine fever virus (ASFV) in pigs and wild boars.

PubMed

Woźniakowski, Grzegorz; Frączyk, Magdalena; Kowalczyk, Andrzej; Pomorska-Mól, Małgorzata; Niemczuk, Krzysztof; Pejsak, Zygmunt

2017-02-15

The study reports the development of a polymerase cross-linking spiral reaction (PCLSR) for the detection of African swine fever virus (ASFV) DNA in blood collected from infected pigs and wild boars. The method uses 3 specifically designed primers. Two outer-spiral primers comprising of 3' sequences complementary to ASFV p72 gene sequence and 5'end sequences complementary to exogenous gene of black widow alpha-latrotoxin as well as additional ASFV specific cross-linking primer. The method is specific exclusively to ASFV DNA without cross-reactions with cDNA of classical swine fever virus (CSFV), porcine reproductive respiratory syndrome (PRRSV) or porcine epidemic diarrhea virus (PEDV). The sensitivity of this technique reached 7.2 × 10 2 copies per μl -1 of plasmid containing p72 gene. The PCLSR was conducted at 65 °C creating cross-linked complex structures. The results of PCLSR were visualized using SYBR Green I dye, gel electrophoresis while the reaction progress was traced using real-time PCR system that resulted in registration of fluorescent curves and melting peaks at 85.3 °C. The developed PCLSR was examined using blood or tissue samples collected from selected 17 ASF cases from infected wild boars and 3 outbreaks in pigs. Further tests have been also conducted using 55 tissue samples from 23 outbreaks and 22 cases. These results showed that PCLSR might be further used for preliminary and cost-effective detection and surveillance of ASFV.

Development, optimization and evaluation of curcumin loaded biodegradable crosslinked gelatin film for the effective treatment of periodontitis.

PubMed

Chauhan, Sheetal; Bansal, Monika; Khan, Gayasuddin; Yadav, Sarita K; Singh, Ashish K; Prakash, Pradyot; Mishra, Brahmeshwar

2018-07-01

Aim of the present study was to prepare curcumin (CUR) loaded biodegradable crosslinked gelatin (GE) film to alleviate the existing shortcomings in the treatment of periodontitis. Gelatin film was optimized to provide anticipated mucoadhesive strength, mechanical properties, folding endurance, and prolonged drug release over treatment duration, for successful application in the periodontitis. The film was developed by using solvent casting technique and "Design of Experiments" approach was employed for evaluating the influence of independent variables on dependent response variables. Solid-state characterization of the film was performed by FTIR, XRD, and SEM. Further, prepared formulations were evaluated for drug content uniformity, surface pH, folding endurance, swelling index, mechanical strength, mucoadhesive strength, in vitro biodegradation, and in vitro drug release behavior. Solid state characterization of the formulation showed that CUR is physico-chemically compatible with other excipients and CUR was entrapped in an amorphous form inside the smooth and uniform film. The optimized film showed degree of crosslinking 51.04 ± 2.4, swelling index 138.10 ± 1.25, and folding endurance 270 ± 3 with surface pH around 7.0. Crosslinker concentrations positively affected swelling index and biodegradation of film due to altered matrix density of the polymer. Results of in vitro drug release demonstrated the capability of the developed film for efficiently delivering CUR in a sustained manner up to 7 days. The developed optimized film could be considered as a promising delivery strategy to administer medicament locally into the periodontal pockets for the safe and efficient management of periodontitis.

Enzyme-catalyzed crosslinkable hydrogels: emerging strategies for tissue engineering.

PubMed

Teixeira, Liliana S Moreira; Feijen, Jan; van Blitterswijk, Clemens A; Dijkstra, Pieter J; Karperien, Marcel

2012-02-01

State-of-the-art bioactive hydrogels can easily and efficiently be formed by enzyme-catalyzed mild-crosslinking reactions in situ. Yet this cell-friendly and substrate-specific method remains under explored. Hydrogels prepared by using enzyme systems like tyrosinases, transferases and lysyl oxidases show interesting characteristics as dynamic scaffolds and as systems for controlled release. Increased attention is currently paid to hydrogels obtained via crosslinking of precursors by transferases or peroxidases as catalysts. Enzyme-mediated crosslinking has proven its efficiency and attention has now shifted to the development of enzymatically crosslinked hydrogels with higher degrees of complexity, mimicking extracellular matrices. Moreover, bottom-up approaches combining biocatalysts and self-assembly are being explored for the development of complex nano-scale architectures. In this review, the use of enzymatic crosslinking for the preparation of hydrogels as an innovative alternative to other crosslinking methods, such as the commonly used UV-mediated photo-crosslinking or physical crosslinking, will be discussed. Photo-initiator-based crosslinking may induce cytotoxicity in the formed gels, whereas physical crosslinking may lead to gels which do not have sufficient mechanical strength and stability. These limitations can be overcome using enzymes to form covalently crosslinked hydrogels. Herewith, we report the mechanisms involved and current applications, focusing on emerging strategies for tissue engineering and regenerative medicine. Copyright © 2011 Elsevier Ltd. All rights reserved.

Link establishment criterion and topology optimization for hybrid GPS satellite communications with laser crosslinks

NASA Astrophysics Data System (ADS)

Li, Lun; Wei, Sixiao; Tian, Xin; Hsieh, Li-Tse; Chen, Zhijiang; Pham, Khanh; Lyke, James; Chen, Genshe

2018-05-01

In the current global positioning system (GPS), the reliability of information transmissions can be enhanced with the aid of inter-satellite links (ISLs) or crosslinks between satellites. Instead of only using conventional radio frequency (RF) crosslinks, the laser crosslinks provide an option to significantly increase the data throughput. The connectivity and robustness of ISL are needed for analysis, especially for GPS constellations with laser crosslinks. In this paper, we first propose a hybrid GPS communication architecture in which uplinks and downlinks are established via RF signals and crosslinks are established via laser links. Then, we design an optical crosslink assignment criteria considering the practical optical communication factors such as optical line- of-sight (LOS) range, link distance, and angular velocity, etc. After that, to further improve the rationality of establishing crosslinks, a topology control algorithm is formulated to optimize GPS crosslink networks at both physical and network layers. The RF transmission features for uplink and downlink and optical transmission features for crosslinks are taken into account as constraints for the optimization problem. Finally, the proposed link establishment criteria are implemented for GPS communication with optical crosslinks. The designs of this paper provide a potential crosslink establishment and topology control algorithm for the next generation GPS.

Synthesis and properties of reprocessable sulfonated polyimides cross-linked via acid stimulation for use as proton exchange membranes

NASA Astrophysics Data System (ADS)

Zhang, Boping; Ni, Jiangpeng; Xiang, Xiongzhi; Wang, Lei; Chen, Yongming

2017-01-01

Cross-linked sulfonated polyimides are one of the most promising materials for proton exchange membrane (PEM) applications. However, these cross-linked membranes are difficult to reprocess because they are insoluble. In this study, a series of cross-linkable sulfonated polyimides with flexible pendant alkyl side chains containing trimethoxysilyl groups is successfully synthesized. The cross-linkable polymers are highly soluble in common solvents and can be used to prepare tough and smooth films. Before the cross-linking reaction is complete, the membranes can be reprocessed, and the recovery rate of the prepared films falls within an acceptable range. The cross-linked membranes are obtained rapidly when the cross-linkable membranes are immersed in an acid solution, yielding a cross-linking density of the gel fraction of greater than 90%. The cross-linked membranes exhibit high proton conductivities and tensile strengths under hydrous conditions. Compared with those of pristine membranes, the oxidative and hydrolytic stabilities of the cross-linked membranes are significantly higher. The CSPI-70 membrane shows considerable power density in a direct methanol fuel cell (DMFC) test. All of these results suggest that the prepared cross-linked membranes have great potential for applications in proton exchange membrane fuel cells.

N(4)C-ethyl-N(4)C cross-linked DNA: synthesis and characterization of duplexes with interstrand cross-links of different orientations.

PubMed

Noronha, Anne M; Noll, David M; Wilds, Christopher J; Miller, Paul S

2002-01-22

The preparation and physical properties of short DNA duplexes that contain a N(4)C-ethyl-N(4)C interstrand cross-link are described. Duplexes that contain an interstrand cross-link between mismatched C-C residues and duplexes in which the C residues of a -CG- or -GC- step are linked to give "staggered" interstrand cross-links were prepared using a novel N(4)C-ethyl-N(4)C phosphoramidite reagent. Duplexes with the C-C mismatch cross-link have UV thermal transition temperatures that are 25 degrees C higher than the melting temperatures of control duplexes in which the cross-link is replaced with a G-C base pair. It appears that this cross-link stabilizes adjacent base pairs and does not perturb the structure of the helix, a conclusion that is supported by the CD spectrum of this duplex and by molecular models. An even higher level of stabilization, 49 degrees C, is seen with the duplex that contains a -CG- staggered cross-link. Molecular models suggest that this cross-link may induce propeller twisting in the cross-linked base pairs, and the CD spectrum of this duplex exhibits an unusual negative band at 298 nm, although the remainder of the spectrum is similar to that of B-form DNA. Mismatched C-C or -CG- staggered cross-linked duplexes that have complementary overhanging ends can undergo self-ligation catalyzed by T4 DNA ligase. Analysis of the ligated oligomers by nondenaturing polyacrylamide gel electrophoresis shows that the resulting oligomers migrate in a manner similar to that of a mixture of non-cross-linked control oligomers and suggests that these cross-links do not result in significant bending of the helix. However, the orientation of the staggered cross-link can have a significant effect on the structure and stability of the cross-linked duplex. Thus, the thermal stability of the duplex that contains a -GC- staggered cross-link is 10 degrees C lower than the melting temperature of the control, non-cross-linked duplex. Unlike the -CG- staggered cross-link, in which the cross-linked base pairs can still maintain hydrogen bond contacts, molecular models suggest that formation of the -GC- staggered cross-link disrupts hydrogen bonding and may also perturb adjacent base pairs leading to an overall reduction in helix stability. Duplexes with specifically positioned and oriented cross-links can be used as substrates to study DNA repair mechanisms.

Fabricating and Characterizing Physical Properties of Electrospun Polypeptide-based Nanofibers

NASA Astrophysics Data System (ADS)

Khadka, Dhan Bahadur

This dissertation has aimed to fabricate polypeptide based biomaterial and characterize physical properties. Electrospinning is used as a tool for the sample fabrication. Project focused on determining the feasibility of electrospinning of certain synthetic polypeptides and certain elastin-like peptides from aqueous feedstocks and to characterize physical properties of polymer aqueous solution, cast film and spun fibers and fiber mats. The research involves peptide design, polymer electrospinning, fibers crosslinking, determining the extent of crosslinking, fibers protease degradation study, fibers stability and self-organization analysis, structure and composition determination by various spectroscopy and microscopy techniques and characterization of mechanical properties of individual suspended fibers. Fiber mats of a synthetic cationic polypeptide poly(L-ornithine) (PLO) and an anionic co-polypeptide of L-glutamic acid and L-tyrosine (PLEY) of defined composition have been produced by electrospinning. Fibers were obtained from polymer aqueous solution at concentrations of 20-45% (w/v) in PLO and at concentrations of 20-60% (w/v) in PLEY. Applied voltage and spinneret-collector distance were also found to influence polymer spinnability and fibers morphology. Oriented fibers were obtained by parallel electrodes geometry. Fiber diameter and morphology was analyzed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). PLO fibers exposed on glutaraldehyde (GTA) vapor rendered fiber mats water-insoluble. A common chemical reagent, carbodiimide was used to crosslink PLEY fibers. Fiber solubility in aqueous solution varied as a function of crosslinking time and crosslinker concentration. Crosslink density has been quantified by a visible-wavelength dye-based method. Degradation of crosslinked fibers by different proteases has been demonstrated. Investigation of crosslinked PLEY fibers has provided insight into the mechanisms of stability at different pH values. Variations in fiber morphology, elemental composition and stability have been studied by microscopy and energy-dispersive X-ray spectroscopy (EDX), following the treatment of samples at different pH values in the 2-12 range. Fiber stability has been interpreted with reference to the pH dependence of the UV absorbance and fluorescence of PLEY chains in solution. The data show that fiber stability is crucially dependent on the extent of side chain ionization, even after crosslinking. Self-organization kinetics of electrospun PLO and PLEY fibers during solvent annealing has been studied. After being crosslinked in situ , fibers were annealed in water at 22 °C. Analysis by Fourier transform infrared spectroscopy (FTIR) has revealed that annealing involved fiber restructuring with an overall time constant of 29 min for PLO and 63 min for PLEY, and that changes in the distribution of polymer conformations occurred during the first 13 min of annealing. There was a substantial decrease in the amount of Na+ bound to PLEY fibers during annealing. Kinetic modeling has indicated that two parallel pathways better account for the annealing trajectory than a single pathway with multiple transition states. Taken together, the results will advance the rational design of polypeptides for peptide-based materials, especially materials prepared by electrospinning. It is believed that this research will increase basic knowledge of polymer electrospinning and advance the development of electrospun materials, especially in medicine and biotechnology. The study has yielded two advances on previous work in the area: avoidance of an animal source of peptides and avoidance of inorganic solvent. The present results thus advance the growing field of peptide-based materials. Non-woven electrospun fiber mats made of polypeptides are increasingly considered attractive for basic research and technology development in biotechnology, medicine and other areas. (Abstract shortened by UMI.)

Radiation-Induced Chemical Reactions in Hydrogel of Hydroxypropyl Cellulose (HPC): A Pulse Radiolysis Study.

PubMed

Yamashita, Shinichi; Ma, Jun; Marignier, Jean-Louis; Hiroki, Akihiro; Taguchi, Mitsumasa; Mostafavi, Mehran; Katsumura, Yosuke

2016-12-01

We performed studies on pulse radiolysis of highly transparent and shape-stable hydrogels of hydroxypropyl cellulose (HPC) that were prepared using a radiation-crosslinking technique. Several fundamental aspects of radiation-induced chemical reactions in the hydrogels were investigated. With radiation doses less than 1 kGy, degradation of the HPC matrix was not observed. The rate constants of the HPC composing the matrix, with two water decomposition radicals [hydroxyl radical ( • OH) and hydrated electron ([Formula: see text])] in the gels, were determined to be 4.5 × 10 9 and 1.8 × 10 7 M -1 s -1 , respectively. Direct ionization of HPC in the matrix slightly increased the initial yield of [Formula: see text], but the additionally produced amount of [Formula: see text] disappeared immediately within 200 ps, indicating fast recombination of [Formula: see text] with hole radicals on HPC or on surrounding hydration water molecules. Reactions of [Formula: see text] with nitrous oxide (N 2 O) and nitromethane (CH 3 NO 2 ) were also examined. Decay of [Formula: see text] due to scavenging by N 2 O and CH 3 NO 2 were both slower in hydrogels than in aqueous solutions, showing slower diffusions of the reactants in the gel matrix. The degree of decrease in the decay rate was more effective for N 2 O than for CH 3 NO 2 , revealing lower solubility of N 2 O in gel than in water. It is known that in viscous solvents, such as ethylene glycol, CH 3 NO 2 exhibits a transient effect, which is a fast reaction over the contact distance of reactants and occurs without diffusions of reactants. However, such an effect was not observed in the hydrogel used in the current study. In addition, the initial yield of [Formula: see text], which is affected by the amount of the scavenged precursor of [Formula: see text], in hydrogel containing N 2 O was slightly higher than that in water containing N 2 O, and the same tendency was found for CH 3 NO 2 .

Soft materials with recoverable shape factors from extreme distortion states

DOE PAGES

Goff, Jonathan; Sulaiman, Santy; Arkles, Barry; ...

2016-01-20

We present elastomeric polysiloxane nanocomposites with elongations of >5000% (more than 3× greater than any previously reported material) with excellent shape recovery. Highly deformable materials are desirable for the fabrication of stretchable implants and microfluidic devices. No crosslinking or domain formation is observed by a variety of analytical techniques, suggesting that their elastomeric behavior is caused by polymer chain entanglements.

Identification of potentially cytotoxic lesions induced by UVA photoactivation of DNA 4-thiothymidine in human cells

PubMed Central

Reelfs, Olivier; Macpherson, Peter; Ren, Xiaolin; Xu, Yao-Zhong; Karran, Peter; Young, Antony R.

2011-01-01

Photochemotherapy—in which a photosensitizing drug is combined with ultraviolet or visible radiation—has proven therapeutic effectiveness. Existing approaches have drawbacks, however, and there is a clinical need to develop alternatives offering improved target cell selectivity. DNA substitution by 4-thiothymidine (S4TdR) sensitizes cells to killing by ultraviolet A (UVA) radiation. Here, we demonstrate that UVA photoactivation of DNA S4TdR does not generate reactive oxygen or cause direct DNA breakage and is only minimally mutagenic. In an organotypic human skin model, UVA penetration is sufficiently robust to kill S4TdR-photosensitized epidermal cells. We have investigated the DNA lesions responsible for toxicity. Although thymidine is the predominant UVA photoproduct of S4TdR in dilute solution, more complex lesions are formed when S4TdR-containing oligonucleotides are irradiated. One of these, a thietane/S5-(6-4)T:T, is structurally related to the (6-4) pyrimidine:pyrimidone [(6-4) Py:Py] photoproducts induced by UVB/C radiation. These lesions are detectable in DNA from S4TdR/UVA-treated cells and are excised from DNA more efficiently by keratinocytes than by leukaemia cells. UVA irradiation also induces DNA interstrand crosslinking of S4TdR-containing duplex oligonucleotides. Cells defective in repairing (6-4) Py:Py DNA adducts or processing DNA crosslinks are extremely sensitive to S4TdR/UVA indicating that these lesions contribute significantly to S4TdR/UVA cytotoxicity. PMID:21890905

The effect of electron-beam irradiation and halogen-free flame retardants on properties of poly butylene terephthalate

NASA Astrophysics Data System (ADS)

Hooshangi, Zhila; Feghhi, Seyed Amir Hossein; Sheikh, Nasrin

2015-03-01

Engineering plastics like Poly (butylene terephthalate) due to their desirable properties have various industrial applications. Neat PBT is highly combustible, so it is necessary to improve significantly its fire retardancy to meet the fire safety requirements. The combustion performance of PBT can be improved by addition of appropriate flame retardant additives. In this study we have investigated the effect of halogen free flame retardants, i.e. melamine and aluminum phosphate, and instantaneously electron beam radiation-induced crosslinking in the presence of Triallyl cyanurate on various properties of PBT. The results of gel content showed that a dose range of 200-400 kGy leads to high cross linked structure in this polymer. Also mechanical experiments showed that its structure became rigid and fragile due to irradiation. Radiation crosslinking of this polymer made its dielectric loss coefficient ten times lower than non-irradiated polymer, but had no effect on its dielectric constant. Moreover the addition of the fire retardant additives as impurity decreased the dielectric loss coefficient. TGA analysis in nitrogen exhibited that irradiation increases char formation and use of the fire retardant additives leads to reduction of onset temperature and formation of higher char quantity than pure PBT. According to the results of UL-94, irradiated samples burned with lower speed and less dripping in vertical and horizontal positions than pure polymer. Finally irradiation of the polymers containing fire retardant additives with a dose of 400 kGy led to self-extinguishing and non-dripping and reach to V-0 level in the UL-94 V.

Human SNM1B is required for normal cellular response to both DNA interstrand crosslink-inducing agents and ionizing radiation.

PubMed

Demuth, Ilja; Digweed, Martin; Concannon, Patrick

2004-11-11

DNA interstrand crosslinks (ICLs) are critical lesions for the mammalian cell since they affect both DNA strands and block transcription and replication. The repair of ICLs in the mammalian cell involves components of different repair pathways such as nucleotide-excision repair and the double-strand break/homologous recombination repair pathways. However, the mechanistic details of mammalian ICL repair have not been fully delineated. We describe here the complete coding sequence and the genomic organization of hSNM1B, one of at least three human homologs of the Saccharomyces cerevisiae PSO2 gene. Depletion of hSNM1B by RNA interference rendered cells hypersensitive to ICL-inducing agents. This requirement for hSNM1B in the cellular response to ICL has been hypothesized before but never experimentally verified. In addition, siRNA knockdown of hSNM1B rendered cells sensitive to ionizing radiation, suggesting the possibility of hSNM1B involvement in homologous recombination repair of double-strand breaks arising as intermediates of ICL repair. Monoubiquitination of FANCD2, a key step in the FANC/BRCA pathway, is not affected in hSNM1B-depleted HeLa cells, indicating that hSNM1B is probably not a part of the Fanconi anemia core complex. Nonetheless, similarities in the phenotype of hSNM1B-depleted cells and cultured cells from patients suffering from Fanconi anemia make hSNM1B a candidate for one of the as yet unidentified Fanconi anemia genes not involved in monoubiquitination of FANCD2.

DNA damage under simulated extraterrestrial conditions in bacteriophage T7

NASA Astrophysics Data System (ADS)

Fekete, A.; Kovács, G.; Hegedüs, M.; Módos, K.; Rontó, Gy.; Lammer, H.; Panitz, C.

The experiment ``Phage and uracil response'' (PUR) will be accommodated in the EXPOSE facility of the ISS aiming to examine and quantify the effect of specific space conditions on bacteriophage T7 and isolated T7 DNA thin films. To achieve this new method was elaborated for the preparation of DNA and nucleoprotein thin films (1). During the EXPOSE Experiment Verification Tests (EVT) the samples were exposed to vacuum (10 -6 Pa), to monochromatic (254 nm) and polychromatic (200-400 nm) UV radiation in air as well in simulated space vacuum. Using neutral density (ND) filters dose-effect curves were performed in order to define the maximum doses tolerated, and we also studied the effect of temperature in vacuum as well as the influence of temperature fluctuations. We obtained substantial evidence that DNA lesions (e.g. strand breaks, DNA-protein cross-links, DNA-DNA cross-links) accumulate throughout exposure. DNA damage was determined by quantitative PCR using 555 bp and 3826 bp fragments of T7 DNA (2) and by neutral and alkaline agarose gel electrophoresis; the structural/chemical effects were analyzed by spectroscopic and microscopical methods. Characteristic changes in the absorption spectrum, in the electrophoretic pattern of DNA and the decrease of the amount of the PCR products have been detected indicating the damage of isolated and intraphage DNA. Preliminary results suggest a synergistic action of space vacuum and UV radiation with DNA being the critical target. Fekete et al. J. Luminescence 102-103, 469-475, 2003 Hegedüs et al. Photochem. Photobiol. 78, 213-219, 2003

Aqueous multiphoton lithography with multifunctional silk-centred bio-resists.

PubMed

Sun, Yun-Lu; Li, Qi; Sun, Si-Ming; Huang, Jing-Chun; Zheng, Bo-Yuan; Chen, Qi-Dai; Shao, Zheng-Zhong; Sun, Hong-Bo

2015-10-16

Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag(+) or silk/[AuCl4](-) aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 10(4)-Ω(-1 ) m(-1)-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems.

Aqueous multiphoton lithography with multifunctional silk-centred bio-resists

PubMed Central

Sun, Yun-Lu; Li, Qi; Sun, Si-Ming; Huang, Jing-Chun; Zheng, Bo-Yuan; Chen, Qi-Dai; Shao, Zheng-Zhong; Sun, Hong-Bo

2015-01-01

Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag+ or silk/[AuCl4]− aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 104-Ω−1 m−1-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems. PMID:26472600

Aqueous multiphoton lithography with multifunctional silk-centred bio-resists

NASA Astrophysics Data System (ADS)

Sun, Yun-Lu; Li, Qi; Sun, Si-Ming; Huang, Jing-Chun; Zheng, Bo-Yuan; Chen, Qi-Dai; Shao, Zheng-Zhong; Sun, Hong-Bo

2015-10-01

Silk and silk fibroin, the biomaterial from nature, nowadays are being widely utilized in many cutting-edge micro/nanodevices/systems via advanced micro/nanofabrication techniques. Herein, for the first time to our knowledge, we report aqueous multiphoton lithography of diversiform-regenerated-silk-fibroin-centric inks using noncontact and maskless femtosecond laser direct writing (FsLDW). Initially, silk fibroin was FsLDW-crosslinked into arbitrary two/three-dimensional micro/nanostructures with good elastic properties merely using proper photosensitizers. More interestingly, silk/metal composite micro/nanodevices with multidimension-controllable metal content can be FsLDW-customized through laser-induced simultaneous fibroin oxidation/crosslinking and metal photoreduction using the simplest silk/Ag+ or silk/[AuCl4]- aqueous resists. Noticeably, during FsLDW, fibroin functions as biological reductant and matrix, while metal ions act as the oxidant. A FsLDW-fabricated prototyping silk/Ag microelectrode exhibited 104-Ω-1 m-1-scale adjustable electric conductivity. This work not only provides a powerful development to silk micro/nanoprocessing techniques but also creates a novel way to fabricate multifunctional metal/biomacromolecule complex micro/nanodevices for applications such as micro/nanoscale mechanical and electrical bioengineering and biosystems.

Use of radiation in the production of hydrogels

NASA Astrophysics Data System (ADS)

Lugao, Ademar B.; Malmonge, Sônia Maria

2001-12-01

The first hydrogel for wound dressing processed by radiation left the laboratories in Poland in 1986 by the hands of its inventor Janusz M. Rosiak and soon, after formal tests, arrived in the local market (1992). It was a technological breakthrough due to its product characteristics as pain reliever and enhanced healing properties besides its clever production process combining sterilization and crosslinking in a simultaneous operation. IAEA invited professor Rosiak to support the transference of his technology for many laboratories around the world. The laboratories of developing countries, which face all kinds of restrictions, were seduced by the simplicity of the process and low cost of its raw materials. This was the seed of the flourishing activities in hydrogel dressings in Brazil and other developing countries. The technology transfer of the radiation production of hydrogel dressings and other hydrogels to the Brazilian industry is under way. The usual issues associated with radiation processing arise from this experience, i.e. capital costs, misinformation about radiation and lack of expertise on radiation processing. Some other issues concerning local market and social peculiarities also add to the problem. Notwithstanding, many different opportunities arise from those challenges. These technical and commercial issues are roughly: (i) There are plenty of new hydrogels in the market and all say the same. What else radiation processed hydrogels can say? (ii) Regarding to hydrogels and its industrial production as market product, what are the unique characteristics of radiation processing? It was shown that the radiation is a powerful tool for producing hydrogels the same basic formula with improved flexibility, control and purity.

Application of a fast sorting algorithm to the assignment of mass spectrometric cross-linking data.

PubMed

Petrotchenko, Evgeniy V; Borchers, Christoph H

2014-09-01

Cross-linking combined with MS involves enzymatic digestion of cross-linked proteins and identifying cross-linked peptides. Assignment of cross-linked peptide masses requires a search of all possible binary combinations of peptides from the cross-linked proteins' sequences, which becomes impractical with increasing complexity of the protein system and/or if digestion enzyme specificity is relaxed. Here, we describe the application of a fast sorting algorithm to search large sequence databases for cross-linked peptide assignments based on mass. This same algorithm has been used previously for assigning disulfide-bridged peptides (Choi et al., ), but has not previously been applied to cross-linking studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkali-catalyzed low temperature wet crosslinking of plant proteins using carboxylic acids.

PubMed

Reddy, Narendra; Li, Ying; Yang, Yiqi

2009-01-01

We report the development of a new method of alkali-catalyzed low temperature wet crosslinking of plant proteins to improve their breaking tenacity without using high temperatures or phosphorus-containing catalysts used in conventional poly(carboxylic acid) crosslinking of cellulose and proteins. Carboxylic acids are preferred over aldehyde-containing crosslinkers for crosslinking proteins and cellulose because of their low toxicity and cost and ability to improve the desired properties of the materials. However, current knowledge in carboxylic acid crosslinking of proteins and cellulose requires the use of carboxylic acids with at least three carboxylic groups, toxic phosphorous-containing catalysts and curing at high temperatures (150-185 degrees C). The use of high temperatures and low pH in conventional carboxylic acid crosslinking has been reported to cause substantial strength loss and/or undesired changes in the properties of the crosslinked materials. In this research, gliadin, soy protein, and zein fibers have been crosslinked with malic acid, citric acid, and butanetetracarboxylic acid to improve the tenacity of the fibers without using high temperatures and phosphorus-containing catalysts. The new method of wet crosslinking using carboxylic acids containing two or more carboxylic groups will be useful to crosslink proteins for various industrial applications.

The changes in crosslink contents in tissues after formalin fixation.

PubMed

Abe, Masashi; Takahashi, Masaaki; Horiuchi, Kentaro; Nagano, Akira

2003-07-01

The aim of this study was to detect crosslinks of collagen and elastin in formalin-fixed tissue, to perform quantification of these crosslinks, and to investigate the effects of formalin fixation on crosslink contents in human yellow ligament and cartilage. Pyridinoline (Pyr) is a stable and nonreducible crosslink of collagen. Pentosidine (Pen) is a senescent crosslink formed between arginine and lysine in matrix proteins, including collagen. Desmosine (Des) and its isomer isodesmosine (Isodes) are crosslinks specifically found in elastin. It is useful to measure crosslink contents of collagen and elastin as a way of investigating the properties of various tissues or their pathological changes. If it is possible to evaluate crosslinks of collagen and elastin in formalin-fixed tissues, we can investigate crosslinks in a wide variety of tissues. We used HPLC to compare the concentrations of Pyr, Pen, Des, and Isodes in the formalin-fixed tissues with their concentrations in the frozen tissues. Pyr and Pen were detected in both the formalin-fixed yellow ligament and the cartilage, and their concentrations were not significantly affected by or related to the duration of formalin fixation. Des and Isodes were detected in the formalin-fixed yellow ligament but in significantly lower amounts compared to the frozen samples. We concluded that crosslinks of collagen were preserved in formalin, but crosslinks of elastin were not preserved in it. The reason for this might be that formalin did not fix elastin tissues sufficiently or it destroyed, masked, or altered elastin crosslinks.

Intra-molecular cross-linking of acidic residues for protein structure studies.

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

Kruppa, Gary Hermann; Young, Malin M.; Novak, Petr

2005-03-01

Intra-molecular cross-linking has been suggested as a method of obtaining distance constraints that would be useful in developing structural models of proteins. Recent work published on intra-molecular cross-linking for protein structural studies has employed commercially available primary amine selective reagents that can cross-link lysine residues to other lysine residues or the amino terminus. Previous work using these cross-linkers has shown that for several proteins of known structure, the number of cross-links that can be obtained experimentally may be small compared to what would be expected from the known structure, due to the relative reactivity, distribution, and solvent accessibility of themore » lysines in the protein sequence. To overcome these limitations we have investigated the use of cross-linking reagents that can react with other reactive sidechains in proteins. We used 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) to activate the carboxylic acid containing residues, aspartic acid (D), glutamic acid (E), and the carboxy terminus (O), for cross-linking reactions. Once activated, the DEO sidechains can react to form 'zero-length' cross-links with nearby primary amine containing resides, lysines (K) and the amino terminus (X), via the formation of a new amide bond. We also show that the EDC-activated DEO sidechains can be cross-linked to each other using dihydrazides, two hydrazide moieties connected by an alkyl cross-linker ann of variable length. Using these reagents, we have found three new 'zero-length' cross-links in ubiquitin consistent with its known structure (M1-E16, M1-E18, and K63-E64). Using the dihydrazide cross-linkers, we have identified 2 new cross-links (D21-D32 and E24-D32) unambiguously. Using a library of dihydrazide cross-linkers with varying arm length, we have shown that there is a minimum arm length required for the DEO-DEO cross-links of 5.8 angstroms. These results show that additional structural information can be obtained by exploiting new cross-linker chemistry, increasing the probability that the protein target of choice will yield sufficient distance constraints to develop a structural model.« less

Investigation of Radiation and Chemical Resistance of Flexible HLW Transfer Hose

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

E. Skidmore; Billings, K.; Hubbard, M.

A chemical transfer hose constructed of an EPDM (ethylene-propylene diene monomer) outer covering with a modified cross-linked polyethylene (XLPE) lining was evaluated for use in high level radioactive waste transfer applications. Laboratory analysis involved characterization of the hose liner after irradiation to doses of 50 to 300 Mrad and subsequent exposure to 25% NaOH solution at 93 C for 30 days, simulating 6 months intermittent service. The XLPE liner mechanical and structural properties were characterized at varying dose levels. Burst testing of irradiated hose assemblies was also performed. Literature review and test results suggest that radiation effects below doses ofmore » 100 kGy are minimal, with acceptable property changes to 500 kGy. Higher doses may be feasible. At a bounding dose of 2.5 MGy, the burst pressure is reduced to the working pressure (1.38 MPa) at room temperature. Radiation exposure slightly reduces liner tensile strength, with more significant decrease in liner elongation. Subsequent exposure to caustic solutions at elevated temperature slightly increases elongation, suggesting an immersion/hydrolytic effect or possible thermal annealing of radiation damage. This paper summarizes the laboratory results and recommendations for field deployment.« less

LIGHT SOURCE: Physical design of a 10 MeV LINAC for polymer radiation processing

NASA Astrophysics Data System (ADS)

Feng, Guang-Yao; Pei, Yuan-Ji; Wang, Lin; Zhang, Shan-Cai; Wu, Cong-Feng; Jin, Kai; Li, Wei-Min

2009-06-01

In China, polymer radiation processing has become one of the most important processing industries. The radiation processing source may be an electron beam accelerator or a radioactive source. Physical design of an electron beam facility applied for radiation crosslinking is introduced in this paper because of it's much higher dose rate and efficiency. Main part of this facility is a 10 MeV travelling wave electron linac with constant impedance accelerating structure. A start to end simulation concerning the linac is reported in this paper. The codes Opera-3d, Poisson-superfish and Parmela are used to describe electromagnetic elements of the accelerator and track particle distribution from the cathode to the end of the linac. After beam dynamic optimization, wave phase velocities in the structure have been chosen to be 0.56, 0.9 and 0.999 respectively. Physical parameters about the main elements such as DC electron gun, iris-loaded periodic structure, solenoids, etc, are presented. Simulation results proves that it can satisfy the industrial requirement. The linac is under construction. Some components have been finished. Measurements proved that they are in a good agreement with the design values.

A diagnostic technique used to obtain cross range radiation centers from antenna patterns

NASA Technical Reports Server (NTRS)

Lee, T. H.; Burnside, W. D.

1988-01-01

A diagnostic technique to obtain cross range radiation centers based on antenna radiation patterns is presented. This method is similar to the synthetic aperture processing of scattered fields in the radar application. Coherent processing of the radiated fields is used to determine the various radiation centers associated with the far-zone pattern of an antenna for a given radiation direction. This technique can be used to identify an unexpected radiation center that creates an undesired effect in a pattern; on the other hand, it can improve a numerical simulation of the pattern by identifying other significant mechanisms. Cross range results for two 8' reflector antennas are presented to illustrate as well as validate that technique.

Photo-inducible Crosslinked Nanoassemblies for pH-Controlled Drug Release

PubMed Central

Dickerson, Matthew; Winquist, Nickolas; Bae, Younsoo

2014-01-01

Purpose To control drug release from block copolymer nanoassemblies by variation in the degree of photo-crosslinking and inclusion of acid sensitive linkers. Methods Poly(ethylene glycol)-poly(aspartate-hydrazide-cinnamate) (PEG-CNM) block copolymers were prepared and conjugated with a model drug, doxorubicin (DOX), through acid sensitive hydrazone linkers. The block copolymers formed photo-inducible, self-assembled nanoassemblies (piSNAs), which were used to produce photo-inducible crosslinked nanoassemblies (piCNAs) through UV crosslinking. The nanoassemblies were characterized to determine particle size, surface charge, pH- and crosslinking-dependent DOX release, in vitro cytotoxicity, and intracellular uptake as a function of photo-crosslinking degree. Results Nanoassemblies with varying photo-crosslinking degrees were successfully prepared while retaining particle size and surface charge. Photo-crosslinking caused no noticeable change in DOX release from the nanoassemblies at pH 7.4, but the DOX-loaded nanoassemblies modulated drug release as a function of crosslinking at pH 6.0. The nanoassemblies showed similar cytotoxicity regardless of crosslinking degrees, presumably due to the low cellular uptake and cell nucleus drug accumulation. Conclusion Photo-crosslinking is useful to control drug release from pH-sensitive block copolymer nanoassemblies as a function of crosslinking without altering the particle properties, and thus providing unique tools to investigate the pharmaceutical effects of drug release on cellular response. PMID:24254196

Identification of Crosslinked Peptides after Click-based Enrichment Using Sequential CID and ETD Tandem Mass Spectrometry

PubMed Central

Chowdhury, Saiful M.; Du, Xiuxia; Tolić, Nikola; Wu, Si; Moore, Ronald J.; Mayer, M. Uljana; Smith, Richard D.; Adkins, Joshua N.

2010-01-01

Chemical crosslinking combined with mass spectrometry can be a powerful approach for the identification of protein-protein interactions and for providing constraints on protein structures. However, enrichment of crosslinked peptides is crucial to reduce sample complexity before mass spectrometric analysis. In addition compact crosslinkers are often preferred to provide short spacer lengths, surface accessibility to the protein complexes, and must have reasonable solubility under condition where the native complex structure is stable. In this study, we present a novel compact crosslinker that contains two distinct features: 1) an alkyne tag and 2) a small molecule detection tag (NO2-) to maintain reasonable solubility in water. The alkyne tag enables enrichment of the crosslinked peptide after proteolytic cleavage after coupling of an affinity tag using alkyne-azido click chemistry. Neutral loss of the small NO2- moiety provides a secondary means of detecting crosslinked peptides in MS/MS analyses, providing additional confidence in peptide identifications. We show the labeling efficiency of this crosslinker, which we termed CLIP (Click-enabled Linker for Interacting Proteins) using ubiquitin. The enrichment capability of CLIP is demonstrated for crosslinked ubiquitin in highly complex E. coli cell lysates. Sequential CID-MS/MS and ETD-MS/MS of inter-crosslinked peptides (two peptides connected with a crosslinker) are also demonstrated for improved automated identification of crosslinked peptides. PMID:19496583

Comparison of glutaraldehyde and carbodiimides to crosslink tissue engineering scaffolds fabricated by decellularized porcine menisci.

PubMed

Gao, Shuang; Yuan, Zhiguo; Guo, Weimin; Chen, Mingxue; Liu, Shuyun; Xi, Tingfei; Guo, Quanyi

2017-02-01

The objectives of this study were to fabricate porous scaffolds using decellularized meniscus, and to explore a preferable crosslinking condition to enhance mechanical properties of scaffolds. Moreover, the microstructure, porosity, biodegradation and cytotoxicity were also evaluated. EDAC or GTA in different concentration was used to crosslink scaffolds. FTIR demonstrated functional groups change in crosslinking process. SEM photography showed that crosslinked scaffolds had blurry edges, which resulted scaffolds crosslinked by 1.2mol/l EDAC had smaller porosity than other groups. The structure change enhanced antidegradation property. After immersing in enzyme solution for 96h, scaffolds crosslinked by GTA and EDAC could maintain their mass >70% and 80%. Most importantly, mechanical properties of crosslinked scaffolds were also improved. Uncrosslinked Scaffolds had only 0.49kPa in compression modulus and 12.81kPa in tensile modulus. The compression and tensile modulus of scaffolds crosslinked by 1.0% GTA were 1.42 and 567.44kPa respectively. The same value of scaffolds crosslinked by 1.2mol/l EDAC were 1.49 and 532.50kPa. Scaffolds crosslinked by 1.0% and 2.5% GTA were toxic to cells, while EDAC groups showed no cytotoxicity. Chondrocytes could proliferate and infiltrate within scaffolds after seeding. Overall, 1.2mol/l EDAC was a preferable crosslinking condition. Copyright © 2016 Elsevier B.V. All rights reserved.

Xilmass: A New Approach toward the Identification of Cross-Linked Peptides.

PubMed

Yılmaz, Şule; Drepper, Friedel; Hulstaert, Niels; Černič, Maša; Gevaert, Kris; Economou, Anastassios; Warscheid, Bettina; Martens, Lennart; Vandermarliere, Elien

2016-10-18

Chemical cross-linking coupled with mass spectrometry plays an important role in unravelling protein interactions, especially weak and transient ones. Moreover, cross-linking complements several structural determination approaches such as cryo-EM. Although several computational approaches are available for the annotation of spectra obtained from cross-linked peptides, there remains room for improvement. Here, we present Xilmass, a novel algorithm to identify cross-linked peptides that introduces two new concepts: (i) the cross-linked peptides are represented in the search database such that the cross-linking sites are explicitly encoded, and (ii) the scoring function derived from the Andromeda algorithm was adapted to score against a theoretical tandem mass spectrometry (MS/MS) spectrum that contains the peaks from all possible fragment ions of a cross-linked peptide pair. The performance of Xilmass was evaluated against the recently published Kojak and the popular pLink algorithms on a calmodulin-plectin complex data set, as well as three additional, published data sets. The results show that Xilmass typically had the highest number of identified distinct cross-linked sites and also the highest number of predicted cross-linked sites.

Reduction-responsive interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry for drug controlled release

NASA Astrophysics Data System (ADS)

Dai, Yu; Wang, Hongquan; Zhang, Xiaojin

2017-12-01

To improve the stability of polymeric micelles, here we describe interlayer-crosslinked micelles prepared from star-shaped copolymer via click chemistry. The formation of interlayer-crosslinked micelles was investigated and confirmed by proton nuclear magnetic resonance, Fourier-transform infrared spectroscopy, and fluorescence spectroscopy. The morphology of un-crosslinked micelles and crosslinked micelles observed by transmission electron microscope is both uniform nano-sized spheres (approximately 20 nm). The crosslinking enhances the stability of polymeric micelles and improves the drug loading capacity of polymeric micelles. The interlayer-crosslinked micelles prepared from star-shaped copolymer and a crosslinker containing a disulfide bond are reduction-responsive and can release the drug quickly in the presence of the reducing agents such as glutathione (GSH).

Constitutive Modeling of Crosslinked Nanotube Materials

NASA Technical Reports Server (NTRS)

Odegard, G. M.; Frankland, S. J. V.; Herzog, M. N.; Gates, T. S.; Fay, C. C.

2004-01-01

A non-linear, continuum-based constitutive model is developed for carbon nanotube materials in which bundles of aligned carbon nanotubes have varying amounts of crosslinks between the nanotubes. The model accounts for the non-linear elastic constitutive behavior of the material in terms of strain, and is developed using a thermodynamic energy approach. The model is used to examine the effect of the crosslinking on the overall mechanical properties of variations of the crosslinked carbon nanotube material with varying degrees of crosslinking. It is shown that the presence of the crosslinks has significant effects on the mechanical properties of the carbon nanotube materials. An increase in the transverse shear properties is observed when the nanotubes are crosslinked. However, this increase is accompanied by a decrease in axial mechanical properties of the nanotube material upon crosslinking.

Long constructs in the thoracic and lumbar spine with a minimally invasive technique.

PubMed

Roldan, H; Perez-Orribo, L; Spreafico, M; Ginoves-Sierra, M

2011-04-01

Literature about long implants used together with a minimally invasive spine surgery (MISS) technique is scarce. Our objective is to contribute our surgical experience in this field and to specifically focus on several technical details. A digitally-dissected canal along the paravertebral muscles was created linking the stab wounds on each side in relation with the pedicles to be cannulated. Screws were inserted following the percutaneous technique. Long rods were modelled, threaded through the extender sleeves along the paravertebral canal and pushed into the screw heads with the reduction forceps. When fusion was needed, the facet complex was decorticated with a drill. To insert a cross-link, a canal between the 2 rods was digitally created and the spinous process was drilled. 8 patients underwent surgery (age range: 25-77 years). Indications were postosteomyelitis kyphosis in 3 patients, bone tumor in 3, and spine fracture in 2. No blood transfusions were necessary during or after surgery. A cross-link was inserted in 2 patients. Posterolateral bone fusion was attempted in 4, but radiologically identifiable in none. In one patient a cantilever manoeuvre was done to correct kyphosis. Mean duration of surgery was 4 h. There were no clinical complications related to the operation or the hardware (mean follow-up of 7.14 months, range: 1-15 months). The application of MISS techniques can be broadened to long spinal constructs to assess fractures, tumors or deformity, especially in elderly or debilitated patients. Nevertheless, posterolateral fusion is still a challenge through these limited exposures. © Georg Thieme Verlag KG Stuttgart · New York.

Affects of Microgravity on the Polymerization and Material Properties of Biomedical Grade Polymers

NASA Astrophysics Data System (ADS)

Crane, Deborah J.

2002-01-01

the material of choice in the production of acetabular cups for hip and tibial cradles for knee orthopeadic implant components for over 30 years. Although UHMWPE is used for more than 1.5 million implants a year in the United States alone and more than 3 million implant surgeries a year worldwide, problems with debris particle formation, pitting and fracture continue to induce premature failure of implant components. chains produced during polymerization are capable of packing into crystalline structures called lamellae, which are embedded within randomly oriented amorphous regions. Crosslinks, or tie molecules bridge the crystalline structures, which contribute to the materials' toughness and strength as a biomedical material. Research has been conducted providing evidence that a crosslinked gradient at the articulating surface of the polymer component provides resistance to surface degradation and subsequent debris formation. Recently, the introduction of highly crosslinked UHMWPE had proven to reduce some of the problems associated with the applications of this polymer as a biomedical material and was seen as the answer to solving the continuing problems associated with UHMWPE implant components. Yet current research into the fatigue characteristics of highly crosslinked UHMWPE has shown that subsurface crack propagation and subsequent delamination continues to produce problematic debris generation. Studies have shown that various sterilization and accelerated aging (to emulate natural oxidation rates) protocols adversely effects the material properties. Additional research has shown that alignment of the lamellae, caused by processing technique, fabrication or surface articulation may be the precursor to debris particle formation. Processing techniques performed under high pressure has proven to effect the width of the crystalline lamellae and therefore, the material's response to wear and fracture. UHMWP due to a microgravity environment, which could be extended to include other polymers. Polymerization as well as polymer processing in a microgravity environment may affect the length and orientation of the molecular chains, the degree of crosslinking, and distribution of amorphous to crystalline portions of the material, thus changing the ultimate properties of the polymer. Small polymer samples would be produced from the resin for testing and analysis. This research would include the effect of micro-g processing by compression molded vs. ram extruded samples for analysis. Morphological alterations in the material could be monitored using Transmission Electron Microscopy and associated properties such as toughness, density and crystallinity could be determined and compared to terra produced materials using conventional mechanical testing, density gradient columns and calorimetry techniques. If alterations are evident, fatigue testing can be performed on small specimens in order to determine the material's resistance to crack initiation and propagation. number of orthopaedic implant recipients and could be extended for use in robotics and other beneficial applications. Although polymers exhibit the greatest biocompatibility, problems with debris particle generation continue to reduce the effectiveness of UHMWPE as a biomedical material. Further polymer research in a microgravity environment may prove to produce the desired alterations in the materials' morphology and associated properties, therefore providing millions of people with superior orthopaedic implant components and lessen the occurrences of repeat surgery.

Acquisition of relative interstrand crosslinker resistance and PARP inhibitor sensitivity in Fanconi anemia head and neck cancers

PubMed Central

Lombardi, Anne J.; Hoskins, Elizabeth E.; Foglesong, Grant D.; Wikenheiser-Brokamp, Kathryn A.; Wiesmüller, Lisa; Hanenberg, Helmut; Andreassen, Paul R.; Jacobs, Allison J.; Olson, Susan B.; Keeble, Winifred W.; Hays, Laura E.; Wells, Susanne I.

2015-01-01

Purpose Fanconi anemia (FA) is an inherited disorder associated with a constitutional defect in the FA DNA repair machinery that is essential for resolution of DNA interstrand crosslinks. Individuals with FA are predisposed to formation of head and neck squamous cell carcinomas (HNSCCs) at a young age. Prognosis is poor, partly due to patient intolerance of chemotherapy and radiation requiring dose reduction, which may lead to early recurrence of disease. Experimental Design Using HNSCC cell lines derived from the tumors of FA patients, and murine HNSCC cell lines derived from the tumors of wild type and Fancc−/− mice, we sought to define FA-dependent chemosensitivity and DNA repair characteristics. We utilized DNA repair reporter assays to explore the preference of FA HNSCC cells for non-homologous end joining (NHEJ). Results Surprisingly, interstrand crosslinker (ICL) sensitivity was not necessarily FA-dependent in human or murine cell systems. Our results suggest that the increased Ku-dependent NHEJ that is expected in FA cells did not mediate relative ICL resistance. ICL exposure resulted in increased DNA damage sensing and repair by poly(ADP-ribose) polymerase (PARP) in FA-deficient cells. Moreover, human and murine FA HNSCC cells were sensitive to PARP inhibition, and sensitivity of human cells was attenuated by FA gene complementation. Conclusions The observed reliance upon PARP-mediated mechanisms reveals a means by which FA HNSCCs can acquire relative resistance to the ICL-based chemotherapy that is a foundation of HNSCC treatment, as well as a potential target for overcoming chemoresistance in the chemosensitive individual. PMID:25609062

Mechanisms of plastic deformation in highly cross-linked UHMWPE for total hip components--the molecular physics viewpoint.

PubMed

Takahashi, Yasuhito; Shishido, Takaaki; Yamamoto, Kengo; Masaoka, Toshinori; Kubo, Kosuke; Tateiwa, Toshiyuki; Pezzotti, Giuseppe

2015-02-01

Plastic deformation is an unavoidable event in biomedical polymeric implants for load-bearing application during long-term in-vivo service life, which involves a mass transfer process, irreversible chain motion, and molecular reorganization. Deformation-induced microstructural alterations greatly affect mechanical properties and durability of implant devices. The present research focused on evaluating, from a molecular physics viewpoint, the impact of externally applied strain (or stress) in ultra-high molecular weight polyethylene (UHMWPE) prostheses, subjected to radiation cross-linking and subsequent remelting for application in total hip arthroplasty (THA). Two different types of commercial acetabular liners, which belong to the first-generation highly cross-linked UHMWPE (HXLPE), were investigated by means of confocal/polarized Raman microprobe spectroscopy. The amount of crystalline region and the spatial distribution of molecular chain orientation were quantitatively analyzed according to a combined theory including Raman selection rules for the polyethylene orthorhombic structure and the orientation distribution function (ODF) statistical approach. The structurally important finding was that pronounced recrystallization and molecular reorientation increasingly appeared in the near-surface regions of HXLPE liners with increasing the amount of plastic (compressive) deformation stored in the microstructure. Such molecular rearrangements, occurred in response to external strains, locally increase surface cross-shear (CS) stresses, which in turn trigger microscopic wear processes in HXLPE acetabular liners. Thus, on the basis of the results obtained at the molecular scale, we emphasize here the importance of minimizing the development of irrecoverable deformation strain in order to retain the pristine and intrinsically high wear performance of HXLPE components. Copyright © 2014 Elsevier Ltd. All rights reserved.

The effect of radiation-induced cross-linking on the relaxation of taut tie molecules during annealing of drawn LDPE

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

Rong Jiang Yan; Yunxia Luo; Bingzheng Jiang

1993-02-05

Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by [sup 60]Co-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and themore » degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the [alpha] transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2,016 cm[sup [minus]1] on that of the band at 1,894 cm[sup [minus]1] is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.« less

Engineered 3D-scaffolds of photocrosslinked chitosan-gelatin hydrogel hybrids for chronic wound dressings and regeneration.

PubMed

Carvalho, Isadora C; Mansur, Herman S

2017-09-01

Wound repair is one of the most complex biological processes in human life. To date, no ideal biomaterial solution has been identified, which that encompasses all functions and properties of real skin tissue. Thus, this study focused on the synthesis of new biocompatible hybrid hydrogel scaffolds based on methacrylate-functionalized high molecular mass chitosan with gelatin-A photocrosslinked with UV radiation to tailor matrix network properties. These hybrid hydrogels were produced via freeze-drying and were extensively characterized by swelling and degradation measurements, Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy (UV-Vis), scanning electron microscopy (SEM-EDS), and micro-computed tomography (micro-CT). The results demonstrated that hydrogels were produced with broadly designed swelling degrees typically ranging from 500% to 2000%, which were significantly dependent on the relative concentration of polymers and irradiation time for crosslinking. Analogously, degradation was reduced with increased photocrosslinking of the network. Moreover, insights into the mechanism of photochemical crosslinking were suggested based on FTIR and UV-Vis analyses of the characteristic functional groups involved in the reactions. SEM analysis associated with micro-CT imaging of the hybrid scaffolds showed uniformly interconnected 3D porous structures, with architectural features affected by the crosslinking of the network. These hydrogels were biocompatible, with live cell viability responses of human embryonic kidney (HEK293T) cells being above 95%. Hence, novel hybrid hydrogels were designed and produced with tunable properties through photocrosslinking and with a biocompatible response suitable for use in wound dressing and skin tissue repair applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Interactions between cations and peat organic matter monitored with NMR wideline, static and FFC NMR relaxometry

NASA Astrophysics Data System (ADS)

Schaumann, Gabriele E.; Conte, Pellegrino; Jäger, Alexander; Alonzo, Giuseppe; Bertmer, Marko

2010-05-01

The molecular size of humic substances is still under debate and is believed to range up to several hundred thousands Dalton, although a number of recent studies suggest much lower molecular weights. Nowadays an increasing number of authors suggest a model of molecular aggregates. One explanation why results on the molecular mass of humic materials are contradictory, may be that individual OM molecules are linked via intermolecular interactions, by bridges of water molecules or by cations bridging cation exchange sites (Schaumann, 2006a, b). Properties of such cross-linked systems can be similar to macromolecular systems revealing covalent cross-links. In this context, multivalent cations play an important ecological role, serving as reversible cross-linking agent. Formation and disruption of such cation bridges may close or open sorption sites in soil organic matter. Although cross-linking by multivalent cations has been proposed in many studies, the cross-linking effect has not yet been demonstrated on the molecular scale. The objective of this study was to investigate the interactions between cations and peat organic matter using NMR wideline techniques as well as static and fast field cycling (FFC) NMR relaxometry. Peat treated with solutions containing either Na+, Ca2+ or Al3+ was investigated in air-dried state for longitudinal relaxation times (T1) and NMR wideline characteristics. T1 distributions were separated into two Gaussian functions which were interpreted to represent two proton populations belonging to two environments of differing mobility. The relaxation rates (R1 = T1-1) in the cation treated samples spread over a range of 87-123 s-1 (R1a: fast component) and 32-42 s-1 (R1b: slow component). The rates in all treatments are significantly different from each other. and decrease in the order conditioned sample > desalinated sample > Na-treated sample. The treatment with multivalent cations affects R1a and R1b in different ways and needs more detailed explanation. Wideline proton NMR spectra can be used to quantify proton containing material, mainly water, based on their mobility. Spectra were decomposed into a Gaussian and Lorentzian line and changes to mobility after heat treatment indicate the water binding strength. In this study, differences in the various NMR parameters on the cation treatments will be presented and discussed with respect to the crosslinking hypothesis.

Silane cross-linkable ethylene-propylene elastomer compositions prepared by reactive processing

NASA Astrophysics Data System (ADS)

Kozawa, Eiji; Nakajima, Yasuo; Kim, Jae Kyung

2015-05-01

Thermoplastic Elastomers (TPEs) have received attention as the alternative materials of EPDM due to an advantage for mass production. In recent years, by the progress of polymerization technology, Ethylene-propylene Elastomer (EP), one of the TPEs, is beginning to be applied to many products because of its good properties as rubber. However, as much as a complete replacement for EPDM, it is not provided with sufficient properties. In such circumstance, we found that EP's performance properties can be further enhanced via chemical modification such as cross-linking. The advent of a newer technique, involving the grafting of organo-functional silane onto the polymer chain in the reaction extrusion process is more attractive due to various industrial advantages. Although the functionalization of the EP by silane grafting through reactive processing is very useful, the silane grafting process of EP has a difficulty. It is most likely a consequence of the nature of the PP chain scission (β-scission), which is the dominant reaction in PP when subjected to free radicals at elevated temperature during processing. Therefore, the objective of our current work is to investigate a reactive extrusion process for the silane cross-linkable EP while minimizing the degradation, as well as evaluate the properties of the modified polymer.

Spontaneous stacking of purple membranes during immobilization with physical cross-linked poly(vinyl alcohol) hydrogel with retaining native-like functionality of bacteriorhodopsin

NASA Astrophysics Data System (ADS)

Yokoyama, Yasunori; Tanaka, Hikaru; Yano, Shunsuke; Takahashi, Hiroshi; Kikukawa, Takashi; Sonoyama, Masashi; Takenaka, Koshi

2017-05-01

We previously discovered the correlation between light-induced chromophore color change of a photo-receptor membrane protein bacteriorhodopsin (bR) and its two-dimensional crystalline state in the membrane. To apply this phenomenon to a novel optical memory device, it is necessary that bR molecules are immobilized as maintaining their structure and functional properties. In this work, a poly(vinyl alcohol) (PVA) hydrogel with physical cross-linkages (hydrogen bonds between PVA chains) that resulted from repeated freezing-and-thawing (FT) cycles was used as an immobilization medium. To investigate the effects of physically cross-linked PVA gelation on the structure and function of bR in purple membranes (PMs), spectroscopic techniques were employed against PM/PVA immobilized samples prepared with different FT cycle numbers. Visible circular dichroism spectroscopy strongly suggested PM stacking during gelation. X-ray diffraction data also indicated the PM stacking as well as its native-like crystalline lattice even after gelation. Time-resolved absorption spectroscopy showed that bR photocycle behaviors in PM/PVA immobilized samples were almost identical to that in suspension. These results suggested that a physically cross-linked PVA hydrogel is appropriate for immobilizing membrane proteins in terms of maintaining their structure and functionality.

Modified n-HA/PA66 scaffolds with chitosan coating for bone tissue engineering: cell stimulation and drug release.

PubMed

Zou, Qin; Li, Junfeng; Niu, Lulu; Zuo, Yi; Li, Jidong; Li, Yubao

2017-09-01

The dipping-drying procedure and cross-linking method were used to make drug-loaded chitosan (CS) coating on nano-hydroxyapatite/polyamide66 (nHA/PA66) composite porous scaffold, endowing the scaffold controlled drug release functionality. The prefabricated scaffold was immersed into an aqueous drug/CS solution in a vacuum condition and then crosslinked by vanillin. The structure, porosity, composition, compressive strength, swelling ratio, drug release and cytocompatibility of the pristine and coating scaffolds were investigated. After coating, the scaffold porosity and pore interconnection were slightly decreased. Cytocompatibility performance was observed through an in vitro experiment based on cell attachment and the MTT assay by MG63 cells which revealed positive cell viability and increasing proliferation over the 11-day period in vitro. The drug could effectively release from the coated scaffold in a controlled fashion and the release rate was sustained for a long period and highly dependent on coating swelling, suggesting the possibility of a controlled drug release. Our results demonstrate that the scaffold with drug-loaded crosslinked CS coating can be used as a simple technique to render the surfaces of synthetic scaffolds active, thus enabling them to be a promising high performance biomaterial in bone tissue engineering.

Immobilization techniques to avoid enzyme loss from oxidase-based biosensors: a one-year study.

PubMed

House, Jody L; Anderson, Ellen M; Ward, W Kenneth

2007-01-01

Continuous amperometric sensors that measure glucose or lactate require a stable sensitivity, and glutaraldehyde crosslinking has been used widely to avoid enzyme loss. Nonetheless, little data is published on the effectiveness of enzyme immobilization with glutaraldehyde. A combination of electrochemical testing and spectrophotometric assays was used to study the relationship between enzyme shedding and the fabrication procedure. In addition, we studied the relationship between the glutaraldehyde concentration and sensor performance over a period of one year. The enzyme immobilization process by glutaraldehyde crosslinking to glucose oxidase appears to require at least 24-hours at room temperature to reach completion. In addition, excess free glucose oxidase can be removed by soaking sensors in purified water for 20 minutes. Even with the addition of these steps, however, it appears that there is some free glucose oxidase entrapped within the enzyme layer which contributes to a decline in sensitivity over time. Although it reduces the ultimate sensitivity (probably via a change in the enzyme's natural conformation), glutaraldehyde concentration in the enzyme layer can be increased in order to minimize this instability. After exposure of oxidase enzymes to glutaraldehyde, effective crosslinking requires a rinse step and a 24-hour incubation step. In order to minimize the loss of sensor sensitivity over time, the glutaraldehyde concentration can be increased.

Enhanced Biological Response of AVS-Functionalized Ti-6Al-4V Alloy through Covalent Immobilization of Collagen.

PubMed

Rezvanian, Parsa; Daza, Rafael; López, Patricia A; Ramos, Milagros; González-Nieto, Daniel; Elices, Manuel; Guinea, Gustavo V; Pérez-Rigueiro, José

2018-02-20

This study presents the development of an efficient procedure for covalently immobilizing collagen molecules on AVS-functionalized Ti-6Al-4V samples, and the assessment of the survival and proliferation of cells cultured on these substrates. Activated Vapor Silanization (AVS) is a versatile functionalization technique that allows obtaining a high density of active amine groups on the surface. A procedure is presented to covalently bind collagen to the functional layer using EDC/NHS as cross-linker. The covalently bound collagen proteins are characterized by fluorescence microscopy and atomic force microscopy and their stability is tested. The effect of the cross-linker concentration on the process is assessed. The concentration of the cross-linker is optimized and a reliable cleaning protocol is developed for the removal of the excess of carbodiimide from the samples. The results demonstrate that the covalent immobilization of collagen type I on Ti-6Al-4V substrates, using the optimized protocol, increases the number of viable cells present on the material. Consequently, AVS in combination with the carbodiimide chemistry appears as a robust method for the immobilization of proteins and, for the first time, it is shown that it can be used to enhance the biological response to the material.

Nondestructive assessment of collagen hydrogel cross-linking using time-resolved autofluorescence imaging.

PubMed

Sherlock, Benjamin E; Harvestine, Jenna N; Mitra, Debika; Haudenschild, Anne; Hu, Jerry; Athanasiou, Kyriacos A; Leach, J Kent; Marcu, Laura

2018-03-01

We investigate the use of a fiber-based, multispectral fluorescence lifetime imaging (FLIm) system to nondestructively monitor changes in mechanical properties of collagen hydrogels caused by controlled application of widely used cross-linking agents, glutaraldehyde (GTA) and ribose. Postcross-linking, fluorescence lifetime images are acquired prior to the hydrogels being processed by rheological or tensile testing to directly probe gel mechanical properties. To preserve the sterility of the ribose-treated gels, FLIm is performed inside a biosafety cabinet (BSC). A pairwise correlation analysis is used to quantify the relationship between mean hydrogel fluorescence lifetimes and the storage or Young's moduli of the gels. In the GTA study, we observe strong and specific correlations between fluorescence lifetime and the storage and Young's moduli. Similar correlations are not observed in the ribose study and we postulate a reason for this. Finally, we demonstrate the ability of FLIm to longitudinally monitor dynamic cross-link formation. The strength of the GTA correlations and deployment of our fiber-based FLIm system inside the aseptic environment of a BSC suggests that this technique may be a valuable tool for the tissue engineering community where longitudinal assessment of tissue construct maturation in vitro is highly desirable. (2018) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE).

Design and Printing Strategies in 3D Bioprinting of Cell-Hydrogels: A Review.

PubMed

Lee, Jia Min; Yeong, Wai Yee

2016-11-01

Bioprinting is an emerging technology that allows the assembling of both living and non-living biological materials into an ideal complex layout for further tissue maturation. Bioprinting aims to produce engineered tissue or organ in a mechanized, organized, and optimized manner. Various biomaterials and techniques have been utilized to bioprint biological constructs in different shapes, sizes and resolutions. There is a need to systematically discuss and analyze the reported strategies employed to fabricate these constructs. We identified and discussed important design factors in bioprinting, namely shape and resolution, material heterogeneity, and cellular-material remodeling dynamism. Each design factors are represented by the corresponding process capabilities and printing parameters. The process-design map will inspire future biomaterials research in these aspects. Design considerations such as data processing, bio-ink formulation and process selection are discussed. Various printing and crosslinking strategies, with relevant applications, are also systematically reviewed. We categorized them into 5 general bioprinting strategies, including direct bioprinting, in-process crosslinking, post-process crosslinking, indirect bioprinting and hybrid bioprinting. The opportunities and outlook in 3D bioprinting are highlighted. This review article will serve as a framework to advance computer-aided design in bioprinting technologies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polysulfone hemodiafiltration membranes with enhanced anti-fouling and hemocompatibility modified by poly(vinyl pyrrolidone) via in situ cross-linked polymerization.

PubMed

Zhu, Lijing; Song, Haiming; Wang, Jiarong; Xue, Lixin

2017-05-01

Poly(vinyl pyrrolidone) (PVP) and its copolymers have been widely employed for the modification of hemodiafiltration membranes due to their excellent hydrophilicity, antifouling and hemocompatibility. However, challenges still remain to simplify the modification procedure and to improve the utilization efficiency. In this paper, antifouling and hemocompatibility polysulfone (PSf) hemodiafiltration membranes were fabricated via in situ cross-linked polymerization of vinyl pyrrolidone (VP) and vinyltriethoxysilane (VTEOS) in PSf solutions and non-solvent induced phase separation (NIPS) technique. The prepared membranes were characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), which suggested that VP and VTEOS have been cross-linked copolymerized in PSf membranes. The modified PSf membranes with high polymer content showed improved hydrophilicity, ultrafiltration and protein antifouling ability. In addition, the modified PSf membranes showed lower protein adsorption, inhibited platelet adhesion and deformation, prolonged the activated partial thromboplastin time (APTT), prothrombin time (PT), and decreased the content of fibrinogen (FIB) transferring to fibrin, indicating enhanced hemocompatibility. In a word, the present work provides a simple and effective one-step modification method to construct PSf membranes with improved hydrophilicity, antifouling and hemocompatibility. Copyright © 2017 Elsevier B.V. All rights reserved.

Photouncaged Sequence-specific Interstrand DNA Cross-Linking with Photolabile 4-oxo-enal-modified Oligonucleotides

PubMed Central

Sun, Jingjing; Tang, Xinjing

2015-01-01

DNA cross-linking technology is an attractive tool for the detection, regulation, and manipulation of genes. In this study, a series of photolabile 4-oxo-enal-modified oligonucleotides functionalized with photosensitive ο-nitrobenzyl derivatives were rationally designed as a new kind of photocaged cross-linking agents. A comprehensive evaluation of cross-linking reactions for different nucleobases in complementary strands under different conditions suggested that the modified DNA oligonucleotides tended to form interstrand cross-linking to nucleobases with the potential of thymidine > guanosine » cytidine ~ adenosine. Different from previous literature reports that cytidine and adenosine were preferential cross-linked nucleobases with 4-oxo-enal moieties, our study represents the first example of DNA cross-linking for T and G selectivity using 4-oxo-enal moiety. The cross-linked adducts were identified and their cross-linking mechanism was also illustrated. This greatly expands the applications of 4-oxo-enal derivatives in the studies of DNA damage and RNA structure PMID:26020694

Photouncaged Sequence-specific Interstrand DNA Cross-Linking with Photolabile 4-oxo-enal-modified Oligonucleotides.

PubMed

Sun, Jingjing; Tang, Xinjing

2015-05-28

DNA cross-linking technology is an attractive tool for the detection, regulation, and manipulation of genes. In this study, a series of photolabile 4-oxo-enal-modified oligonucleotides functionalized with photosensitive ο-nitrobenzyl derivatives were rationally designed as a new kind of photocaged cross-linking agents. A comprehensive evaluation of cross-linking reactions for different nucleobases in complementary strands under different conditions suggested that the modified DNA oligonucleotides tended to form interstrand cross-linking to nucleobases with the potential of thymidine > guanosine » cytidine ~ adenosine. Different from previous literature reports that cytidine and adenosine were preferential cross-linked nucleobases with 4-oxo-enal moieties, our study represents the first example of DNA cross-linking for T and G selectivity using 4-oxo-enal moiety. The cross-linked adducts were identified and their cross-linking mechanism was also illustrated. This greatly expands the applications of 4-oxo-enal derivatives in the studies of DNA damage and RNA structure.

Effect of Rubber Polarity on Cluster Formation in Rubbers Cross-Linked with Diels–Alder Chemistry

PubMed Central

2017-01-01

Diels–Alder chemistry has been used for the thermoreversible cross-linking of furan-functionalized ethylene/propylene (EPM) and ethylene/vinyl acetate (EVM) rubbers. Both furan-functionalized elastomers were successfully cross-linked with bismaleimide to yield products with a similar cross-link density. NMR relaxometry and SAXS measurements both show that the apolar EPM-g-furan precursor contains phase-separated polar clusters and that cross-linking with polar bismaleimide occurs in these clusters. The heterogeneously cross-linked network of EPM-g-furan contrasts with the homogeneous network in the polar EVM-g-furan. The heterogeneous character of the cross-links in EPM-g-furan results in a relatively high Young’s modulus, whereas the more uniform cross-linking in EVM-g-furan results in a higher tensile strength and elongation at break. PMID:29213149

Cross-linked polyelectrolyte for direct methanol fuel cells applications based on a novel sulfonated cross-linker

NASA Astrophysics Data System (ADS)

Li, Mingyu; Zhang, Gang; Xu, Shuai; Zhao, Chengji; Han, Miaomiao; Zhang, Liyuan; Jiang, Hao; Liu, Zhongguo; Na, Hui

2014-06-01

A novel type of cross-linked proton exchange membrane of lower methanol permeation and high proton conductivity is prepared, based on a newly synthesized sulfonated cross-linker: carboxyl terminated benzimidazole trimer bearing sulfonic acid groups (s-BI). Compared to membranes cross-linked with non-sulfonated cross-linker (BI), SPEEK/s-BI-n membranes show higher IEC values and proton conductivities. Meanwhile, oxidative stability and mechanical property of SPEEK/s-BI-n membranes are obviously improved. Among SPEEK/s-BI-n membranes, SPEEK/s-BI-2 exhibits high proton conductivity, low swelling ratio (0.122 S cm-1 and 15.2% at 60 °C, respectively) and low methanol permeability coefficient. These results imply that the cross-linked membranes prepared with the newly sulfonated cross-linker are promising for the direct methanol fuel cells (DMFCs) application.

Desmosine-Inspired Cross-Linkers for Hyaluronan Hydrogels

NASA Astrophysics Data System (ADS)

Hagel, Valentin; Mateescu, Markus; Southan, Alexander; Wegner, Seraphine V.; Nuss, Isabell; Haraszti, Tamás; Kleinhans, Claudia; Schuh, Christian; Spatz, Joachim P.; Kluger, Petra J.; Bach, Monika; Tussetschläger, Stefan; Tovar, Günter E. M.; Laschat, Sabine; Boehm, Heike

2013-06-01

We designed bioinspired cross-linkers based on desmosine, the cross-linker in natural elastin, to prepare hydrogels with thiolated hyaluronic acid. These short, rigid cross-linkers are based on pyridinium salts (as in desmosine) and can connect two polymer backbones. Generally, the obtained semi-synthetic hydrogels are form-stable, can withstand repeated stress, have a large linear-elastic range, and show strain stiffening behavior typical for biopolymer networks. In addition, it is possible to introduce a positive charge to the core of the cross-linker without affecting the gelation efficiency, or consequently the network connectivity. However, the mechanical properties strongly depend on the charge of the cross-linker. The properties of the presented hydrogels can thus be tuned in a range important for engineering of soft tissues by controlling the cross-linking density and the charge of the cross-linker.

Discovery of Undefined Protein Crosslinking Chemistry: A Comprehensive Methodology Utilizing 18O-labeling and Mass Spectrometry

PubMed Central

Liu, Min; Zhang, Zhongqi; Zang, Tianzhu; Spahr, Chris; Cheetham, Janet; Ren, Da; Sunny Zhou, Zhaohui

2013-01-01

Characterization of protein crosslinking, particularly without prior knowledge of the chemical nature and site of crosslinking, poses a significant challenge due to their intrinsic structural complexity and the lack of a comprehensive analytical approach. Towards this end, we have developed a generally applicable workflow—XChem-Finder that involves four stages. (1) Detection of crosslinked peptides via 18O-labeling at C-termini. (2) Determination of the putative partial sequences of each crosslinked peptide pair using a fragment ion mass database search against known protein sequences coupled with a de novo sequence tag search. (3) Extension to full sequences based on protease specificity, the unique combination of mass, and other constraints. (4) Deduction of crosslinking chemistry and site. The mass difference between the sum of two putative full-length peptides and the crosslinked peptide provides the formulas (elemental composition analysis) for the functional groups involved in each cross- linking. Combined with sequence restraint from MS/MS data, plausible crosslinking chemistry and site were inferred, and ultimately, confirmed by matching with all data. Applying our approach to a stressed IgG2 antibody, ten cross-linked peptides were discovered and found to be connected via thioether originating from disulfides at locations that had not been previously recognized. Furthermore, once the crosslink chemistry was revealed, a targeted crosslink search yielded four additional crosslinked peptides that all contain the C-terminus of the light chain. PMID:23634697

A molecular cross-linking approach for hybrid metal oxides.

PubMed

Jung, Dahee; Saleh, Liban M A; Berkson, Zachariah J; El-Kady, Maher F; Hwang, Jee Youn; Mohamed, Nahla; Wixtrom, Alex I; Titarenko, Ekaterina; Shao, Yanwu; McCarthy, Kassandra; Guo, Jian; Martini, Ignacio B; Kraemer, Stephan; Wegener, Evan C; Saint-Cricq, Philippe; Ruehle, Bastian; Langeslay, Ryan R; Delferro, Massimiliano; Brosmer, Jonathan L; Hendon, Christopher H; Gallagher-Jones, Marcus; Rodriguez, Jose; Chapman, Karena W; Miller, Jeffrey T; Duan, Xiangfeng; Kaner, Richard B; Zink, Jeffrey I; Chmelka, Bradley F; Spokoyny, Alexander M

2018-04-01

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO 2 , to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as 'molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B 12 (OH) 12 ] 2- . This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO 2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

Cross-Linking and Mass Spectrometry Methodologies to Facilitate Structural Biology: Finding a Path through the Maze

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

Merkley, Eric D.; Cort, John R.; Adkins, Joshua N.

2013-09-01

Multiprotein complexes, rather than individual proteins, make up a large part of the biological macromolecular machinery of a cell. Understanding the structure and organization of these complexes is critical to understanding cellular function. Chemical cross-linking coupled with mass spectrometry is emerging as a complementary technique to traditional structural biology methods and can provide low-resolution structural information for a multitude of purposes, such as distance constraints in computational modeling of protein complexes. In this review, we discuss the experimental considerations for successful application of chemical cross-linking-mass spectrometry in biological studies and highlight three examples of such studies from the recent literature.more » These examples (as well as many others) illustrate the utility of a chemical cross-linking-mass spectrometry approach in facilitating structural analysis of large and challenging complexes.« less

Confocal Raman microscopy to monitor extracellular matrix during dental pulp stem cells differentiation

NASA Astrophysics Data System (ADS)

Salehi, Hamideh; Collart-Dutilleul, Pierre-Yves; Gergely, Csilla; Cuisinier, Frédéric J. G.

2015-07-01

Regenerative medicine brings promising applications for mesenchymal stem cells, such as dental pulp stem cells (DPSCs). Confocal Raman microscopy, a noninvasive technique, is used to study osteogenic differentiation of DPSCs. Integrated Raman intensities in the 2800 to 3000 cm-1 region (C-H stretching) and the 960 cm-1 peak (ν1 PO43-) were collected (to image cells and phosphate, respectively), and the ratio of two peaks 1660 over 1690 cm-1 (amide I bands) to measure the collagen cross-linking has been calculated. Raman spectra of DPSCs after 21 days differentiation reveal several phosphate peaks: ν1 (first stretching mode) at 960 cm-1, ν2 at 430 cm-1, and ν4 at 585 cm-1 and collagen cross-linking can also be calculated. Confocal Raman microscopy enables monitoring osteogenic differentiation in vitro and can be a credible tool for clinical stem cell based research.

Insight into the ionotropic gelation of chitosan using tripolyphosphate and pyrophosphate as cross-linkers.

PubMed

Sacco, Pasquale; Paoletti, Sergio; Cok, Michela; Asaro, Fioretta; Abrami, Michela; Grassi, Mario; Donati, Ivan

2016-11-01

Ionotropic gelation of chitosan by means of opposite charged ions represents an efficient alternative to covalent reticulation because of milder condition of use and, in general, higher biocompatibility of the resulting systems. In this work 90° light scattering (turbidimetry), circular dichroism (CD) and 1 H NMR measurements have been performed to study the interactions between the biopolymer and ionic cross-linkers tripolyphosphate (TPP) and pyrophosphate (PPi) in dilute solutions. Thereafter, a dialysis-based technique was exploited to fabricate tridimensional chitosan hydrogels based on both polyanions. Resulting matrices showed a different mechanical behavior because of their peculiar mesh-texture at micro/nano-scale: in the present contribution we demonstrate that TPP and PPi favor the formation of homogeneous and inhomogeneous systems, respectively. The different texture of networks could be exploited in future for the preparation of systems for the controlled release of molecules. Copyright © 2016 Elsevier B.V. All rights reserved.

Combinatorial Methodology for Screening Selectivity in Polymeric Pervaporation Membranes.

PubMed

Godbole, Rutvik V; Ma, Lan; Doerfert, Michael D; Williams, Porsche; Hedden, Ronald C

2015-11-09

Combinatorial methodology is described for rapid screening of selectivity in polymeric pervaporation membrane materials for alcohol-water separations. The screening technique is demonstrated for ethanol-water separation using a model polyacrylate system. The materials studied are cross-linked random copolymers of a hydrophobic comonomer (n-butyl acrylate, B) and a hydrophilic comonomer (2-hydroxyethyl acrylate, H). A matrix of materials is prepared that has orthogonal variations in two key variables, H:B ratio and cross-linker concentration. For mixtures of ethanol and water, equilibrium selectivities and distribution coefficients are obtained by combining swelling measurements with high-throughput HPLC analysis. Based on the screening results, two copolymers are selected for further study as pervaporation membranes to quantify permeability selectivity and the flux of ethanol. The screening methodology described has good potential to accelerate the search for new membrane materials, as it is adaptable to a broad range of polymer chemistries.

A molecular cross-linking approach for hybrid metal oxides

NASA Astrophysics Data System (ADS)

Jung, Dahee; Saleh, Liban M. A.; Berkson, Zachariah J.; El-Kady, Maher F.; Hwang, Jee Youn; Mohamed, Nahla; Wixtrom, Alex I.; Titarenko, Ekaterina; Shao, Yanwu; McCarthy, Kassandra; Guo, Jian; Martini, Ignacio B.; Kraemer, Stephan; Wegener, Evan C.; Saint-Cricq, Philippe; Ruehle, Bastian; Langeslay, Ryan R.; Delferro, Massimiliano; Brosmer, Jonathan L.; Hendon, Christopher H.; Gallagher-Jones, Marcus; Rodriguez, Jose; Chapman, Karena W.; Miller, Jeffrey T.; Duan, Xiangfeng; Kaner, Richard B.; Zink, Jeffrey I.; Chmelka, Bradley F.; Spokoyny, Alexander M.

2018-03-01

There is significant interest in the development of methods to create hybrid materials that transform capabilities, in particular for Earth-abundant metal oxides, such as TiO2, to give improved or new properties relevant to a broad spectrum of applications. Here we introduce an approach we refer to as `molecular cross-linking', whereby a hybrid molecular boron oxide material is formed from polyhedral boron-cluster precursors of the type [B12(OH)12]2-. This new approach is enabled by the inherent robustness of the boron-cluster molecular building block, which is compatible with the harsh thermal and oxidizing conditions that are necessary for the synthesis of many metal oxides. In this work, using a battery of experimental techniques and materials simulation, we show how this material can be interfaced successfully with TiO2 and other metal oxides to give boron-rich hybrid materials with intriguing photophysical and electrochemical properties.

Large patternable metal nanoparticle sheets by photo/e-beam lithography

NASA Astrophysics Data System (ADS)

Saito, Noboru; Wang, Pangpang; Okamoto, Koichi; Ryuzaki, Sou; Tamada, Kaoru

2017-10-01

Techniques for micro/nano-scale patterning of large metal nanoparticle sheets can potentially be used to realize high-performance photoelectronic devices because the sheets provide greatly enhanced electrical fields around the nanoparticles due to localized surface plasmon resonances. However, no single metal nanoparticle sheet currently exists with sufficient durability for conventional lithographical processes. Here, we report large photo and/or e-beam lithographic patternable metal nanoparticle sheets with improved durability by incorporating molecular cross-linked structures between nanoparticles. The cross-linked structures were easily formed by a one-step chemical reaction; immersing a single nanoparticle sheet consisting of core metals, to which capping molecules ionically bond, in a dithiol ethanol solution. The ligand exchange reaction processes were discussed in detail, and we demonstrated 20 μm wide line and space patterns, and a 170 nm wide line of the silver nanoparticle sheets.

Detection of ASC Speck Formation by Flow Cytometry and Chemical Cross-linking.

PubMed

Hoss, Florian; Rolfes, Verena; Davanso, Mariana R; Braga, Tarcio T; Franklin, Bernardo S

2018-01-01

Assembly of a relatively large protein aggregate or "speck" formed by the adaptor protein ASC is a common downstream step in the activation of most inflammasomes. This unique feature of ASC allows its visualization by several imaging techniques and constitutes a reliable and feasible readout for inflammasome activation in cells and tissues. We have previously described step-by-step protocols to generate immortalized cell lines stably expressing ASC fused to a fluorescent protein for measuring inflammasome activation by confocal microscopy, and immunofluorescence of endogenous ASC in primary cells. Here, we present two more methods to detect ASC speck formation: (1) Assessment of ASC speck formation by flow cytometry; and (2) Chemical cross-linking of ASC followed by immunoblotting. These methods allow for the discrimination of inflammasome-activated versus non-activated cells, the identification of lineage-specific inflammasome activation in complex cell mixtures, and sorting of inflammasome-activated cells for further analysis.

Optimization of β-cyclodextrin cross-linked polymer for monitoring of quercetin

NASA Astrophysics Data System (ADS)

Zhu, Xiashi; Ping, Wenhui

2014-11-01

A novel method for the separation/analysis of quercetin was described, which was based on the investigation of the inclusion interactions of β-cyclodextrin cross-linked polymer (β-CDCP) with quercetin (Qu) and the adsorption behavior of Qu on β-CDCP. The inclusion interaction of β-CDCP with Qu was studied through FTIR, TGA and 13C NMR. Under the optimum conditions, the preconcentration factor of the proposed method was approximately 8.8, the β-CDCP could be used repeatedly for 30 times and offered better recovery. The linear range, limit of detection (LOD) and the relative standard deviation (RSD) was found to be 0.10-12.0 μg mL-1, 4.6 ng mL-1 and 3.10% (n = 3, c = 2.0 μg mL-1) respectively. This technique had been successfully applied to the determination of Qu in real samples.

Crosslinking method of hyaluronic-based hydrogel for biomedical applications

PubMed Central

Khunmanee, Sureerat; Jeong, Younghyen; Park, Hansoo

2017-01-01

In the field of tissue engineering, there is a need for advancement beyond conventional scaffolds and preformed hydrogels. Injectable hydrogels have gained wider admiration among researchers as they can be used in minimally invasive surgical procedures. Injectable gels completely fill the defect area and have good permeability and hence are promising biomaterials. The technique can be effectively applied to deliver a wide range of bioactive agents, such as drugs, proteins, growth factors, and even living cells. Hyaluronic acid is a promising candidate for the tissue engineering field because of its unique physicochemical and biological properties. Thus, this review provides an overview of various methods of chemical and physical crosslinking using different linkers that have been investigated to develop the mechanical properties, biodegradation, and biocompatibility of hyaluronic acid as an injectable hydrogel in cell scaffolds, drug delivery systems, and wound healing applications. PMID:28912946

Chromatographic evaluation of self-immobilized stationary phases for reversed-phase liquid chromatography.

PubMed

Bottoli, Carla B G; Collins, Kenneth E; Collins, Carol H

2003-02-14

The preparation of stationary phases for HPLC using polymers deposited on silica usually includes an immobilization step involving cross-linking by free radicals induced by ionizing radiation or by other radical initiators. The present paper reports changes which occur at ambient temperature in the character of poly(methyloctylsiloxane) deposited on porous silica particles as a function of the time interval between particle loading and column packing. Column performance and retention factors increase with time and these changes are attributed to rearrangement (self-assembly) which result in "self-immobilization" of the polymer molecules on the silica surface.

Electron Beam Materials Irradiators

NASA Astrophysics Data System (ADS)

Cleland, Marshall R.

2012-06-01

Radiation processing is a well established method for enhancing the properties of materials and commercial products by treating them with ionizing energy in the form of high-energy electrons, X-rays, and gamma rays. Beneficial effects include polymerizing, cross-linking, grafting and degrading plastics, sterilizing single-use medical devices, disinfecting and disinfesting fresh foods, purifying drinking water, treating wastewater and other toxic waste materials that harm the environment, and many other applications that are still being evaluated. Industrial electron accelerators of several types have been developed and are being used for these applications. More than 1800 electron accelerators are presently installed in facilities worldwide for these purposes.

Method for the preparation of thin-skinned asymmetric reverse osmosis membranes and products thereof

NASA Technical Reports Server (NTRS)

Wydeven, T. J. (Inventor); Katz, M. G.

1984-01-01

A method for preparing water insoluble asymmetric membranes from water soluble polymers is discussed. The process involves casting a film of the polymer, partially drying it, and then contacting it with a concentrated solution of a transition metal salt. The transition metal ions render the polymer insoluable and are believed to form a complex with it. Optionally, the polymer is crosslinked with heat or radiation. The most preferred polymer is poly(vinyl alcohol). The most preferred complexing salt is copper sulfate. The process and the metal ion linked membranes are discussed. The membranes are reverse osmosis membranes.

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

PubMed Central

Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao

2017-01-01

Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed. PMID:28051190

Mechanically tunable actin networks using programmable DNA based cross-linkers

NASA Astrophysics Data System (ADS)

Schnauss, Joerg; Lorenz, Jessica; Schuldt, Carsten; Kaes, Josef; Smith, David

Cells employ multiple cross-linkers with very different properties. Studies of the entire phase space, however, were infeasible since they were restricted to naturally occurring cross-linkers. These components cannot be controllably varied and differ in many parameters. We resolve this limitation by forming artificial actin cross-linkers, which can be controllably varied. The basic building block is DNA enabling a well-defined length variation. DNA can be attached to actin binding peptides with known binding affinities. We used bulk rheology to investigate mechanical properties of these networks. We were able to reproduce mechanical features of actin networks cross-linked by fascin by using a short version of our artificial complex with a high binding affinity. Additionally, we were able to resemble findings for the cross-linker alpha-actinin by employing a long cross-linker with a low binding affinity. Between these natural limits we investigated three different cross-linker lengths each with two different binding affinities. With these controlled variations we are able to precisely screen the phase space of cross-linked actin networks by changing only one specific parameter and not the entire set of properties as in the case of naturally occurring cross-linking complexes.

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

NASA Astrophysics Data System (ADS)

Li, Jinghui; Chen, Zhuo; Umar, Ahmad; Liu, Yang; Shang, Ying; Zhang, Xiaokai; Wang, Yao

2017-01-01

Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed.

Effect of crosslink torsional stiffness on elastic behavior of semiflexible polymer networks

NASA Astrophysics Data System (ADS)

Hatami-Marbini, H.

2018-02-01

Networks of semiflexible filaments are building blocks of different biological and structural materials such as cytoskeleton and extracellular matrix. The mechanical response of these systems when subjected to an applied strain at zero temperature is often investigated numerically using networks composed of filaments, which are either rigidly welded or pinned together at their crosslinks. In the latter, filaments during deformation are free to rotate about their crosslinks while the relative angles between filaments remain constant in the former. The behavior of crosslinks in actual semiflexible networks is different than these idealized models and there exists only partial constraint on torques at crosslinks. The present work develops a numerical model in which two intersecting filaments are connected to each other by torsional springs with arbitrary stiffness. We show that fiber networks composed of rigid and freely rotating crosslinks are the limiting case of the present model. Furthermore, we characterize the effects of stiffness of crosslinks on effective Young's modulus of semiflexible networks as a function of filament flexibility and crosslink density. The effective Young's modulus is determined as a function of the mechanical properties of crosslinks and is found to vanish for networks composed of very weak torsional springs. Independent of the stiffness of crosslinks, it is found that the effective Young's modulus is a function of fiber flexibility and crosslink density. In low density networks, filaments primarily bend and the effective Young's modulus is much lower than the affine estimate. With increasing filament bending stiffness and/or crosslink density, the mechanical behavior of the networks becomes more affine and the stretching of filaments depicts itself as the dominant mode of deformation. The torsional stiffness of the crosslinks significantly affects the effective Young's modulus of the semiflexible random fiber networks.

In vitro cross-linking of elastin peptides and molecular characterization of the resultant biomaterials.

PubMed

Heinz, Andrea; Ruttkies, Christoph K H; Jahreis, Günther; Schräder, Christoph U; Wichapong, Kanin; Sippl, Wolfgang; Keeley, Fred W; Neubert, Reinhard H H; Schmelzer, Christian E H

2013-04-01

Elastin is a vital protein and the major component of elastic fibers which provides resilience to many vertebrate tissues. Elastin's structure and function are influenced by extensive cross-linking, however, the cross-linking pattern is still unknown. Small peptides containing reactive allysine residues based on sequences of cross-linking domains of human elastin were incubated in vitro to form cross-links characteristic of mature elastin. The resultant insoluble polymeric biomaterials were studied by scanning electron microscopy. Both, the supernatants of the samples and the insoluble polymers, after digestion with pancreatic elastase or trypsin, were furthermore comprehensively characterized on the molecular level using MALDI-TOF/TOF mass spectrometry. MS(2) data was used to develop the software PolyLinX, which is able to sequence not only linear and bifunctionally cross-linked peptides, but for the first time also tri- and tetrafunctionally cross-linked species. Thus, it was possible to identify intra- and intermolecular cross-links including allysine aldols, dehydrolysinonorleucines and dehydromerodesmosines. The formation of the tetrafunctional cross-link desmosine or isodesmosine was unexpected, however, could be confirmed by tandem mass spectrometry and molecular dynamics simulations. The study demonstrated that it is possible to produce biopolymers containing polyfunctional cross-links characteristic of mature elastin from small elastin peptides. MALDI-TOF/TOF mass spectrometry and the newly developed software PolyLinX proved suitable for sequencing of native cross-links in proteolytic digests of elastin-like biomaterials. The study provides important insight into the formation of native elastin cross-links and represents a considerable step towards the characterization of the complex cross-linking pattern of mature elastin. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of different crosslinking treatments on the physical properties of collagen membranes.

PubMed

Charulatha, V; Rajaram, A

2003-02-01

The physical properties of collagen-based biomaterials are profoundly influenced by the method and extent of crosslinking. In this study, the influence of various crosslinking treatments on the physical properties of reconstituted collagen membranes was assessed. Five crosslinking agents viz., GTA, DMS, DTBP, a combination of DMS and GTA and acyl azide method were used to stabilize collagen matrices. Crosslinking density, swelling ratio, thermo-mechanical properties, stress-strain characteristics and resistance to collagenase digestion were determined to evaluate the physical properties of crosslinked matrices. GTA treatment induced the maximum number of crosslinks (13) while DMS treatment induced the minimum (7). Of the two diimidoesters (DMS and DTBP), DTBP was a more effective crosslinking agent due to the presence of disulphide bonds in the DTBP crosslinks. T(s) for DTBP and DMS crosslinked collagen were 80 degrees C and 70 degrees C, and their HIT values were 5.4 and 2.85MN/m(2), respectively. Low concentration of GTA (0.01%) increased the crosslinking density of an already crosslinked matrix (DMS treated matrix) from 7 to 12. Lowest fracture energy was observed for the acyl azide treated matrix (0.61MJ/m(3)) while the highest was observed for the GTA treated matrix (1.97MJ/m(3)). The tensile strength of GTA treated matrix was maximum (12.4MPa) and that of acyl azide treated matrix was minimum (7.2MPa). GTA, DTBP and acyl azide treated matrices were equally resistant to collagenase degradation with approximately 6% solubilization after 5h while the DMS treated was least stable with 52.4% solubilization after the same time period. The spatial orientation of amino acid side chain residues on collagen plays an important role in determining the crosslinking density and consequent physical properties of the collagen matrix.

Hemostatic potential of natural/synthetic polymer based hydrogels crosslinked by gamma radiation

NASA Astrophysics Data System (ADS)

Barba, Bin Jeremiah D.; Tranquilan-Aranilla, Charito; Abad, Lucille V.

2016-01-01

Various raw materials and hydrogels prepared from their combination were assessed for hemostatic capability using swine whole blood clotting analysis. Initial screening showed efficient coagulative properties from κ-carrageenan and its carboxymethylated form, and α-chitosan, even compared to commercial products like QuikClot Zeolite Powder. Blending natural and synthetic polymers formed into hydrogels using gamma radiation produced materials with improved properties. KC and CMKC hydrogels were found to have the lowest blood clotting index in granulated form and had the higher capacity for platelet adhesion in foamed form compared to GelFoam. Possible mechanisms involved in the evident thrombogenicity of the materials include adsorption of platelets and related proteins that aid in platelet activation (primary hemostasis), absorption of water to concentrate protein factors that control the coagulation cascade, contact activation by its negatively charged surface and the formation of gel-blood clots.

A new strategy to produce low-density polyethylene (LDPE)-based composites simultaneously with high flame retardancy and high mechanical properties

NASA Astrophysics Data System (ADS)

Shen, Liguo; Li, Jianxi; Li, Renjie; Lin, Hongjun; Chen, Jianrong; Liao, Bao-Qiang

2018-04-01

In this study, a new strategy which blends low-density polyethylene (LDPE), magnesium hydroxide (MH) and lauryl acrylate by electron-beam radiation for production of LDPE-based composites with high performance was proposed. It was found that, MH played main roles in flame retardancy but reduced processing flow and mechanical properties of the composites. Meanwhile, melt flow rate (MFR) increased while viscosity of the composites decreased with lauryl acrylate content increased, facilitating LDPE composites processing. Electron beam radiation could prompt crosslinking of lauryl acrylate, which significantly enhanced the mechanical properties of LDPE composites. Meanwhile, lauryl acrylate addition only slightly decreased the flame retardancy, suggesting that LDPE composites could remain high flame retardancy even when lauryl acrylate content was high. The study highly demonstrated the feasibility to produce LDPE-based composites simultaneously with high flame retardancy and high mechanical properties by the blending strategy provided in this study.

Multipurpose hardened spacecraft insulation

NASA Technical Reports Server (NTRS)

Steimer, Carlos H.

1990-01-01

A Multipurpose Hardened Spacecraft Multilayer Insulation (MLI) system was developed and implemented to meet diverse survivability and performance requirements. Within the definition and confines of a MLI assembly (blanket), the design: (1) provides environmental protection from natural and induced nuclear, thermal, and electromagnetic radiation; (2) provides adequate electrostatic discharge protection for a geosynchronous satellite; (3) provides adequate shielding to meet radiated emission needs; and (4) will survive ascent differential pressure loads between enclosed volume and space. The MLI design is described which meets these requirements and design evolution and verification is discussed. The application is for MLI blankets which closeout the area between the laser crosslink subsystem (LCS) equipment and the DSP spacecraft cabin. Ancillary needs were implemented to ease installation at launch facility and to survive ascent acoustic and vibration loads. Directional venting accommodations were also incorporated to avoid contamination of LCS telescope, spacecraft sensors, and second surface mirrors (SSMs).

Synthesis and characterization of superabsorbent polymer prepared by radiation-induced graft copolymerization of acrylamide onto carboxymethyl cellulose for controlled release of agrochemicals

NASA Astrophysics Data System (ADS)

Hemvichian, Kasinee; Chanthawong, Auraruk; Suwanmala, Phiriyatorn

2014-10-01

Superabsorbent polymer (SAP) was synthesized by radiation-induced grafting of acrylamide (AM) onto carboxymethyl cellulose (CMC) in the presence of a crosslinking agent, N,N‧-methylenebisacrylamide (MBA). The effects of various parameters, such as dose, the amount of CMC, AM, MBA and ionic strength on the swelling ratio were investigated. In order to evaluate its controlled release potential, SAP was loaded with potassium nitrate (KNO3) as an agrochemical model and its potential for controlled release of KNO3 was studied. The amount of released KNO3 was analyzed by an inductively coupled plasma mass spectrometry (ICP-MS). The results from controlled release experiment agreed very well with the results from swelling experiment. The synthesized SAP was characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The obtained SAP exhibited a swelling ratio of 190 g/g of dry gel.

Polymeric salt bridges for conducting electric current in microfluidic devices

DOEpatents

Shepodd, Timothy J [Livermore, CA; Tichenor, Mark S [San Diego, CA; Artau, Alexander [Humacao, PR

2009-11-17

A "cast-in-place" monolithic microporous polymer salt bridge for conducting electrical current in microfluidic devices, and methods for manufacture thereof is disclosed. Polymeric salt bridges are formed in place in capillaries or microchannels. Formulations are prepared with monomer, suitable cross-linkers, solvent, and a thermal or radiation responsive initiator. The formulation is placed in a desired location and then suitable radiation such as UV light is used to polymerize the salt bridge within a desired structural location. Embodiments are provided wherein the polymeric salt bridges have sufficient porosity to allow ionic migration without bulk flow of solvents therethrough. The salt bridges form barriers that seal against fluid pressures in excess of 5000 pounds per square inch. The salt bridges can be formulated for carriage of suitable amperage at a desired voltage, and thus microfluidic devices using such salt bridges can be specifically constructed to meet selected analytical requirements.

Understanding RNA-Chromatin Interactions Using Chromatin Isolation by RNA Purification (ChIRP).

PubMed

Chu, Ci; Chang, Howard Y

2016-01-01

ChIRP is a novel and easy-to-use technique for studying long noncoding RNA (lncRNA)-chromatin interactions. RNA and chromatin are cross-linked in vivo using formaldehyde or glutaraldehyde, and purified using biotinylated antisense oligonucleotides that hybridize to the target RNA. Co-precipitated DNA is then purified and analyzed by quantitative PCR (qPCR) or high-throughput sequencing.

Autonomic Composite Hydrogels by Reactive Printing: Materials and Oscillatory Response (Postprint)

DTIC Science & Technology

2013-11-01

properties such as polyacrylamide (PAAm)14,17 and gelatin ,2,15 and employing novel synthesis techniques and catalyst binding chemistries such as UV...compatible with additive processing (manufacturing) tech- niques. For example, the thermal gelation characteristics of gelatin enable printing of self...supporting structures by extruding hot gelatin (low viscosity) onto a cold substrate (high viscosity).2,15 Glutaraldehyde crosslinking of co-printed, or

DNA cross-linking by dehydromonocrotaline lacks apparent base sequence preference.

PubMed

Rieben, W Kurt; Coulombe, Roger A

2004-12-01

Pyrrolizidine alkaloids (PAs) are ubiquitous plant toxins, many of which, upon oxidation by hepatic mixed-function oxidases, become reactive bifunctional pyrrolic electrophiles that form DNA-DNA and DNA-protein cross-links. The anti-mitotic, toxic, and carcinogenic action of PAs is thought to be caused, at least in part, by these cross-links. We wished to determine whether the activated PA pyrrole dehydromonocrotaline (DHMO) exhibits base sequence preferences when cross-linked to a set of model duplex poly A-T 14-mer oligonucleotides with varying internal and/or end 5'-d(CG), 5'-d(GC), 5'-d(TA), 5'-d(CGCG), or 5'-d(GCGC) sequences. DHMO-DNA cross-links were assessed by electrophoretic mobility shift assay (EMSA) of 32P endlabeled oligonucleotides and by HPLC analysis of cross-linked DNAs enzymatically digested to their constituent deoxynucleosides. The degree of DNA cross-links depended upon the concentration of the pyrrole, but not on the base sequence of the oligonucleotide target. Likewise, HPLC chromatograms of cross-linked and digested DNAs showed no discernible sequence preference for any nucleotide. Added glutathione, tyrosine, cysteine, and aspartic acid, but not phenylalanine, threonine, serine, lysine, or methionine competed with DNA as alternate nucleophiles for cross-linking by DHMO. From these data it appears that DHMO exhibits no strong base preference when forming cross-links with DNA, and that some cellular nucleophiles can inhibit DNA cross-link formation.

Cross-Link Guided Molecular Modeling with ROSETTA

PubMed Central

Leitner, Alexander; Rosenberger, George; Aebersold, Ruedi; Malmström, Lars

2013-01-01

Chemical cross-links identified by mass spectrometry generate distance restraints that reveal low-resolution structural information on proteins and protein complexes. The technology to reliably generate such data has become mature and robust enough to shift the focus to the question of how these distance restraints can be best integrated into molecular modeling calculations. Here, we introduce three workflows for incorporating distance restraints generated by chemical cross-linking and mass spectrometry into ROSETTA protocols for comparative and de novo modeling and protein-protein docking. We demonstrate that the cross-link validation and visualization software Xwalk facilitates successful cross-link data integration. Besides the protocols we introduce XLdb, a database of chemical cross-links from 14 different publications with 506 intra-protein and 62 inter-protein cross-links, where each cross-link can be mapped on an experimental structure from the Protein Data Bank. Finally, we demonstrate on a protein-protein docking reference data set the impact of virtual cross-links on protein docking calculations and show that an inter-protein cross-link can reduce on average the RMSD of a docking prediction by 5.0 Å. The methods and results presented here provide guidelines for the effective integration of chemical cross-link data in molecular modeling calculations and should advance the structural analysis of particularly large and transient protein complexes via hybrid structural biology methods. PMID:24069194

Study of Reactive Melt Processing Behavior of Externally Plasticized Cellulose Acetate in Presence of Isocyanate

PubMed Central

Erdmann, Rafael; Kabasci, Stephan; Kurek, Joanna; Zepnik, Stefan

2014-01-01

Two types of externally plasticized cellulose acetate (CA) were chemically modified using 4,4'-methylene diphenyl diisocyanate (MDI) as crosslinking agent. Crosslinking was performed in the molten state by means of melt mixing in an internal mixer. The viscoelastic properties of the non-crosslinked, externally plasticized CA show typical temperature dependence, similar to conventional thermoplastics. A strong increase in storage modulus is observed with increasing crosslink density indicating that the crosslinked compounds exhibit predominately elastic response. The complex viscosity also increases considerably with increasing crosslink density and does not reach the typical Newtonian plateau at low radial frequencies any more. The viscoelastic properties correlate well with the data recorded online during reactive melt processing in the internal mixer. In comparison to the non-crosslinked CA, the crosslinked compounds show higher glass transition temperature, higher VICAT softening temperatures, improved thermal stability and lower plasticizer evaporation at evaluated temperatures. PMID:28788273

'Genipin' - the natural water soluble cross-linking agent and its importance in the modified drug delivery systems: an overview.

PubMed

Manickam, Balamurugan; Sreedharan, Rajesh; Elumalai, Manogaran

2014-01-01

One of the popular approaches in controlling drug delivery from the polymeric carriers is suitably achieved by the inclusion of crosslinking agents into the formulations at different concentrations. Nevertheless, addition of the chemical crosslinkers such as glutaraldehyde, formaldehyde etc, used in the drug delivery systems causes very serious cytotoxic reactions. These chemical crosslinking agents did not offer any significant advantageous effects when compared to the natural crosslinking agents for instance genipin, which is quite less toxic, biocompatible and offers very stable crosslinked products. Based on the earlier reports the safety of this particular natural crosslinker is very well established, since it has been widely used as a Chinese traditional medicine for long-time, isolated from fruits of the plant Gardenia jasminoides Ellis. This concise article largely portrayed the value of this unique natural crosslinker, utilized in controlling the drug delivery from the various formulations.

Study of Reactive Melt Processing Behavior of Externally Plasticized Cellulose Acetate in Presence of Isocyanate.

PubMed

Erdmann, Rafael; Kabasci, Stephan; Kurek, Joanna; Zepnik, Stefan

2014-12-04

Two types of externally plasticized cellulose acetate (CA) were chemically modified using 4,4'-methylene diphenyl diisocyanate (MDI) as crosslinking agent. Crosslinking was performed in the molten state by means of melt mixing in an internal mixer. The viscoelastic properties of the non-crosslinked, externally plasticized CA show typical temperature dependence, similar to conventional thermoplastics. A strong increase in storage modulus is observed with increasing crosslink density indicating that the crosslinked compounds exhibit predominately elastic response. The complex viscosity also increases considerably with increasing crosslink density and does not reach the typical Newtonian plateau at low radial frequencies any more. The viscoelastic properties correlate well with the data recorded online during reactive melt processing in the internal mixer. In comparison to the non-crosslinked CA, the crosslinked compounds show higher glass transition temperature, higher VICAT softening temperatures, improved thermal stability and lower plasticizer evaporation at evaluated temperatures.

Yield and Failure Behavior Investigated for Cross-Linked Phenolic Resins Using Molecular Dynamics

NASA Technical Reports Server (NTRS)

Monk, Joshua D.; Lawson, John W.

2016-01-01

Molecular dynamics simulations were conducted to fundamentally evaluate the yield and failure behavior of cross-linked phenolic resins at temperatures below the glass transition. Yield stress was investigated at various temperatures, strain rates, and degrees of cross-linking. The onset of non-linear behavior in the cross-linked phenolic structures was caused by localized irreversible molecular rearrangements through the rotation of methylene linkers followed by the formation or annihilation of neighboring hydrogen bonds. The yield stress results, with respect to temperature and strain rate, could be fit by existing models used to describe yield behavior of amorphous glasses. The degree of cross-linking only indirectly influences the maximum yield stress through its influence on glass transition temperature (Tg), however there is a strong relationship between the degree of cross-linking and the failure mechanism. Low cross-linked samples were able to separate through void formation, whereas the highly cross-linked structures exhibited bond scission.

Evaluation of Gentamicin and Lidocaine Release Profile from Gum Acacia-crosslinked-poly(2-hydroxyethylmethacrylate)-carbopol Based Hydrogels.

PubMed

Singh, Baljit; Dhiman, Abhishek

2017-01-01

No doubt, the prevention of infection is an indispensable aspect of the wound management, but, simultaneous wound pain relief is also required. Therefore, herein this article, incorporation of antibiotic agent 'gentamicin' and pain relieving agent 'lidocaine' into hydrogel wound dressings, prepared by using acacia gum, carbopol and poly(2-hydroxyethylmethacrylate) polymers, has been carried out. The hydrogels were evaluated as a drug carrier for model drugs gentamicin and lidocaine. Synthesis of hydrogel wound dressing was carried out by free radical polymerization technique. The drug loading was carried out by swelling equilibrium method and gel strength of hydrogels was measured by a texture analyzer. Porous microstructure of the hydrogel was observed in cryo-SEM images. The hydrogel showed mesh size 37.29 nm, cross-link density 2.19× 10-5 mol/cm3, molecular weight between two cross-links 60.25× 10-3 g/mol and gel strength 0.625±0.112 N in simulated wound fluid. It is concluded that the pH of swelling medium has influenced the network structure of hydrogel i.e., molecular weight of the polymer chain between two neighboring cross links, crosslink density and the corresponding mesh size. A good correlation was established between gel strength and network parameters. Cryo-SEM images showed porous morphology of hydrogels. These hydrogels were found to be biodegradable and antimicrobial in nature. Drug release occurred through Fickian diffusion mechanism and release profile was best fitted in first order model. Overall it is concluded that modification in GA has led to formation of a porous hydrogels for wound dressing applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

What the ultimate polymeric electro-optic materials will be: guest-host, crosslinked, or side-chain?

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Zhang, Hua; Oh, Min-Cheol; Dalton, Larry R.; Steier, William H.

2003-07-01

Material processing and device fabrication of many different electro-optic (EO) polymers developed at USC are reviewed. Detailed discussion is given to guest-host CLD/APCs, crosslinking perfluorocyclobutane (PFCB) polymer CX1, and thermally stable side-chain polymers CX2 and CX3. Excellent EO performance (1.4V at 1.31 μm, 2.1 V at 1.55 μm) was achieved in CLD/APC Mach-Zehnder modulators (2-cm, push-pull). CLD/APCs also possess low optical losses (1.2 dB/cm in slab waveguides and in thick core channel waveguides). However, the guest-host materials only have limited thermal stability (110-132 °C in short term, <60 °C in long term) and require special techniques in device fabrication. The crosslinking polymer CX1 was able to provide long-term stability at 85 oC when fully cured. It also has a low optical loss (comparable to CLD/APCs) before curing and decent EO coefficient when poled at 180 °C. However, after the films were poled at the crosslinking temperatures (200 °C or above), the transmissions of the waveguides and EO activity became very poor due to poling-induced chromophore degradation. By judicial molecular design of both chromophore and monomer structures to suppress thermal motion of polymer segments, we were able to realize the same or even better thermal stability in side-chain polymers CX2 and CX3. Since no curing is needed, devices can be poled at their optimal poling temperatures, and all good properties can be obtained simultaneously. Despite the excellent solubility in chlorinated solvents, these side-chain polymers are resistant to some other organic solvents or solutions such as acetone, photoresist and various UV-curable liquids.

Hydrogels with Spatially and Temporally Controlled Properties to Control Cellular Interactions

NASA Astrophysics Data System (ADS)

Burdick, Jason

2011-03-01

Stem cells (e.g., mesenchymal stem cells, MSCs) respond to many cues from their microenvironment, which may include chemical signals, mechanics, and topography. Importantly, these cues may be incorporated into scaffolding to control stem cell differentiation and optimize their ability to produce tissues in regenerative medicine. Despite the significant amount of work in this area, the materials have been primarily static and uniform. To this end, we have developed a sequential crosslinking process that relies on our ability to crosslinked functional biopolymers (e.g., methacrylated hyaluronic acid, HA) in two steps, namely a Michael-type addition reaction to partially consume reactive groups and then a light-initiated free-radical polymerization to further crosslink the material. With light exposure during the second step comes control over the material in space (via masks and lasers) and time (via intermittent light exposure). We are applying this technique for numerous applications. For example, when the HA hydrogels are crosslinked with MMP degradable peptides with thiol termini during the first step, a material that can be degraded by cells is obtained. However, cell-mediated degradation is obstructed with the introduction of kinetic chains during the second step, leading to spatially controlled cell degradability. Due to the influence of cellular spreading on MSC differentiation, we have controlled cell fates by controlling their spread ability, for instance towards osteoblasts in spread areas and adipocytes when cell remained rounded. We are also using the process of stiffening with time to investigate mechanically induced differentiation, particularly in materials with evolving mechanics. Overall, these advanced HA hydrogels provide us the opportunity to investigate diverse and controlled material properties on MSC interactions.

Crosslinking with transglutaminase does not change metabolic effects of sodium caseinate in model beverage in healthy young individuals

PubMed Central

2012-01-01

Background Postprandial metabolic and appetitive responses of proteins are dependent on protein source and processing technique prior to ingestion. Studies on the postprandial effects of enzymatic crosslinking of milk proteins are sparse. Our aim was to study the effect of transglutaminase (TG)-induced crosslinking of sodium caseinate on postprandial metabolic and appetite responses. Whey protein was included as reference protein. Methods Thirteen healthy individuals (23.3 ± 1.1 y, BMI 21.7 ± 0.4 kg/m2) participated in a single-blind crossover design experiment in which the subjects consumed three different isovolumic (500 g) pourable beverages containing either sodium caseinate (Cas, 29 g), TG-treated sodium caseinate (Cas-TG, 29 g) or whey protein (Wh, 30 g) in a randomized order. Blood samples were collected at baseline and for 4 h postprandially for the determination of plasma glucose, insulin and amino acid (AA) concentrations. Gastric emptying (GE) was measured using the 13 C-breath test method. Appetite was assessed using visual analogue scales. Results All examined postprandial responses were comparable with Cas and Cas-TG. The protein type used in the beverages was reflected as differences in plasma AA concentrations between Wh and Cas, but there were no differences in plasma glucose or insulin responses. A tendency for faster GE rate after Wh was detected. Appetite ratings or subsequent energy intake did not differ among the protein beverages. Conclusions Our results indicate that the metabolic responses of enzymatically crosslinked and native sodium caseinate in a liquid matrix are comparable, suggesting similar digestion and absorption rates and first pass metabolism despite the structural modification of Cas-TG. PMID:22657838

Crosslinking with transglutaminase does not change metabolic effects of sodium caseinate in model beverage in healthy young individuals.

PubMed

Juvonen, Kristiina R; Lille, Martina E; Laaksonen, David E; Mykkänen, Hannu M; Niskanen, Leo K; Herzig, Karl-Heinz; Poutanen, Kaisa S; Karhunen, Leila J

2012-06-01

Postprandial metabolic and appetitive responses of proteins are dependent on protein source and processing technique prior to ingestion. Studies on the postprandial effects of enzymatic crosslinking of milk proteins are sparse. Our aim was to study the effect of transglutaminase (TG)-induced crosslinking of sodium caseinate on postprandial metabolic and appetite responses. Whey protein was included as reference protein. Thirteen healthy individuals (23.3 ± 1.1 y, BMI 21.7 ± 0.4 kg/m2) participated in a single-blind crossover design experiment in which the subjects consumed three different isovolumic (500 g) pourable beverages containing either sodium caseinate (Cas, 29 g), TG-treated sodium caseinate (Cas-TG, 29 g) or whey protein (Wh, 30 g) in a randomized order. Blood samples were collected at baseline and for 4 h postprandially for the determination of plasma glucose, insulin and amino acid (AA) concentrations. Gastric emptying (GE) was measured using the 13 C-breath test method. Appetite was assessed using visual analogue scales. All examined postprandial responses were comparable with Cas and Cas-TG. The protein type used in the beverages was reflected as differences in plasma AA concentrations between Wh and Cas, but there were no differences in plasma glucose or insulin responses. A tendency for faster GE rate after Wh was detected. Appetite ratings or subsequent energy intake did not differ among the protein beverages. Our results indicate that the metabolic responses of enzymatically crosslinked and native sodium caseinate in a liquid matrix are comparable, suggesting similar digestion and absorption rates and first pass metabolism despite the structural modification of Cas-TG.

A novel bio-orthogonal cross-linker for improved protein/protein interaction analysis.

PubMed

Nury, Catherine; Redeker, Virginie; Dautrey, Sébastien; Romieu, Anthony; van der Rest, Guillaume; Renard, Pierre-Yves; Melki, Ronald; Chamot-Rooke, Julia

2015-02-03

The variety of protein cross-linkers developed in recent years illustrates the current requirement for efficient reagents optimized for mass spectrometry (MS) analysis. To date, the most widely used strategy relies on commercial cross-linkers that bear an isotopically labeled tag and N-hydroxysuccinimid-ester (NHS-ester) moieties. Moreover, an enrichment step using liquid chromatography is usually performed after enzymatic digestion of the cross-linked proteins. Unfortunately, this approach suffers from several limitations. First, it requires large amounts of proteins. Second, NHS-ester cross-linkers are poorly efficient because of their fast hydrolysis in water. Finally, data analysis is complicated because of uneven fragmentation of complex isotopic cross-linked peptide mixtures. We therefore synthesized a new type of trifunctional cross-linker to overrule these limitations. This reagent, named NNP9, comprises a rigid core and bears two activated carbamate moieties and an azido group. NNP9 was used to establish intra- and intermolecular cross-links within creatine kinase, then to map the interaction surfaces between α-Synuclein (α-Syn), the aggregation of which leads to Parkinson's disease, and the molecular chaperone Hsc70. We show that NNP9 cross-linking efficiency is significantly higher than that of NHS-ester commercial cross-linkers. The number of cross-linked peptides identified was increased, and a high quality of MS/MS spectra leading to high sequence coverage was observed. Our data demonstrate the potential of NNP9 for an efficient and straightforward characterization of protein-protein interfaces and illustrate the power of using different cross-linkers to map thoroughly the surface interfaces within protein complexes.

Lung Cancer: Posttreatment Imaging: Radiation Therapy and Imaging Findings.

PubMed

Benveniste, Marcelo F; Welsh, James; Viswanathan, Chitra; Shroff, Girish S; Betancourt Cuellar, Sonia L; Carter, Brett W; Marom, Edith M

2018-05-01

In this review, we discuss the different radiation delivery techniques available to treat non-small cell lung cancer, typical radiologic manifestations of conventional radiotherapy, and different patterns of lung injury and temporal evolution of the newer radiotherapy techniques. More sophisticated techniques include intensity-modulated radiotherapy, stereotactic body radiotherapy, proton therapy, and respiration-correlated computed tomography or 4-dimensional computed tomography for radiotherapy planning. Knowledge of the radiation treatment plan and technique, the completion date of radiotherapy, and the temporal evolution of radiation-induced lung injury is important to identify expected manifestations of radiation-induced lung injury and differentiate them from tumor recurrence or infection. Published by Elsevier Inc.

Inverted bulk-heterojunction solar cell with cross-linked hole-blocking layer

PubMed Central

Udum, Yasemin; Denk, Patrick; Adam, Getachew; Apaydin, Dogukan H.; Nevosad, Andreas; Teichert, Christian; S. White, Matthew.; S. Sariciftci, Niyazi.; Scharber, Markus C.

2014-01-01

We have developed a hole-blocking layer for bulk-heterojunction solar cells based on cross-linked polyethylenimine (PEI). We tested five different ether-based cross-linkers and found that all of them give comparable solar cell efficiencies. The initial idea that a cross-linked layer is more solvent resistant compared to a pristine PEI layer could not be confirmed. With and without cross-linking, the PEI layer sticks very well to the surface of the indium–tin–oxide electrode and cannot be removed by solvents used to process PEI or common organic semiconductors. The cross-linked PEI hole-blocking layer functions for multiple donor–acceptor blends. We found that using cross-linkers improves the reproducibility of the device fabrication process. PMID:24817837

Detection of proteolytic activity by covalent tethering of fluorogenic substrates in zymogram gels.

PubMed

Deshmukh, Ameya A; Weist, Jessica L; Leight, Jennifer L

2018-05-01

Current zymographic techniques detect only a subset of known proteases due to the limited number of native proteins that have been optimized for incorporation into polyacrylamide gels. To address this limitation, we have developed a technique to covalently incorporate fluorescently labeled, protease-sensitive peptides using an azido-PEG3-maleimide crosslinker. Peptides incorporated into gels enabled measurement of MMP-2, -9, -14, and bacterial collagenase. Sensitivity analysis demonstrated that use of peptide functionalized gels could surpass detection limits of current techniques. Finally, electrophoresis of conditioned media from cultured cells resulted in the appearance of several proteolytic bands, some of which were undetectable by gelatin zymography. Taken together, these results demonstrate that covalent incorporation of fluorescent substrates can greatly expand the library of detectable proteases using zymographic techniques.

Bypass of a psoralen DNA interstrand cross-link by DNA polymerases beta, iota, and kappa in vitro

PubMed Central

Smith, Leigh A.; Makarova, Alena V.; Samson, Laura; Thiesen, Katherine E.; Dhar, Alok; Bessho, Tadayoshi

2012-01-01

Repair of DNA inter-strand cross-links in mammalian cells involves several biochemically distinctive processes, including the release of one of the cross-linked strands and translesion DNA synthesis (TLS). In this report, we investigated in vitro TLS activity of psoralen DNA inter-strand cross-link by three DNA repair polymerases, DNA polymerase beta, kappa and iota. DNA polymerase beta is capable of bypassing a psoralen cross-link with a low efficiency. Cell extracts prepared from DNA polymerase beta knockout mouse embryonic fibroblast showed a reduced bypass activity of the psoralen cross-link and purified DNA polymerase beta restored the bypass activity. In addition, DNA polymerase iota mis-incorporated thymine across the psoralen cross-link and DNA polymerase kappa extended these mis-paired primer ends, suggesting that DNA polymerase iota may serve as an inserter and DNA polymerase kappa may play a role as an extender in the repair of psoralen DNA inter-strand cross-links. The results demonstrated here indicate that multiple DNA polymerases could participate in TLS steps in mammalian DNA inter-strand cross-link repair. PMID:23106263

Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s

NASA Astrophysics Data System (ADS)

Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun

2018-01-01

Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

Mossbauer spectrometer radiation detector

NASA Technical Reports Server (NTRS)

Singh, J. J. (Inventor)

1973-01-01

A Mossbauer spectrometer with high efficiencies in both transmission and backscattering techniques is described. The device contains a sodium iodide crystal for detecting radiation caused by the Mossbauer effect, and two photomultipliers to collect the radiation detected by the crystal. When used in the transmission technique, the sample or scatterer is placed between the incident radiation source and the detector. When used in a backscattering technique, the detector is placed between the incident radiation source and the sample of scatterer such that the incident radiation will pass through a hole in the crystal and strike the sample. Diagrams of the instrument are provided.

Microbes encapsulated within crosslinkable polymers

DOEpatents

Chidambaram, Devicharan; Liu, Ying; Rafailovich, Miriam H

2013-02-05

The invention relates to porous films comprising crosslinked electrospun hydrogel fibers. Viable microbes are encapsulated within the crosslinked electrospun hydrogel fibers. The crosslinked electrospun hydrogel fibers are water insoluble and permeable. The invention also relates to methods of making and using such porous films.

Lignin-derived thermoplastic co-polymers and methods of preparation

DOEpatents

Naskar, Amit K.; Saito, Tomonori; Pickel, Joseph M.; Baker, Frederick S.; Eberle, Claude Clifford; Norris, Robert E.; Mielenz, Jonathan Richard

2014-06-10

The present invention relates to a crosslinked lignin comprising a lignin structure having methylene or ethylene linking groups therein crosslinking between phenyl ring carbon atoms, wherein said crosslinked lignin is crosslinked to an extent that it has a number-average molecular weight of at least 10,000 g/mol, is melt-processible, and has either a glass transition temperature of at least 100.degree. C., or is substantially soluble in a polar organic solvent or aqueous alkaline solution. Thermoplastic copolymers containing the crosslinked lignin are also described. Methods for producing the crosslinked lignin and thermoplastic copolymers are also described.

Mixed-Isotope Labeling with LC-IMS-MS for Characterization of Protein–Protein Interactions by Chemical Cross-Linking

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

Merkley, Eric D.; Baker, Erin S.; Crowell, Kevin L.

2013-02-20

Chemical cross-linking of proteins followed by proteolysis and mass spectrometric analysis of the resulting cross-linked peptides can provide insights into protein structure and protein-protein interactions. However, cross-linked peptides are by necessity of low stoichometry and have different physicochemical properties than linear peptides, routine unambiguous identification of the cross-linked peptides has remained difficult. To address this challenge, we demonstrated the use of liquid chromatography and ion mobility separations coupled with mass spectrometry in combination with a heavy-isotope labeling method. The combination of mixed-isotope cross-linking and ion mobility provided unique and easily interpretable spectral multiplet features for the intermolecular cross-linked peptides. Applicationmore » of the method to two different homodimeric proteins - SrfN, a virulence factor from Salmonella Typhimurium and SO_2176, a protein of unknown function from Shewanella oneidensis- revealed several cross-linked peptides from both proteins that were identified with a low false discovery rate (estimated using a decoy approach). A greater number of cross-linked peptides were identified using ion mobility drift time information in the analysis than when the data were summed across the drift time dimension before analysis. The identified cross-linked peptides migrated more quickly in the ion mobility drift tube than the unmodified peptides.« less

Studies of the permeation properties of glomerular basement membrane: cross-linking renders glomerular basement membrane permeable to protein.

PubMed

Walton, H A; Byrne, J; Robinson, G B

1992-03-20

Cross-linking glomerular basement membrane (GBM) has been shown to render it more permeable to protein. Isolated pig GBM was cross-linked with dimethylmalonimidate which reacts selectively with lysine epsilon-NH2 groups or with glutaraldehyde, a less selective cross-linking agent. Studies of the ultrafiltration properties of these materials in vitro using cytochrome c, myoglobin, bovine serum albumin and immunoglobulin showed that cross-linking had markedly increased solvent and protein fluxes as compared with native membranes particularly at higher pressures. Filtration studies with serum demonstrated that the cross-linked membranes were more permeable to serum proteins. Thickness measurements under pressure indicated that cross-linked membrane was less compressed than native membrane as pressure was increased. Pore theory did not provide a suitable model for analysis of the results, but analysis of the results using the fibre-matrix hypothesis indicated that cross-linking had the effect of bundling together the fibres (type IV collagen) in the GBM matrix. The effect of cross-linking on filtration could be explained by a combination of contraction of the membrane, fibre bundling and increased rigidity compared with native membrane. Cross-linking of GBM might lead to long-term damage of the glomerular capillary wall in nephritis, so promoting proteinuria.