Strong Cross-linking Research Articles

Novel pectin-based carriers for colonic drug delivery

Pectin-based hydrogel carriers have been studied and shown to have promising applications for drug delivery to the lower GI tract, especially to the colonic region. However, making sure these hydrogel carriers can pass through the upper GI tract and reach the targeted regions, after oral administration, still remains a challenge to overcome. A solution to this problem is to promote stronger cross-linking interactions within the pectin-based hydrogel network. The combined usage of a divalent cation (Ca2+) and the cationic biopolymer oligochitosan has shown to improve the stability of pectin-based hydrogel systems – suggesting that these two cross-linkers may be used to eventually help improve pectin-based hydrogel systems for colonic drug delivery methods.

Lyase-catalyzed degradation of alginate in the gelled state: Effect of gelling ions and lyase specificity

Lyase-catalyzed degradation has been proposed as a more cell-friendly alternative to dissolution of alginate gels than using chelating agents. In this study, we investigated the effect of lyase specificity on degradation of alginate gels, including the effect of crosslinking ions with different affinity for the polymer. Degradation kinetics and products were analyzed. In particular, the degradation products were characterized using novel methods for alginate sequence determination by chromatography. Lyase-catalyzed gel disruption worked well for gels crosslinked with calcium, but was less effective when barium was included in the gel formulation. The importance of crosslinking of long G-blocks in maintaining the structural integrity of the gels was identified. The failure to degrade these long G-blocks, either due to protection of the G-blocks by strong ionic crosslinking or due to lack of lyase activity on G–G linkages, resulted in retained resistance to mechanical disruption of the gel.

Initial results from mechanical compression of the cornea during crosslinking for keratoconus

To compare refractive changes after corneal crosslinking with and without mechanical compression of the cornea. In a prospective, open, randomized case-control study conducted at the Department of Ophthalmology, Umeå University Hospital, Sweden, sixty eyes of 43 patients with progressive keratoconus aged 18-28 years planned for corneal crosslinking and corresponding age- and sex-matched control subjects were included. The patients were randomized to conventional corneal crosslinking (CXL; n = 30) or corneal crosslinking with mechanical compression using a flat rigid contact lens sutured to the cornea during treatment (CRXL; n = 30). Subjective refraction and ETDRS best spectacle-corrected visual acuity (BSCVA), axial length measurement, keratometry and pachymetry were performed before and 1 and 6 months after treatment. The keratoconus patients had poorer BSCVA, higher refractive astigmatism and higher keratometry readings than the control subjects at baseline (p < 0.01). In the CXL group, BSCVA increased from 0.19 ± 0.26 to 0.14 ± 0.18 logMar (p = 0.03), and the spherical equivalent improved from -1.9 ± 2.8 D to -1.4 ± 2.4 D (p = 0.03). Maximum keratometry readings decreased after CXL from 53.1 ± 4.9 D to 52.6 ± 5.2 D (p = 0.02), and the axial length decreased in the CXL group, likely due to post-treatment corneal thinning (p = 0.03). In the CRXL group, all the above variables were unaltered (p > 0.05). At 6 months, the refractive results from CRXL did not surpass those of conventional CXL treatment. Rather, some variables indicated a slightly inferior effect. Possibly, stronger crosslinking would be necessary to stabilize the cornea in the flattened configuration achieved by the rigid contact lens.

The role of acrylonitrile in controlling the structure and properties of nanostructured ionomer films.

Ionomers are polymers which contain ionic groups that are covalently bound to the main chain. The presence of a small percentage of ionic groups strongly affects the polymer's mechanical properties. Here, we examine a new family of nanostructured ionomer films prepared from core-shell polymer nanoparticles containing acrylonitrile (AN), 1,3-butadiene (Bd) and methacrylic acid (MAA). Three new AN-containing dispersions were investigated in this study. The core-shell nanoparticles contained a PBd core. The shells contained copolymerised Bd, AN and MAA, i.e., PBd-AN-MAA. Three types of crosslinking were present in these films: covalent crosslinks (from Bd); strong physical crosslinks (involving ionic bonding of RCOO(-) and Zn(2+)) and weaker physical crosslinks (from AN). We examined and compared the roles of AN and ionic crosslinking (from added Zn(2+)) on the structure and mechanical properties of the films. The FTIR spectroscopy data showed evidence for RCOOH-nitrile hydrogen bonding with tetrahedral geometry. DMTA studies showed that AN copolymerised within the PBd-AN-MAA phase uniformly. Tensile stress-strain data showed that inclusion of AN increased elasticity and toughness. Analysis showed that about 33 AN groups were required to provide an elastically-effective chain. However, only 1.5 to 2 ionically bonded RCOO(-) groups were required to generate an elastically-effective chain. By contrast to ionic bonding, AN inclusion increased the modulus without compromising ductility. Our results show that AN is an attractive, versatile, monomer for increasing the toughness of nanostructured ionomers and this should also be the case for other nanostructured polymer elastomers.

Degradation of Gluten in Wheat Bran and Bread Drink by Means of a Proline-Specific Peptidase

Gluten-free wheat bran and bread drink were produced by degrading gluten with Aspergillus niger prolyl endopeptidase (AN-PEP). For this purpose, bran from native and germinated wheat grains as well as bread drink were mixed with AN-PEP and incubated at 50°C under different conditions. The amount of enzyme activity (1.2 • 10-4 - 8.7 • 10-1 U), the incubation time (0-72 h), and the pH value (1.0-9.0) were systematically altered. The gluten content was monitored by a competitive ELISA using the R5 antibody. Gluten in two wheat bran samples produced in the laboratory was degraded below the threshold for gluten-free foods of 20 mg/kg. This was not possible in a commercial wheat bran sample that had potentially been heat-treated leading to strong crosslinking of gluten by incorporation of gliadins into the glutenin fraction, possible formation of isopeptide crosslinks and, thus, poor digestibility. In contrast, gluten in bread drink was easily degraded after a short incubation time of 30 min and low AN-PEP activity. No significant differences of the quality parameters between treated and untreated products were found. Remarkably, bran from germinated grains was strongly enriched in nutritionally positive compounds such as dietary fiber and folates compared to native grains. Thus, wheat bran from germinated grains rendered gluten-free by treatment with AN-PEP can contribute to increasing the nutritional value of the gluten-free diet.

Novel On‐Demand Bioadhesion to Soft Tissue in Wet Environments

Current methods of tissue fixation rely on mechanical-related technologies developed from the clothing and carpentry industries. Herein, a novel bioadhesive method that allows tuneable adhesion and is also applicable to biodegradable polyester substrates is described. Diazirine is the key functional group that allows strong soft tissue crosslinking and on-demand adhesion based on a free radical mechanism. Plasma post-irradiation grafting makes it possible to graft diazirine onto PLGA substrates. When the diazirine-PLGA films, placed on wetted ex vivo swine aortas, are activated with low intensity UV light, lap shear strength of up to 450 ± 50 mN cm(-2) is observed, which is one order of magnitude higher than hydrogel bioadhesives placed on similar soft tissues. The diazirine-modified PLGA thin films could be added on top of previously developed technologies for minimally invasive surgeries. The present work is focused on the chemistry, grafting, and lap shear strength of the alkyl diazirine-modified PLGA bioadhesive films.

Stromatolitic knobs in Storr's Lake (San Salvador, Bahamas): a model system for formation and alteration of laminae

The initial lamination in young, metabolically active Scytonema knobs developing in Storr's Lake (Bahamas) results from the iterative succession of two different stages of microbial growth at the top of this microbialite. Stage 1 is dominated by vertically oriented cyanobacterial filaments and is characterized by a high porosity of the fabric. Stage 2 shows a higher microbial density with the filaments oriented horizontally and with higher carbonate content. The more developed, dense microbial community associated with Stage 2 of the Scytonema knobs rapidly degrades extracellular organic matter (EOM) and coupled to this, precipitates carbonate. The initial nucleation forms high-Mg calcite nanospheroids that progressively replace the EOM. No precipitation is observed within the thick sheath of the Scytonema filaments, possibly because of strong cross-linking of calcium and EOM (forming EOM-Ca-EOM complexes), which renders Ca unavailable for carbonate nucleation (inhibition process). Eventually, organominerals precipitate and form an initial lamina through physicochemical and microbial processes, including high rates of photosynthetic activity that lead to (13) C-enriched DIC available for initial nucleation. As this lamina moves downward by the iterative production of new laminae at the top of the microbialite, increased heterotrophic activity further alters the initial mineral product at depth. Although some rare relic preservation of 'Stage 1-Stage 2' laminae in subfossil knobs exists, the very fine primary lamination is considerably altered and almost completely lost when the knobs develop into larger and more complex morphologies due to the increased accommodation space and related physicochemical and/or biological alteration. Despite considerable differences in microstructure, the emerging ecological model of community succession leading to laminae formation described here for the Scytonema knobs can be applied to the formation of coarse-grained, open marine stromatolites. Therefore, both fine- and coarse-grained extant stromatolites can be used as model systems to understand the formation of microbialites in the fossil record.

Buckminsterfullerene: A Strong, Covalently Bonded, Reinforcing Filler and Reversible Cross-Linker in the Form of Clusters in a Polymer.

A Buckminsterfullerene/polyisoprene (C60/PI) composite was synthesized at high-temperature, high-pressure (HP&HT) conditions. The composite has significantly improved tensile strength and Young's modulus, by up to 49% and 88% per wt % C60, respectively, which is much higher than for corresponding composites with carbon nanotube (CNT) fillers. The reinforcing action of C60 fillers is different from that of CNTs as C60 becomes covalently bonded to PI chains, and C60 clusters in PI form C60-C60 covalent bonds. The latter are reversible and break by heating at 1 bar, which suggests improved recyclability of the material and indicates that carbon nanostructures can be used as strong reversible cross-linkers ("vulcanizers") in elastomers.

Quantitation of fixative-induced morphologic and antigenic variation in mouse and human breast cancers

Quantitative Image Analysis (QIA) of digitized whole slide images for morphometric parameters and immunohistochemistry of breast cancer antigens was used to evaluate the technical reproducibility, biological variability, and intratumoral heterogeneity in three transplantable mouse mammary tumor models of human breast cancer. The relative preservation of structure and immunogenicity of the three mouse models and three human breast cancers was also compared when fixed with representatives of four distinct classes of fixatives. The three mouse mammary tumor cell models were an ER+/PR+ model (SSM2), a Her2+ model (NDL), and a triple negative model (MET1). The four breast cancer antigens were ER, PR, Her2, and Ki67. The fixatives included examples of (1) strong cross-linkers, (2) weak cross-linkers, (3) coagulants, and (4) combination fixatives. Each parameter was quantitatively analyzed using modified Aperio Technologies ImageScope algorithms. Careful pre-analytical adjustments to the algorithms were required to provide accurate results. The QIA permitted rigorous statistical analysis of results and grading by rank order. The analyses suggested excellent technical reproducibility and confirmed biological heterogeneity within each tumor. The strong cross-linker fixatives, such as formalin, consistently ranked higher than weak cross-linker, coagulant and combination fixatives in both the morphometric and immunohistochemical parameters.

Development of a green binder system for paper products

BackgroundIt is important for industries to find green chemistries for manufacturing their products that have utility, are cost-effective and that protect the environment. The paper industry is no exception. Renewable resources derived from plant components could be an excellent substitute for the chemicals that are currently used as paper binders. Air laid pressed paper products that are typically used in wet wipes must be bound together so they can resist mechanical tearing during storage and use. The binders must be strong but cost-effective. Although chemical binders are approved by the Environmental Protection Agency, the public is demanding products with lower carbon footprints and that are derived from renewable sources.ResultsIn this project, carbohydrates, proteins and phenolic compounds were applied to air laid, pressed paper products in order to identify potential renewable green binders that are as strong as the current commercial binders, while being organic and renewable. Each potential green binder was applied to several filter paper strips and tested for strength in the direction perpendicular to the cellulose fibril orientation. Out of the twenty binders surveyed, soy protein, gelatin, zein protein, pectin and Salix lignin provided comparable strength results to a currently employed chemical binder.ConclusionsThese organic and renewable binders can be purchased in large quantities at low cost, require minimal reaction time and do not form viscous solutions that would clog sprayers, characteristics that make them attractive to the non-woven paper industry. As with any new process, a large-scale trial must be conducted along with an economic analysis of the procedure. However, because multiple examples of “green” binders were found that showed strong cross-linking activity, a candidate for commercial application will likely be found.

Mapping the signal peptide binding and oligomer contact sites of the core subunit of the pea twin arginine protein translocase.

Twin arginine translocation (Tat) systems of thylakoid and bacterial membranes transport folded proteins using the proton gradient as the sole energy source. Tat substrates have hydrophobic signal peptides with an essential twin arginine (RR) recognition motif. The multispanning cpTatC plays a central role in Tat operation: It binds the signal peptide, directs translocase assembly, and may facilitate translocation. An in vitro assay with pea (Pisum sativum) chloroplasts was developed to conduct mutagenesis and analysis of cpTatC functions. Ala scanning mutagenesis identified mutants defective in substrate binding and receptor complex assembly. Mutations in the N terminus (S1) and first stromal loop (S2) caused specific defects in signal peptide recognition. Cys matching between substrate and imported cpTatC confirmed that S1 and S2 directly and specifically bind the RR proximal region of the signal peptide. Mutations in four lumen-proximal regions of cpTatC were defective in receptor complex assembly. Copurification and Cys matching analyses suggest that several of the lumen proximal regions may be important for cpTatC-cpTatC interactions. Surprisingly, RR binding domains of adjacent cpTatCs directed strong cpTatC-cpTatC cross-linking. This suggests clustering of binding sites on the multivalent receptor complex and explains the ability of Tat to transport cross-linked multimers. Transport of substrate proteins cross-linked to the signal peptide binding site tentatively identified mutants impaired in the translocation step.

Effects of Hydrolysed Whey Proteins on the Techno-Functional Characteristics of Whey Protein-Based Films.

Pure whey protein isolate (WPI)-based cast films are very brittle due to its strong formation of protein cross-linking of disulphide bonding, hydrogen bonding as well as hydrophobic and electrostatic interactions. However, this strong cross-linking is the reason for its final barrier performance. To overcome film brittleness of whey protein layers, plasticisers like glycerol are used. It reduces intermolecular interactions, increases the mobility of polymer chains and thus film flexibility can be achieved. The objective of this study was to investigate the influence of hydrolysed whey protein isolate (WPI) in whey protein isolate-based cast films on their techno-functional properties. Due to the fact, that the addition of glycerol is necessary but at the same time increases the free volume in the film leading to higher oxygen and water vapour permeability, the glycerol concentration was kept constant. Cast films with different ratios of hydrolysed and not hydrolysed WPI were produced. They were characterised in order to determine the influence of the lower molecular weight caused by the addition of hydrolysed WPI on the techno-functional properties. This study showed that increasing hydrolysed WPI concentrations significantly change the mechanical properties while maintaining the oxygen and water vapour permeability. The tensile and elastic film properties decreased significantly by reducing the average molecular weight whereas the yellowish coloration and the surface tension considerably increased. This study provided new data which put researchers and material developers in a position to tailor the characteristics of whey protein based films according to their intended application and further processing.

Hybrid organic PVDF–inorganic M–rGO–TiO2 (M = Ag, Pt) nanocomposites for multifunctional volatile organic compound sensing and photocatalytic degradation–H2 production

This work focused on the development of a hybrid organic-inorganic TiO2 nanocomposite, which demonstrates the first ever report on harmful volatile organic compound (VOC) sensing and photocatalytic degradation-H2 production. The sensing and photocatalytic properties are enhanced by the synergetic effects of well-structured TiO2 nanotubes, metal nanoparticles and reduced graphene oxide loading for enhanced light absorption and charge-transfer kinetics. Hybridization of a functionalized TiO2 nanocomposite with a polyvinylidene fluoride (PVDF) matrix induced strong cross-linking networks between the inorganic-organic components, which promote mechanical reinforcement-flexibility and highly porous asymmetric structures. The developed solution processable nanocomposite has immense potential to remedy the global environmental and energy issues by producing clean water/air and energy from organic compound waste.

Thermal dissolution of Shenfu coal in different solvents

The thermal dissolution (TD) behaviors of Shenfu (SF) coal, a kind of Chinese sub-bituminous coal at different temperatures in different solvents were investigated in this study. The results show that almost all of the ash in the raw coal was transferred into the TD residue. The TD soluble yield (TDSY) of SF coal increased with the raising of TD temperatures from 300 to 360°C for 60min with 1-methylnaphthalene (1-MN) as solvent, and the highest TDSY of 56% was obtained at 360°C. Further raising temperature to 380°C, the TDSY decreased rapidly. The highest TDSY obtained at 360°C can be attributed to the partial pyrolysis of SF coal.When N-methyl-2-pyrrolidinone (NMP) or methanol was added into 1-MN, the TDSY greatly increased. Especially, when 20% NMP was added, the TDSY reached up to 75%. Since NMP is a strongly polar solvent, it can dissociate the strong cross-links in the coal, resulting in the increase of the TDSY. However, when both of NMP and methanol were added into 1-MN, the TDSY dramatically decreased, indicating that there are some interactions between the two solvents.Crude methyl naphthalene oil (CMNO) was a more effective solvent for the TD of SF coal than 1-MN, and its TDSY achieved 66% at 360°C for 60min. Addition of various polar solvents into CMNO, the TDSY decreased, especially for the addition of methanol, the TDSY decreased by about 15%. The result indicated that methanol may react with some active fractions in CMNO, resulting in the decrease of the TD effect. When both of NMP and methanol were added into CMNO, the TDSY dramatically decreased due to the interaction between them. The TD soluble fractions (TDSFs) obtained from various solvents were characterized by elemental and FTIR analyses.

Effects of hybrid hardener on properties of a composite bipolar plate for polymer electrolyte membrane fuel cells

The effects of a hybrid hardener on the mechanical and electrical properties and corrosion resistance of conductive graphite based epoxy composites for the bipolar plate of polymer electrolyte membrane fuel cells (PEMFC) is investigated. Diaminodiphenylsulfone (DDS) is used as an additional hardener in order to enhance the physicochemical properties of graphite-based bisphenol type epoxy-cresol novolac phenol resin composites. The characteristics of the graphite composites, based on epoxy resin respectively with and without DDS, are compared in order to shed light on the curing behaviors of the epoxy/graphite composites. The tensile strength and conductivity of the epoxy/graphite composites with DDS are much higher than those without DDS. From the results of the scanning electron microscope and optical microscope analyses, the morphology of the epoxy/graphite composite with DDS was evaluated and is shown to be more compact than that without DDS. This is attributed to the strong crosslinking effect of DDS. This epoxy/graphite composite can be successfully molded as a real bipolar plate, with fairly good physicochemical properties through a compression molding process. Open image in new window

Modification of the organic matter of brown coals with nitrous oxide

The results of the treatment of brown coals from the Kansk-Achinsk Basin in an atmosphere of nitrous oxide are given. It was established that the main products of nitrous oxide interaction with the organic matter of brown coal are soluble low-molecular-weight products (ketones and aromatic acids) and oxodiazoline structures in a coal matrix. The thermal-oxidative degradation of terminal oxygen-containing groups, which accompanied this process, facilitated the formation of strong crosslinks and the strengthening of a supramolecular structure.

Mechanical properties of graphene papers

Graphene-based paper materials attract particular interests recently owing to their outstanding properties, the key of which is their layer-by-layer hierarchical structures similar to many biological materials such as bone, teeth and nacre, combining intralayer strong sp2 bonds and interlayer crosslinks for efficient load transfer. Here we firstly study the mechanical properties of various interlayer and intralayer crosslinks through first-principles calculations, and then perform continuum model analysis for the overall mechanical properties of graphene-based paper materials. We find that there is a characteristic length scale l0, defined as Dh0/4G, where D is the stiffness of the graphene sheet, h0 and G are height of interlayer crosslink and shear modulus respectively. When the size of the graphene sheets exceeds 3l0, the tension–shear (TS) chain model, which is widely used for nanocomposites, fails to predict the overall mechanical properties of the graphene-based papers. Instead we proposed here a deformable tension–shear (DTS) model by considering elastic deformation of graphene sheets, also the interlayer and intralayer crosslinks. The DTS is then applied to predict the mechanical properties of graphene papers under tensile loading. According to the results we thus obtain, optimal design strategies are proposed for graphene papers with ultrahigh stiffness, strength and toughness.

Mechanical properties of crosslinks controls failure mechanism of hierarchical intermediate filament networks

Intermediate filaments are one of the key components of the cytoskeleton in eukaryotic cells, and their mechanical properties are found to be equally important for physiological function and disease. While the mechanical properties of single full length filaments have been studied, how the mechanical properties of crosslinks affect the mechanical property of the intermediate filament network is not well understood. This paper applies a mesoscopic model of the intermediate network with varied crosslink strengths to investigate its failure mechanism under the extreme mechanical loading. It finds that relatively weaker crosslinks lead to a more flaw tolerant intermediate filament network that is also 23% stronger than the one with strong crosslinks. These findings suggest that the mechanical properties of interfacial components are critical for bioinspired designs which provide intriguing mechanical properties.

The relative contribution of calcium, zinc and oxidation-based cross-links to the stiffness ofArion subfuscusglue

Metal ions are present in many different biological materials, and are capable of forming strong cross-links in aqueous environments. The relative contribution of different metal-based cross-links was measured in the defensive glue produced by the terrestrial slug Arion subfuscus. This glue contains calcium, magnesium, zinc, manganese, iron and copper. These metals are essential to the integrity of the glue and to gel stiffening. Removal of all metals caused at least a 15-fold decrease in the storage modulus of the glue. Selectively disrupting cross-links involving hard Lewis acids such as calcium reduced the stiffness of the glue, while disrupting cross-links involving borderline Lewis acids such as zinc did not. Calcium is the most common cation bound to the glue (40 mmol l(-1)), and its charge is balanced primarily by sulphate at 82-84 mmol l(-1). Thus these ions probably play a primary role in bringing polymers together directly. Imine bonds formed as a result of protein oxidation also contribute substantially to the stiffness of the glue. Disrupting these bonds with hydroxylamine caused a 33% decrease in storage modulus of the glue, while stabilizing them by reduction with sodium borohydride increased the storage modulus by 40%. Thus a combination of metal-based bonds operates in this glue. Most likely, cross-links directly involving calcium play a primary role in bringing together and stabilizing the polymer network, followed by imine bond formation and possible iron coordination.

Effect of Hydro-Thermal Treatment with CaO Addition on the Coking Properties of Shengfu Coal

Shengfu (SF) coal was hydro-thermally treated with and without CaO addition at different temperatures and the crucible coking determinations were carried out to evaluate the effects. The results show that hydro-thermal treatment can obviously increase the micro-strength index (MSI) of the coke and particle coke strength after reaction (PSR), and decrease particle coke reactivity index (PRI), which are beneficial for metallurgical coke to increase the gas permeability in blast furnace. Addition of CaO during hydro-thermal treatment at 150-250°C greatly promotes the effects of hydro-thermal treatment. However, hydro-thermal treatment at 300°C with CaO results in dramatic decrease in MSI and PSR due to the enhanced hydrolysis reactions at this temperature by CaO to form strong cross-linking in the treated coal.