High Molecular Weight Material Research Articles

Scanning electron micrographs of high density polyethylene fracture surfaces

Three high density polythylenes with widely differing molecular weights have been subjected to a fast fracture process and studied by scanning electron micrography. Two polymers in the low to medium molecular weight range show evidence of substantial melting during facture, in support of some previous work. On the other hand the ultra high molecular weight material seems to deform on a more massive scale without recognisable relics of a melting process.

Crosslinking of bimodal polyethylene

Two bimodal polyethylenes, differing only in polymerisation order, were investigated with respect to crosslinking behaviour and network properties. The crosslinked materials were examined using size exclusion chromatography (SEC), gel-content measurements, and calculations of the network density. Dynamic mechanical analyses in the melt were performed to monitor the crosslinking and to provide another measure of the network density. The experiments were performed to investigate any potential influence of the polymerisation order on the crosslinking as well as to study the network formation in the crosslinked polymers. The bimodal polyethylenes were also compared to two monomodal polyethylenes representing the short chain branched, high molecular weight fraction, and the linear, low molecular weight fraction, respectively. The SEC measurements clearly showed how the crosslinking starts with the consumption of the high molecular weight fraction. The gel-content measurement showed the importance of a high molecular weight material for the gel formation. The network density calculations demonstrated how long chains can give rise to apparent networks which are mainly due to chain entanglements. The experiments showed that the polymerisation order for the bimodal polyethylenes has no effect on the crosslinking.

Radiopaque polymeric spinal cages: a prototype study

Back pain, originating from degeneration of intervertebral discs, is often alleviated by the insertion of one or more interbody fusion cages. The function of the cage is to restore the height between two adjacent vertebrae and to mediate osseous fusion. Most commercial cages consist of titanium or a titanium alloy, while polymeric cages, mostly consisting of polyether-etherketone (PEEK), are also in use. Titanium is known for its excellent biocompatibility. Titanium cages can be located easily with imaging techniques based on X-ray absorption (e.g. CT scans). However, they introduce artefacts in magnetic resonance (MR images). PEEK cages, on the other hand, do not show up in CT images. For this reason, small metallic markers are usually incorporated. The markers reveal the position of the cage, albeit indirectly. PEEK cages are clearly and integrally seen on MR images, as they are essential free of water. There are no artefacts or disturbances; this feature, as well as its strength, makes PEEK particularly attractive for the construction of cages. Here, we introduce new all-polymeric cages on the basis of an iodine-containing methacrylic copolymer (I-copolymer). This material has been prepared from methylmethacrylate and 2-[4-iodobenzoyl]-oxo-ethylmethacrylate. Copolymerisation of both monomers results in a high molecular weight material. Cytocompatibility experiments reveal that the material contains no toxic leachables and that cells can well adhere to and proliferate on the I-copolymer. Compression experiments at physiologically relevant strains disclose mechanical characteristics comparable to PEEK. The advantage of cages prepared from this I-copolymer over commercially available cages is that the present cage contains no metallic components, implying that it is compatible with MR imaging, and the presence of the iodine atoms ensures X-ray visibility.

Generation of Fluorescent Adducts of Malondialdehyde and Amino Acids: Toward an Understanding of Lipofuscin¶

Lipofuscin is a yellow-brown, highly fluorescent pigment that undergoes an age-related progressive accumulation in animal cells, mainly in postmitotic cells. It is a heterogeneous, high–molecular weight material associated with proteins, lipids and nucleic acids. Lipofuscin is implicated in many aspects of human health, including aging, oxidative stress, macular degeneration, lipid peroxidation, atherosclerosis, dementia (Alzheimer's Disease) and diseases associated with prions. Although the fluorescent properties of lipofuscin have long been recognized, neither histologists nor chemists have yet isolated the pigments themselves or characterized their optical properties. We have prepared lipofuscinlike species by reacting malondialdehyde (MDA) with cysteine (Cys). MDA: Cys adducts 3:2 and 2:2 are two of those that have been identified among the many that were present in the reaction. Whereas previous attempts to synthesize lipofuscinlike species resulted in compounds that were either nonfluorescent or emitted principally in the blue, the MDA:Cys adducts reported in this study are not only fluorescent but also emit over a broader range.

Generation of Fluorescent Adducts of Malondialdehyde and Amino Acids: Toward an Understanding of Lipofuscin¶

Lipofuscin is a yellow-brown, highly fluorescent pigment that undergoes an age-related progressive accumulation in animal cells, mainly in postmitotic cells. It is a heterogeneous, high-molecular weight material associated with proteins, lipids and nucleic acids. Lipofuscin is implicated in many aspects of human health, including aging, oxidative stress, macular degeneration, lipid peroxidation, atherosclerosis, dementia (Alzheimer's Disease) and diseases associated with prions. Although the fluorescent properties of lipofuscin have long been recognized, neither histologists nor chemists have yet isolated the pigments themselves or characterized their optical properties. We have prepared lipofuscinlike species by reacting malondialdehyde (MDA) with cysteine (Cys). MDA:Cys adducts 3:2 and 2:2 are two of those that have been identified among the many that were present in the reaction. Whereas previous attempts to synthesize lipofuscinlike species resulted in compounds that were either nonfluorescent or emitted principally in the blue, the MDA:Cys adducts reported in this study are not only fluorescent but also emit over a broader range.

Degradation or polymerisation of Phenol Red dye depending to the catalyst system used

The degradation of Phenol Red dye (belonging to the phenolsulphonephthaleinic class) by laccase in the presence or absence of the mediator 1-hydroxybenzotriazole (HOBT), was investigated. Decolourisation of Phenol Red with laccase alone was limited with a maximum decolourisation degree of around 40% after 48 h. This strange behaviour is due to the mechanisms developed in this system generating intermediate compounds that formed high molecular weight materials. However, the laccase–HOBT couple with high redox potential was able to complete degradation of this dye.

Influence of molecular weight on the fracture properties of aliphatic polyketone terpolymers

The influence of polymer molecular weight on the mechanical properties of aliphatic polyketones was investigated. The molecular weight varied from 100,000 to 300,000 g mol −1. The crystallinity was found to be independent of polymer molecular weight, as was the glass transition temperature. The yield strength and stiffness of the aliphatic polyketone terpolymers were also found to be independent of molecular weight. The post yield behaviour showed strong dependency on polymer chain length. The draw stress was increased significantly with higher molecular weight material. The impact resistance was increased with molecular weight, resulting in ductile fractures with large energy consumption upon fracture. The brittle-to-ductile transition temperature was lowered with increasing chain length. The difference in material deformation was linked to the higher mechanical connectivity and more stable post yield behaviour of the polymers with an increased molecular weight.

Synthesis and characterization of a fully aromatic polyazomethine with rotaxane architecture

AbstractThis paper reports the preparation and characterization of a new aromatic polyazomethine with rotaxane architecture. The complex of β‐cyclodextrin and 1,4‐phenylenediamine was treated with N‐n‐butyl‐3,6‐diformylcarbazole, which is large enough to prevent dethreading. The polycondensation reaction was performed in N,N‐dimethylformamide leading to polyazomethine soluble in polar solvents. Measurements made by gel permeation chromatography of the dimethylformamide‐soluble (DMF) soluble polyazomethine show the presence of high molecular weight material. The structure and thermal properties of the resulting polymer were characterized by IR, 1H NMR, TGA and DSC techniques. Copyright © 2003 Society of Chemical Industry

Anti-inflammatory constituents, aloesin and aloemannan in Aloe species and effects of tanshinon VI in Salvia miltiorrhiza on heart

Cinnamoyl, p-coumaroyl, feruloyl, caffeoyl aloesin, and related compounds were isolated from Aloe species. The antiinflammatory and antioxidative activities of these compounds were examined based on the structure-activity relationship. It was suggested that the bioactivities may link to acyl ester groups in aloesin, together with those of aloesin-related compounds. However, investigations using the contact hypersensitivity response indicated a preventive effect of aloesin on the UV-B-induced immune suppression. Furthermore, aloesin inhibited tyrosine hydroxylase and dihydroxyphenylalanine (DOPA) oxidase activities of tyrosinase from normal human melanocyte cell lysates. These results show that aloesin prevents not only UV-B-induced immune suppression, but also could be a positive pigment-altering agent for cosmetic application. In preclinical study, aloe extract was investigated using phagocytosis and nitroblue tetrazolium chloride (NBT) reduction in adult bronchial asthma, and high molecular-weight materials, such as polysaccharide and glycoprotein fractions, were identified as active ingredients. The neutral polysaccharides, aloemannan and acemannan showed antitumor, antiinflammatory and immunosuppressive activities, and glycoprotein fractions with bradykinindegrading and cell proliferation-stimulating activities were identified from the nondialysate fraction of the gel part of Aloe species. Verectin fractionated from Aloe vera gel was examined biochemically and immunochemically, and verectin antibody was used in the appraisal of commercial Aloe vera gel products. It was reported that aloesin stimulates the proliferation of cultured human hepatoma SK-Hep 1 cells. Thus aloesin, related compounds, and high molecular-weight materials, such as aloemannan and verectin, may act in concert to exert therapeutic properties for wounds, burns and inflammation. The biodisposition of fluoresceinylisothiocyanate (FITC)--labeled aloemannan (FITC-AM) with the homogenate from some organs in mice was demonstrated, and FITC-AM was metabolized to a smaller molecule (MW 3000) by the large intestinal microflora in feces. The modified aloe polysaccharide (MW: 80000) with cellulase under restricted conditions, immunologically stimulated the recovery of UV-B-induced tissue in jury. Thus the modified polysaccharides of aloemannan, together with acemannan (MW: about 600000), are expected to participate in biological activity following oral administration. The effects of tanshinone VI, a diterpenoid isolated from Salvia miltiorrhiza, on the heart are reviewed. First, the effects on the posthypoxic recovery of contractile function of perfused rat hearts were examined. Hypoxia/reoxygenation induced a release of purine nucleosides and bases (ATP metabolites) and resulted in little recovery of contractile force of reoxygenated hearts. Pretreatment of the perfused heart with 42 nM tanshinone VI under hypoxic conditions attenuated the release of ATP metabolites during hypoxia/reoxygenation. Treatment with tanshinone VI enhanced the posthypoxic recovery of myocardial contractility. These results show that tanshinone VI may protect the heart against hypoxia/reoxygenation injury and improve the posthypoxic cardiac function. Second, the effects of tanshinone VI on in vitro myocardial remodeling were examined. Cardiomyocytes and cardiac fibroblasts were isolated from neonatal rat hearts, and simultaneously prepared insulin-like growth factor-1 (IGF-1) induced the hypertrophy of cardiomyocytes. IGF-1 increased the collagen synthesis of cardiac fibroblasts, that is, in vitro fibrosis. The hypertrophy of cardiomyocytes was attenuated in the presence of tanshinone VI in the culture medium. The fibrosis of cardiac fibroblasts was decreased by treatment with tanshinone VI. When tanshinone VI was added to cardiac fibroblast-conditioned medium, the medium-mediated hypertrophy of cardiomyocytes was also attenuated. These results show that tanshinone VI may attenuate in vitro cardiac remodeling. The series of studies has shown that tanshinone VI protects the myocardium against hypoxia/reoxygenation injury and attenuates progression of in vitro myocardial remodeling, suggesting that tanshinone VI is a possible agent for the treatment of cardiac disease with contractile failure.

A high molecular weight reversible coordination polymer of PdCl2 and 1,12-bis(diphenylphosphino)dodecaneElectronic supplementary information (ESI) available: experimental details, SEC results and NMR spectra. See http://www.rsc.org/suppdata/cc/b3/b301874a/

1,12-Bis(diphenylphosphino)dodecane and PdCl2 are shown to form linear supramolecular polymers in equilibrium with cyclic structures; high molecular weight material was obtained by melt polymerisation.

Adsorption of Humic Substances onto Kaolin Clay Related to Their Structural Features

Eleven well characterized humic substances (HSs) were adsorbed from aqueous solution onto a Na‐kaolin clay. The adsorption affinity (KL), maximum adsorption capacity (b), a coefficient of desorption hysteresis (H), and the concentration of irreversibly adsorbed HS (IHS) were derived from adsorption‐desorption isotherms. These parameters were correlated with structural features of the HS. The adsorption affinity was shown to correlate directly with the aromaticity of the HS and inversely with their polarity, expressed as the O/C atomic ratio. A dependency between polarity and maximum adsorption capacity was not confirmed. The parameters b, H, and IHS expose close correlation with the molecular weight (MW) and the partial negative charge of HS (Z) at the operating pH value. The following quantitative relationship was obtained: b = 715 − 0.06 × MW − 529 × Z (r = 0.92). It allows a selection of HS with respect to the largest content of organic matter in HS‐kaolin clay complexes. Among the HS studied the high molecular weight materials enriched with C‐ and H‐substituted aromatics, such as coal and peat humic acids (HAs), are shown to be the most preferential materials for preparing stable HS‐clay complexes.

Controlled flux behaviour of membrane processes

Controlling ultrafiltration (UF) and microfiltration (MF) membrane fluxes at or around a region where fouling is minimal can provide an interesting and economic operating regime. Selectivity may be enhanced and cleaning may be easier. For a given flux it is sometimes possible to filter a product suspension at the same trans-membrane pressure (TMP) as for pure water (PWP), but this can require a lot of energy input to maintain cross-flow or high shear in other ways if high fluxes are required. The critical flux is the flux above which one starts to observe fouling. By operating at lower cross-flow velocities and just above the critical flux, and thus, with lower TMPs, periodic cleaning can be effected by temporarily stopping permeation. A change in feed rate demands a change in flux which is obtained by temporarily increasing energy inputs. Controlled flux improves macromolecular fractionation. As flux increases the rejection of high molecular weight materials decreases whilst that of lower molecular weight materials decreases. This paper discusses the causes of fouling and the use controlled flux operation to mitigate its effects.

The cornucopia of beam applications

Three themes touched upon in this brief review are: a historical perspective of non-semiconductor ion implantation; novel research directions that have evolved from ion beam-based research; and a new way to view the preponderance of techniques to generate beams. Surface modification of materials by ion beams began with ∼100 keV monomer, singly charged ions and over the years expanded to lower energy, higher current, neutral or multiply charged species and higher molecular weights. As a result of the expansion of beam production to very high molecular weight materials, a new way to view the relationship of beams to high technology is discussed.

Cell cycle-dependent dynamic association of cyclin/Cdk complexes with human DNA replication proteins.

We have previously described the isolation of a replication competent (RC) complex from calf thymus, containing DNA polymerase alpha, DNA polymerase delta and replication factor C. Here, we describe the isolation of the RC complex from nuclear extracts of synchronized HeLa cells, which contains DNA replication proteins associated with cell-cycle regulation factors like cyclin A, cyclin B1, Cdk2 and Cdk1. In addition, it contains a kinase activity and DNA polymerase activities able to switch from a distributive to a processive mode of DNA synthesis, which is dependent on proliferating cell nuclear antigen. In vivo cross-linking of proteins to DNA in synchronized HeLa cells demonstrates the association of this complex to chromatin. We show a dynamic association of cyclins/Cdks with the RC complex during the cell cycle. Indeed, cyclin A and Cdk2 associated with the complex in S phase, and cyclin B1 and Cdk1 were present exclusively in G(2)/M phase, suggesting that the activity, as well the localization, of the RC complex might be regulated by specific cyclin/Cdk complexes.

Chemical characterization of galactomannans and arabinogalactans from two arabica coffee infusions as affected by the degree of roast.

Galactomannans and arabinogalactans compose almost exclusively the polysaccharide fraction of roasted coffee infusions. To increase the knowledge about the effect of the degree of roast (DR) in the amount and chemical structure of the galactomannans and arabinogalactans, two arabica coffees of different geographical origins (Costa Rica and Brazil) were roasted for three degrees of roast (DRs 4.7-5.0, 8.7, and 10% of dry weight loss of green coffee beans, on a dry basis). The high molecular weight material was extracted with hot water and dialyzed (molecular weight cutoff >12 kDa), and the material was separated in three cold-water-soluble fractions by graded addition of ethanol. The degree of polymerization and the degree of branching of the galactomannans decreased with the increase of the DR. As the DR increased, less branched arabinogalactans were extracted. The relative amount of terminally linked arabinosyl residues of the arabinogalactans decreased with the increase in DR, and the terminally linked galactosyl residues increased. Also, the size of the arabinosyl side chains of the arabinogalactans decreased with the increase in DR.

Physicochemical properties of potato starch illuminated with visible polarised light

Suspensions (30%, w/w) of potato starch in pure water were illuminated for 5–50 h by linearly polarised visible light (λ>500 nm) under stream of nitrogen. Effects of the illumination on the transition enthalpy, melting temperature, the pasting viscosity profiles, and iodine binding capacity of illuminated starch were examined. Starch illuminated in water for 50 h showed lower melting temperature T p (60.57 °C) and transition enthalpy Δ H (10.01 J/g) than original potato starch soaked in water for the same period. After 25 h illumination in water the peak paste viscosity, P v, of starch decreased in order to raise after 50 h illumination. Illumination in water initially degraded starch but prolonged illumination resulted in crosslinking into material of higher molecular weight.

Tailored Semiconducting Polymers: Living Radical Polymerization and NLO-Functionalization of Triphenylamines

This paper describes the preparation of various polymers with triarylamine side groups. High molecular weight materials were obtained by free radical polymerization utilizing the gel effect. Polymers with a narrow polydispersity and a predetermined molecular weight could be prepared by living radical polymerization. The Tg could, thereby, be controlled between 50 and 140°C either by using different monomers or by varying the molecular weight. Living radical polymerization allowed in addition the preparation of block copolymers. The triarylamine side groups could be transformed into NLO-chromophores by reaction with tetracyanoethylene. This leads to the incorporation of tricyanoethylene acceptor groups. As this reaction can be performed selectively on one block in block copolymers, microphase separated structures are accessible, which possess charge transport moieties in one phase and NLO-chromophores in the other phase.

The role of molecular weight and temperature on the elastic and viscoelastic properties of a glassy thermoplastic polyimide

Mechanical testing of the elastic and viscoelastic response of an advanced thermoplastic polyimide (LaRC™-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The notched tensile strength was shown to be a strong function of both molecular weight and temperature, whereas stiffness was only a strong function of temperature. A critical molecular weight was observed at a weight-average molecular weight of M ̄ w ∼22 000 g/mol below which the notched tensile strength decreases rapidly. This critical molecular weight transition is temperature-independent. Low molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. Furthermore, low molecular weight materials have increased creep compliance and creep compliance rate and are more sensitive to temperature than the high molecular weight materials. At long timescales (>1100 h) physical ageing serves to significantly decrease the creep compliance and creep rate of all the materials tested. Low molecular weight materials are less influenced by the effects of physical ageing.

Formation of triacylglycerol core aldehydes during rapid oxidation of corn and sunflower oils with tert-butyl hydroperoxide/Fe2+.

The lipid ester core aldehydes formed during a rapid oxidation (7.8 M tert-butyl hydroperoxide, 90 min at 37 degrees C) of the triacylglycerols of purified corn and sunflower oils were isolated as dinitrophenylhydrazones by preparative thin-layer chromatography and identified by reversed-phase high-performance liquid chromatography with on-line electrospray ionization mass spectrometry and by reference to standards. A total of 113 species of triacylglycerol core aldehydes were specifically identified, accounting for 32-53% of the 2,4-dinitrophenylhydrazine (DNPH)-reactive material of high molecular weight representing 25-33% of the total oxidation products. The major core aldehyde species (50-60% of total triacylglycerol core aldehydes) were the mono(9-oxo)nonanoyl- and mono(12-oxo)-9,10-epoxy dodecenoyl- or (12-oxo)-9-hydroxy-10,11-dodecenoyl-diacylglycerols. A significant proportion of the total (9-oxo)nonanoyl and epoxidized (12-oxo)-9,10-dodecenoyl core aldehydes was found in complex combinations with hydroperoxy or hydroxy fatty acyl groups (6-10% of total triacylglycerol core aldehydes). Identified were also di(9-oxo)nonanoylmonoacylglycerols (0.5% of total) and tri(9-oxo)nonanoylglycerols (trace). The identification of the oxoacylglycerols was consistent with the products anticipated from tert-butyl hydroperoxide oxidation of the major species of corn and sunflower oil triacylglycerols (mainly linoleoyl esters). However, the anticipated (13-oxo)-9,11-tridecadienoyl aldehyde-containing acylglycerols were absent because of further oxidation of the dienoic core aldehyde. A significant proportion of the unsaturated triacylglycerol core aldehydes contained tert-butyl groups linked to the unsaturated fatty chains via peroxide bridges (2-9%). The study demonstrates that rapid peroxidation with tert-butyl hydroperoxide constitutes an effective method for enriching natural oils and fats in triacylglycerol core aldehydes for biochemical and metabolic testing.

Fighting Infectious Diseases with Inhibitors of Microbial Adhesion to Host Tissues

The majority of infectious diseases are initiated by the adhesion of pathogenic organisms to the tissues of the host. In many cases this adhesion is mediated by lectins present on the surface of the infectious organism that bind to complementary carbohydrates on the surface of the host tissues. Soluble carbohydrates recognized by the bacterial lectins block the adhesion of the bacteria to animal cells in vitro. Moreover, such carbohydrates have been shown to protect against experimental infection by lectin–carrying bacteria of different mammals, such as mice, rabbits, calves, and monkeys. Agents other than carbohydrates also block adhesion, as demonstrated with cranberry juice as well as with low and high molecular weight preparations isolated from the juice. Both kinds of preparation inhibited the adhesion in vitro of Escherichia coli to different animal cells. In addition, the high molecular weight material acted similarly on the adhesion of Helicobacter pylori to human gasrointenstinal cells, and on the coaggregation of oral bacteria. Furthermore, in limited clinical studies regular drinking of cranberry juice had a significant preventive effect on bacteriuria, and the high molecular weight constituent of the juices was also effective in decreasing the salivary level of Streptococus mutans, the major cause of tooth decay. Because the inhibitors of adhesion examined are not bactericidal, the selection of resistant inhibitor strains is unlikely to occur. Together, these findings may lead to new therapeutic strategies that are in dire need because of the world–wide increase in antibiotic resistant bacteria.