Influence of Structural Characteristics on Stretching-Driven Swelling of Polyrotaxane Gels with Movable Cross Links

2012 ◽  
Vol 45 (16) ◽  
pp. 6733-6740 ◽  
Author(s):  
Akihiro Konda ◽  
Koichi Mayumi ◽  
Kenji Urayama ◽  
Toshikazu Takigawa ◽  
Kohzo Ito
1986 ◽  
Vol 240 (1) ◽  
pp. 107-114 ◽  
Author(s):  
S W Crawford ◽  
R P Mecham ◽  
H Sage

The structural relationships and intermolecular organization among the proteins associated with pulmonary surfactant are largely unknown. We studied the pulmonary-surfactant-associated proteins in the bronchoalveolar lavage fluid obtained from a patient with the clinical syndrome of alveolar proteinosis. The major proteins with Mr values of 32,000-36,000 and 62,000 formed thiol-dependent complexes (Mr greater than 400,000) with intermolecular disulphide bonds present in the collgenase-sensitive domains of these proteins. In contrast, other proteins, which were collagenase-insensitive, formed thiol-dependent oligomers that were not covalently linked to the major proteins. The associations of these proteins in the surfactant of a normal individual were similar. By amino acid analysis, two-dimensional peptide mapping and bacterial-collagenase digestion the 32,000-36,000-Mr and 62,000-Mr proteins were nearly identical. Differences in CNBr cleavage products suggested that the larger of the proteins was formed by non-disulphide, covalent, cross-links in the collagenase-sensitive domains of the 32,000-36,000-Mr proteins. Thus the evidence suggested that the lipid-associated proteins of Mr 32,000-36, 000 contained both disulphide and non-disulphide cross-links in the collagen-like N-terminal region of the proteins and form higher-Mr complexes. This organization may support the three-dimensional conformation of surfactant in the alveolar space.


Processes ◽  
2019 ◽  
Vol 8 (1) ◽  
pp. 16 ◽  
Author(s):  
Sanaz Khalighi ◽  
Ralf G. Berger ◽  
Franziska Ersoy

Sugar beet fibre (fibrex) is an abundant side-stream from the sugar refining industry. A self-produced laccase from Funalia trogii (LccFtr) (0.05 U/µg FA) successfully cross-linked fibrex to an edible gel. Dynamic oscillation measurements of the 10% fibrex gels showed a storage modulus of 5.52 kPa and loss factors ≤ 0.36 in the range from 20 to 80 Hz. Comparing storage stability of sweetened 10% fibrex gels with sweetened commercial 6% gelatin gels (10% and 30% d-sucrose) indicated a constant storage modulus and loss factors ≤ 0.7 during four weeks of storage in fibrex gels. Loss factors of sweetened gelatin gels were ≤0.2, and their storage modulus decreased from 9 to 7 kPa after adding d-sucrose and remained steady for four weeks of storage. Fibrex gel characteristics, including high water holding capacity, swelling ratio in saliva, and heat resistance are attributed to a covalently cross-linked network. Vanillin, as a mediator, and citrus pectin did not enhance covalent cross-links and elastic properties of the fibrex gels. Thus, laccase as an oxidative agent provided gels with a solid and stable texture. Fibrex gels may find uses in pharmaceutical and other industrial applications, which require a heat-resistant gel that forms easily at room temperature. They also represent an ethical alternative for manufacturing vegan, halal, and kosher food.


1991 ◽  
Vol 248 ◽  
Author(s):  
Y. Yang ◽  
N. Ichise ◽  
Z. Li ◽  
Q. Yuan ◽  
J. E. Mark ◽  
...  

AbstractThere are a variety of gels (highly swollen solids) that are of considerable interest to polymer scientists, materials scientists, and ceramists. One type consists of typical organic polymers such as polyethylene or polystyrene, in networks which are formed by means of physical cross links, such as crystallites or physical aggregates. Such gels are thermoreversible in that liquefaction occurs upon heating. Another type consists of chain-like structures permanently bonded into covalent networks. These permanently branched and cross-linked chains can be either organic (phenol-formaldehyde resins, epoxies, etc.), or inorganic [silica (SiO2), titania (TiO2), zirconia (ZrO2), etc.] Both the organic and inorganic covalent types have been used to prepare aerogels, and the inorganic ones are now much used to prepare high-tech ceramics by the new sol-gel route.In the case of the thermoreversible, organic polymer gels, moduli can be measured as a function of concentration, temperature, and structural characteristics of the polymer (molecular weight, molecular weight distribution, and nature and degree of any chain branching). Such equilibrium results give information on the nature of the gels, including the influence of morphology, and the presence of dangling-chain irregularities. Measurements carried out as a function of time, for example, on polyethylene homopolymers and copolymers, can give information about their gelation kinetics.In the case of the ceramic materials, the evolution of the shear modulus with time is very useful in establishing induction times, rates of gelation, and aging effects. Correlation of such information with results of scattering studies can give much insight into the nature of the sol-gel process.


2013 ◽  
Vol 2013 ◽  
pp. 1-29 ◽  
Author(s):  
M. P. M. Marques

Since the introduction of cisplatin to oncology in 1978, Pt(II) and Pd(II) compounds have been intensively studied with a view to develop the improved anticancer agents. Polynuclear polyamine complexes, in particular, have attracted special attention, since they were found to yield DNA adducts not available to conventional drugs (through long-distance intra- and interstrand cross-links) and to often circumvent acquired cisplatin resistance. Moreover, the cytotoxic potency of these polyamine-bridged chelates is strictly regulated by their structural characteristics, which renders this series of compounds worth investigating and their synthesis being carefully tailored in order to develop third-generation drugs coupling an increased spectrum of activity to a lower toxicity. The present paper addresses the latest developments in the design of novel antitumor agents based on platinum and palladium, particularly polynuclear chelates with variable length aliphatic polyamines as bridging ligands, highlighting the close relationship between their structural preferences and cytotoxic ability. In particular, studies by vibrational spectroscopy techniques are emphasised, allowing to elucidate the structure-activity relationships (SARs) ruling anticancer activity.


2012 ◽  
Vol 445 ◽  
pp. 380-385 ◽  
Author(s):  
Sedat Alkoy ◽  
A. Serkan Tekdas ◽  
Emre Tekel ◽  
Recep Olukkent

Piezoceramics are usually shaped into three dimensional bulk form using dry pressing or slip casting methods. However, certain applications require piezoceramics to be shaped in one dimensional fiber or two dimensional ribbon form. In this study, piezoceramic fibers and curved piezoceramic ribbons were fabricated using a novel alginate gelation method. Alginate is a natural linear polymer that is obtained from brown kelp. In the presence of multivalent cations, it forms ionic cross-links and gels in a three dimensional network form. In our study, gelation conditions of alginate containing aqueous slips of lead zirconate titanate based piezoelectric ceramic powders were investigated. Piezoelectric ceramic fibers and ceramic ribbons were prepared by sintering of gelled powders for transducer applications. Structural characteristics of these ceramics and electrical characteristics of piezodevices prepared from these ceramics were investigated and reported.


Author(s):  
R. Gronsky

The phenomenon of clustering in Al-Ag alloys has been extensively studied since the early work of Guinierl, wherein the pre-precipitation state was characterized as an assembly of spherical, ordered, silver-rich G.P. zones. Subsequent x-ray and TEM investigations yielded results in general agreement with this model. However, serious discrepancies were later revealed by the detailed x-ray diffraction - based computer simulations of Gragg and Cohen, i.e., the silver-rich clusters were instead octahedral in shape and fully disordered, atleast below 170°C. The object of the present investigation is to examine directly the structural characteristics of G.P. zones in Al-Ag by high resolution transmission electron microscopy.


Author(s):  
V. Annamalai ◽  
L.E. Murr

Economical recovery of copper metal from leach liquors has been carried out by the simple process of cementing copper onto a suitable substrate metal, such as scrap-iron, since the 16th century. The process has, however, a major drawback of consuming more iron than stoichiometrically needed by the reaction.Therefore, many research groups started looking into the process more closely. Though it is accepted that the structural characteristics of the resultant copper deposit cause changes in reaction rates for various experimental conditions, not many systems have been systematically investigated. This paper examines the deposit structures and the kinetic data, and explains the correlations between them.A simple cementation cell along with rotating discs of pure iron (99.9%) were employed in this study to obtain the kinetic results The resultant copper deposits were studied in a Hitachi Perkin-Elmer HHS-2R scanning electron microscope operated at 25kV in the secondary electron emission mode.


Author(s):  
G. M. Michal

Several TEM investigations have attempted to correlate the structural characteristics to the unusual shape memory effect in NiTi, the consensus being the essence of the memory effect is ostensible manifest in the structure of NiTi transforming martensitic- ally from a B2 ordered lattice to a low temperature monoclinic phase. Commensurate with the low symmetry of the martensite phase, many variants may form from the B2 lattice explaining the very complex transformed microstructure. The microstructure may also be complicated by the enhanced formation of oxide or hydride phases and precipitation of intermetallic compounds by electron beam exposure. Variants are typically found in selfaccommodation groups with members of a group internally twinned and the twins themselves are often observed to be internally twinned. Often the most salient feature of a group of variants is their close clustering around a given orientation. Analysis of such orientation relationships may be a key to determining the nature of the reaction path that gives the transformation its apparently perfect reversibility.


Author(s):  
John M. Murray ◽  
Rob Ward

The eukaryotic flagellum is constructed from 11 parallel tubular elements arranged as 9 peripheral fibers (doublet microtubules) and 2 central fibers (singlet microtubules). The primary motion generating component has been found to be arranged as axially periodic “arms” bridging the adjacent doublets. The dynein, comprising the arms, has been isolated and characterized from several different cilia and flagella. Various radial and azimuthal cross-links stabilize the axially aligned microtubules, and probably play some role in controlling the form of the flagella beat cycle.


Author(s):  
Christopher Viney

Light microscopy is a convenient technique for characterizing molecular order in fluid liquid crystalline materials. Microstructures can usually be observed under the actual conditions that promote the formation of liquid crystalline phases, whether or not a solvent is required, and at temperatures that can range from the boiling point of nitrogen to 600°C. It is relatively easy to produce specimens that are sufficiently thin and flat, simply by confining a droplet between glass cover slides. Specimens do not need to be conducting, and they do not have to be maintained in a vacuum. Drybox or other controlled environmental conditions can be maintained in a sealed chamber equipped with transparent windows; some heating/ freezing stages can be used for this purpose. It is relatively easy to construct a modified stage so that the generation and relaxation of global molecular order can be observed while specimens are being sheared, simulating flow conditions that exist during processing. Also, light only rarely affects the chemical composition or molecular weight distribution of the sample. Because little or no processing is required after collecting the sample, one can be confident that biologically derived materials will reveal many of their in vivo structural characteristics, even though microscopy is performed in vitro.


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