• Elastomers and Composites
• /
• v.49 no.1
• /
• pp.24-30
• /
• 2014

3-Amino-1,2,4-triazole (ATA) (2.5 and 5.0 phr) was incorporated into a immiscible maleated ethylene propylene diene rubber(mEPDM)/maleated high density polyethylene(mHDPE) (50 wt%/50 wt%) blend by melt mixing. Effects of the ATA on structure, mechanical and rheological properties of the blend was investigated. FT-IR and DMA results revealed that supramolecular hydrogen bonding interactions between the polymer chains occur by reaction of ATA with maleic anhydride grafted onto the component polymers in the blend, which induces the physical crosslinks in the blend. FE-SEM analysis showed that mEPDM forms a dispersed phase in continuous mHDPE matrix, and the blend with the ATA has finer phase morphology as compared to the blend without the ATA. By the addition of ATA in the blend, there were significant increases in tensile strength, modulus and elongation-at-break as well as elastic recoverability. Melt rheology studies revealed that ATA induced substantial increase in storage modulus and complex viscosity of the blend at the melt state.

• Elastomers and Composites
• /
• v.44 no.3
• /
• pp.196-208
• /
• 2009

Sophisticated polymeric materials with 'responsive' properties are beginning to reach the market. The use of reversible, noncovalent interactions is a recurring design principle for responsive materials. Recently developed hydrogen-bonding units allow this design principle to be taken to its extreme. Supramolecular polymers, where hydrogen bonds are the only force keeping the monomers together, form materials whose (mechanical) properties respond strongly to a change in temperature or solvent. In this review, we describe some examples of hydrogen-bonded supramolecular polymers that can be utilized for self-healing materials. Synthesis of a rubber-like material that can be recycled might not seem exciting. But one that can also repeatedly repair itself at room temperature, without adhesives, really stretches the imagination. Autonomic healing materials respond without external intervention to environmental stimuli in a nonlinear and productive fashion, and have great potential for advanced engineering systems.

• Journal of Photoscience
• /
• v.9 no.2
• /
• pp.106-109
• /
• 2002

Archaeal rhodopsins possess retinal molecule as their chromophores, and their light-energy and light-signal conversions are triggered by all-trans to 13-cis isomerization of the retinal chromophore. Relaxation through structural changes of protein then leads to functional processes, proton pump in bacteriorhodopsin (bR) and transducer activation in phoborhodopsin (pR). It is known that sensory rhodopsins can pump protons in the absence of their transducers. Thus, there should be common and specific features in their protein structural changes for function. In this paper, our r ecent studies on pR from Natronobacterium pharaonis (ppR) by means of low-temperature Fourier-transform infrared (FTIR) spectroscopy are compared with those of bR. In particular, protein structural changes upon retinal photoisomerization are studied. Comparative investigation of ppR and bR revealed the similar structures of the polyene chain of the chromophore and water-containing hydrogen-bonding network, whereas the structural changes upon photoisomerization were more extended in ppR than in bR. Extended protein structural changes were clearly shown by the assignment of the C=O stretch of Asnl05. FTIR studies of a ppR mutant with the same retinal binding site as in bR revealed that the Schiff base region is important to determine their colors.

• Journal of Photoscience
• /
• v.9 no.2
• /
• pp.311-313
• /
• 2002

X-ray structures of pharaonis phoborhodopsin (ppR) show the different direction of the side chain of Arg72 from that of the corresponding residue (Arg82) of bacteriorhodopsin, BR. For BR, this residue is considered to play an important role in the proton pumping. In order to investigate the role of Arg72 in ppR, we constructed Arg72 mutants of R72A, R72K and R72Q, and measured the photocycle and proton pumping activities. The pH-titration curves on the absorption maximum of the mutants were shifted to alkaline in comparison of that of the wild-type. This may imply the increase of pKa of D75, suggesting the presence of the (probably electric) interaction between D75 and Arg72. Rate constants of the M-decay were 3-7 times faster than that of the wild-type, and the time for the completion of the photocycling was also reduced. Using Sn0$_2$ electrode, the rate of transmembrane proton transport was measured upon illumination. The photo-induced proton pumping activities were estimated after the corrections that are the percentages of the associated form of D75 (which has no pumping activity) and the photocycling rates. R72A and R72Q showed the reduced activity while R72K did not reduce the activity.

• Korean Journal of Crystallography
• /
• v.11 no.1
• /
• pp.22-27
• /
• 2000

The structure of cis-(malonato)[(4R,5R)-4,5-bis(aminomethyl)-2-isopropyl-1,3-dioxolane]platinum(II) with a potent anticancer activity has been determined by the X-ray crystallographic method. Crystal data are as follows: Pt(C/sub 11/H/sub 20/N₂O/sub 6/), M/sub 4/=471.38, monoclinic, P2₁, a=7.112(1), b=33.615(3), c=7.135(1)Å, β=116.80(1)°, V=1522.6(3)Å, and Z=4. The two independent molecules with very similar structures are approximately related by pseudo two-fold screw axis symmetry, which makes the monolinic cell look like the orthorhombic cell with one molecule in the asymmetric unit and space group C222₁. The crystal packing mode is similar to that of the analogue with the dimethyl substituents instead of the isopropyl group. The Pt atom is coordinate to two O and two N atoms in a square planar structure. The six-membered chelate ring in the leaving ligand assumes a conformation intermediate between the half chair and the boat forms. The seven-membered ring in the carrier ligand assumes a twist-chair conformation and the oxolane ring assumes an envelope conformation. Crystal packing consists of the extensive hydrogen-bonding network in the two-dimensional molecular layers and weak van der Waals interactions between these layers.

• Molecules and Cells
• /
• v.43 no.9
• /
• pp.784-792
• /
• 2020

Arginine kinase (AK), a bioenergy-related enzyme, is distributed widely in invertebrates. The role of highly conserved histidines in AKs is still unascertained. In this study, the highly conserved histidine 284 (H284) in AK of Daphnia magna (DmAK) was replaced with alanine to elucidate the role of H284. We examined the alteration of catalytic activity and structural changes of H284A in DmAK. The catalytic activity of H284A was reduced dramatically compared to that in wild type (WT). Thus the crystal structure of H284A displayed several structural changes, including the alteration of D324, a hydrogen-bonding network around H284, and the disruption of π-stacking between the imidazole group of the H284 residue and the adenine ring of ATP. These findings suggest that such alterations might affect a conformational change of the specific loop consisting of G310-V322 at the antiparallel β-sheet region. Thus, we speculated that the H284 residue might play an important role in the conformational change of the specific loop when ATP binds to the substrate-binding site of DmAK.

• Journal of Adhesion and Interface
• /
• v.4 no.3
• /
• pp.33-40
• /
• 2003

In this work, diglycidyl ether of bisphenol A (DGEBA)/polyetherimide (PEI) blends were cured using 4,4-diaminodiphenyl methane (DDM). And the effects of addition of different PEI contents to neat DGEBA were investigated in the thermal properties and fracture toughness of the blends. The contents of contents of containing PEI were varied in 0, 2.5, 5, 7.5, and 10 phr. The cure activation energies ($E_a$) of the cured specimens were determined by Kissinger equation and the mechanical interfacial properties of the specimens were performed by critical stress intensity factor ($K_{IC}$). Also their surfaces were examined by using a scanning electron microscope (SEM) and the surface energetics of blends was determined by contact angles. As a result, $E_a$ and $K_{IC}$ showed maximum values in the 7.5 phr PEI. This result was interpreted in the increment of the network structure of DGEBA/PEI blends. Also, the surface energetics of the DGEBA/PEI blends showed a similar behavior with the results of $K_{IC}$. This was probably due to the improving of specific or polor component of the surface free energy of DGEBA/PEI blends, resulting in increasing the hydrogen bonding of the hydroxyl and imide groups of the blends.

• Proceedings of the Korean Fiber Society Conference
• /
• 1990.06b
• /
• pp.36-37
• /
• 1990

In the past, facile dissolution of cellulose has been hampered by the lack of suitable nondegrading solvents. Recently, this problem has been solved in our laboratory by the discovery of an inexpensive, convenient solvent system, that is the mixture of $NH_3\;and\;NH_4SCN$, for cellulose. Also, the $cellulose/NH_3/NH_4SCN$ solution system has been found to form the anisotropic, i.e., liquid crystalline phase. It is believed that both the cholesterio and the nematic phase occur. This finding has prompted extensive on-going researoh on the formation of the liquid crystalline phase from an inexpensive natural source such as cellulose since the nematic phase is envisioned as an excellent precursor sources for products with desirable properties, for example, high modulus and high strength. This interest naturally leads to a desire to understand the theological properties of the nematic phase so that the transformation of the nematic phase to the solid state with desirable properties can be efficiently accomplished, ;From this point of view, the theological behavior of the $cellulose/NH3_/NH_4SCN$ system has been studied as a function of shear rate and shear stress over a wide range of solvent compositions, cellulose concentration, centrifugation and urea contents, Results indicate that the viscosity decreases with increasing shear rate. A marked shear thinning behavior and a quasi-Newtonian behavior were observed in the low shear rate region and in the high shear rate region, respectively for all solvent compositions. The $cellulose/NH_3/NH_4SCN$ solution system only exhibited the viscosity increase with increasing cellulose concentration and failed to show the viscosity drop generally observed at the point of incipience of liquid crystal formation, This may be due to the gel-like nature of the solution by the association of the rodlike molecules into bundles which may serve as crosslinking points giving the cellulose solution a network structure. Also, simply hydrogen bonding may be so restrictive of molecular mobility that a viscosity drop is blocked. In addition to the above results, yield stress and thixotropy were also observed in the $cellulose/NH_3/NB_4SCN$ solution system which are characteristics of liquid crystal and gel, The results of the effect of centrifugation on viscosity show that viscosity decreases by the application of centrifugation. This may be explained by the change of the piled polydomain structure to the dispersed polydomain structure due to the pressure gradient generated during centrifugation.ation.

• Journal of the Korean Institute of Gas
• /
• v.2 no.4
• /
• pp.18-24
• /
• 1998

Polyurethane (PU) synthesized from 4,4'-diphenylmethane diisocyanate having high functionality (f=2.9) and polyester polyol have been investigated by differential scanning calorimeter (DSC), dynamic mechanical thermal analyzer (DMTA), and Fourier transform infrared spectroscope (FT-IR). From the DSC measurement of polyurethane, a single transition temperature ($T_g$) was observed. This result indicates that polyurethanes synthesized in this work have homogeneous network structure due to high functionality of diisocyanate. It was also found that the $T_g$ of polyurethane was increased as hard segment content was increased. The results from DMTA measurement are consistent with DSC results. In order to investigate the effect of thermal annealing on the $T_g$ of polyurethane, the samples were annealed at various annealing conditions. $T_gs$ of polyurethanes were found to increased with annealing temperature. From swelling experiment and FT-IR studies, it was found that the $T_g$ was increased as crosslinking density of polyurethane was increased.