• Title/Summary/Keyword: Hydrogen Network

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$^{15}$N NMR Relaxation Study of the Catalytic Residues in Y14F Mutant Ketosteroid Isomerase

  • Yoon, Ye-Jeong;Lee, Hyeong-Ju;Kim, Chul;Lee, Hee-Cheon
    • Journal of the Korean Magnetic Resonance Society
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    • v.8 no.2
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    • pp.77-85
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    • 2004
  • $^1$H-detected $^{15}$N NMR was employed to investigated the effect of mutation (Y14F) on the dynamic properties of catalytic residues in ${\Delta}^5$-3- ketosteroid isomerase (KSI) from Conamonas testosteroni. In particular, the backbone dynamics of the catalytic residues have been studied in free enzyme and its complex with a steroid ligand, 19-nortestosterone hemisuccinate, by $^{15}$N relaxation measurements. The relaxation data were analyzed using the model-free formalism to extract the model-free parameters (S$^2$, ${\tau}_e$, and R$_{ex}$). The results show that the mutation causes a significant decrease in the order parameter (S$^2$) for the catalytic residues of free Y14F KSI, presumably due to breakdown of the hydrogen bond network by mutation. In addition, the order parameters of Phe-14 and Asp-99 increased slightly upon ligand binding, indicating a slight restriction of the high-frequency (pico- to nanosecond) internal motions of the residues in the complexed Y14F KSI, while the order parameter of Tyr-55 decreased significantly upon ligand binding.

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The Roles of Peroxiredoxin and Thioredoxin in Hydrogen Peroxide Sensing and in Signal Transduction

  • Netto, Luis E.S.;Antunes, Fernando
    • Molecules and Cells
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    • v.39 no.1
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    • pp.65-71
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    • 2016
  • A challenge in the redox field is the elucidation of the molecular mechanisms, by which $H_2O_2$ mediates signal transduction in cells. This is relevant since redox pathways are disturbed in some pathologies. The transcription factor OxyR is the $H_2O_2$ sensor in bacteria, whereas Cys-based peroxidases are involved in the perception of this oxidant in eukaryotic cells. Three possible mechanisms may be involved in $H_2O_2$ signaling that are not mutually exclusive. In the simplest pathway, $H_2O_2$ signals through direct oxidation of the signaling protein, such as a phosphatase or a transcription factor. Although signaling proteins are frequently observed in the oxidized state in biological systems, in most cases their direct oxidation by $H_2O_2$ is too slow ($10^1M^{-1}s^{-1}$ range) to outcompete Cys-based peroxidases and glutathione. In some particular cellular compartments (such as vicinity of NADPH oxidases), it is possible that a signaling protein faces extremely high $H_2O_2$ concentrations, making the direct oxidation feasible. Alternatively, high $H_2O_2$ levels can hyperoxidize peroxiredoxins leading to local building up of $H_2O_2$ that then could oxidize a signaling protein (floodgate hypothesis). In a second model, $H_2O_2$ oxidizes Cys-based peroxidases that then through thiol-disulfide reshuffling would transmit the oxidized equivalents to the signaling protein. The third model of signaling is centered on the reducing substrate of Cys-based peroxidases that in most cases is thioredoxin. Is this model, peroxiredoxins would signal by modulating the thioredoxin redox status. More kinetic data is required to allow the identification of the complex network of thiol switches.

Insight into Structural Aspects of Histidine 284 of Daphnia magna Arginine Kinase

  • Rao, Zhili;Kim, So Young;Li, Xiaotong;Kim, Da Som;Kim, Yong Ju;Park, Jung Hee
    • Molecules and Cells
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    • v.43 no.9
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    • pp.784-792
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    • 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.

Injectable hydrogels delivering therapeutic agents for disease treatment and tissue engineering

  • Lee, Jin Hyun
    • Biomaterials Research
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    • v.22 no.4
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    • pp.235-248
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    • 2018
  • Background: Injectable hydrogels have been extensively researched for the use as scaffolds or as carriers of therapeutic agents such as drugs, cells, proteins, and bioactive molecules in the treatment of diseases and cancers and the repair and regeneration of tissues. It is because they have the injectability with minimal invasiveness and usability for irregularly shaped sites, in addition to typical advantages of conventional hydrogels such as biocompatibility, permeability to oxygen and nutrient, properties similar to the characteristics of the native extracellular matrix, and porous structure allowing therapeutic agents to be loaded. Main body: In this article, recent studies of injectable hydrogel systems applicable for therapeutic agent delivery, disease/cancer therapy, and tissue engineering have reviewed in terms of the various factors physically and chemically contributing to sol-gel transition via which gels have been formed. The various factors are as follows: several different non-covalent interactions resulting in physical crosslinking (the electrostatic interactions (e.g., the ionic and hydrogen bonds), hydrophobic interactions, ${\pi}$-interactions, and van der Waals forces), in-situ chemical reactions inducing chemical crosslinking (the Diels Alder click reactions, Michael reactions, Schiff base reactions, or enzyme-or photo-mediated reactions), and external stimuli (temperatures, pHs, lights, electric/magnetic fields, ultrasounds, or biomolecular species (e.g., enzyme)). Finally, their applications with accompanying therapeutic agents and notable properties used were reviewed as well. Conclusion: Injectable hydrogels, of which network morphology and properties could be tuned, have shown to control the load and release of therapeutic agents, consequently producing significant therapeutic efficacy. Accordingly, they are believed to be successful and promising biomaterials as scaffolds and carriers of therapeutic agents for disease and cancer therapy and tissue engineering.

A merging framework for improving field scale root-zone soil moisture measurement with Cosmic-ray neutron probe over Korean Peninsula

  • Nguyen, Hoang Hai;Choi, Minha
    • Proceedings of the Korea Water Resources Association Conference
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    • 2019.05a
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    • pp.154-154
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    • 2019
  • Characterization of reliable field-scale root-zone soil moisture (RZSM) variability contribute to effective hydro-meterological monitoring. Although a promising cosmic-ray neutron probe (CRNP) holds the pontential for field-scale RZSM measurement, it is often restricted at deeper depths due to the non-unique sensitivity of CRNP-measured fast neutron signal to other hydrogen pools. In this study, a merging framework relied on coupling cosmic-ray soil moisture with a representative additional RZSM, was introduced to scale shallower CRNP effective depth to represent root-zone layer. We tested our proposed framework over a densely vegetated region in South Korea covering a network of one CRNP and nine in-situ point measurements. In particular, cosmic-ray soil moisture and ancillary RZSM retrieved from the most time stable location were considered as input datasets; whereas the remaining point locations were used to generate a reference RZSM product. The errors between these two input datasets and the reference were forecasted by a linear autoregressive model. A linear combination of forecasts was then employed to compute a suitable weight for merging two input products from the predicted errors. The performance of merging framework was evaluated against reference RZSM in comparison to the two original products and a commonly used exponential filter technique. The results of this study showed that merging framework outperformed other products, demonstrating its robustness in improving field-scale RZSM. Moreover, a strong relationship between the quality of input data and the performance merging framework in light of CRNP effective depth variation has been also underlined via the merging framework.

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MULTILAYER SPECTRAL INVERSION OF SOLAR Hα AND CA II 8542 LINE SPECTRA WITH HEIGHT-VARYING ABSORPTION PROFILES

  • Chae, Jongchul;Cho, Kyuhyoun;Kang, Juhyung;Lee, Kyoung-Sun;Kwak, Hannah;Lim, Eun-Kyung
    • Journal of The Korean Astronomical Society
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    • v.54 no.5
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    • pp.139-155
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    • 2021
  • We present an updated version of the multilayer spectral inversion (MLSI) recently proposed as a technique to infer the physical parameters of plasmas in the solar chromosphere from a strong absorption line. In the original MLSI, the absorption profile was constant over each layer of the chromosphere, whereas the source function was allowed to vary with optical depth. In our updated MLSI, the absorption profile is allowed to vary with optical depth in each layer and kept continuous at the interface of two adjacent layers. We also propose a new set of physical requirements for the parameters useful in the constrained model fitting. We apply this updated MLSI to two sets of Hα and Ca II line spectral data taken by the Fast Imaging Solar Spectrograph (FISS) from a quiet region and an active region, respectively. We find that the new version of the MLSI satisfactorily fits most of the observed line profiles of various features, including a network feature, an internetwork feature, a mottle feature in a quiet region, and a plage feature, a superpenumbral fibril, an umbral feature, and a fast downflow feature in an active region. The MLSI can also yield physically reasonable estimates of hydrogen temperature and nonthermal speed as well as Doppler velocities at different atmospheric levels. We conclude that the MLSI is a very useful tool to analyze the Hα line and the Ca II 8542 line spectral daya, and will promote the investigation of physical processes occurring in the solar photosphere and chromosphere.

Media Characteristics of PVA-derivative Hydrogels Using a CGA Technique (CGA 제조기법을 응용한 PVA 하이드로젤의 담체 특성)

  • Yoon, Mi-Hae; Kwon, Sung-Hyun;Cho, Dae-Chul
    • Journal of Environmental Science International
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    • v.18 no.3
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    • pp.299-308
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    • 2009
  • We manufactured PVA-derived hydrogels using a foam generation technique that has been widely used to prepare colloidal gas aphrons(CGA). These gels were differentiated to the conventional gels such as for medical or pharmaceutical applications, which have tiny pores and some crystalline structure. Rather these should be used in de-pollution devices or adhesion of cells or biomolecules. The crosslinkers used in this work were amino acid, organic acid, sugars and lipids(vitamins). The structures of the gels were observed in a scanned electron microscope. Amino acids gels showed remarkably higher swelling ratios probably because their typical functional groups help constructing a highly crosslinked network along with hydrogen bonds. Boric acid and starch would catalyze dehydration while structuring to result in much lower water content and accordingly high gel content, leading to less elastic, hard gels. Bulky materials such as ascorbic acid or starch produced, in general, large pores in the matrices and also nicotinamide, having large hydrophobic patches was likely to enlarge pore size of its gels as well since the hydrophobicity would expel water molecules, thus leading to reduced swelling. Hydrophilicity(or hydrophobicity), functional groups which are involved in the reaction or physical linkage, and bulkiness of crosslinkers were found to be more critical to gel's cross linking structure and its density than molecular weights that seemed to be closely related to pore sizes. Microscopic observation revealed that pores were more or less homogeneous and their average sizes were $20{\mu}m$ for methionine, $10-15{\mu}m$ for citric acid, $50-70{\mu}m$ for L-ascorbic acid, $30-40{\mu}m$ for nicotinamide, and $70-80{\mu}m$ for starch. Also a sensory test showed that amino acid and glucose gels were more elastic meanwhile acid and nicotinamide gels turned out to be brittle or non-elastic at their high concentrations. The elasticity of a gel was reasonably correlated with its water content or swelling ratio. In addition, the PVA gel including 20% ascorbic acid showed fair ability of cell adherence as 0.257mg/g-hydrogel and completely degraded phenanthrene(10 mM) in 240 h.

Cure Behaviors and Fracture Toughness of PEl/Difunctional Epoxy Blends (PEI/DGEBA 블랜드계의 열적특성 및 파괴인성)

  • Park, Soo-Jin;Jin, Sung-Yeol;Kaang, Shinyoung
    • Journal of Adhesion and Interface
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    • v.4 no.3
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    • pp.33-40
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    • 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.

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Rheological Behavior of Lyotropilc Solutions of Cellulose in the $NH_3/NH_4SCN$ Solvent System

  • Jo, Jae-Jeong;Cuculo, J.A.;Theil, M.H.
    • Proceedings of the Korean Fiber Society Conference
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    • 1990.06b
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    • pp.36-37
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    • 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.

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Studies of Annealing Effect on the Properties of the Rigid Polyurethane (열처리에 따른 경질 폴리우레탄의 물성 변화 연구)

  • Kang S. J.;Jung H. C.;Kim W. N.;Lee Y. B.;Choe K. H.;Hong S. H.;Kim S. B.
    • Journal of the Korean Institute of Gas
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    • v.2 no.4
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    • pp.18-24
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    • 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.

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